Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • 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
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

• the present invention relates to a curable resin composition for electronic materials.
• Patent Document 1 describes (A) a polymer compound, (B) ammonium polyphosphate, (C) aluminum hydroxide and/or magnesium hydroxide, (D) a polyhydric alcohol, (E) a compound having a melamine skeleton, and , (F) a flame-retardant resin composition containing hollow ceramic beads and/or expanded graphite is disclosed.
• the flame-retardant resin composition of Patent Document 1 has a problem in that it has a high viscosity and is difficult to apply to electronic materials.
• the present invention has excellent coating properties, can be easily applied to electronic materials, and can impart flame retardancy to electronic materials or improve the flame retardancy of electronic materials.
• the present invention provides a synthetic resin composition.
• the curable resin composition for electronic materials of the present invention is characterized by containing a curable resin, a phosphorus compound, and a polyhydric alcohol.
• the curable resin may be a one-component curable resin or a two-component curable resin.
• the one-component curable resin includes a polymer that is cured by introducing a crosslinked structure by moisture, light irradiation, or heat.
• the two-component curable resin includes a polymer that is cured by introducing a crosslinked structure by mixing a base resin and a curing agent.
• One-component curable resin examples include polymers having hydrolyzable silyl groups, hydrolytically crosslinkable silicone polymers, polymers having hydrolyzable isocyanate groups, photocrosslinkable polymers, etc. It is preferable that the polymer contains a polymer having a silyl group.
• hydrolyzable group of the hydrolyzable silyl group is hydrolyzed to generate a silanol group ( ⁇ SiOH) in the presence of water. Then, the silanol groups undergo dehydration condensation to form a crosslinked structure.
• Hydrolytically crosslinkable silicone polymers and polymers having hydrolysable isocyanate groups are produced by the hydrolyzable isocyanate group forming a urea bond (-NHCONH-) while generating carbon dioxide in the presence of water. Forms a crosslinked structure.
• a hydrolyzable silyl group is a group in which 1 to 3 hydrolyzable groups are bonded to a silicon atom.
• the hydrolyzable group of the hydrolyzable silyl group is not particularly limited, and includes, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, and a mercapto group. group, alkenyloxy group, oxime group, etc.
• an alkoxysilyl group is preferable because the hydrolysis reaction is mild.
• alkoxysilyl groups include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; propyldimethoxysilyl group, methyldimethoxysilyl group, and methyldiethoxysilyl group. dialkoxysilyl groups such as; and monoalkoxysilyl groups such as dimethylmethoxysilyl group and dimethylethoxysilyl group.
• a hydrolyzable isocyanate group refers to an isocyanate group that can form a urea bond (-NHCONH-) through hydrolysis.
• the polymer having a hydrolyzable silyl group is not particularly limited, and includes, for example, polyalkylene oxide having a hydrolysable silyl group, acrylic polymer having a hydrolysable silyl group, and urethane having a hydrolysable silyl group. Examples include polyolefin-based polymers and polyolefin-based polymers having a hydrolyzable silyl group.
• the polymer having a hydrolyzable silyl group preferably contains a polyalkylene oxide having a hydrolyzable silyl group.
• the polymer having a hydrolyzable silyl group may be used alone or in combination of two or more kinds.
• the content of the polymer having a hydrolyzable silyl group in the curable resin is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, More preferably 90% by mass or more, and even more preferably 100% by mass.
• the hydrolyzable silyl group is preferably an alkoxysilyl group, more preferably a dialkoxysilyl group, more preferably a dimethoxysilyl group, and more preferably a propyldimethoxysilyl group.
• the polyalkylene oxide having a hydrolyzable silyl group preferably has on average 1 to 4 hydrolyzable silyl groups in one molecule.
• the number of hydrolyzable silyl groups in the polyalkylene oxide having hydrolyzable silyl groups is within the above range, the flame retardance of the cured product of the curable resin composition for electronic materials will be improved.
• the polyalkylene oxide having a hydrolyzable silyl group preferably has a hydrolyzable silyl group at at least one of both ends of its main chain.
• the average number of hydrolyzable silyl groups per molecule in the polyalkylene oxide having a hydrolyzable silyl group is determined by the concentration of the hydrolyzable silyl groups in the polyalkylene oxide determined by 1 H-NMR, and It can be calculated based on the number average molecular weight of polyalkylene oxide determined by GPC method.
• the polyalkylene oxide constituting the polyalkylene oxide having a hydrolyzable silyl group has a main chain having the general formula: -(R 1 -O) m - (wherein R 1 has 1 to 14 carbon atoms) represents an alkylene group, and m is the number of repeating units and is a positive integer).
• the main chain skeleton of the polyalkylene oxide may consist of only one type of repeating unit, or may consist of two or more types of repeating units.
• an alkylene group is a divalent atomic group formed by removing two hydrogen atoms bonded to two different carbon atoms in an aliphatic saturated hydrocarbon, and includes both linear and branched groups. Contains atomic groups.
• alkylene groups examples include ethylene group, propylene group [-CH(CH 3 )-CH 2 -], trimethylene group [-CH 2 -CH 2 -CH 2 -], butylene group, amylene group [-(CH 2 ) 5 -], hexylene group, etc.
• polyalkylene oxide examples include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer.
• polypropylene oxide is preferred. According to polypropylene oxide, the viscosity of the curable resin composition for electronic materials can be reduced and the coating properties can be improved, and the curable resin composition for electronic materials can be accurately applied to a narrow coating area.
• the number average molecular weight of the polyalkylene oxide having a hydrolyzable silyl group is preferably 3,000 or more, more preferably 10,000 or more.
• the number average molecular weight of the polyalkylene oxide having a hydrolyzable silyl group is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less.
• the number average molecular weight of the polyalkylene oxide is 3000 or more, the polyalkylene oxide does not easily thermally decompose into low molecular weight substances, so the cured product of the curable resin composition for electronic materials has excellent flame retardancy. There is.
• the number average molecular weight of the polyalkylene oxide is 50,000 or less, the coating properties of the curable resin composition for electronic materials are improved, and the composition can be coated accurately on desired locations of small electronic materials.
• the weight average molecular weight of the polyalkylene oxide having a hydrolyzable silyl group is preferably 3,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more.
• the weight average molecular weight of the polyalkylene oxide having a hydrolyzable silyl group is preferably 70,000 or less, more preferably 60,000 or less, and even more preferably 50,000 or less.
• the weight average molecular weight of the polyalkylene oxide is 3000 or more, the polyalkylene oxide does not easily thermally decompose into low molecular weight substances, so the cured product of the curable resin composition for electronic materials has excellent flame retardancy. There is.
• the weight average molecular weight of the polyalkylene oxide is 70,000 or less, the coating properties of the curable resin composition for electronic materials are improved, and the composition can be coated accurately on desired locations of small electronic materials.
• the number average molecular weight and weight average molecular weight of the polyalkylene oxide having a hydrolyzable silyl group refer to values measured by GPC (gel permeation chromatography) in terms of polystyrene.
• the number average molecular weight and weight average molecular weight of the polyalkylene oxide having a hydrolyzable silyl group can be measured, for example, using the following measuring device and measuring conditions.
• Measuring device manufactured by TOSOH, product name “HLC-8121GPC/HT” Measurement conditions Column: TSKgelGMHHR-H(20)HT x 3 TSKguardcolumn-HHR(30)HT x 1
• Mobile phase o-DCB 1.0mL/min
• Detector Blythe refractometer Standard material: Polystyrene (manufactured by TOSOH, molecular weight: 500-8420000) Elution conditions: 145°C SEC temperature: 145°C
• polyalkylene oxides having a hydrolyzable silyl group can be used.
• examples of polyalkylene oxides having a hydrolyzable silyl group include Kaneka's product names "MS Polymer S-203", “MS Polymer S-303", “MS Polymer S-303H”, and “Silyl Examples include “Polymer SAT-200”, “Silyl Polymer SAT-350”, and “Silyl Polymer SAT-400".
• polyalkylene oxides having a hydrolyzable silyl group include Asahi Glass Co., Ltd.'s product names "Excestar ESS-3620", “Excestar ESS-2420”, “Excestar ESS2410", and “Excestar ESS3430". Can be mentioned.
• a polyalkylene oxide whose main chain is polypropylene oxide and which has a (methoxymethyl)dimethoxysilyl group at the end of the polypropylene oxide is commercially available from Kaneka Corporation under the trade name "HS-2".
• a polyalkylene oxide whose main chain is polypropylene oxide and has an isopropyldimethoxymethylsilyl group at the end of the polypropylene oxide is commercially available from Kaneka Corporation under the trade name "SAX720".
• the content of polyalkylene oxide having a hydrolyzable silyl group in the curable resin is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, more preferably 90% by mass or more, and even more preferably 100% by mass.
• an alkoxysilyl group is preferable, a trialkoxysilyl group is more preferable, and a trimethoxysilyl group is more preferable because the hydrolysis reaction is mild.
• a silyl group is particularly preferred.
• the average number of hydrolyzable silyl groups in one molecule is preferably one or more, more preferably two or more.
• the average number of hydrolyzable silyl groups in one molecule is preferably 4 or less, more preferably 2.5 or less.
• the flame retardancy of the cured product of the curable resin composition for electronic materials is improved.
• the number of hydrolyzable silyl groups is 4 or less, the viscosity of the curable resin composition for electronic materials is reduced and the coating properties are improved, and the curable resin composition for electronic materials can be applied to narrow coating areas.
• the acrylic polymer having a hydrolyzable silyl group preferably has a hydrolyzable silyl group at at least one of both ends of its main chain.
• an acrylic polymer having a hydrolyzable silyl group may be used in combination with an acrylic polymer not having a hydrolysable silyl group.
• the number of hydrolyzable silyl groups per molecule in both is preferably 0.3 or more, more preferably 0.5 or more.
• the number of hydrolyzable silyl groups is 0.3 or more, the curability of the curable resin composition for electronic materials is improved.
• the number of hydrolyzable silyl groups per molecule in both is preferably 2.0 or less, more preferably 1.8 or less.
• the number of hydrolyzable silyl groups is 2.0 or less, the viscosity of the curable resin composition for electronic materials is reduced and the coating properties are improved, and the curable resin composition for electronic materials can be coated in narrow coating areas.
• the curable resin composition for electronic materials can be applied with high precision to the coating area, and when the curable resin composition for electronic materials is applied to the coating area, the curable resin composition for electronic materials flows smoothly at the coating area, resulting in excellent leveling. have sex.
• the method of introducing a hydrolyzable silyl group into an acrylic polymer is not particularly limited.
• a hydrolyzable silyl examples include a method of hydrosilylation using a hydrosilane having a group.
• the average number of hydrolyzable silyl groups per molecule in the acrylic polymer having hydrolyzable silyl groups is as follows: It is calculated based on the concentration of hydrolyzable silyl groups and the number average molecular weight of the acrylic polymer having hydrolyzable silyl groups determined by GPC method.
• the main chain skeleton of the acrylic polymer having a hydrolyzable silyl group is preferably a copolymer of monomers containing methyl (meth)acrylate and butyl (meth)acrylate, and monomers containing methyl methacrylate and butyl acrylate.
• a copolymer of monomers containing methyl methacrylate and n-butyl acrylate is more preferable.
• the acrylic polymer having a hydrolyzable silyl group whose main chain skeleton is the above copolymer the flame retardance of the cured product of the curable resin composition for electronic materials is improved.
• (meth)acrylate means methacrylate and/or acrylate.
• the content of the methyl (meth)acrylate component is preferably 3% by mass or more, more preferably 5% by mass or more.
• the content of the methyl (meth)acrylate component is preferably 70% by mass or less, more preferably 50% by mass or less.
• the curable resin composition for electronic materials can be applied accurately to the application area, and when the curable resin composition for electronic materials is applied to the application area, the curable resin composition for electronic materials flows smoothly at the application area. Has excellent leveling properties. By setting the content of the methyl (meth)acrylate component to 70% by mass or less, the viscosity of the curable resin composition for electronic materials is reduced and the coating properties are improved, and the curable resin composition for electronic materials can be made into a narrow material. Coating can be applied to the coating area with high precision.
• the content of the butyl (meth)acrylate component is preferably 30 to 97% by mass, more preferably 50 to 95% by mass.
• a content of the butyl (meth)acrylate component of 30% by mass or more the viscosity of the curable resin composition for electronic materials is reduced, the coating properties are improved, and the curable resin composition for electronic materials can be narrowed. Coating can be applied to the coating area with high precision.
• the monomers used in the polymer constituting the main chain skeleton include methyl acrylate, methyl methacrylate, butyl acrylate, and butyl methacrylate, as well as other monomers. It may also contain a monomer. Examples of other monomers include styrene, indene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, and divinylbenzene.
• the method for polymerizing the acrylic polymer having a hydrolyzable silyl group is not particularly limited, and known methods can be used, such as free radical polymerization, anionic polymerization, cationic polymerization, and UV radical polymerization. Examples include various polymerization methods such as living anionic polymerization, living cationic polymerization, and living radical polymerization.
• the weight average molecular weight of the acrylic polymer having a hydrolyzable silyl group is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, particularly preferably 3,000 to 15,000. According to the acrylic polymer having a hydrolyzable silyl group and having a weight average molecular weight within the above range, the viscosity of the curable resin composition for electronic materials can be reduced and the coatability can be improved, and the curable resin composition for electronic materials can be improved.
• the resin composition can be accurately applied to a narrow application area, and when the curable resin composition for electronic materials is applied to the application area, the curable resin composition for electronic materials can be applied to the application area. Flows smoothly and has excellent leveling properties.
• the number average molecular weight of the acrylic polymer having a hydrolyzable silyl group is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, particularly preferably 3,000 to 15,000. According to the acrylic polymer having a hydrolyzable silyl group and having a weight average molecular weight within the above range, the viscosity of the curable resin composition for electronic materials can be reduced and the coatability can be improved, and the curable resin composition for electronic materials can be improved.
• the resin composition can be accurately applied to a narrow application area, and when the curable resin composition for electronic materials is applied to the application area, the curable resin composition for electronic materials can be applied to the application area. Flows smoothly and has excellent leveling properties.
• the number average molecular weight and weight average molecular weight of the acrylic polymer having a hydrolyzable silyl group can be measured, for example, using the following measuring device and measuring conditions.
• Measuring device manufactured by TOSOH, product name “HLC-8121GPC/HT” Measurement conditions Column: TSKgelGMHHR-H(20)HT x 3 TSKguardcolumn-HHR(30)HT x 1
• Detector Blythe refractometer Standard material: Polystyrene (manufactured by TOSOH, molecular weight: 500-8420000) Elution conditions: 145°C SEC temperature: 145°C
• the urethane-based polymer refers to a polymer having a main chain formed by repeating urethane bonds (-NHCOO-).
• a urethane-based polymer having a hydrolyzable silyl group has a plurality of hydrolyzable silyl groups in the main chain of the urethane-based polymer.
• the urethane-based polymer having a hydrolyzable silyl group preferably has hydrolyzable silyl groups at both ends of the main chain of the urethane-based polymer.
• polyolefin polymer having hydrolyzable silyl group examples include polyethylene polymers and polypropylene polymers.
• a polyolefin polymer having a hydrolyzable silyl group has a plurality of hydrolyzable silyl groups in the main chain of the polyolefin polymer.
• the polyolefin polymer having a hydrolyzable silyl group preferably has hydrolyzable silyl groups at both ends of the main chain of the polyolefin polymer.
• a silicone polymer is a polymer having a molecular chain (main chain) formed by repeating siloxane bonds (-Si-O-).
• the main chain of the silicone polymer is preferably linear.
• a hydrolyzable group is bonded to a part of the silicon atoms constituting the main chain of the silicone polymer.
• the cured product of the curable resin composition for electronic materials expands rapidly at the initial stage of combustion, reducing the spread of fire due to burning of the electronic materials. It is possible to impart excellent flame retardancy to electronic materials.
• Hydrolyzable groups are not particularly limited and include, for example, hydrogen atoms, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups, etc. are mentioned, and an alkoxy group is preferred.
• alkoxy group examples include methoxy group, ethoxy group, propoxy group, butoxy group, and methoxy group and ethoxy group are preferred.
• the hydrolytically crosslinkable silicone polymer causes a condensation reaction in the hydrolyzable groups to form a crosslinked structure in the presence of moisture or a crosslinking agent, using a catalyst as necessary.
• a hydrolytically crosslinkable silicone polymer has an alkoxy group as a hydrolyzable group, a portion of the alkoxy group is hydrolyzed to generate a hydroxy group, and this hydroxy group and alkoxy group undergo dealcoholization condensation. A reaction occurs to form a crosslinked structure.
• the content of hydrolyzable groups in the hydrolytically crosslinkable silicone polymer is preferably 5% by mass or more, more preferably 10% by mass or more.
• the content of hydrolyzable groups in the hydrolytically crosslinkable silicone polymer is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.
• the content of the hydrolyzable group is 5% by mass or more, the hardness of the combustion residue of the cured product of the curable resin composition for electronic materials is improved, and the coating of the curable resin composition for electronic materials is improved. It exists stably at certain locations and can impart excellent flame retardancy to electronic materials.
• the content of hydrolyzable groups in the hydrolytically crosslinkable silicone polymer is determined by the concentration of hydrolyzable groups in the hydrolytically crosslinkable silicone polymer determined by 1 H-NMR and by the GPC method. It can be calculated based on the number average molecular weight of the hydrolytically crosslinkable silicone polymer.
• the content of hydrolyzable groups in the hydrolytically crosslinkable silicone polymer is preferably 5 mol% or more, more preferably 10 mol% or more.
• the content of hydrolyzable groups in the hydrolytically crosslinkable silicone polymer is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 35 mol% or less.
• the content of the hydrolyzable group is 5 mol% or more, the hardness of the combustion residue of the cured product of the curable resin composition for electronic materials is improved, and the coating of the curable resin composition for electronic materials is improved. It exists stably at certain locations and can impart excellent flame retardancy to electronic materials.
• the content of hydrolyzable groups in the hydrolytically crosslinkable silicone polymer is determined by the concentration of hydrolyzable groups in the hydrolytically crosslinkable silicone polymer determined by 1 H-NMR and by the GPC method. It can be calculated based on the number average molecular weight of the hydrolytically crosslinkable silicone polymer.
• a methyl group or a phenyl group is bonded to some of the silicon atoms in the hydrolytically crosslinkable silicone polymer.
• the hydrolytically crosslinkable silicone polymer preferably has a silicon atom to which a methyl group or phenyl group is bonded. It is more preferable that the hydrolytically crosslinkable silicone polymer has a silicon atom to which a phenyl group is bonded.
• the hydrolyzable silicone polymer preferably has a silicon atom to which a methyl group and a phenyl group are bonded.
• the flame retardance of the curable resin composition for electronic materials can be improved.
• the content of phenyl groups is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more.
• the content of phenyl groups is preferably 80 mol% or less, more preferably 70 mol% or less, more preferably 60 mol% or less, more preferably 50 mol% or less, and 40 mol% or less. The following is more preferable, and 35 mol% or less is more preferable.
• the content of phenyl groups is 10 mol% or more, the flame retardance of the curable resin composition for electronic materials can be improved.
• the content of phenyl groups is 80 mol% or less, the viscosity of the curable resin composition for electronic materials is reduced, and the coatability of the curable resin composition for electronic materials is improved.
• the "number of phenyl groups” refers to the number of siloxane bonds (-Si-O-) formed by repeating It refers to the total number of phenyl groups bonded to silicon atoms that make up the linear molecular chain (main chain) (polysiloxane).
• “Number of bonds of silicon atoms” refers to the number of bonds used to construct the main chain from the four bonds that silicon atoms have, excluding the bonds used to construct the main chain. Refers to the total number of remaining bonds.
• the bonds used to construct the main chain refer only to the bonds bonded to oxygen.
• the content of methyl groups is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, more preferably 40 mol% or more, and 50 mol%. More preferably, 55 mol% or more is more preferable.
• the content of methyl groups is preferably 98 mol% or less, more preferably 96 mol% or less, more preferably 95 mol% or less, more preferably 90 mol% or less, and 80 mol% or less. The following is more preferable, and 70 mol% or less is more preferable.
• the content of methyl groups is 10 mol% or more, the viscosity of the curable resin composition for electronic materials is reduced, and the coatability of the curable resin composition for electronic materials is improved.
• the content of methyl groups is 98 mol% or less, the flame retardance of the curable resin composition for electronic materials is improved.
• the phenyl group content and methyl group content refer to values measured in the following manner.
• the concentration of methyl groups and the concentration of phenyl groups in the hydrolytically crosslinkable silicone polymer are calculated by MNR measurement from the signal intensity ratio determined from Si-NMR. For example, the measurement can be performed using the following measuring device and measurement conditions.
• Solvent Deuterated chloroform Concentration: 29Si approximately 5wt/vol% Temperature: 24.85°C (298K) Number of scans: 360 times Chemical shift standard: TMS 0.0ppm
• the total content of phenyl groups and methyl groups is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more.
• the total content of phenyl groups and methyl groups is preferably 99 mol% or less, more preferably 96 mol% or less, and even more preferably 95 mol% or less.
• the flame retardance of the curable resin composition for electronic materials can be improved.
• the total content of phenyl groups and methyl groups is 99 mol% or less, the curing reaction of the curable resin composition for electronic materials proceeds smoothly, so the obtained cured product has excellent hardness. .
• the viscosity at 25° C. of the hydrolytically crosslinkable silicone polymer is preferably 5 Pa ⁇ s or more, more preferably 10 mPa ⁇ s or more, and even more preferably 13 Pa ⁇ s or more.
• the viscosity at 25° C. of the hydrolytically crosslinkable silicone polymer is preferably 1000 Pa ⁇ s or less, more preferably 500 Pa ⁇ s or less, and even more preferably 300 Pa ⁇ s or less.
• the viscosity at 25°C is 5 Pa ⁇ s or more, the viscosity of the cured product of the curable resin composition for electronic materials will improve, and the curable resin composition for electronic materials will not separate during the curing process and will be uniform.
• the mixed state is maintained, and as a result, the flame retardance of the cured product of the curable resin composition for electronic materials is improved.
• the viscosity at 25° C. is 1000 Pa ⁇ s or less, the coating properties of the curable resin composition for electronic materials are improved.
• the viscosity of the hydrolytically crosslinkable silicone polymer at 25°C is a value measured using a B-type viscosity clock at 20°C and a rotational speed of 60 rpm in accordance with JIS Z8803.
• the content of the hydrolytically crosslinkable silicone polymer in the curable resin is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. It is more preferably 100% by mass or more, and more preferably 100% by mass.
• polymer having hydrolyzable isocyanate group examples include urethane polymers having a hydrolyzable isocyanate group.
• the urethane polymer refers to a polymer having a main chain formed by repeating urethane bonds (-NHCOO-).
• a urethane polymer having a hydrolyzable isocyanate group has a plurality of hydrolyzable isocyanate groups in the main chain of the urethane polymer.
• the urethane polymer having hydrolyzable isocyanate groups preferably has hydrolyzable isocyanate groups at both ends of the main chain of the urethane polymer.
• Urethane polymers include polyether urethane polymers made from polyether polyols and polyester urethane polymers made from polyester polyols, but may be any of these.
• the content of the polymer having a hydrolyzable isocyanate group in the curable resin is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, More preferably 90% by mass or more, and even more preferably 100% by mass.
• a photocrosslinkable polymer has a photocrosslinkable group in its molecule, and is cured by forming chemical bonds between molecules to form a crosslinked structure by irradiation with light such as ultraviolet rays.
• the photocrosslinkable group may form a chemical bond by irradiation with light.
• the photocrosslinkable group is not particularly limited and includes, for example, a thiol group, a glycidyl group, an oxetanyl group, a vinyl group, a (meth)acryloyl group, a benzophenone group, a benzoin group, a thioxanthone group, and a benzophenone group, a benzoin group. and thioxanthone group are preferred, and benzophenone group is more preferred.
• (meth)acryloyl means methacryloyl or acryloyl.
• the main chain structure of the photocrosslinkable polymer is not particularly limited, and examples thereof include polyolefin polymers, acrylic polymers, epoxy polymers, cyanoacrylate polymers, and the like.
• Examples of the method for introducing a photocrosslinkable group into the main chain include a method of polymerizing a monomer composition containing a photocrosslinkable group-containing monomer.
• the photocrosslinkable group-containing monomer is not particularly limited, and examples include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-(meth)acryloyloxybenzophenone, 4-[2-((meth)acryloyloxy) ) Ethoxy] benzophenone, 4-(meth)acryloyloxy-4'-methoxybenzophenone, 4-(meth)acryloyloxyethoxy-4'-methoxybenzophenone, 4-(meth)acryloyloxy-4'-bromobenzophenone, 4- Examples include (meth)acryloyloxyethoxy-4'-bromobenzophenone, and 4-(meth)acryloyloxybenzophenone and 4-[2-((meth)acryloyloxy)ethoxy]benzophenone are preferred.
• the ultraviolet crosslinkable group-containing monomer (D) may be used alone or in combination of two or more.
• the content of the photocrosslinkable polymer in the curable resin is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. is more preferable, and 100% by mass is more preferable.
• the two-component curable resin is not particularly limited, and examples thereof include isocyanate polymers, glycidyl polymers, and the like.
• the isocyanate-based polymer is a two-component curable resin consisting of a main resin containing polyisocyanate and a curing agent containing polyol. By mixing the main ingredient and the curing agent and reacting the polyisocyanate and polyol, urethane bonds are formed, crosslinked, and cured.
• polyisocyanate examples include aromatic aliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and the like.
• aromatic aliphatic diisocyanate examples include diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,3-bis(1-isocyanato-1-methylethyl)benzene, 1,4-bis(1 -isocyanato-1-methylethyl)benzene, ⁇ , ⁇ '-diisocyanato-1,4-diethylbenzene, and urethane prepolymers having isocyanate groups at both ends.
• aliphatic diisocyanates examples include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, and the like. It will be done.
• alicyclic diisocyanate examples include isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate.
• polyols examples include polyurethane polyols, polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, and castor oil polyols.
• the glycidyl polymer is a two-component curable resin consisting of a main ingredient containing an epoxy polymer and a curing agent.
• the epoxy polymer is not particularly limited, and includes, for example, a bisphenol A type epoxy polymer obtained by reacting bisphenol A and epichlorohydrin, and a bisphenol A type epoxy polymer obtained by reacting bisphenol F and epichlorohydrin.
• Nitrogen-containing epoxy polymers such as bisphenol F-type epoxy polymers, hydrogenated products thereof, glycidyl ester type epoxy polymers, novolac type epoxy polymers, urethane-modified epoxy polymers, triglycidyl isocyanurate, etc. , a rubber-modified epoxy polymer containing polybutadiene or NBR, and the like.
• the curing agent is not particularly limited, and examples thereof include amine curing agents, acid anhydride curing agents, polyamide curing agents, imidazole curing agents, polymerkaplan curing agents, and the like.
• amine curing agent examples include aliphatic polyamines such as polyoxypropylenetriamine, diethylenetriamine, and triethylenetetramine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 2,4,6-tris(dimethylaminomethyl)phenol, and the like. and aromatic polyamines.
• acid anhydride curing agents examples include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, hetacetic anhydride, dodecenylsuccinic anhydride, and the like.
• polyamide curing agent examples include dimer acid.
• the content of the two-component curable resin in the curable resin is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. is more preferable, and 100% by mass is more preferable.
• the curable resin composition for electronic materials contains a phosphorus compound. Because the curable resin composition for electronic materials contains a phosphorus compound, the cured product of the curable resin composition for electronic materials expands in the event of a fire, protecting the electronic materials and providing excellent flame retardancy for electronic materials. can be given gender.
• the phosphorus-based compound only needs to contain a phosphorus atom in its molecule.
• the phosphorus compound is not particularly limited.
• the phosphorus compound is preferably ammonium polyphosphate or a poorly water-soluble phosphorus compound, and more preferably ammonium polyphosphate. Note that the phosphorus compounds may be used alone or in combination of two or more.
• the content of ammonium polyphosphate in the phosphorus compound is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more. Preferably, 100% by mass is more preferable.
• the content of the poorly water-soluble phosphorus compound in the phosphorus compound is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. is more preferable, and 100% by mass is more preferable.
• the poorly water-soluble phosphorus compound is not particularly limited, and examples thereof include poorly water-soluble aluminum phosphite, monobasic aluminum phosphate, dibasic aluminum phosphate, tertiary aluminum phosphate, aluminum metaphosphate, and condensed aluminum phosphate.
• examples include inorganic phosphorus compounds, poorly water-soluble organic phosphorus compounds such as melam polyphosphate, melamine polyphosphate, melem polyphosphate, etc. It is preferable to include a poorly water-soluble inorganic phosphorus compound, and aluminum phosphite or primary phosphoric acid. It is more preferable that ammonium is included, and it is even more preferable that aluminum phosphite is included.
• the poorly water-soluble phosphorus compounds may be used alone or in combination of two or more kinds.
• “Poorly water-soluble phosphorus compound” refers to a phosphorus compound whose saturation concentration (solubility) of a saturated solution obtained by dissolving the phosphorus compound in 100 g of water at 25°C is 0.03 g/100 g-H 2 O or less. .
• a solution solution is prepared by supplying an excessive amount of the phosphorus compound to the extent that a slight precipitate is formed, and stirring and dissolving the compound in 1000 g of water at 25°C.
• a saturated solution is prepared by suction-filtering the solution through a Type 5 C filter paper in accordance with JIS P3801 to remove undissolved components in the solution. The saturated solution is heated to 100° C.
• solubility g/100g-H 2 O
• some water is absorbed by the filter paper in the process of removing insoluble matter, but the amount is extremely small compared to 1000 g of water, so the mass of water absorbed by the filter paper affects the solubility value. It has no effect and can be ignored.
• the content of the phosphorus compound in the curable resin composition for electronic materials is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, more preferably 70 parts by mass or more, based on 100 parts by mass of the curable resin. More preferably 80 parts by mass or more, more preferably 90 parts by mass or more, more preferably 100 parts by mass or more, and even more preferably 110 parts by mass or more.
• the content of the phosphorus compound in the curable resin composition for electronic materials is preferably 200 parts by mass or less, more preferably 180 parts by mass or less, more preferably 160 parts by mass or less, based on 100 parts by mass of the curable resin. More preferably, it is 140 parts by mass or less.
• the cured product of the curable resin composition for electronic materials expands more effectively in the event of a fire, protects the electronic materials more reliably, and provides even better electronic materials. It can also impart flame retardancy.
• the content of the phosphorus compound is 200 parts by mass or less, the hardness of the combustion residue in the cured product of the curable resin composition for electronic materials improves, and it stably exists in the coating area of the electronic material, which improves the hardness of the combustion residue. can provide excellent flame retardancy.
• the curable resin composition for electronic materials contains a polyhydric alcohol.
• the expandability of the cured product of the curable resin composition for electronic materials is improved.
• the cured product of the curable resin composition for electronic materials can effectively expand in the event of a fire, stably protect the electronic materials, and provide the electronic materials with excellent flame retardancy.
• Polyhydric alcohol has multiple hydroxyl groups (-OH) in its molecule.
• the number of hydroxyl groups in the polyhydric alcohol is preferably 4 or more.
• the number of hydroxyl groups in the polyhydric alcohol is preferably 10 or less.
• the number of hydroxyl groups in the polyhydric alcohol is 10 or less, the viscosity of the curable resin composition for electronic materials is reduced and the coating properties are improved, and the curable resin composition for electronic materials can be coated in a narrow coating area. can be coated with high precision.
• the number of hydroxyl groups in the polyhydric alcohol is 10 or less, the shape retention of the combustion residue in the cured product of the curable resin composition for electronic materials improves, and it stably exists in the coating area of the electronic material. , it is possible to impart excellent flame retardancy to electronic materials.
• Polyhydric alcohols are not particularly limited, and include, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, pentylene glycol, 1,4 -Butanediol, 1,2-propanediol, dipropylene glycol, polyethylene glycol, xylitol, mannitol, maltitol, lactitol, sorbitol, xylitol, erythritol, etc., and expansion of cured products of curable resin compositions for electronic materials
• pentaerythritol, dipentaerythritol, tripentaerythritol, and polypentaerythritol have improved properties.
• polyhydric alcohols may be used alone or in combination of two or
• the polyhydric alcohol may be a diol represented by general formula (2).
• the diol is preferably a polymer containing a repeating unit represented by general formula (2).
• HO-(R 2 -O)n-OH (2) [In formula (2), R 2 represents an alkylene group having 1 to 14 carbon atoms, and n is the number of repeating units and is a positive integer. ]
• the alkylene group is a divalent atomic group formed by removing two hydrogen atoms bonded to two different carbon atoms in an aliphatic saturated hydrocarbon, and includes both linear and branched groups. Contains atomic groups. Note that the term "branched" includes cases where one carbon (methyl group) is bonded as a side chain.
• alkylene groups examples include ethylene group, propylene group [-CH 2 -CH 2 -CH 2 - (trimethylene group), -CH(CH 3 )-CH 2 -], butylene group, amylene group, hexylene group, etc. Can be mentioned.
• polyhydric alcohol may be a polyol represented by general formula (3).
• R 3 , R 4 and R 5 each represent an alkylene group having 1 to 14 carbon atoms.
• R 3 , R 4 and R 5 may be the same or different.
• p is a positive integer from 1 to 100.
• w, x and y are the numbers of repeating units and are positive integers. When p is a positive integer of 2 or more, the plurality of R 4 and x may be the same or different.
• the alkylene group is a divalent atomic group formed by removing two hydrogen atoms bonded to two different carbon atoms in an aliphatic saturated hydrocarbon, and is a linear group. Contains both shaped and branched atomic groups. Note that the term "branched" includes cases where one carbon (methyl group) is bonded as a side chain.
• alkylene groups examples include ethylene group, propylene group [-CH 2 -CH 2 -CH 2 - (trimethylene group), -CH(CH 3 )-CH 2 -], butylene group, amylene group, hexylene group, etc. Can be mentioned.
• the content of polyhydric alcohol in the curable resin composition for electronic materials is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the curable resin. More preferably 15 parts by mass or more.
• the content of polyhydric alcohol in the curable resin composition for electronic materials is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, more preferably 80 parts by mass or less, based on 100 parts by mass of the curable resin. More preferably, it is 70 parts by mass or less.
• the content of polyhydric alcohol is 1 part by mass or more, the shape retention of combustion residue in the cured product of the curable resin composition for electronic materials improves, and it stably exists in the coated area of the electronic material, Excellent flame retardancy can be imparted to electronic materials.
• the content of polyhydric alcohol is 100 parts by mass or less, the viscosity of the curable resin composition for electronic materials is reduced and the coating properties are improved, and the curable resin composition for electronic materials can be applied to narrow coating areas. Can be coated with high precision.
• the content of polyhydric alcohol is 100 parts by mass or less, the shape retention of combustion residue in the cured product of the curable resin composition for electronic materials improves, and it stably exists in the coated area of the electronic material, Excellent flame retardancy can be imparted to electronic materials.
• the ratio of the phosphorus compound content to the polyhydric alcohol content is preferably 0.5 or more, and 0.8 The above is more preferable, 0.9 or more is more preferable, 1.0 or more is more preferable, 1.2 or more is more preferable, and 1.3 or more is more preferable.
• the ratio of the phosphorus compound content to the polyhydric alcohol content is preferably 6.0 or less, and 5.5 The following is more preferable, 5.0 or less is more preferable, 4.5 or less is more preferable, and 4.0 or less is more preferable.
• the ratio of the phosphorus compound content to the polyhydric alcohol content is 0.5 or more
• combustion in the cured product of the curable resin composition for electronic materials may occur.
• the shape retention of the residue is improved, and it stably exists in the coating area of the electronic material, making it possible to impart excellent flame retardancy to the electronic material.
• the ratio of the phosphorus compound content to the polyhydric alcohol content is 6.0 or less
• the viscosity of the curable resin composition for electronic materials is reduced.
• the coating properties can be improved, and the curable resin composition for electronic materials can be applied accurately to a narrow coating area.
• the curable resin composition for electronic materials preferably contains titanium oxide.
• the hardness of the combustion residue of the cured product of the curable resin composition for electronic materials is further improved by the reaction between titanium oxide and the phosphorus compound. Electronic materials can be more reliably protected in the event of a fire, and the flame retardance of electronic materials can be improved.
• the average particle diameter of titanium oxide is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, and even more preferably 0.02 ⁇ m or more.
• the average particle diameter of titanium oxide is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, and even more preferably 5 ⁇ m or less.
• the average particle diameter of titanium oxide is 0.05 ⁇ m or more, the viscosity of the curable resin composition for electronic materials is prevented from increasing rapidly, and the coatability of the curable resin composition for electronic materials is improved. .
• the average particle diameter of titanium oxide refers to the particle diameter D50 at which the cumulative frequency from the smaller particle diameter side in the volume-based particle size distribution measured by laser diffraction is 50% by mass.
• the content of titanium oxide in the curable resin composition for electronic materials is preferably 1 part by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and 8 parts by mass or more, based on 100 parts by mass of the curable resin. Parts by mass or more are more preferable.
• the content of titanium oxide in the curable resin composition for electronic materials is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, more preferably 16 parts by mass or less, and 14 parts by mass or less, based on 100 parts by mass of the curable resin. It is more preferably 12 parts by mass or less, more preferably 12 parts by mass or less.
• the content of titanium oxide is 1 part by mass or more, the hardness of the combustion residue of the cured product of the curable resin composition for electronic materials is further improved due to the reaction between titanium oxide and the phosphorus compound, and in the event of a fire, It stably exists at the coating site of the curable resin composition for electronic materials in electronic materials, and can impart excellent flame retardancy to the electronic materials.
• the content of titanium oxide is 20 parts by mass or less, the viscosity of the curable resin composition for electronic materials is reduced to improve coating properties, and the curable resin composition for electronic materials can be applied accurately to narrow coating areas. Can be applied well.
• the curable resin composition for electronic materials preferably contains glass frit.
• Glass frit acts as a binder to bind the combustion residue of the curable resin and feldspars in the combustion residue of the cured product of the curable resin composition for electronic materials, and the combustion residue has excellent hardness. has. Therefore, the combustion residue of the cured product of the curable resin composition for electronic materials stably exists in the area where the curable resin composition for electronic materials is applied, imparting excellent flame retardancy to the electronic material. can do.
• glass constituting the glass frit examples include phosphoric acid glass, boric acid glass, bismuth oxide glass, silicate glass, and sodium oxide glass. is preferred, and phosphate glass is more preferred.
• These glass frits include B 2 O 3 , P 2 O 5 , ZnO, SiO 2 , Bi 2 O 3 , Al 2 O 3 , BaO, CaO, MgO, MnO 2 , ZrO 2 , TiO 2 , CeO 2 , SrO , V 2 O 5 , SnO 2 , Li 2 O, Na 2 O, K 2 O, CuO, Fe 2 O 3 and the like by adjusting a predetermined component ratio.
• the content of glass frit in the curable resin composition for electronic materials is preferably 5 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 40 parts by mass or more based on 100 parts by mass of the curable resin.
• the content of glass frit in the curable resin composition for electronic materials is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 80 parts by mass or less based on 100 parts by mass of the curable resin.
• the content of glass frit is 200 parts by mass or less, the viscosity of the curable resin composition for electronic materials is reduced and the coating properties are improved, and the curable resin composition for electronic materials can be applied accurately to narrow coating areas. Can be applied well.
• the curable resin composition for electronic materials may contain a silanol condensation catalyst.
• the silanol condensation catalyst is a catalyst for promoting curing of the curable resin by a condensation reaction when the curable resin is a polymer having a hydrolyzable silyl group or a hydrolytically crosslinkable silicone polymer.
• silanol condensation catalyst examples include dibutyltin diacetylacetonate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, Bis(dibutyltin lauric acid) oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(monoester malate), tin octylate, dibutyltin octoate, dioctyltin oxide, dibutyltin bis(triethoxysilicate), bis (dibutyltin bistriethoxysilicate) oxide and organic tin compounds such as dibutyltin oxybisethoxysilicate; organic titanium compounds such as tetra-n-butoxytitanate and te
• silanol condensation catalyst 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane is preferred. According to such a silanol condensation catalyst, the curing speed of the curable resin composition for electronic materials can be easily adjusted.
• the content of the silanol condensation catalyst in the curable resin composition for electronic materials is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and 0.3 parts by mass based on 100 parts by mass of the curable resin. Part or more is more preferable.
• the content of the silanol condensation catalyst in the curable resin composition for electronic materials is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, more preferably 6 parts by mass or less, based on 100 parts by mass of the curable resin. More preferably, it is 5 parts by mass or less.
• the content of the silanol condensation catalyst in the curable resin composition for electronic materials is 0.1 parts by mass or more, the curing speed of the curable resin composition for electronic materials is increased, and the curable resin composition for electronic materials is improved. It is possible to shorten the time required for hardening the object.
• the content of the silanol condensation catalyst in the curable resin composition for electronic materials is 10 parts by mass or less, the curable resin composition for electronic materials has an appropriate curing speed, and the curable resin composition for electronic materials The storage stability and handling properties of the product can be improved.
• the curable resin composition for electronic materials further contains a dehydrating agent. According to the dehydrating agent, when the curable resin composition for electronic materials is stored, it is possible to suppress the curing of the curable resin composition for electronic materials due to moisture contained in the air. .
• Dehydrating agents include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; and methyl orthoformate. , ethyl orthoformate, methyl orthoacetate, and ester compounds such as ethyl orthoacetate. These dehydrating agents may be used alone or in combination of two or more. Among them, vinyltrimethoxysilane is preferred.
• the content of the dehydrating agent in the curable resin composition for electronic materials is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more based on 100 parts by mass of the curable resin.
• the content of the dehydrating agent in the curable resin composition for electronic materials is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the curable resin.
• the content of the dehydrating agent in the curable resin composition for electronic materials is 0.5 parts by mass or more, the effect obtained by the dehydrating agent can be sufficiently obtained.
• the content of the dehydrating agent in the curable resin composition for electronic materials is 20 parts by mass or less, the curable resin composition for electronic materials has excellent curability.
• the curable resin composition for electronic materials may contain thixotropic agents, antioxidants, ultraviolet absorbers, pigments, dyes, antisettling agents, aminosilane coupling agents, thixotropic agents, and plasticizers within the range that does not impair its physical properties.
• Other additives such as agents and solvents may also be included. Among these, thixotropy imparting agents, ultraviolet absorbers, and antioxidants are preferred.
• the curable resin composition for electronic materials preferably contains a black pigment (for example, carbon black, etc.) as a pigment.
• a black pigment for example, carbon black, etc.
• the curable resin composition for electronic materials preferably contains an aminosilane coupling agent.
• an aminosilane coupling agent By using an aminosilane coupling agent, the rubber elasticity and adhesiveness of the cured product of the curable resin composition for electronic materials can be improved.
• the aminosilane coupling agent means a compound containing a silicon atom to which an alkoxy group is bonded in one molecule and a functional group containing a nitrogen atom.
• aminosilane coupling agent examples include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxy.
• the aminosilane coupling agents include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.
• Ethoxysilane is preferred, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane is more preferred.
• the content of the aminosilane coupling agent in the curable resin composition for electronic materials is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the curable resin.
• the content of the aminosilane coupling agent is within the above range, the rubber elasticity and adhesiveness of the cured product of the curable resin composition for electronic materials can be improved.
• the thixotropy imparting agent may be any agent as long as it can impart thixotropy to the curable resin composition for electronic materials.
• Preferred examples of the thixotropic agent include hydrogenated castor oil, fatty acid bisamide, and fumed silica.
• the content of the thixotropic agent in the curable resin composition for electronic materials is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the curable resin.
• the content of the thixotropic agent in the curable resin composition for electronic materials is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, based on 100 parts by mass of the curable resin.
• the curable resin composition for electronic materials when the content of the thixotropy imparting agent in the curable resin composition for electronic materials is 200 parts by mass or less, the curable resin composition for electronic materials has an appropriate viscosity, and the curable resin for electronic materials The ease of handling the composition is improved.
• the ultraviolet absorber examples include benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers, with benzotriazole-based ultraviolet absorbers being preferred.
• the content of the ultraviolet absorber in the curable resin composition for electronic materials is preferably 0.1 parts by mass or more based on 100 parts by mass of the curable resin.
• the content of the ultraviolet absorber in the curable resin composition for electronic materials is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the curable resin.
• the antioxidant examples include hindered phenolic antioxidants, monophenolic antioxidants, bisphenol antioxidants, and polyphenolic antioxidants, with hindered phenolic antioxidants being preferred. It will be done.
• the content of the antioxidant in the curable resin composition for electronic materials is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, based on 100 parts by mass of the curable resin.
• the content of the antioxidant in the curable resin composition for electronic materials is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the curable resin.
• the curable resin composition for electronic materials preferably contains a hindered amine light stabilizer. According to the hindered amine light stabilizer, it is possible to provide a curable resin composition for electronic materials that can maintain excellent rubber elasticity for a longer period of time after curing.
• hindered amine light stabilizer examples include a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate. , bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, dibutylamine/1,3,5-triazine/N,N'-bis(2,2,6,6-tetramethyl-4 - Polycondensate of piperidyl-1,6-hexamethylene diamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[ ⁇ 6-(1,1,3,3- Tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl ⁇ (2,2,6,6-tetramethyl-4-piperidyl)imino ⁇ hexamethylene ⁇ (2,2,6,6 -tetramethyl-4-piperidyl)imino], a polycon
• hindered amine light stabilizer NOR type hindered amine light stabilizer is preferably mentioned. According to the NOR type hindered amine light stabilizer, it is possible to provide a curable resin composition for electronic materials in which a decrease in rubber elasticity over time after curing is suppressed.
• the NOR type hindered amine light stabilizer has a NOR structure in which an alkyl group (R) is bonded to a nitrogen atom (N) contained in a piperidine ring skeleton via an oxygen atom (O).
• the number of carbon atoms in the alkyl group in the NOR structure is preferably 1 to 20, more preferably 1 to 18, and particularly preferably 18.
• Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cyclic alkyl group (saturated alicyclic hydrocarbon group).
• Examples of straight-chain alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, and n-decyl group.
• Examples include groups.
• Examples of the branched alkyl group include isopropyl, isobutyl, sec-butyl, and tert-butyl.
• Examples of the cyclic alkyl group saturated alicyclic hydrocarbon group
• examples of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a hydroxyl group.
• Examples of the NOR type hindered amine light stabilizer include a hindered amine light stabilizer represented by the following formula (I).
• NOR-type hindered amine light stabilizer When using a NOR-type hindered amine light stabilizer, it is preferable to use the NOR-type hindered amine light stabilizer in combination with a benzotriazole-based ultraviolet absorber or a triazine-based ultraviolet absorber. Thereby, it is possible to provide a curable resin composition for electronic materials in which the decline in rubber elasticity over time after curing is more suppressed.
• the content of the hindered amine light stabilizer in the curable resin composition for electronic materials is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the curable resin.
• the content of the hindered amine light stabilizer in the curable resin composition for electronic materials is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the curable resin.
• a curable resin composition for electronic materials can be produced by mixing a curable resin, a phosphorus compound, a polyhydric alcohol, and additives added as necessary.
• the curable resin composition for electronic materials may be suspended or emulsified in an aqueous solvent to form a suspension or emulsion.
• the curable resin composition for electronic materials may be in the form of a solution dissolved in a solvent.
• the water solvent include alcohols such as ethyl alcohol, methyl alcohol, and isopropyl alcohol, and water.
• the solvent include xylene, toluene, acetone, and the like.
• the curable resin composition for electronic materials uses a phosphorus compound and a polyhydric alcohol in combination, so that the cured product of the curable resin composition for electronic materials exhibits excellent expandability when exposed to heat during a fire. Has flame retardant properties.
• the curable resin composition for electronic materials has a low viscosity, so it has excellent coating properties and can be accurately applied to predetermined narrow coating areas of electronic materials, which are becoming increasingly smaller. be able to. Therefore, the curable resin composition for electronic materials can be coated accurately on predetermined areas of electronic materials without affecting the performance of the electronic materials, and can be applied to electronic materials and/or electronic devices containing electronic materials. It can impart flame resistance or improve flame retardancy.
• the curable resin composition for electronic materials contains a hydrolytically crosslinkable silicone polymer, a phosphorus compound, and a polyhydric alcohol
• the hydrolytically crosslinkable silicone polymer quickly reacts in the early stages of combustion during a fire. It is possible to further reduce the spread of fire caused by expansion and combustion of the electronic material.
• superior expandability can be imparted to the curable resin composition for electronic materials. Therefore, the curable resin composition for electronic materials can impart superior flame retardancy to electronic materials and/or electronic devices including electronic materials, or can further improve flame retardance.
• electronic devices are not particularly limited, and include, for example, car navigation systems, mobile phones, smartphones, game consoles, digital cameras, televisions, DVD players, electronic dictionaries, calculators, hard disk recorders, personal computers, video cameras, printers, and liquid crystal display devices. Examples include displays, plasma displays, radios, and electronic musical instruments.
• Electronic devices are becoming smaller and lighter, and the electronic materials that make up electronic devices are also becoming smaller.
• Such electronic materials are not particularly limited, and include, for example, printed wiring boards, light emitting diodes (LEDs), light emitting diode mounting boards, flexible copper clad laminates, bonding sheets, touch panels, sensor substrates, and the like.
• the method of applying the curable resin composition for electronic materials to a predetermined application area of the electronic material is not particularly limited, and includes, for example, a coating method using a brush, and a coating method using a known coating device. Examples include methods.
• the viscosity of the curable resin composition for electronic materials is preferably 500 mPa ⁇ s or more, more preferably 1000 mPa ⁇ s or more, and even more preferably 3000 mPa ⁇ s or more.
• the viscosity of the curable resin composition for electronic materials is preferably 200,000 mPa ⁇ s or less, more preferably 100,000 mPa ⁇ s or less, and even more preferably 50,000 mPa ⁇ s or less.
• the viscosity of the curable resin composition for electronic materials was measured at 23° C., 10 rpm, and rotor No. It refers to the value measured using a BH type viscometer under the conditions of 5.
• the curable resin composition for electronic materials coated on electronic materials produces a cured product by curing the curable resin.
• the curable resin may be cured by a known method (for example, supply of moisture, irradiation of light such as ultraviolet rays, heating, etc.) depending on the type of curable resin.
• the cured product of the curable resin composition for electronic materials expands due to combustion due to heat during a fire and generates combustion residue, and this combustion residue is stably disposed at the coated area even in the event of a fire. It maintains a good flame retardant state and exhibits excellent flame retardancy.
• the curable resin composition for electronic materials of the present invention has excellent coating properties due to its low viscosity, and can be applied to desired areas of electronic materials accurately and without impairing the functions of the electronic materials. Can be easily applied.
• the cured product produced by curing the curable resin composition for electronic materials expands due to heat such as a fire.
• the combustion residue of the cured product expands and covers the electronic material or the electronic device including the electronic material, thereby protecting the electronic material and the like from fire and suppressing the spread of the fire.
• the combustion residue of the cured product of the curable resin composition for electronic materials stably exists in the area where the curable resin composition for electronic materials is coated, and provides excellent flame retardancy to the electronic material.
• the flame retardancy of electronic materials can be improved.
• [Curable resin] Polyalkylene oxide having a hydrolyzable silyl group (polyalkylene oxide whose main chain skeleton is made of polypropylene oxide and has a dimethoxysilyl group at the end of the main chain, number average molecular weight: 38,000, weight average molecular weight: 49,000, manufactured by Kaneka Corporation)
• Product name: “Excestar S303H”) ⁇ Hydrolyzable crosslinkable silicone polymer 1 (manufactured by Momentive Performance Materials Japan LLC, product name "XR31-B2230”, hydrolyzable group: alkoxy group, content of alkoxy group: 5 mol%, phenyl group content: 30 mol%, methyl group content: 65 mol%, viscosity at 25°C: 16 Pa s, silicon atoms forming the linear main chain are used to form the main chain.
• a methyl group, a phenyl group, or an alkoxy group is bonded to each bond that is not used, and a methyl group and a phenyl group are bonded to some silicon atoms.
• ⁇ Hydrolyzable crosslinkable silicone polymer 2 manufactured by Momentive Performance Materials Japan, product name "XR31-B2733", hydrolyzable group: alkoxy group, content of alkoxy group: 5 mol%, methyl group Content: 95 mol%, viscosity at 25°C: 250 Pa ⁇ s, Regarding the silicon atoms that make up the linear main chain, each bond that is not used to make up the main chain has methyl group or alkoxy group is bonded.
• test sheet having a thickness of 1.5 mm was prepared using a curable resin composition for electronic materials, and was cured at 23° C. for 7 days.
• the test sheet was cut into a flat rectangular shape measuring 15 mm long x 130 mm wide x 1.5 mm thick to prepare 5 test pieces.
• the test was conducted based on the UL94V-0 standard. Specifically, one end of the test piece in the lateral direction was held using a clamp and the test piece was hung vertically. Next, a burner is used to apply a flame to the other end (lower end) in the horizontal direction of the vertically hung test piece, and after the burner is removed from the flame, Flame retardancy was measured by applying a flame to the other end using a burner for 3 seconds. Evaluation was made based on the following criteria. A: For each test piece, the afterflame time after two times of flame contact was within 10 seconds, and the total afterflame time of the five test pieces was within 50 seconds. Further, after the second flame contact, there were no test pieces that continued to glow for 30 seconds or more.
• the curable resin composition for electronic materials was filled into a capacitive syringe, and the syringe was attached to an air dispenser (Performus X100, manufactured by Nordson), and the coatability was measured. Substrates were prepared in which coating grooves with groove widths of 0.5 mm, 1.0 mm, and 2.0 mm were formed. Note that the coating grooves having groove widths of 0.5 mm, 1.0 mm, and 2.0 mm were referred to as "coating grooves 1 to 3" in that order.
• viscosity The viscosity of the curable resin composition for electronic materials was measured at 23° C., 10 rpm, and rotor No. It was measured using a BH type viscometer under the conditions of 5.
• the combustion residue of the cured product produced by curing the curable resin composition for electronic materials of the present invention expands and coats electronic materials or electronic devices containing electronic materials, thereby protecting electronic materials from fire. This can prevent the spread of fire.

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• 2023
  • 2023-03-22 WO PCT/JP2023/011197 patent/WO2023182347A1/ja active Application Filing
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