Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

Definitions

• the present invention relates to a composition, a transfer film, a semiconductor package, and a method for manufacturing a semiconductor package.
• insulating films are provided between wiring and between each layer for the purposes of forming and protecting circuit wiring.
• display devices equipped with touch panels such as capacitive input devices (for example, organic electroluminescence (EL) display devices and liquid crystal display devices)
• insulating films are provided for the purposes of forming and protecting conductive patterns such as the electrode pattern corresponding to the sensor of the recognition section, the wiring of the peripheral wiring section, and the wiring of the extraction wiring section.
• Patent Document 1 discloses a composition that contains a photopolymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and an epoxy resin.
• an object of the present invention is to provide a new composition capable of forming a film having a small linear expansion coefficient and excellent adhesion to metals.
• Another object of the present invention is to provide a transfer film, a semiconductor package, and a method for producing a semiconductor package, which are related to the above composition.
• Requirement 1 The polysilsesquioxane has a functional group that interacts with a metal.
• Requirement 2 The composition further comprises a compound X which is a compound different from the polysilsesquioxane and has a functional group that interacts with a metal.
• [2] Further comprising a polymerization initiator, The composition according to [1], wherein the polysilsesquioxane includes a polysilsesquioxane having a polymerizable group.
• composition according to [1] or [2], wherein the polysilsesquioxane comprises a cage-type polysilsesquioxane.
• polysilsesquioxane comprises a cage-type polysilsesquioxane.
• polysilsesquioxane has a chain-like hydrocarbon group.
• polysilsesquioxane has a weight average molecular weight of 5,000 to 50,000.
• content of the polysilsesquioxane is 50 to 99 mass% based on the total solid content of the composition.
• composition according to [2], wherein the polymerization initiator is a radical polymerization initiator.
• the content of the polymerization initiator is 0.01 to 10 mass % based on the total solid content of the composition.
• compound X is at least one selected from the group consisting of a compound represented by the formula (1) described below, a hydrolysate of a compound represented by the formula (1), and a hydrolysis condensate of a compound represented by the formula (1).
• the present invention it is possible to provide a composition capable of forming a film having a small linear expansion coefficient and excellent adhesion to metals. Furthermore, according to the present invention, there can be provided a transfer film, a semiconductor package, and a method for producing a semiconductor package, which are related to the above composition.
• FIG. 2 is a schematic diagram showing an example of a layer structure of a transfer film.
• a numerical range expressed using “to” means a range that includes the numerical values before and after “to” as the lower and upper limits.
• the “content” of the component means the total content of those two or more components.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
• the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
• a combination of two or more preferred aspects is a more preferred aspect.
• process refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.
• the temperature condition may be 25°C.
• the temperature when performing each of the above steps may be 25°C unless otherwise specified.
• the term "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more.
• the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
• actinic rays or “radiation” refers to, for example, the bright line spectrum of a mercury lamp such as g-line, h-line, and i-line, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB).
• light refers to actinic rays or radiation.
• exposure includes not only exposure to far ultraviolet light, extreme ultraviolet light, such as that typified by mercury lamps and excimer lasers, and X-rays, but also drawing with particle beams such as electron beams and ion beams.
• solids of a composition refers to the components that form the film formed using the composition.
• a solvent e.g., an organic solvent and water
• liquid components that form a film are also considered to be solids.
• the content ratio of each repeating unit in a polymer is a molar ratio.
• the molecular weight when there is a molecular weight distribution is the weight average molecular weight (Mw).
• Mw weight average molecular weight
• Mn number average molecular weight
• (meth)acrylic acid is a concept that includes both acrylic acid and methacrylic acid
• (meth)acryloyl group is a concept that includes both acryloyl group and methacryloyl group
• (meth)acrylate is a concept that includes both acrylate and methacrylate
• (meth)acrylamide group is a concept that includes both acrylamide group and methacrylamide group.
• the bond direction of a divalent group is not limited unless otherwise specified.
• Y is -CO-O- in a compound represented by the formula "X-Y-Z”
• the compound may be either "X-O-CO-Z" or "X-CO-O-Z”.
• the layer thickness is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 ⁇ m or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 ⁇ m.
• SEM scanning electron microscope
• TEM transmission electron microscope
• composition The composition of the present invention will be described in detail below.
• the composition of the present invention (hereinafter, also simply referred to as the “composition”) contains polysilsesquioxane and satisfies at least one of requirements 1 and 2.
• Requirement 1 The polysilsesquioxane has a functional group that interacts with a metal.
• Requirement 2 The composition further contains a compound X which is a compound different from the polysilsesquioxane and has a functional group that interacts with a metal.
• the present inventors speculate as follows.
• the mechanism by which the effects are obtained is not limited by the following speculation. In other words, even if the effects are obtained by a mechanism other than the following, it is included in the scope of the present invention.
• the film formed by the composition of the present invention has a small linear expansion coefficient, and by satisfying at least one of requirements 1 and 2, the film has excellent adhesion to metal.
• the composition of the present invention can form a film exhibiting desired properties from a material different from existing resin systems (e.g., epoxy resins).
• a smaller linear expansion coefficient of a film formed from the composition is simply referred to as "smaller linear expansion coefficient”
• better adhesion to metal of a film formed from the composition is simply referred to as “better adhesion to metal”
• achieving at least one of a better linear expansion coefficient and better adhesion to metal is also referred to as “better effects of the present invention.
• composition of the present invention comprises a polysilsesquioxane.
• polysilsesquioxane refers to a polymer having a constitutional unit in which one organic group and three oxygen atoms are bonded to one silicon atom.
• the skeleton structure of the polysilsesquioxane is not particularly limited, and may be any of a cage-type polysilsesquioxane, a ladder-type polysilsesquioxane, a double-decker type polysilsesquioxane, and a random type polysilsesquioxane, with a ladder-type polysilsesquioxane or a cage-type polysilsesquioxane being preferred.
• the above-mentioned cage polysilsesquioxane may be either a complete cage polysilsesquioxane or an incomplete cage polysilsesquioxane, with a complete cage polysilsesquioxane being preferred.
• the cage polysilsesquioxane may be any of a T8 polysilsesquioxane consisting of eight of the structural units T3 described below, a T10 polysilsesquioxane consisting of ten of the structural units T3 described below, and a T12 polysilsesquioxane consisting of twelve of the structural units T3 described below.
• the composition preferably contains at least one selected from ladder-type polysilsesquioxanes and cage-type polysilsesquioxanes, more preferably contains a cage-type polysilsesquioxane, and even more preferably contains a ladder-type polysilsesquioxane and a cage-type polysilsesquioxane.
• the skeletal structure of the polysilsesquioxane can be identified from the molecular weight obtained by GPC and the constituent units determined from the peak positions in 29 Si-NMR spectrum measurement.
• the cage polysilsesquioxane is detected in GPC as a peak whose peak top molecular weight corresponds to the molecular weight of T8 polysilsesquioxane, T10 polysilsesquioxane, or T12 polysilsesquioxane.
• the molecular weight of each of the above cage polysilsesquioxanes is appropriately calculated depending on the substituents that the cage polysilsesquioxane has, but is often detected as a peak at a weight average molecular weight (Mw) of 300 to 4,000.
• the polysilsesquioxane has a functional group that interacts with a metal (interactive group). Even when the composition contains the compound X described below, the polysilsesquioxane may have an interactive group.
• the mode of interaction between the interactive group and the metal is not particularly limited, and examples thereof include a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, an acid-base interaction, a van der Waals bond, and a metallic bond, with a coordinate bond being preferred.
• the interactive group can be appropriately selected depending on the metal to be interacted with and the mode of interaction, but a group containing a nitrogen atom, an oxygen atom, or a sulfur atom is preferred.
• Specific examples of the interactive group include an amino group (-NR N 2 ), an epoxy group, a thiol group (-SH), a cyano group (-CN), a nitrogen-containing heterocyclic group, a hydrazine group, a guanidine group, a phosphoric acid group (-PO 4 H 2 ), a phosphonic acid group (-PO 3 H 2 ), a carboxylic acid group (-COOH), a sulfo group (-SO 3 H), a hydroxy group (-OH), a phosphonic acid ester bond-containing group, a sulfonic acid ester bond-containing group, a boronic acid group (-BO 2 H 2 ), a thioether bond-containing group, and a disulfide bond-containing group, and an amino group
• Each of R 1 N independently represents a hydrogen atom, an alkyl group, or an aryl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 3.
• the alkyl group may have a substituent, and examples of the substituent include a hydroxy group, a halogen atom, and an aryl group described later.
• the number of carbon atoms in the aryl group is preferably 4 to 12, and the aryl group is preferably a phenyl group.
• the aryl group may have a substituent, and examples of the substituent include a hydroxy group, a halogen atom, and the above-mentioned alkyl group.
• nitrogen-containing heterocyclic group examples include nitrogen-containing aromatic heterocyclic groups such as pyridyl, oxazolyl, triazine, pyrrole, pyrazole, imidazole, pyrazole, triazole, benzimidazole, and benztriazole, as well as nitrogen-containing aliphatic heterocyclic groups such as imidazolidinyl, pyrrolidinyl, pyrazolidinyl, piperidinyl, and piperazinyl, with pyridyl, oxazolyl, imidazolidinyl, and pyrrolidinyl being preferred.
• nitrogen-containing aromatic heterocyclic groups such as pyridyl, oxazolyl, triazine, pyrrole, pyrazole, imidazole, pyrazole, triazole, benzimidazole, and benztriazole
• nitrogen-containing aliphatic heterocyclic groups such as imidazolidinyl,
• the acidic groups such as the phosphate group, phosphonate group, carboxylate group, and sulfo group may be in the form of a salt in the composition.
• the salt include salts with metal cations and salts with ammonium cations.
• the hydroxy group may be either an alcoholic hydroxy group (a hydroxy group bonded to an aliphatic group) or a phenolic hydroxy group (a hydroxy group bonded to an aromatic ring group), with a phenolic hydroxy group being preferred.
• metals with which the interactive group interacts include copper (Cu), silver (Ag), gold (Au), cobalt (Co), ruthenium (Ru), tungsten (W), titanium (Ti), tantalum (Ta), molybdenum (Mo), germanium (Ge), zirconium (Zr), tin (Sn), nickel (Ni), palladium (Pd), aluminum (Al), indium (In), iron (Fe), zinc (Zn), and platinum (Pt). Copper or silver is preferred, and copper is more preferred.
• the interactive group is preferably a functional group that interacts with copper.
• the polysilsesquioxane has a polymerizable group, since the film formed from the composition has a smaller linear expansion coefficient and is more excellent in thermocycling resistance.
• the polymerizable group include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group, and the radical polymerizable group is preferred.
• the radical polymerizable group is preferably a group having an ethylenically unsaturated double bond.
• the group having an ethylenically unsaturated double bond include a vinyl group, a styryl group, a (meth)acryloyl group, a (meth)acrylamide group, an allyl group, and a vinyl ether group, and the vinyl group, the styryl group, or the (meth)acryloyl group is preferred, and the styryl group is more preferred.
• the polymerizable group may function as the above-mentioned interactive group.
• the polysilsesquioxane has a chain-like hydrocarbon group, since this allows a film formed from the composition to have better conformability to unevenness and the composition can be suitably used as a transfer film.
• the chain hydrocarbon group include a chain alkyl group, a chain alkenyl group, and a chain alkynyl group, with a chain alkyl group being preferred.
• the chain hydrocarbon group may be either a straight chain or a branched chain, and is preferably a straight chain.
• the chain hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and even more preferably 4 to 12 carbon atoms.
• R 1 's each independently represent a monovalent organic group
• X 1 's each independently represent a hydrogen atom or an alkyl group.
• a plurality of R 1 's may be the same or different from each other.
• the polysilsesquioxane may be a copolymer containing a plurality of constitutional units having different R 1 's.
• R 1 each independently represents a monovalent organic group.
• the monovalent organic group include a hydrocarbon group and a heteroatom-containing group.
• the hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
• the aliphatic hydrocarbon group may be either a chain or a cyclic group, preferably a chain group.
• the chain aliphatic hydrocarbon group may be either a straight chain or a branched chain group, preferably a straight chain group.
• the aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 3 to 12 carbon atoms.
• the monovalent organic group represented by R 1 is preferably a group selected from the group consisting of an interactive group-containing group, a polymerizable group-containing group, and a chain hydrocarbon group.
• the monovalent organic group represented by R 1 may be, for example, a group having both an interactive group and a polymerizable group.
• the interactive group-containing group is a monovalent organic group containing an interactive group, and is preferably a group represented by -L Z -ZR .
• ZR represents an interactive group.
• the definition and preferred embodiments of the interactive group are as described above.
• L and Z represent a single bond or a divalent linking group.
• the divalent linking group include a divalent aliphatic hydrocarbon group (preferably having 1 to 6 carbon atoms), a divalent aromatic ring group (preferably a phenylene group), -O-, -CO-, and a combination thereof.
• the divalent aliphatic hydrocarbon group and the divalent aromatic ring group may have a substituent, and the substituent is preferably the above-mentioned interactive group.
• LZ is preferably a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, --O--, or a combination thereof.
• the definition and preferred embodiments of the chain-like hydrocarbon group are the same as the chain-like hydrocarbon group that is preferably possessed by the polysilsesquioxane described above.
• X1 represents a hydrogen atom or an alkyl group.
• the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
• Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
• the polysilsesquioxane preferably contains a structural unit selected from the structural unit T2 and the structural unit T3.
• the total content of the structural units selected from the structural units T2 and T3 is preferably 50 mol% or more, more preferably 70 mol% or more, based on the total of all structural units of the polysilsesquioxane.
• the upper limit is not particularly limited, and may be 100 mol%.
• the content of each of the structural units can be calculated, for example, from the peak position and peak area ratio in 29 Si-NMR spectrum measurement.
• the polysilsesquioxane contains a structural unit having a polymerizable group.
• a structural unit having a polymerizable group a structural unit selected from the structural units T1 to T3 in which R1 is a polymerizable group-containing group is preferable.
• the content of the structural unit having a polymerizable group is preferably from 10 to 90 mol %, more preferably from 30 to 70 mol %, and even more preferably from 40 to 60 mol %, based on the total of all structural units of the polysilsesquioxane.
• the polysilsesquioxane contains a structural unit having a chain-like hydrocarbon group.
• a structural unit having a chain-like hydrocarbon group a structural unit selected from the structural units T1 to T3 in which R1 is a chain-like hydrocarbon group is preferable.
• the content of the structural unit having a chain hydrocarbon group is preferably from 10 to 90 mol %, more preferably from 30 to 70 mol %, and even more preferably from 40 to 60 mol %, based on the total of all structural units of the polysilsesquioxane.
• R 1 has the same meaning as R 1 in formulas (T1) to (T3) described above, and the preferred embodiments are also the same.
• each X2 independently represents a hydrolyzable group.
• the hydrolyzable group include an alkoxy group, an aryloxy group, and a halogen atom, with an alkoxy group being preferred.
• the alkoxy group is preferably a group represented by -OX 1.
• X 1 has the same meaning as X 1 in formulae (T1) and (T2), and the preferred embodiments are also the same.
• the aryl group in the aryloxy group is preferably a phenyl group.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.
• the weight average molecular weight (Mw) of the polysilsesquioxane is preferably from 1,000 to 150,000, more preferably from 3,000 to 100,000, and even more preferably from 5,000 to 50,000.
• the number average molecular weight (Mn) of the polysilsesquioxane is preferably from 500 to 100,000, more preferably from 1,000 to 10,000, and even more preferably from 2,500 to 7,000.
• the polydispersity index (PDI, Mw/Mn) of the polysilsesquioxane is usually 1.0 or more, preferably 1.0 to 8.0, and more preferably 1.5 to 6.0.
• the composition includes a compound X which is a compound different from the polysilsesquioxane and which has a functional group (interactive group) that interacts with a metal.
• the composition may include compound X even if the polysilsesquioxane has an interactive group.
• the definition and preferred embodiments of the interactive group contained in the compound X are the same as those of the interactive group that may be contained in the polysilsesquioxane described above.
• the number of interactive groups possessed by compound X is not particularly limited as long as it is 1 or more, but 1 to 3 is preferred.
• the molecular weight of compound X is preferably 100 to 2000, more preferably 150 to 1000, and even more preferably 180 to 600.
• compound X has a group that interacts with the polysilsesquioxane that is different from the interactive group.
• the group that interacts with the polysilsesquioxane is preferably a group that forms a covalent bond with a functional group of the polysilsesquioxane, and more preferably a group that forms a covalent bond with a Si-OX 1 group of the polysilsesquioxane.
• X 1 is as described above.
• compound X is at least one selected from the group consisting of a compound represented by formula (1), a hydrolysate of a compound represented by formula (1), and a hydrolysis condensate of a compound represented by formula (1).
• each X independently represents a hydroxyl group or a hydrolyzable group
• L represents a single bond or a divalent linking group
• Z represents a functional group that interacts with a metal (an interactive group).
• each X independently represents a hydroxy group or a hydrolyzable group.
• the hydrolyzable group include an alkoxy group, an aryloxy group, and a halogen atom.
• the alkyl group in the alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
• the aryl group in the aryloxy group is preferably a phenyl group.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.
• L represents a single bond or a divalent linking group.
• the divalent linking group include a divalent aliphatic hydrocarbon group, a divalent aromatic ring group, -O-, -CO-, and a combination thereof, with the proviso that the group adjacent to -Si(X) 3 is a divalent aliphatic hydrocarbon group or a divalent aromatic ring group.
• the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
• the divalent aromatic ring group preferably has 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and more preferably 6 carbon atoms.
• the divalent linking group is preferably a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a group formed by combining a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms with --O--.
• Z represents a functional group that interacts with a metal (an interactive group).
• the definition and preferred embodiments of the interactive group represented by Z are the same as those of the interactive group contained in the compound X.
• Examples of compounds represented by formula (1) include organotrialkoxysilane compounds and organotrichlorosilane compounds, with organotrialkoxysilane compounds being preferred.
• the hydrolysate of the compound represented by formula (1) may be any of a complete hydrolysate in which all of the hydrolyzable groups have been hydrolyzed, a partial hydrolysate in which some of the hydrolyzable groups have been hydrolyzed, and a mixture thereof.
• the hydrolyzate may be dehydration-condensed with the silanol groups in the system to form a hydrolysis-condensate.
• the hydrolysis-condensate may be a complete hydrolysis-condensate in which all of the hydrolyzed groups are condensed, a partial hydrolysis-condensate in which some of the hydrolysis groups are condensed, or a mixture thereof.
• the hydrolysis product may be condensed with polysilsesquioxane.
• KBM-585, KBM-303, KBM-803, KBM-802, KBM-402, KBM-403, KBM-903, KBM-603, KBM-602, KBM-573, KBM-903, and X-12-1214A can be used.
• a known silane coupling agent can also be used.
• the compound X may be used alone or in combination of two or more kinds.
• the content of compound X is preferably from 0.005 to 20.0 mass %, more preferably from 0.01 to 10 mass % (10.0 mass %), based on the total solid content of the composition.
• the mass ratio of the content of compound X to the content of polysilsesquioxane is preferably from 0.0001 to 0.3, and more preferably from 0.001 to 0.1.
• composition satisfies at least one of requirements 1 and 2.
• Requirement 1 The polysilsesquioxane has a functional group that interacts with a metal.
• Requirement 2 The composition further includes a compound X which is a compound different from polysilsesquioxane and has a functional group that interacts with a metal.
• the composition may contain a polymerization initiator.
• the composition preferably contains a polymerization initiator.
• the polymerization initiator may be any one of a radical polymerization initiator, an anionic polymerization initiator, and a cationic polymerization initiator, with a radical polymerization initiator being preferred.
• the polymerization initiator may be either a thermal polymerization initiator or a photopolymerization initiator.
• Radical polymerization initiators include thermal radical polymerization initiators and photoradical polymerization initiators.
• Thermal radical polymerization initiators include, for example, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(N-butyl-2-methylpropionamide), dimethyl-1,1'-azobis(1-cyclohexanecarboxylate), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride; 1,1-di(t-hexyl)azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride;
• peroxides include organic peroxides such as t
• photoradical polymerization initiators examples include oxime ester compounds (photopolymerization initiators having an oxime ester structure), aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure), hydroxyacetophenone compounds (photopolymerization initiators having a hydroxyacetophenone structure), acylphosphine oxide compounds (photopolymerization initiators having an acylphosphine oxide structure), and bistriphenylimidazole compounds (photopolymerization initiators having a bistriphenylimidazole structure).
• oxime ester compounds photopolymerization initiators having an oxime ester structure
• aminoacetophenone compounds photopolymerization initiators having an aminoacetophenone structure
• hydroxyacetophenone compounds photopolymerization initiators having a hydroxyacetophenone structure
• acylphosphine oxide compounds photopolymerization initiators having an acylphosphine oxide structure
• oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (product name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (product name: IRGACURE OXE-02, manufactured by BASF), [ 8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazoyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF Corporation), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl
• aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, Omnirad series, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).
• photoradical polymerization initiators include 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819) are also included.
• photopolymerization initiators include those described in paragraphs 0031 to 0042 of JP 2011-095716 A and paragraphs 0064 to 0081 of JP 2015-014783 A.
• the polymerization initiator may be used alone or in combination of two or more kinds.
• the content of the polymerization initiator is preferably from 0.005 to 20.0 mass %, more preferably from 0.01 to 10 mass %, based on the total solid content of the composition.
• the composition may include a surfactant.
• the surfactant include fluorine-based surfactants, hydrocarbon-based surfactants, and silicone-based surfactants. Silicone-based surfactants are preferred as the surfactant. From the viewpoint of improving environmental compatibility, it is also preferred that the surfactant does not contain a fluorine atom.
• fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heat is applied, the functional group having the fluorine atom is cleaved and the fluorine atom is volatilized.
• fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), Megafac DS-21, etc.).
• the fluorosurfactant may be a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
• the fluorosurfactant may be a block polymer.
• the fluorine-based surfactant may be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups).
• examples of the fluorine-based surfactant include fluorine-containing polymers having a group having an ethylenically unsaturated double bond in the side chain, specifically, Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).
• fluorosurfactants from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group with seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.
• PFOA perfluorooctanoic acid
• PFOS perfluorooctanesulfonic acid
• fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, and F-780 (all manufactured by DIC); EXP. MFS-324, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP.
• hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters.
• glycerol trimethylolpropane
• trimethylolethane trimethylolethane
• propoxylates e.g., glycerol propoxylate and glycerol ethoxylate
• polyoxyethylene lauryl ether polyoxyethylene stearyl ether
• polyoxyethylene oleyl ether polyoxyethylene octylphenyl
• hydrocarbon surfactants include, for example, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic 304, 701, 704, 901, 904, and 150R1, and HYDROPALAT WE 3323 (all manufactured by BASF); Solsperse 20000 (manufactured by Lubrizol Nippon Corporation); NCW-101, NCW-1001, and NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (all manufactured by Takemoto Oil Co., Ltd.); Olfine E1010, Surfynol 104, 400, and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.).
• silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and/or ends, and polymers having repeating units with hydrophilic groups in the side chains and repeating units with groups with siloxane bonds in the side chains.
• silicone surfactants polymers having repeating units with hydrophilic groups in the side chains and repeating units with groups with siloxane bonds in the side chains are preferred.
• the above polymers may be either random copolymers or block copolymers.
• the repeating unit having a group with a siloxane bond in the side chain is preferably a repeating unit represented by formula (SX1) or a repeating unit represented by formula (SX2).
• R each independently represents an alkyl group having 1 to 3 carbon atoms
• R1 represents a hydrogen atom or a methyl group
• L1 represents a single bond or a divalent organic group.
• the R's may be the same or different.
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents an alkylene group having 1 to 10 carbon atoms.
• R 3 represents an alkyl group having 1 to 4 carbon atoms.
• n represents an integer of 5 to 50.
• the repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).
• R4 and R5 each independently represent a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.
• silicone surfactants include, for example, EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2, and S-506 (all manufactured by DIC Corporation); DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Corporation); X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-2 2-4515, KF-6004, KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP
• the surfactant may be used alone or in combination of two or more kinds.
• the content of the surfactant is preferably from 0.01 to 3.0 mass %, more preferably from 0.05 to 1.0 mass %, and even more preferably from 0.1 to 0.8 mass %, based on the total solid content of the composition.
• the composition may contain a polymerizable compound.
• the polymerizable compound is a compound different from the various components described above.
• the polymerizable compound is a compound having one or more polymerizable groups in the molecule.
• the polymerizable group may be the polymerizable group that the polysilsesquioxane may have, and is preferably a group having an ethylenically unsaturated double bond, more preferably a (meth)acryloyl group, a vinyl group, or a styryl group, and even more preferably a (meth)acryloyl group.
• the number of polymerizable groups that the polymerizable compound has is preferably 1 or 2 or more, more preferably 2 to 10, and even more preferably 2 to 6.
• the polymerizable compound include a polymerizable compound having one polymerizable group in one molecule (hereinafter also referred to as a "monofunctional polymerizable compound”), a polymerizable compound having two polymerizable groups in one molecule (hereinafter also referred to as a "bifunctional polymerizable compound”), and a polymerizable compound having three or more polymerizable groups in one molecule (hereinafter also referred to as a "trifunctional or higher functional polymerizable compound”).
• the polymerizable compound is preferably a difunctional polymerizable compound or a tri- or higher functional polymerizable compound.
• bifunctional polymerizable compounds include polyethylene glycol (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.
• bifunctional polymerizable compounds include, for example, diethylene glycol dimethacrylate (2G, manufactured by Shin-Nakamura Chemical Co., Ltd.), triethylene glycol dimethacrylate (3G, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol #200 dimethacrylate (4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), SR205NS (manufactured by Sartomer Co.,
• tri- or higher functional polymerizable compounds examples include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.
• (tri/tetra/penta/hexa)(meth)acrylate is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate
• (tri/tetra)(meth)acrylate” is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.
• polymerizable compounds examples include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, etc., manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, etc., manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300, etc., manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135, etc., manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.).
• Examples of the polymerizable compound include urethane (meth)acrylates (preferably tri- or higher functional urethane (meth)acrylates).
• the number of polymerizable groups in the urethane (meth)acrylate is preferably 6 or more, more preferably 8 or more.
• the upper limit is preferably 20 or less.
• trifunctional or higher urethane (meth)acrylates examples include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA, and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.); UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).
• the polymerizable compounds may be used alone or in combination of two or more.
• the content of the polymerizable compound is preferably from 0.1 to 15.0% by mass, and more preferably from 1.0 to 10.0% by mass, based on the total solid content of the composition.
• the composition may contain other additives in addition to those mentioned above.
• other additives include solvents, fillers, heterocyclic compounds, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, hydrogen donor compounds, impurities, plasticizers, sensitizers, and maleimide compounds.
• the composition may include a solvent.
• the solvent is not particularly limited as long as it can dissolve or disperse various components other than the solvent that may be contained in the composition.
• the solvent include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone, methyl isobutyl ketone, methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents, lactone solvents, and solvents containing two or more of these.
• water alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol
• the solvent may be used alone or in combination of two or more.
• the content of the solvent is preferably from 50 to 1,900 parts by mass, more preferably from 100 to 1,200 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the composition.
• the composition may also include a filler.
• the average particle size of the filler is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 150 nm or less.
• the lower limit of the average particle size of the filler is more than 0 nm, and is preferably 5 nm or more, and more preferably 10 nm or more.
• the average particle size of the filler is also preferably 5 to 300 nm, and more preferably 10 to 150 nm.
• the average particle size of the filler is a value calculated by the following particle size measurement method.
• Particle size measurement method A rectangular region of 3 ⁇ m ⁇ 10 ⁇ m in a cross section along the normal direction of the surface of a composition layer formed using the composition is observed with a scanning electron microscope, and the operation of measuring the long diameters of all fillers observed within the above-mentioned region is performed at five different points in the composition layer, and the average value of the long diameters of all fillers measured in each operation is regarded as the average particle size of the filler.
• the composition is applied onto a substrate (preferably a glass substrate) to form a composition layer.
• the thickness of the composition layer is preferably 3 ⁇ m or more.
• a drying treatment may be performed as necessary after the composition is applied.
• a cross section along the normal direction of the surface (surface opposite to the substrate side) of the obtained composition layer is cut out, and a rectangular area of 3 ⁇ m ⁇ 10 ⁇ m of the cross section is observed with a scanning electron microscope, and the major axis of all fillers observed within the area is measured.
• S-4800 manufactured by Hitachi High-Tech Corporation is used. The magnification during observation is 50,000 times.
• the above operation is carried out at five different locations in the composition layer, and the average value (arithmetic mean value) of all the major axis lengths of the filler particles measured in each operation is defined as the average particle size of the filler.
• the above-mentioned major axis refers to the length of the longest line segment among the line segments connecting any two points on the contour line of the outer shape of the filler in the observed image. Furthermore, when the filler particles are aggregated to form aggregates in the observed image, the major axis of each filler particle that constitutes the aggregate is measured.
• the filler is preferably an inorganic filler.
• the filler include silicon dioxide (silica); silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as chiandoped glass; alumina, barium sulfate, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, cordierite, zirconium tungstate, and manganese nitride.
• the filler preferably contains at least one selected from the group consisting of silicon dioxide (silica), boron nitride, barium sulfate, and silicates, and more preferably contains silicon dioxide (silica).
• the shape of the filler may be either spherical or non-spherical (eg, crushed or fibrous), with spherical being preferred.
• the filler may be surface-treated.
• the surface treatment include a treatment for introducing a functional group and a treatment using a known surface treatment agent.
• the functional group include a polymerizable group (such as a polymerizable group that may be possessed by polysilsesquioxane) and a hydrophobic group.
• the surface treatment agent include a silane coupling agent, a silazane compound, and a titanate coupling agent.
• methods for surface treatment of the filler include a dry method in which the surface treatment is performed in a gas phase, and a wet method in which the surface treatment is performed in a liquid phase.
• Fillers include, for example, NHM-5N (Tokuyama Corporation, silicon dioxide, solids concentration 100% by mass), NHM-3N (Tokuyama Corporation, silicon dioxide, solids concentration 100% by mass), Seahoster KE-S30 (Nippon Shokubai Co., Ltd., silicon dioxide, solids concentration 100% by mass), YA050C-MJE (Admatechs Co., Ltd., silicon dioxide, MEK slurry with solids concentration of 50% by mass), SFP-20M (Denka Co., Ltd., silicon dioxide), and PMA-ST (Nissan Chemical Co., Ltd., silicon dioxide).
• Examples include MEK-ST-L (Nissan Chemical Industries, Ltd., silicon dioxide), MEK-AC-5140Z (Nissan Chemical Industries, Ltd., silicon dioxide), MEK-EC-2430Z (Nissan Chemical Industries, Ltd., solids concentration 30% by mass), barium sulfate (Nihon Solvay, solids concentration 100% by mass), Y50SP-AM1 (Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass), and Y50SZ-AM1 (Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass).
• the fillers may be used alone or in combination of two or more.
• the content of the filler is preferably from 10 to 90 mass %, more preferably from 30 to 80 mass %, based on the total solid content of the composition.
• heterocyclic compound examples include various components described in WO 2022/039027.
• plasticizers and sensitizers examples include those described in paragraphs 0097 to 0119 of WO 2018/179640.
• maleimide compound examples include known maleimide compounds and the maleimide compounds described in WO 2022/102756.
• the composition may contain impurities.
• impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Since halide ions, sodium ions, and potassium ions are easily mixed in as impurities, it is preferable to set the content to the following.
• the content of impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the composition.
• the lower limit is often 0 ppb by mass or more, relative to the total mass of the composition, and may be 1 ppb by mass or more, or 0.1 ppm by mass or more.
• Methods for adjusting the impurity content include, for example, using raw materials with low impurity contents as the raw materials for the various components that may be included in the composition, purifying the various components that may be included in the composition before use, and preventing the inclusion of impurities when preparing the composition.
• the impurity content can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
• ICP Inductively Coupled Plasma
• the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane is preferably small.
• the content of each of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the composition.
• the lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, relative to the total mass of the composition.
• the content of these compounds can be adjusted in the same manner as for the above-mentioned impurities, and the content of these compounds can be quantified by known measurement methods.
• the composition of the present invention can form a film.
• the method of forming the film is not particularly limited, and may be, for example, a method of applying the composition to a substrate, drying the composition, and curing the composition.
• the curing treatment may be, for example, a curing treatment used in step 3 in the method of manufacturing a semiconductor package described later. That is, the film is preferably a cured film of the composition.
• some or all of the components contained in the composition may have reacted (e.g., condensation of unreacted silanol groups in the polysilsesquioxane, polymerization of polymerizable groups, and reaction of the polysilsesquioxane with compound X) by the above-mentioned curing treatment, and some of the components contained in the composition (e.g., solvent) may have been removed.
• reacted e.g., condensation of unreacted silanol groups in the polysilsesquioxane, polymerization of polymerizable groups, and reaction of the polysilsesquioxane with compound X
• the average thickness of the film is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, even more preferably 3.0 ⁇ m or more, and particularly preferably 5.0 ⁇ m or more, in terms of superior insulation properties.
• the average thickness of the film is preferably 40 ⁇ m or less, more preferably 25 ⁇ m or less, even more preferably 20 ⁇ m or less, and particularly preferably 19 ⁇ m or less, in terms of superior pattern resolution.
• the transfer film of the present invention has a temporary support and a composition layer formed using the above-mentioned composition.
• FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a transfer film.
• the transfer film 100 shown in FIG. 1 has a configuration in which a temporary support 12, a composition layer 14, and a cover film 16 are laminated in this order. 1 has a cover film 16, the transfer film may have no cover film 16. As described later, the transfer film may further have an intermediate layer and/or a thermoplastic resin layer. Each component of the transfer film will be described in detail below.
• the transfer film has a temporary support.
• the temporary support is a member that supports the composition layer, and is ultimately removed by a peeling treatment.
• the temporary support may have either a single-layer structure or a multi-layer structure.
• the temporary support is preferably a film, more preferably a resin film.
• the temporary support is also preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat. Examples of the film include polyethylene terephthalate (PET) film (e.g., biaxially stretched polyethylene terephthalate film, etc.), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, and polyethylene terephthalate film is preferred.
• PET polyethylene terephthalate
• the temporary support is preferably free of deformation such as wrinkles and scratches.
• the temporary support is preferably highly transparent, because it can be pattern-exposed through the temporary support.
• the transmittance at any wavelength of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more.
• the upper limit is preferably less than 100%.
• Preferred values of the transmittance at any wavelength are, for example, 87%, 92%, and 98%.
• the haze of the temporary support is preferably small.
• the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.
• the lower limit is preferably 0% or more.
• the number of fine particles, foreign matter, and defects contained in the temporary support is small.
• the number of fine particles, foreign matter, and defects having a diameter of 1 ⁇ m or more in the temporary support is preferably 50 pieces/10 mm2 or less , more preferably 10 pieces/10 mm2 or less , even more preferably 3 pieces/10 mm2 or less , and particularly preferably 0 pieces/10 mm2 .
• the thickness of the temporary support is preferably from 5 to 200 ⁇ m, and from the viewpoints of ease of handling and versatility, it is more preferably from 5 to 150 ⁇ m, further preferably from 5 to 50 ⁇ m, and particularly preferably from 5 to 35 ⁇ m.
• the thickness of the temporary support can be calculated as the average value of any five points measured by observing a cross section with a SEM (scanning electron microscope).
• the surface of the temporary support which comes into contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, or the like.
• the exposure dose of UV irradiation is preferably 10 to 2000 mJ/ cm2 , more preferably 50 to 1000 mJ/ cm2 .
• Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength range of 150 to 450 nm. The lamp power and illuminance can be adjusted as appropriate.
• Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 ⁇ m, a biaxially oriented polyethylene terephthalate film having a thickness of 12 ⁇ m, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 ⁇ m.
• the temporary support may be a recycled product. Examples of recycled products include those obtained by cleaning and chipping used films and forming the resulting materials into films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).
• the temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support for the purpose of imparting handleability.
• the diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 ⁇ m.
• the thickness of the lubricant layer is preferably 0.05 to 1.0 ⁇ m.
• temporary supports include, for example, Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).
• composition layer is a layer formed using the above composition.
• the various components that can be contained in the composition layer are the same as the various components that can be contained in the above composition, and the preferred embodiments are also the same.
• the preferred numerical ranges of the contents of the various components in the composition layer are the same as the preferred ranges obtained by replacing the above "contents (% by mass) of the various components relative to the total solid content of the composition” with “contents (% by mass) of the various components relative to the total mass of the composition layer.”
• the content of the polysilsesquioxane is preferably 5.0% by mass or more relative to the total solid content of the composition” should be replaced with "The content of the polysilsesquioxane is preferably 5.0% by mass or more relative to the total mass of the composition layer.”
• composition layer further contains a solvent.
• the solvent has the same meaning as the solvent that the above composition may contain, and the preferred embodiments are also the same.
• the transfer film may have other layers in addition to those mentioned above.
• the transfer film may have an intermediate layer and/or a thermoplastic resin layer.
• Examples of the intermediate layer and the thermoplastic resin layer include those described in paragraphs 0164 to 0204 of WO 2021/166719, the contents of which are incorporated herein by reference.
• the transfer film may have a cover film.
• the number of fish eyes having a diameter of 80 ⁇ m or more contained in the cover film is preferably 5 or less per square meter.
• Fish eyes are foreign matter, unmelted matter, and/or oxidized deterioration products of the material that are introduced into the film when the material is thermally melted and the film is produced by a method such as kneading, extrusion and/or biaxial stretching and casting.
• the arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and even more preferably 0.03 ⁇ m or more. If Ra is within this range, for example, when the transfer film is long, the winding property of the transfer film is excellent. Furthermore, from the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, and even more preferably 0.30 ⁇ m or less.
• cover film examples include a polyethylene terephthalate film, a polypropylene film, a polystyrene film, and a polycarbonate film.
• cover film examples include the cover films described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.
• cover films examples include Alphan (registered trademark) FG-201 (manufactured by Oji F-Tex Co., Ltd.), Alphan (registered trademark) E-201F (manufactured by Oji F-Tex Co., Ltd.), Therapeel (registered trademark) 25WZ (manufactured by Toray Advanced Film Co., Ltd.), and Lumirror (registered trademark) 16QS62 (16KS40) (manufactured by Toray Industries, Inc.).
• the cover film may be a recycled product.
• a recycled product may be a product obtained by cleaning and chipping a used film, and then forming the obtained material into a film.
• a commercially available recycled product may be the Ecouse series (manufactured by Toray Industries, Inc.).
• the transfer film may include other layers in addition to the layers described above.
• the other layers include, for example, a high refractive index layer.
• high refractive index layers include those described in paragraphs 0168 to 0188 of WO 2021/187549, the contents of which are incorporated herein by reference.
• the transfer film can be produced by a known production method.
• the method for producing the transfer film preferably involves applying a composition onto a temporary support to form a composition layer, and more preferably involves drying a coating of the composition to form a composition layer.
• Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.
• a method for manufacturing the transfer film 100 shown in FIG. 1 includes a method including a step of applying a composition to the surface of the temporary support 12 to form a coating film, and then drying the coating film to form a composition layer 14. Furthermore, a cover film 16 is pressed onto the composition layer of the transfer film produced by the above-mentioned production method to produce the transfer film 100 shown in Fig. 1.
• the transfer film 100 shown in Fig. 1 may be wound up after production and stored as a roll of the transfer film 100.
• the transfer film 100 in the roll form can be provided in that form for the lamination step with a substrate in a roll-to-roll system described below.
• the transfer film may have an intermediate layer and/or a thermoplastic resin layer between the temporary support and the composition layer.
• the composition for forming an intermediate layer the method for forming an intermediate layer, the composition for forming a thermoplastic resin layer, and the method for forming a thermoplastic resin layer are described in paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021/033451, the contents of which are incorporated herein by reference.
• the film formed by using the composition or the transfer film can be used for various applications, such as an insulating film, an electrode protective film, a planarizing film, an overcoat film, a hard coat film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an anti-reflection film, an etching resist, and a plating member. More specifically, examples of the material include protective or insulating films for touch panel electrodes, protective or insulating films for printed wiring boards, protective or insulating films for TFT substrates, interlayer insulating films in build-up substrates for semiconductor packages, organic interposers, color filters, overcoat films for color filters, and etching resists for wiring formation.
• the composition and the transfer film can be suitably used for forming an insulating film, and the insulating film is preferably used as an insulating layer for a semiconductor package. That is, the composition and the transfer film are preferably used for forming an insulating layer for a semiconductor package.
• the method for manufacturing a semiconductor package of the present invention includes the following steps. Step 1: Forming a composition layer on a substrate using a composition; Step 2: Forming a pattern including vias in the composition layer; Step 3: Subjecting the pattern to at least one of heating and exposure. Each step of the method for manufacturing a semiconductor package will be described in detail below.
• Step 1 is a step of forming a composition layer on a substrate using a composition.
• Methods for forming the composition layer include a method of applying a composition and a method using a transfer film.
• the composition may be applied by the method for applying the composition in the above-mentioned method for producing a transfer film.
• the composition layer may be formed by drying a coating of the composition.
• a specific example of a method for forming a composition layer using a transfer film is a method in which the surface of the composition layer in the transfer film opposite the temporary support side is brought into contact with a substrate and the transfer film is laminated to the substrate. Examples of the lamination method include known transfer methods and lamination methods.
• a preferred method is to place a substrate on the surface of the composition layer and apply pressure and heat with a roll or the like.
• the lamination method may be carried out using a known laminator such as a vacuum laminator or an autocut laminator.
• the lamination temperature is not particularly limited, but is preferably from 70 to 130°C.
• a transfer film it is preferable that a roll-to-roll system be used in step 1.
• the substrate to which the transfer film is attached is preferably a resin film or a resin film having a conductive layer.
• the roll-to-roll method refers to a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a step of unwinding the substrate before any step included in the manufacturing method for the laminate of the present invention, and a step of winding the substrate after any step, in which at least any step (preferably all steps or all steps other than the heating step) is performed while the substrate is being transported.
• a known method may be used in a manufacturing method that employs a roll-to-roll system.
• the substrate is preferably a substrate containing a metal, the metal being a metal that interacts with the above-mentioned interactive group, preferably copper or silver, more preferably copper.
• the form of the metal contained in the base material is not particularly limited, and examples thereof include an elemental metal, an alloy, a nitride, an oxide, and a silicide, etc., and an elemental metal or an alloy is preferable, and an elemental metal is more preferable.
• the above-mentioned alloy includes an alloy containing two or more of the metals exemplified as the metals that interact with the above-mentioned interactive group, and an alloy containing copper is preferable.
• the metal may also be present as a conductive metal oxide, such as ITO (indium tin oxide), IZO (indium zinc oxide) and SiO 2.
• Conductivity means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm, and preferably less than 1 ⁇ 10 4 ⁇ cm.
• the substrate is preferably a substrate having a conductive layer made of the above metal.
• substrates having a conductive layer include a glass substrate, a glass epoxy substrate, a silicon substrate, and a resin substrate.
• the substrate may be a light-transmitting substrate such as a glass substrate, and may be, for example, a reinforced glass such as Gorilla Glass manufactured by Corning Inc. Examples of materials contained in the substrate include the materials described in JP-A-2010-086684, JP-A-2010-152809, and JP-A-2010-257492.
• the resin substrate is preferably a resin film having small optical distortion and/or high transparency, such as polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.
• PET polyethylene terephthalate
• polyethylene naphthalate polyethylene naphthalate
• polycarbonate polycarbonate
• triacetyl cellulose polyimide
• the substrate having a conductive layer a resin substrate having a conductive layer is preferred, and a resin film having a conductive layer is more preferred, because they can be manufactured by a roll-to-roll method.
• the substrate having a conductive layer may be a laminate obtained by the above-mentioned method for manufacturing a laminate.
• the conductive layer in the substrate having the conductive layer may be either one layer or two or more layers.
• the conductive layers may be made of different materials.
• the conductive layer may be in a pattern.
• methods for producing a patterned conductive layer include subtractive methods and additive methods such as etching.
• Examples of the etching method include the wet etching method described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching.
• the etching method may also be a method using an etching resist.
• Step 2 is a step of forming a pattern having vias in the composition layer.
• the pattern having vias may be formed only in the composition layer, or may be formed in both the composition layer and the substrate.
• the pattern including vias may be either through holes or via holes.
• the shape of the via may be, for example, a rectangle, a trapezoid, or an inverted trapezoid in cross-sectional shape; and a circle or a rectangle in front shape (the shape of the via when observed from a direction in which the via bottom is visible).
• An inverted trapezoid is preferred as the cross-sectional shape because it increases the adhesion of plated copper to the via wall surface.
• the via size is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less, further preferably 50 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
• the lower limit is preferably 1 ⁇ m or more.
• the number of the vias may be one or more, and is preferably two or more.
• Methods for forming a pattern with vias include, for example, using a drill, a laser, and plasma.
• the method for forming a pattern having vias preferably includes a step of exposing the composition layer to a pattern and a step of developing the exposed composition layer with a developer to form a pattern.
• the composition layer may be exposed from the side opposite the substrate, or from the substrate side of the composition layer.
• the light source used for exposure may be any light source that irradiates light in a wavelength range to which various photosensitive components in the composition layer (e.g., a photopolymerization initiator, etc.) are sensitive (e.g., light in wavelength ranges of 254 nm, 313 nm, 365 nm, 405 nm, etc.).
• various photosensitive components in the composition layer e.g., a photopolymerization initiator, etc.
• Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).
• the exposure dose is preferably from 5 to 200 mJ/ cm2 , and more preferably from 10 to 200 mJ/ cm2 .
• the composition layer When the composition layer is formed using a transfer film, it may be exposed after peeling off the temporary support, or it may be exposed through the temporary support before peeling off the temporary support, and then the temporary support is peeled off.
• the pattern exposure may be exposure through a mask or direct exposure using a laser or the like.
• the mask include a quartz mask, a soda lime glass mask, and a film mask.
• the quartz mask is preferred because it has excellent dimensional accuracy, and the film mask is preferred because it can be easily made large in size.
• the material of the film mask is preferably a polyester film, more preferably a polyethylene terephthalate film, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.).
• Step 3 is a step of performing a curing treatment on the pattern, whereby an insulating film derived from the composition is formed.
• the curing treatment includes, for example, a heat treatment and an exposure treatment, and the curing treatment preferably includes at least a heat treatment.
• the temperature and time of the heat treatment can be appropriately selected depending on the components of the composition.
• the temperature of the heat treatment is preferably from 120 to 400°C, more preferably from 150 to 400°C, and even more preferably from 180 to 350°C.
• the heat treatment time is preferably from 0.5 to 24 hours, more preferably from 1 to 12 hours, and even more preferably from 1 to 9 hours.
• the heat treatment may be carried out in either an air environment or a nitrogen-substituted environment.
• the atmospheric pressure in the heat treatment environment is preferably 8.1 kPa or more, more preferably 50.66 kPa or more.
• the upper limit is preferably 121.6 kPa or less, more preferably 111.46 kPa or less, and even more preferably 101.3 kPa or less.
• the light source and the exposure dose for the exposure treatment can be appropriately selected depending on the type of photosensitive component (for example, photopolymerization initiator) in the composition layer.
• Examples of light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).
• the exposure dose is preferably from 5 to 1000 mJ/ cm2 , and more preferably from 10 to 200 mJ/ cm2 .
• Step 4 In the method for manufacturing a semiconductor package, it is preferable to have, after step 3, a step 4 of forming a circuit pattern on the pattern.
• a semi-additive process is preferable because it is capable of forming fine wiring. Examples of the semi-additive process include the following methods. First, after step 3, the via bottom, via wall surface, and the entire surface of the pattern are subjected to electroless copper plating using a palladium catalyst or the like to form a seed layer.
• the seed layer is for forming a power supply layer for electrolytic copper plating, and the thickness of the seed layer is preferably 0.1 to 2.0 ⁇ m.
• the electroless copper plating process is carried out by reacting copper ions with a reducing agent to deposit metallic copper on the surface of a pattern having vias.
• the catalyst for the electroless plating process is preferably a palladium-tin mixed catalyst.
• the average primary particle size of the mixed catalyst is preferably 10 nm or less.
• the plating composition for the electroless plating process preferably contains hypophosphorous acid as a reducing agent.
• Commercially available electroless copper plating solutions include, for example, “MSK-DK” manufactured by Atotech Japan, and “ThruCup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.
• the composition layer of the transfer film opposite the temporary support onto the electroless copper plating is heat-press the surface of the composition layer of the transfer film opposite the temporary support onto the electroless copper plating using a roll laminator.
• the thickness of the composition layer is preferably 5 to 30 ⁇ m, since this allows the thickness to be greater than the height of the wiring after electrolytic copper plating.
• the composition layer is exposed to light, for example, through a mask having a desired wiring pattern drawn thereon. Examples of the exposure method include the exposure method in step 2. After the exposure, the temporary support of the transfer film is peeled off, and the exposed composition layer is developed using an alkaline developer to form a pattern. After the pattern is formed, the development residue of the composition may be removed using plasma or the like.
• electrolytic copper plating is carried out to form a copper circuit layer and fill vias.
• the pattern is stripped using an alkaline aqueous solution or an amine-based stripper.
• the seed layer between the wirings is removed (flash etching). Flash etching is performed using an oxidizing solution containing, for example, sulfuric acid and an acidic solution such as hydrogen peroxide. Examples of the oxidizing solution include "SAC” manufactured by JCU Corporation and "CPE-800" manufactured by Mitsubishi Gas Chemical Co., Ltd.
• Palladium and the like adhering to the portions between the wirings are removed as necessary. Palladium can be removed using an acidic solution such as nitric acid and hydrochloric acid.
• a post-baking treatment is preferably performed to sufficiently thermally cure any unreacted thermosetting components, thereby improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper.
• a curing temperature of 150 to 240° C. and a curing time of 15 to 500 minutes are preferable.
• the method for manufacturing a semiconductor package may include a roughening step of roughening a pattern having vias.
• the roughening step is preferably carried out after the step 3 and before the step 4.
• the surface of the pattern is roughened to improve adhesion with the circuit wiring.
• smears can also be removed.
• the roughening step may be, for example, a known desmear treatment, and is preferably a treatment in which a roughening liquid is brought into contact with the surface.
• the roughening solution examples include a roughening solution containing chromium and sulfuric acid, a roughening solution containing an alkaline permanganate (such as a sodium permanganate roughening solution), and a roughening solution containing sodium fluoride, chromium, and sulfuric acid.
• a roughening solution containing chromium and sulfuric acid examples include a roughening solution containing chromium and sulfuric acid, a roughening solution containing an alkaline permanganate (such as a sodium permanganate roughening solution), and a roughening solution containing sodium fluoride, chromium, and sulfuric acid.
• the above-mentioned steps can be repeated depending on the number of layers required to manufacture a semiconductor package. It is also preferable to form a solder resist on the outermost layer.
• the semiconductor package is not particularly limited as long as it includes an insulating layer formed from a composition, and is preferably manufactured by the above-mentioned method for manufacturing a semiconductor package.
• a film formed from the composition may be used as an insulating film, or may be used as an organic interposer or insulating film in a so-called build-up substrate.
• Polysilsesquioxane A-1 was synthesized by the following method. Styrylmethoxysilane (0.15 mol), hexyltrimethoxysilane (0.15 mol), and 75.0 g of methyl isobutyl ketone were mixed in a 300 mL three-neck flask and stirred while heating at an external temperature of 80 ° C. 18.0 g of 0.1 mass% aqueous potassium hydroxide solution was added dropwise at an equal rate over 5 minutes, and the mixture was stirred while heating for 5 hours. During heating, the reaction was carried out while removing refluxed methanol from the system using a Dean-Stark apparatus.
• A-2 Polysilsesquioxane synthesized using styrylmethoxysilane (0.15 mol) and decyltrimethoxysilane (0.15 mol), having Mw of 17,600 and Mn of 7,900, and containing a cage-type polysilsesquioxane.
• A-3 Polysilsesquioxane synthesized using phenylmethoxysilane (0.15 mol) and hexyltrimethoxysilane (0.15 mol), having Mw of 10,500 and Mn of 4,400, and containing a cage-type polysilsesquioxane.
• A-4 Polysilsesquioxane synthesized using hexyltrimethoxysilane (0.30 mol), having Mw of 20,000 and Mn of 4,000, and containing a cage-type polysilsesquioxane.
• A-5 An acrylic resin having the following structure. Mw was 27,000 and Mn was 5,500.
• A-6 Polysilsesquioxane synthesized using decyltrimethoxysilane (0.30 mol), having Mw of 1,7000 and Mn of 6,000, containing a cage-type polysilsesquioxane.
• Dicumyl peroxide thermal polymerization initiator Oxe-01: photopolymerization initiator, Irgacure OXE-01, manufactured by BASF Api307: photopolymerization initiator, manufactured by Shenzhen UV-ChemTech Ltd.
• S-506 Silicone-based surfactant, manufactured by DIC Corporation
• F-551A Megafac (registered trademark) F551A, fluorine-based surfactant, manufactured by DIC Corporation
• A-NOD-N polymerizable compound, 1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
• the laminate was heated in an oven (200°C, 1.5 hours), then immersed in 2M hydrochloric acid for 8 hours for peeling treatment, rinsed (pure water at room temperature for 1 hour), and peeled off from the substrate to obtain a free-standing film derived from the composition layer. If the free-standing film could not be peeled off by the above peeling treatment, it was further immersed in 2M hydrochloric acid for about 1 week for peeling.
• the obtained free-standing film was cut into a strip (19 mm x 5 mm), and the linear expansion coefficient was measured using a TMA (thermomechanical analyzer, "TMA450EM” manufactured by TA Instruments).
• the measurement conditions were a heating rate of 10°C/min, a chuck distance of 10 mm, and a load of 40 mN.
• the linear expansion coefficient was measured as a value (ppm/K) in the range of 50°C to 150°C during heating, and was calculated as the average value of three measurements.
• the obtained linear expansion coefficient was evaluated according to the following evaluation criteria.
• a copper-clad polyimide film (Metalloyal, Toray Industries, Inc.) was used as a substrate, and the prepared composition was applied and dried on the substrate to obtain a laminate having a composition layer of 10.0 ⁇ m thickness on the substrate.
• the obtained laminate was exposed to light (high pressure mercury lamp, cumulative illuminance measured with a 365 nm wavelength illuminometer: 100 mJ/cm 2 ) from the side opposite to the substrate side of the composition layer.
• the laminate was heat-treated in an oven (200° C., 1.5 hours) to obtain a sample for evaluation.
• the evaluation samples were subjected to a cross-cut test in accordance with JIS K5600-5-6, and the adhesion between the film formed from the composition and copper was evaluated according to the following evaluation criteria.
• the thickness of the composition layer on the copper pattern was adjusted to be 20 ⁇ m.
• the obtained laminate was exposed to light from the side opposite to the substrate side of the composition layer (high pressure mercury lamp, cumulative illuminance measured with a 365 nm wavelength illuminometer: 100 mJ/cm 2 ).
• thermocycle test was performed on the evaluation sample using a gas-phase heat-cooling tester by leaving it in a gas phase at a temperature of -40°C for 30 minutes and then in a gas phase at a temperature of 180°C for 30 minutes, with this cycle being repeated 100 times. Thereafter, an area of 5 cm x 5 cm of the evaluation sample was observed, and the thermocycle resistance was evaluated according to the following evaluation criteria.
• the prepared composition was applied onto a temporary support (QS62, manufactured by Toray Industries, Inc., 31 ⁇ m thick PET film) and dried at 100° C. to form a composition layer.
• the film thickness of the composition layer was adjusted to 25 ⁇ m after drying.
• a protective film manufactured by Oji F-Tex Co., Ltd., polypropylene film, FG-201, thickness 30 ⁇ m was attached to the side of the composition layer opposite the temporary support to obtain a transfer film.
• the protective film of the obtained transfer film was peeled off, and the film was laminated (rubber roller temperature 100°C, conveying speed 1 m/min, linear pressure 0.6 MPa) onto a copper-clad polyimide film (Metaloyal, manufactured by Toray Industries, Inc.) substrate.
• the temporary support was then peeled off at an angle of 90° to the substrate at a speed of 2 m/min, after which the composition layer was observed and the suitability for transfer film was evaluated according to the following criteria.
• the better the temporary support peelability the more suitable it is for use as a transfer film, i.e., the better the suitability for transfer film.
• A The area of the composition layer remaining on the substrate is 60% or more of the area of the peeled temporary support.
• B The area of the composition layer remaining on the substrate is less than 60% of the area of the peeled temporary support.
• composition of the present invention can form a film that has a small linear expansion coefficient and excellent adhesion to metals.
• the transfer film of each Example was laminated on both sides of a glass epoxy substrate (CCL-EL190T, thickness 1.0 mm, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on which a circuit pattern was formed, and composition layers were formed on both sides of the glass epoxy substrate.
• the lamination was performed using a vacuum laminator manufactured by MCK Corporation under the conditions of substrate temperature: 50°C, rubber roller temperature: 100°C, linear pressure: 3 N/cm, and conveying speed: 2 m/min.

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