Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
  • C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/188—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using encapsulated compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2989—Microcapsule with solid core [includes liposome]

Definitions

• Microcapsule type epoxy resin curing agent master-batch type epoxy resin curing agent composition, one-part epoxy resin composition, and processed product
• the present invention relates to a novel curing agent for epoxy resin, and a one-component epoxy resin composition using the same.
• Epoxy resin has a superior performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc., because of its cured product. It is used for a wide range of applications such as materials and adhesives.
• an epoxy resin composition used for such a purpose a V-type two-component epoxy resin composition in which two components of epoxy resin and a curing agent are mixed and cured at the time of use.
• a two-part epoxy resin composition in which two components of epoxy resin and a curing agent are mixed and cured at the time of use.
• the two-part epoxy resin composition can be cured well at room temperature, it is necessary to store the epoxy resin and the curing agent separately, or mix them after weighing them when using. It may be necessary.
• curing agent is limited, both cannot be mixed in large quantities beforehand. That is, the conventional two-component epoxy resin composition still has room for improvement from the viewpoint of ease of storage, handleability, and blending frequency (production efficiency).
• one-component epoxy resin compositions (or sometimes referred to as "one-component epoxy resin compositions") have been proposed.
• examples of such a one-part epoxy resin composition include dicyandiamide, BF-amine complex, amine salt, and modified imidazole.
• blended latent hardeners such as a compound, with epoxy resin is mentioned.
• these one-component epoxy resin compositions having excellent storage stability tend to be inferior in curability (high temperature or long time is required for curing), and are excellent in curability. Things tend to be inferior in storage stability (-20 ° C !, required to be stored at low temperatures).
• a one-part epoxy resin composition containing dicyandiamide is If it exists, storage stability of 6 months or more can be achieved.
• a one-component epoxy resin composition that can be produced may require a high curing temperature of 170 ° C. or higher.
• the curing temperature can be lowered to about 130 ° C.
• storage stability at room temperature tends to decrease, and storage at low temperatures is required. That is, there has been a strong demand for a one-part epoxy resin composition that can achieve both high curability and excellent storage stability.
• Patent Document 1 (See Patent Literature 2).
• a powerful microcapsule-type curing agent is a curing agent that can achieve both good curability and storage stability.
• Patent Document 1 Japanese Patent Laid-Open No. 1 70523
• Patent Document 2 Japanese Patent Laid-Open No. 2005-344046
• An object of the present invention is to provide a microcapsule type epoxy resin hardener having excellent storage stability and excellent reaction steepness.
• the present inventors have, for example, a core (C) formed using a curing agent for epoxy resin (H) as a starting material, and the core (C When forming a microcapsule type epoxy resin curing agent having a shell (S), the average particle size of the epoxy resin curing agent (H) and the curing agent for small particle size epoxy resin Solving the above problem by defining the content ratio in a specific range and combining it with other components As a result, the present invention has been completed.
• the present invention includes the following microcapsule type epoxy resin hardener, masterbatch type epoxy resin hardener composition, one-part epoxy resin composition, and one-part epoxy resin. Provided is a processed product using the composition.
• a microcapsule type epoxy resin curing agent having a core (C) formed using an epoxy resin hardener (H) as a starting material and a shell (S) covering the core (C). So,
• the epoxy resin curing agent (H) is mainly composed of amine adduct (A), and the amine adduct (A) is obtained by reaction of epoxy resin (el) with an amine compound,
• the average particle size of the epoxy resin hardener (H) is more than 0.3 ⁇ m and 12 m or less, and the average particle size of the epoxy resin hardener (H) is 0.
• the content ratio of the curing agent for small particle size epoxy resin defined by 5 times or less is 0.1% to 15%,
• Said shell (S) is a bonding group that absorbs infrared wave number 1630 ⁇ 1680cm _ 1 (X), a coupling group that absorbs infrared wave number 1680 ⁇ 1725cm _ 1 (y), the wave number 1730 ⁇ 1755cm _ 1
• a hardener for microcapsule type epoxy resin having at least a bonding group (z) that absorbs infrared rays.
• a hardener for microcapsule type epoxy resin having a core (C) formed using epoxy resin hardener (H) as a starting material and a shell (S) covering the core (C). So,
• the epoxy resin curing agent (H) is mainly composed of amine adduct (A), and the amine adduct (A) is obtained by reaction of epoxy resin (el) with an amine compound,
• the average particle diameter of the epoxy resin hardener (H) is more than 0.3 ⁇ m and 12 m or less, and the specific surface area of the epoxy resin hardener (H) is 1 to a 25 m 2 Zg,
• said shell (S) is a bonding group that absorbs infrared wave number 1630 ⁇ 1680cm _ 1 (X), a coupling group that absorbs infrared wave number 1680 ⁇ 1725cm _ 1 (y), microcapsule type epoxy ⁇ curing agent characterized by having the bonding group (z) and at least the surface that absorbs infrared wave number 1730 ⁇ 1755cm _ 1.
• the shell (S) has a urea bond in its structure, but does not have an ester bond.
• the epoxy resin curing agent (H) is mainly composed of amine adduct (A), and the amine adduct (A) is obtained by reaction of epoxy resin (el) with an amine compound,
• the average particle diameter of the epoxy resin hardener (H) is more than 0.3 ⁇ m and not more than 10 ⁇ m.
• the shell (S) has a urea bond in its structure but no ester bond, and the ratio of the thickness of the shell (S) to the average particle diameter of the epoxy resin hardener (H) is: 100: 1.5-5: Curing agent for microcapsule type epoxy resin characterized by being L00: 18.
• the shell (S) has a force having a urea bond in its structure, and does not have a carboxylate bond, [1] to [4], the microcapsule-type epoxy resin hardener according to any one of Agent.
• the epoxy resin curing agent (H) further contains a low-molecular amine compound (B) [1] to
• the shell (S) is selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for epoxy resin (h2), an epoxy resin (e2), and the low molecular amine compound (B).
• the microcapsule type epoxy resin curing agent according to any one of [1] to [8], comprising a reaction product obtained by using two or more kinds as raw materials.
• the total chlorine content of the epoxy resin hardener (H), the epoxy resin (el), or the epoxy resin (e2) is 2500 ppm or less. [1] to [9] ! Hardener for microcapsule type epoxy resin.
• microcapsule type epoxy resin curing agent according to any one of [1] to [10] and the epoxy resin (e3) (microcapsule type epoxy resin curing agent): ( Epoxy resin (e3)) A master-batch type epoxy resin hardener composition containing a mass ratio of 100: 0.1 to L00: 1000.
• the proportion of the diol terminal component in the epoxy resin (e3) is 0.001 to 30% by mass of the basic structural component of the epoxy resin (e3).
• the masterbatch type epoxy resin curing agent composition according to the description.
• the microcapsule-type epoxy resin hardener has a core (C) formed using the epoxy resin hardener (H) as a starting material, and a shell (S) covering the core (C),
• the epoxy resin curing agent (H) is mainly composed of an amine adduct (A) and a low molecular amine compound (B), and the amine adduct (A) is composed of an epoxy resin (el) and an amine compound.
• the average particle size of the epoxy resin hardener (H) is more than 0.3 m and not more than 12 m,
• the solubility parameter of the basic structure of the highly soluble epoxy resin (G) is 8.65-: L1.00, the molecular weight between crosslinks after curing of the basic structure is 105-150, and The content ratio of the terminal component is 0.01 to 20% by mass with respect to the basic structural component, and the microcapsule type epoxy resin curing agent and the epoxy resin (e3) are combined (microcapsule type epoxy).
• Harddener for resin (Epoxy resin (e3)) (mass ratio) as 1 00: 0.1 ⁇ : L00: 1000
• the epoxy resin (e3) and the highly soluble epoxy resin (G) are expressed as (epoxy resin (e 3)): (highly soluble epoxy resin (G)) (mass ratio): 0.1 to: L00: 99 Including, and
• a master-batch type epoxy resin curing agent composition characterized by having a total chlorine content of 2500 ppm or less.
• At least one epoxy resin curing agent (h3) selected from the group consisting of acid anhydrides, phenols, hydrazides, and guanidines (h3), or cyclic boric acid ester
• the masterbatch type epoxy resin curing agent composition according to any one of [11] to [14], comprising a compound.
• At least one epoxy resin curing agent (h3) selected from the group consisting of acid anhydrides, phenols, hydrazides, and guanidines, or cyclic boric acid ester
• Pasty composition film-like composition, adhesive, bonding paste, bonding film, conductive material, anisotropic conductive material, anisotropic conductive film, insulating material, sealing material , Coating materials, paint compositions, pre-predas, heat conductive materials, fuel cell separators
• the microcapsule type epoxy resin curing agent of the present invention has excellent storage stability and excellent reaction steepness.
• the microcapsule-type epoxy resin curing agent of the present embodiment has the following features (I-1) to (I3).
• Curing agent for epoxy resin composition Curing agent for epoxy resin composition having a core (C) formed using (H) as a starting material and a shell (S) covering the core (C).
• the epoxy resin curing agent (H) is mainly composed of amine adduct (A), and the amine adduct (A) is obtained by reaction of epoxy resin (el) with an amine compound.
• the epoxy resin hardener (H) has an average particle size of more than 0.3 ⁇ m and 12 m or less, and the epoxy resin hardener (H) has an average particle size of The content ratio of the hardener for small particle size epoxy resin defined by 0.5 times or less of the diameter is 0.1% to 15%, and the shell (S) is an infrared ray having a wave number of 1630 to 1680 cm _ 1 At least binding group absorbing the (X), a coupling group that absorbs infrared wave number 1680 ⁇ 17 25cm _ 1 (y), an infrared wave number 1730 ⁇ 1755cm _ 1 and a coupling group for absorption (z) a It has to face.
• (1-2) Curing agent for epoxy resin composition Curing agent for epoxy resin composition having a core (C) formed using (H) as a starting material and a shell (S) covering the core (C).
• the epoxy resin curing agent (H) is mainly composed of amine adduct (A), and the amine adduct (A) is obtained by reaction of epoxy resin (el) with an amine compound.
• the average particle size of the epoxy resin hardener (H) is more than 0.3 ⁇ m and not more than 12 m.
• the specific surface area of the epoxy resin curing agent (H) is 1 to 25 m 2 Zg
• the shell (S) is a bonding group (X) that absorbs infrared rays having a wave number of 1630 to 1680 cm _ 1
• the binding group (z) and at least the surface to absorb the wave number 1730 ⁇ 1755cm _ 1 of infrared are 1 to 25 m 2 Zg
• the shell (S) is a bonding group (X) that absorbs infrared rays having a wave number of 1630 to 1680 cm _ 1
• (1-3) Curing agent for epoxy resin, having a core (C) formed using (H) as a starting material and a shell (S) covering the core (C)
• the epoxy resin curing agent (H) is mainly composed of amine adduct (A), and the amine adduct (A) is obtained by reaction of epoxy resin (el) with an amine compound.
• the average particle size of the epoxy resin hardener (H) is more than 0.3 ⁇ m and not more than 10 ⁇ m, and the shell (S) has urea in its structure.
• the ratio of the thickness of the shell (S) to the average particle diameter of the epoxy resin curing agent (H) is 100: 1.5 to L00: 18. is there.
• the core (C) in the present embodiment is formed using a curing agent for epoxy resin (H) as a starting material.
• the epoxy resin hardener (H) contains the amine adduct (A) as a main component.
• the amine adduct (A) is obtained by a reaction between an epoxy resin (el) and an amine compound.
• the “main component” means that the total amount of the specific component accounts for 50% by mass or more, preferably 60% by mass or more, more preferably in the composition containing the specific component. It means 80% by mass or more and may be 100% by mass or more.
• Examples of the epoxy resin (el) include monoepoxy compounds and polyepoxy compounds. It is also possible to use a monoepoxy compound and a polyvalent epoxy compound in combination.
• Examples of the monoepoxy compound include butyl daricidyl ether, hexyl glycidyl ether, phenol glycidyl ether, allyl glycidyl ether, para-tert butyl phenol glycidyl ether, ethylene oxide, propylene oxide, paraxylino reglycidyl.
• Examples include ginoleatenole, glycidinore acetate, glycidino levyrate, glycidino hexate, and glycidyl benzoate. These are one kind alone or 2 More than one species can be used in combination.
• polyvalent epoxy compound examples include bisphenol A, bisphenol F, bisphenol AD, bisphenol, tetramethylbisphenol 8, tetramethylbisphenol, tetramethylbisphenol AD, tetra Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as methylbisphenol S, tetrabromobisphenol 8, tetrachlorobisphenol 8, tetrafluorobisphenol A;
• Epoxy resin containing glycidyl alcohol with other dihydric phenols such as biphenol, dihydroxynaphthalene, 9, 9-bis (4-hydroxyphenol) fluorene;
• Novolac type epoxy resin in which novolaks such as phenol novolak, talesol novolak, bisphenol A novolak, brominated phenol —lunopolac, brominated bisphenol A novolak, etc. are glycidylated.
• Epoxy resin with glycidyl acrylate polyhydric phenols Epoxy resin with glycidyl acrylate polyhydric phenols
• Aliphatic ether type epoxy resin prepared by glycidylation of polyhydric alcohols such as glycerin and polyethylene glycol;
• Ester-type epoxy resin obtained by glycidylation of polycarboxylic acids such as phthalic acid and terephthalic acid;
• Glycidylates of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol
• Amine type epoxy resin such as triglycidyl isocyanurate glycidinole type epoxy resin such as S;
• Etc These can be used alone or in combination of two or more.
• the epoxy resin (el) is preferably a polyvalent epoxy compound from the viewpoint of further improving the storage stability of the epoxy resin composition.
• the polyvalent epoxy compound glycidyl type epoxy resin is preferable from the viewpoint of productivity of amine adduct (productivity is overwhelmingly high).
• an epoxy resin obtained by glycidylating a polyvalent phenol, particularly a bisphenol type epoxy resin is preferable. More specifically, epoxy resin obtained by glycidylating bisphenol A or epoxy resin obtained by glycidylating bisphenol F is preferable. More preferred is an epoxy resin with bisphenol A glycidyl. These can be used alone or in combination.
• the total amount of chlorine contained in the epoxy resin (el) is preferably 2500 ppm or less, more preferably 2000 ppm, from the viewpoint of obtaining an epoxy resin composition having a balance between curability and storage stability. Below, more preferably 1500 ppm or less, more preferably 800 ppm or less, more preferably 400 ppm or less, more preferably 180 ppm or less, more preferably ⁇ m or less, more preferably 80 ppm or less, and further preferably 50 ppm or less.
• the total amount of chlorine contained in the epoxy resin (el) is preferably at least 0.005 ppm, more preferably at least 0.02 ppm, more preferably from the viewpoint of facilitating control of the shell formation reaction. Is 0.05 ppm or more, more preferably 0.1 ppm or more, more preferably 0.2 ppm or more, and still more preferably 0.5 ppm or more. Further, the upper limit is preferably 200 ppm or less, more preferably 80 ppm or less, and still more preferably 50 ppm or less. When the total chlorine amount is 0.1 ppm or more, a shell forming reaction is efficiently performed on the surface of the curing agent, and a shell having excellent storage stability can be obtained.
• total chlorine amount in the present embodiment is the total amount of organic chlorine and inorganic chlorine contained in the compound or composition, and is a value based on mass with respect to the compound or composition. .
• the total amount of chlorine contained in the epoxy resin (el) is measured by the following method. First, using xylene, the epoxy resin composition also extracts the epoxy resin (repeating washing and filtration until the epoxy resin disappears). Next, depressurize the filtrate below 100 ° C. Distill off to obtain an epoxy resin as a measurement target.
• the obtained epoxy resin samples 1 to: LOg is precisely weighed so that the titration amount is 3 to 7 ml, and dissolved in 25 ml of ethylene glycol monobutyl ether. Add 25 ml of 1N KOH propylene glycol solution and boil it for 20 minutes, and titrate the boiled epoxy resin solution with silver nitrate aqueous solution. The total chlorine amount can be obtained by calculation using the titration amount.
• chlorine contained in the 1,2-chlorohydrin group out of all chlorine is generally called hydrolyzable chlorine.
• the amount of hydrolyzable chlorine contained in the epoxy resin (el) is preferably 50 ppm from the viewpoint of achieving both high curability and storage stability and ensuring excellent electrical properties of the resulting cured product. Below, more preferably 20 ppm or less, still more preferably 10 ppm or less, and the lower limit is preferably 0.0 Olppm or more, preferably 0.05 ppm or more.
• the amount of hydrolyzable chlorine is measured by the following method. First, an epoxy resin as a measurement object is obtained in the same manner as the measurement of the total chlorine amount. Dissolve 3 g of the epoxy resin sample obtained in 50 ml of toluene. Add 20 ml of 0.1N KOH methanol solution to it, boil for 15 minutes, and titrate the boiled epoxy resin solution with silver nitrate aqueous solution. The amount of hydrolyzable chlorine is obtained by calculation using the titration amount.
• Examples of the amine compound include a compound having at least one primary amino group and Z or a secondary amino group but not a tertiary amino group, at least one tertiary amino group and at least one Examples thereof include compounds having one active hydrogen group.
• Examples of the compound having at least one primary amino group and Z or secondary amino group but not a tertiary amino group include, for example, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethine.
• Has a tertiary amino group such as rangenamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophorone diamine, aniline, tonoridine, diaminodiphenylenomethane, diaminodiphenylsulfone, etc. Sana, primary amines;
• Etc These can be used alone or in combination of two or more.
• examples of the active hydrogen group include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, and a carboxylic acid. And hydrazide groups.
• the compounds having at least one tertiary amino group and at least one active hydrogen group include 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1 phenoxymethyl-2-dimethylamino.
• Amino alcohols such as ethanol, 2-jetylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyljetanolamine, triethanolamine, N- ⁇ -hydroxyethylmorpholine;
• Aminophenols such as dimethylaminomethyl) phenol, 2, 4, 6 tris (dimethylaminomethyl) phenol;
• Aminomercaptans such as 2-dimethylaminoethanethiol, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine; N, N dimethylaminobenzoic acid, N, N dimethylglycine, nicotinic acid, Aminocarboxylic acids such as iso-cotynic acid and picolinic acid;
• Aminohydrazides such as N, N dimethylglycine hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide;
• Etc These can be used alone or in combination of two or more.
• amine compound a compound having at least one tertiary amino group and at least one active hydrogen group is preferred from the viewpoint of excellent balance between storage stability and curability.
• imidazoles are more preferred, such as 2-methylimidazole, and 2-ethyl-4-methylimidazole.
• the amine adduct (A) can be obtained by the reaction of the epoxy resin (el) and the amine compound as described above.
• the compounding ratio (equivalent ratio) of the epoxy resin (el) and the amine compound is the number of moles (equivalent) of the amine compound relative to the number of epoxy groups of the epoxy resin (e 1). , Preferably 0.5 to 10 equivalents, more preferably 0.8 to 5 equivalents, still more preferably 0.95 to 4 equivalents.
• the equivalent ratio is set to 0.
• the amine adduct (A) may be used in the presence of a solvent, for example, at a temperature of 50 to 250 ° C, for example, 0.1 to LO time, an epoxy resin (el) and an amine compound. Can be obtained by reacting with.
• a solvent for example, at a temperature of 50 to 250 ° C, for example, 0.1 to LO time
• an epoxy resin (el) and an amine compound can be obtained by reacting with.
• the epoxy resin curing agent (H) contains the amine adduct (A) as a main component.
• the epoxy resin curing agent (H) may contain a hardener other than the amine adduct (A).
• Examples of the curing agent other than the amine adduct (A) include one or more compounds selected from the group consisting of carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds and urea compounds, and the above. Reaction product with amine compound described as raw material of amine adduct (A);
• Acid anhydride curing agents such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic acid;
• Phenolic curing agents such as phenolic novolak, talesol novolak, bisphenol A novolak;
• Mercaptan based curing agents such as propylene glycol-modified polymercaptan, trimethylolpropane thiodarconate, polysulfide resin;
• Halogenated boron salt hardener such as trifluoroborane ethylamine salt
• urea-based curing agents such as ferulu 1, 1-dimethylurea
• Phosphine-based curing agents such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate;
• Etc These can be used alone or in combination of two or more.
• Examples of the carboxylic acid compound include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.
• Examples of the sulfonic acid compound include ethanesulfonic acid, p-toluenesulfonic acid, and the like.
• Examples of the urea compound include urea, methylurea, dimethylurea, ethylurea, t-butylurea and the like.
• the Examples of the isocyanate compound include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, polyisocyanate, and the like.
• Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Can be mentioned.
• Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylenomethane diisocyanate, norbornane diisocyanate, 1,4 isocyanatocyclohexane, 1,3 bis (isocyanatomethyl). ) Monocyclohexane, 1,3 bis (2-isocyanatopropyl 2-yl) -cyclohexane, and the like.
• aromatic diisocyanate examples include tolylene diisocyanate, 4,4, -diphenylenemethane diisocyanate, xylene diisocyanate, 1,5 naphthalene diisocyanate, and the like.
• aliphatic triisocyanate examples include 1,6,11-undecanetriisocyanate, 1,8 diisocyanate 4-isocyanate methyloctane, 1,3,6 triisocyanate, and the like.
• examples of the polyisocyanate include polymethylene polyisocyanate and polyisocyanate derived from the diisocyanate compound.
• examples of the polyisocyanate derived from the above diisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophane type polyisocyanate, and calpositimide type polyisocyanate.
• an amine adduct (A) is used from the viewpoint of achieving both the low-temperature curability and the storage stability of the resulting microcapsule type epoxy resin curing agent.
• a low molecular weight amine compound (B) as a main component.
• the ratio of the low molecular weight amine compound (B) to the amine adduct (A) and the low molecular weight amine compound (B) in the total amount is preferably 0.001 to 3% by mass, preferably Is 0.01-2.5% by mass.
• a dense shell can be formed in the shell (S) formation reaction, and the storage stability and solvent resistance are high.
• a curing agent For microcapsule type epoxy resin There is a merit to be able to obtain a curing agent. On the other hand, if it exceeds 3% by mass, it may be difficult to control the shell (S) formation reaction stably.
• the average particle size of the epoxy resin resin curing agent (H) is: 0.3 / zm to 12 / zm or less, preferably ⁇ to 0.4 m or more and 11 m or less, more preferably ⁇ to 0.5 m or more to 5 m or less.
• the average particle size of the epoxy resin curing agent (H) is more than 0.3 m and preferably 10 m or less. Is not less than 0.4 / zm and not more than 10 m, more preferably not less than 0.5 ⁇ m and not more than 5 ⁇ m.
• a microcapsule-type epoxy resin curing agent having a core-shell structure (a structure in which the core (C) is covered with the shell (S)) can be satisfactorily realized. it can. That is, good storage stability is realized. Further, by setting the average particle size to 0.3 ⁇ or more, appropriate hardness can be imparted to the shell (S) covering the core (C). That is, the shell (S) capsule environment can be quickly released during use, and good response steepness can be realized.
• the average particle size is 12 m or less or 10 m or less, the epoxy resin is cured more uniformly during use, and the physical properties of the cured product can be maintained well. Furthermore, if the average particle size is 5 m or less, the epoxy resin during use can be cured more uniformly.
• the microcapsule type epoxy resin curing agent having the feature (1-1) in the present embodiment 0.5 times the average particle size of the epoxy resin curing agent (H).
• the content ratio of the curing agent for small particle size epoxy resin defined below (hereinafter sometimes abbreviated as “small particle size content rate”) is 0.1% to 15%, preferably 0. It is 1% to 13%, more preferably 0.1% to 10%. Setting the small particle size content to 15% or less is preferable from the viewpoint of achieving good solvent resistance.
• the average particle size of the epoxy resin hardener (H) mainly composed of the amine adduct (A) and the low molecular amine compound (B) is set to more than 0.3 ⁇ m and not more than 12 m, and the above
• the latent, long-term storage stability and solvent resistance are extremely excellent, and it exhibits extremely excellent reaction steepness as well as high curability.
• the average particle size and the small particle size content of the epoxy resin curing agent (H) include, for example, a method of precisely controlling crushing of a bulk epoxy resin curing agent, coarse crushing and fine crushing as crushing, and further a desired classifying device within a desired range.
• a method of obtaining the product a method of controlling the conditions of the apparatus for spray-drying the dissolved curing agent for epoxy resin.
• a grinding device a ball mill, an attritor, a beads mill, a jet mill, etc. can be used as necessary, but an impact type grinding device is often used.
• Examples of the impact pulverizer used here include jet mills such as a swirl type powder collision type jet mill and a powder collision type counter jet mill.
• a jet mill is a device that makes solid materials collide with each other by a high-speed jet flow using air or the like as a medium. As a precise control method of pulverization, temperature, humidity, pulverization amount per unit time, etc. can be controlled.
• a sieve for example, a standard sieve such as 325 mesh or 250 mesh
• a classifier There is a method of performing classification by wind power according to the specific gravity of the particles.
• a dry classifier is generally superior to a wet classifier.
• Examples of the spray drying device include a normal spray drying device.
• an epoxy resin having a specific average particle size and a specific small particle size content is used as a method for adjusting the average particle size and the small particle size content of the epoxy resin curing agent (H).
• a method of forming a plurality of fat curing agents (H 2) individually and mixing them appropriately can also be used as a method for adjusting the average particle size and the small particle size content of the epoxy resin curing agent (H).
• a method of forming a plurality of fat curing agents (H 2) individually and mixing them appropriately can also be used. The mixed material can be further classified.
• the mixing machine used for the purpose of mixing such powders is a rotating container type that rotates the container body containing the powder to be mixed, and the mechanical stirring airflow without rotating the container body containing the powder.
• Examples include a container-fixed type that performs mixing by stirring, and a composite type that rotates a container containing powder and performs mixing using other external forces.
• the “average particle diameter” means an average particle diameter defined by a median diameter. More specifically, it refers to the diameter of the status measured by the laser diffraction 'light scattering method using HORIBA LA-920 (HORIBA, Ltd. particle size distribution meter HORIBA LA-920).
• the “small particle size content rate” is also calculated as the particle size frequency histogram force when the average particle size is measured.
• the shape of the epoxy rosin curing agent (H) is not particularly limited, and may be any of spherical, granular, powdery, and amorphous. Among them, the shape is preferably spherical from the viewpoint of reducing the viscosity of the one-component epoxy resin composition.
• the term “spherical” includes not only true spheres but also shapes with rounded irregular corners.
• the specific surface area of the epoxy resin curing agent (H) is 1 to 25m 2Zg. And preferably 1.5 to 20 m 2 Zg, more preferably 2 to 15 m 2 Zg, and still more preferably 2.5 to 10 m 2 Zg.
• the specific surface area is also preferable from the viewpoint of achieving good solvent resistance.
• a specific surface area of lm 2 Zg or more is preferable from the viewpoint of obtaining the average particle diameter in a desired range.
• the reaction steepness the viewpoint of obtaining a homogeneous cured product, Is preferable from the viewpoint of preventing the generation of secondary particles having a large particle size when the composition is blended.
• the specific surface area of the epoxy resin hardener (H), which is the starting material of the core (C) to 1 to 25 m 2 Zg, the potential, long-term storage stability, and solvent resistance are extremely high. It is possible to realize a microcapsule type epoxy resin curing agent that exhibits excellent reaction steepness as well as high curability and has excellent physical properties.
• the “specific surface area” in the present embodiment means a specific surface area measured by a measurement method based on a BET adsorption isotherm using nitrogen Z helium gas.
• the method of controlling the specific surface area by removing particles with a small particle size with a classifier or the method of pulverization there is a method of selecting the pulverization method, such as using a swirl type pulverizer that has less irregularities on the surface of the pulverized particles and less prone to cracking in a counter-type pulverizer that tends to cause relatively fine surface irregularities and cracks on the particle surface. is there. Furthermore, a method of selecting the reaction conditions between the epoxy resin (el) and the amine compound when obtaining the amine adduct (A) is also effective.
• the epoxy resin curing agent (H) is preferably solid at 25 ° C from the viewpoint of high storage stability and an epoxy resin composition. That is, the softening point of the epoxy resin curing agent (H) is preferably more than 25 ° C and 150 ° C or less, more preferably 40 ° C or more, and further preferably 60 ° C or more.
• the total amount of chlorine contained in the epoxy resin curing agent (H) is preferably 2500 ppm or less, more preferably 2000 ppm, from the viewpoint of obtaining an epoxy resin composition having a high balance between curability and storage stability. Below, more preferably 1500 ppm or less, more preferably 8 OOppm or less, more preferably 400 ppm or less, more preferably 180 ppm or less, more preferably lOOppm or less, more preferably 80 ppm or less, and further preferably 50 ppm or less. Further, the total amount of chlorine contained in the epoxy resin curing agent (H) is preferably not less than 0.005 ppm, more preferably not less than 0.02 ppm, more preferably from the viewpoint of facilitating control of the shell formation reaction.
• the shell forming reaction is efficiently performed on the surface of the curing agent, and a shell having excellent storage stability can be obtained.
• the curing agent for microcapsule type epoxy resin in the present embodiment has the core (C) as described above and the shell (S) that covers the core (C).
• the shell (S) comprises an isocyanate compound, an active hydrogen compound, an epoxy resin curing agent (h2), an epoxy resin (e2), and the low molecular amine compound (B).
• Group power It is preferable to contain reaction products obtained using two or more selected raw materials.
• the isocyanate compound described as a raw material of the curing agent other than the amine adduct (A) contained in the epoxy resin curing agent (H) may be V. Can be used.
• Examples of the active hydrogen compound include water, a compound having at least one primary amino group and a Z or secondary amino group, a compound having at least one hydroxyl group, and the like.
• aliphatic amine alicyclic amine, and aromatic amine
• aromatic amine aliphatic amine, alicyclic amine, and aromatic amine
• aliphatic amines examples include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; and ananolexyleneamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine;
• Polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine;
• Polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine; Etc.
• alicyclic amines examples include cyclopropylamine, cyclobutylamine, cyclobenzylamine, cyclohexylamine, and isophorone diamine.
• Aromatic amines include aline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like.
• examples of the compound having at least one hydroxyl group include alcohol compounds and phenolic compounds.
• alcohol compounds include methyl alcohol, propyl alcohol, butylic alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, noral alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, Tesyl alcohol, stearyl alcohol, eicosyl alcohol, arninoreanolenore, clothinoleanolenore, propanolenoleanolenoreole, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol Monoalcohols such as monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl;
• Polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3 butanediol, 1,4 butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol ;
• Two secondary hydroxyl groups in a molecule obtained by reacting a compound having at least one epoxy group with a compound having at least one hydroxyl group, carboxyl group, primary or secondary amino group, or mercapto group
• Polyhydric alcohols such as compounds having the above; and the like. In these alcoholic compounds, the deviation of the first, second, or third alcohol may be used.
• phenolic compounds include monophenols such as carboxylic acid, cresol, xylenol, strong rubachlor, motile, naphthol, catechol, resorcin, hydroquinone, bisphenol 8-bisphenol. And polyphenols such as pyrogallool and phloroglucin.
• monophenols such as carboxylic acid, cresol, xylenol, strong rubachlor, motile, naphthol, catechol, resorcin, hydroquinone, bisphenol 8-bisphenol.
• polyphenols such as pyrogallool and phloroglucin.
• polyhydric alcohols that are preferred from polyhydric alcohols and polyhydric phenols are particularly preferred from the standpoint of latent solvent resistance.
• epoxy resin curing agent (h2) the same curing agent as the epoxy resin curing agent (H) described above can be used.
• the epoxy resin hardener (h2) may be the same as or different from the epoxy resin hardener (H), but is preferably the same.
• the epoxy resin (e2) an epoxy resin similar to the epoxy resin (el) described above, and among them, a polyvalent epoxy compound can be preferably used.
• the epoxy resin (e2) may be the same as or different from the epoxy resin (el) and the epoxy resin (e3) described later.
• the epoxy resin (e2) a plurality of types can be used in combination.
• the epoxy resin usually has an impurity terminal having chlorine bonded to the molecule, but such impurity terminal adversely affects the electrical properties of the cured product. Therefore, the total amount of chlorine contained in the epoxy resin (e2) is preferably 2500 ppm or less, more preferably 150 Oppm or less, and further preferably 500 ppm or less.
• Group power consisting of the above isocyanate compound, active hydrogen compound, epoxy resin curing agent (h2), epoxy resin (e2), and low molecular amine compound (B) selected 2
• reaction conditions for using seeds or more as raw materials but usually a reaction time of 10 minutes to 12 hours in a temperature range of 10 ° C to 150 ° C.
• the mixing ratio is (isocyanate group in the isocyanate compound): (active hydrogen in the active hydrogen compound) (equivalent ratio), preferably 1: 0 . 1-1: The range is 1000.
• the compounding ratio is (epoxy resin hardener (h2)): (epoxy resin (e2)) (mass ratio) And preferably 1: 0.0.001 to 1: 1000, more preferably 1: 0.0.01 to 1: 100.
• the above reaction can be carried out in a dispersion medium if necessary.
• the dispersion medium include solvents, plasticizers, and greaves.
• solvent examples include benzene, toluene, xylene, cyclohexane, mineral spin. Hydrocarbons such as lit and naphtha;
• Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone;
• Esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether etherate;
• Alcohols such as methanol, isopropanol, n-butanol, butylceosolve, butylcarbitol;
• plasticizer examples include phthalic acid diester plasticizers such as dibutyl phthalate and di (2-ethylhexyl) phthalate;
• Aliphatic dibasic acid ester plasticizers such as di (2-ethylhexyl) adipate; Phosphoric acid triester plasticizers such as tricresyl phosphate;
• Glycol ester plasticizers such as polyethylene glycol esters
• greaves examples include silicone greaves, epoxy greaves, phenol greaves and the like.
• the reaction between the epoxy resin (e2) and the epoxy resin hardener (h2) is usually from 10 ° C to
• the reaction is carried out at a temperature of 150 ° C., preferably 0 ° C. to 100 ° C., for a reaction time of 1 to 168 hours, preferably 2 to 72 hours. Further, a solvent, a plasticizer and the like are preferably used as the dispersion medium.
• any of the above-mentioned isocyanate compounds, active hydrogen compounds, epoxy resin curing agent (h2), epoxy resin (e2), and low molecular amine compound (B) can be used.
• Solvents that can be used in two or more reactions and those listed as examples of plasticizers can be used.
• the proportion of the reaction product as described above in the shell (S) is usually 1% by mass or more, preferably 50% by mass or more, and may be 100% by mass.
• the methods (b) and (c) are preferred because the reaction and the coating can be performed simultaneously.
• a dispersion medium a solvent, a plasticizer, a resin, etc. are mentioned.
• the solvent, plasticizer, and resin include those listed as examples of the solvent, plasticizer, and resin that can be used in obtaining the above reaction product.
• an epoxy resin as a dispersion medium because a master one-batch type epoxy resin curing agent composition can be obtained simultaneously with the shell formation.
• the shell (S) formation reaction is usually performed at a temperature of 10 ° C to 150 ° C, preferably 0 ° C to 100 ° C, for 10 minutes to 72 hours, preferably 30 minutes to 24 hours. Done in time.
• the average particle diameter of the epoxy resin curing agent (H) is as follows.
• Storage stability of the microcapsule type epoxy resin curing agent by setting the average particle size of the epoxy resin hardener (H) to 100 and the thickness ratio of the shell (S) to 1.5 or more. Will improve. In addition, by setting the thickness ratio to 18 or less, the reaction steepness of the microcapsule type epoxy resin curing agent is maintained, and the storage stability of the masterbatch type hardener composition obtained by using the same is maintained. Sex and handling! /, Can maintain sex.
• the thickness of the shell (S) in the present embodiment is a value measured by a transmission electron microscope.
• methods for adjusting the thickness ratio include a method of controlling the amount of the material forming the shell (S) and a curing for epoxy resin that exudes from the gaps in the shell (S) film. And a method of controlling the reaction between the agent (H) and the epoxy resin (e2) that reacts when forming the shell (S).
• a method for controlling the ratio of the material forming the shell (S), the shell (S It is also possible to adopt a method of controlling the temperature and Z or time for forming the).
• the shell) absorbs infrared rays having a wave number of 1630 to 1680 cm _1.
• bind group (X) a coupling group that absorbs infrared wave number 1680 ⁇ 1725cm _1 (y), those having at least on the surface and a bonding group (z) which absorbs infrared wave number 1730 ⁇ 1755cm _1.
• urea bonds are particularly useful.
• a buret bond can be mentioned as a particularly useful one.
• particularly useful ones can include urethane bonds.
• linking groups (x), (y) and (z) means that an infrared spectrophotometer (in particular, a Fourier transform infrared spectrophotometer, hereinafter referred to as “FT-IR”). This may be confirmed by measuring infrared absorption using Also, confirm that the bonding groups (x), (y), and (z) have at least the surface of the shell (S) using microscopic FT-IR (FT-IR using microspectroscopy). Can do.
• FT-IR Fourier transform infrared spectrophotometer
• the shell (S) is a bond group (y) and a wavenumber of 173 to absorb binding Gomoto (X) and the infrared wave number 1680 ⁇ 1725Cm _1 for absorbing infrared light of wave number 1630 ⁇ 1680cm _1 0 binding group that absorbs infrared ⁇ 1755cm _1 (z), respectively L ⁇ 1000meqZkg, it is not preferable to have a concentration in the range of 1 ⁇ 1000MeqZkg and L ⁇ 200meqZkg.
• the concentration referred to here is a value relative to the microcapsule type epoxy resin curing agent.
• the concentration of the linking group (X) is lmeqZkg or more, it is advantageous to obtain a capsule type hardener having high resistance against mechanical shearing force. Also, if it is less than lOOOmeqZkg It is advantageous to obtain a high curability. A more preferable concentration range of the linking group (X) is 10 to 300 meqZkg.
• the concentration of the linking group (y) is lmeqZkg or more, it is advantageous to obtain a capsule type hardener having high resistance against mechanical shearing force. Moreover, when it is less than lOOOmeqZkg, it is advantageous for obtaining high curability.
• a more preferable range of the linking group (y) is 10 to 200 meq Zkg.
• the concentration of the linking group (z) is lmeqZkg or more, it is advantageous for forming a shell having high resistance against mechanical shearing force. Moreover, when it is 200 meqZkg or less, it is advantageous for obtaining high curability.
• the concentration range of the linking group (z) is more preferably 5 to: LOOmeqZ kg.
• the ratio of the concentration of the bonding group (z) bonding group to the total concentration of the bonding group (X) and bonding group (y) of the shell (S) is from lOOZl to LOOZlOO in terms of mass ratio. Within this range, the storage stability and curability can be well balanced. Preferably 100Z2 ⁇ : L00Z80, more preferred ⁇ is 100Z5 ⁇ : L00Z60, more preferred ⁇ is 100ZlO ⁇ 100Z50.
• the concentration and concentration ratio of the linking group (X), linking group (y) and linking group (z) can be determined by the method disclosed in Patent Document 1.
• the total thickness of the bonding group (X), the linking group (y), and the linking group (z) in the shell (S) is preferably 5 to LOOOnm in average layer thickness. Storage stability can be obtained at 5 nm or more, and practical curability can be obtained at lOOOnm or less.
• the thickness of the layer can be measured with a transmission electron microscope.
• a particularly preferable total thickness of the bonding groups is 10 to: LOOnm in terms of an average layer thickness.
• the shell (S) preferably does not have a force ester bond having a urea bond in its structure, and particularly preferably does not have a carboxylic acid ester bond.
• carboxylic acid ester bond is not present, it is possible to prevent the carboxylic acid ester bond from undergoing a hydrolysis reaction and damaging the shell (S) and reducing the storage stability in a high humidity state. Moreover, the fall of the hardened
• the shell (S) preferably has a burette bond and a urethane bond in its structure from the viewpoint of the latent solvent resistance.
• the masterbatch type epoxy resin curing agent composition of the present embodiment has any of the following characteristics (II 1) and (II 2).
• microcapsule type epoxy resin curing agent (Epoxy resin (e3)) (mass ratio ) 100: 0. 1 to: L00: It is included at a blending ratio of 1000.
• the solubility parameter of the basic structure of the highly soluble epoxy resin (G) is 8.65-: L1.00, the molecular weight between crosslinks after curing of the basic structure is 105-150, and The terminal component is present in an amount of 0.01 to 20% by mass based on the basic structural component, and the microcapsule type epoxy resin hardener and the epoxy resin (e3) [Pure type epoxy resin hardener]: (Epoxy resin (e3)) (mass ratio) 100: 0.1 ⁇ : L00: 1000 in the mixing ratio, the epoxy resin (e3) and the high Soluble epoxy resin (G) and (Epoxy resin (e3)): (Highly soluble epoxy resin (G)) (mass ratio) 1 00: 0.1 ⁇ : L00: 99 And the total chlorine content is 2500ppm or less.
• epoxy resin (e3) the same epoxy resin as the epoxy resin (el) can be used.
• polyvalent epoxy compounds can be preferably used. Multiple types can be used in combination.
• epoxy resins prepared by glycidylating polyhydric phenols are preferred from the viewpoint of adhesion and heat resistance of the resulting cured product, and bisphenol type epoxy resins are particularly preferable.
• a glycidylated product of bisphenol A and a glycidylated product of bisphenol F are preferred.
• the mixing ratio of the above-described microcapsule type epoxy resin curing agent and epoxy resin (e3) is (microcapsule type epoxy resin curing agent). ): (Epoxy resin ( e 3)) (mass ratio) is usually 100: 0.1 ⁇ : L00: 1000, preferably 100: 1 to: LOO: 100.
• the total amount of chlorine contained in the epoxy resin (e3) is: Preferably it is 2500 ppm or less, More preferably, it is 1500 ppm or less, More preferably, it is 500 ppm or less.
• the total amount of chlorine contained in the master-batch type epoxy resin curing agent composition is 2500 ppm or less! /.
• the diol-terminal impure component strength of the epoxy resin (e3) is preferably 0.001 to 30% by mass, more preferably 0.01, in the basic structural component of the epoxy resin (e3). -25% by mass, more preferably 0.1-20% by mass, more preferably 0.5-18% by mass, still more preferably 1.2-15% by mass.
• the diol terminal impure component means an epoxy resin having a structure in which one or both terminal epoxy groups are ring-opened to form 1,2-glycol.
• Epoxy Oil 1st Volume I published by the Epoxy Oil Technology Association is listed.
• cured material can be improved by making the ratio which the diol terminal impure component of epoxy resin (e3) accounts in the basic structural component of epoxy resin (e3) into 30 mass% or less. Further, by setting the content to 0.001% by mass or more, the curability of the epoxy resin composition can be improved.
• the ratio which the diol terminal impure component of the said epoxy resin (e3) accounts in the basic structural component of an epoxy resin (e3) is the value obtained by the method as described in the term of an Example.
• the masterbatch type epoxy resin curing agent composition having the above feature (ii-2) has a basic structure solubility parameter of 8.65 to L1.00.
• Highly soluble epoxy resin having a molecular weight between crosslinks of 105 to 150 after hardening of the basic structure and a proportion of the diol end component of 0.01 to 20% by mass relative to the basic structure component Includes (G).
• the solubility parameter of the above basic structure is the basis of the highly soluble epoxy resin (G). This value is calculated by substituting the parameters shown in Table 1 into the following formula (1) for the structure in the state when the epoxy group of this structure is cleaved.
• the highly soluble epoxy resin (G) used in the present embodiment in which the solubility parameter of the basic structure is 8.65 to: L1.00 for example, 1, 2— Dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 3-methinole-1,2-dihydroxybenzene, 4-methyl-1,2-dihydroxybenzene, 2-methyl-1,3-dihydroxybenzene, 4-methyl- 1,3-dihydroxybenzene, 2-methyl -1,4-dihydroxybenzene, 3-ethyl-1,2-dihydroxybenzene, 4-ethyl 1,2-dihydroxybenzene, 2-ethyl-1,3-dihydroxybenzene, 4-ethyl-1,3-dihydroxybenzene, 2-ethyl-1,4-dihydroxy Benzene, 3—Propinole 1,2,2 dihydroxybenzene, 4 Propinole 1,2,2 Dihydroxy benzene, 2-Propinole 1,3 Dihydroxy benzene,
• the molecular weight between crosslinks after curing of the basic structure is 105 to 150, preferably ⁇ 107 to 145, more preferably ⁇ 108 to 140, more preferably 109 to 150. 130, more preferably 110-120.
• the intercrosslinking molecular weight is calculated by dividing the monomer molecular weight of the basic structural formula of highly soluble epoxy resin by the number of epoxy groups contained in the basic structural formula.
• the proportion of the diol terminal component is 0.01 to 20% by mass, preferably 0.01, relative to the basic structural component. -15% by mass, more preferably 0.1-10% by mass, still more preferably 0.2-8% by mass.
• the abundance ratio to 20 mass or less is preferable from the viewpoint of not reducing the water resistance of the cured product.
• the content of 0.01% by mass or more is preferable from the viewpoint of not reducing the curability of the epoxy resin composition.
• the abundance ratio of the diol terminal component is calculated by the method described in the Examples section.
• the blending ratio of the above-described epoxy resin (e3) to the above highly soluble epoxy resin (G) is (epoxy resin (e3)): (highly soluble As a functional epoxy resin (G)) (mass ratio), it is usually 100: 0.1 ⁇ : L00: 99, preferably 100: 5 ⁇ : L00: 60, more preferably 100: 10 ⁇ : L00: 50, more preferably Is 100: 15 ⁇ 100: 40.
• Epoxy resin (e3) It is preferable that the amount of highly soluble epoxy resin (G) to be 100 parts by mass or more is 0.1 parts by mass or more from the viewpoint of sufficiently exhibiting low-temperature curability and storage stability. It is. On the other hand, setting it to 99 parts by mass or less is preferable from the viewpoint of suppressing an increase in water absorption.
• the masterbatch type epoxy resin curing agent composition includes, for example, a bulking agent, a reinforcing material, a filler, a pigment, conductive fine particles, an organic solvent, a reactive diluent, a non-reactive diluent, Other additives such as greaves, crystalline alcohol, coupling agent, and cyclic borate ester compound can be contained.
• filler examples include, but are not limited to, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral silicate, mica, asbestos powder, and slate powder. It is done.
• pigments include kaolin, acid aluminum trihydrate, aluminum hydroxide hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, penton, silica, aerosol, litbon, barite, and diacid.
• examples include titanium.
• examples of the conductive fine particles include carbon black, graphite, carbon nanotube, fullerene, iron oxide, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, nano-sized metal crystal, metal Examples include intermetallic compounds.
• organic solvent examples include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and butyl acetate.
• reactive diluents include butyl daricidyl ether, N, N'-glycidyl-o-toluidine, phenol glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 6 Hexanediolididyl ether and the like.
• non-reactive diluents examples include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, and petroleum solvents.
• the resins include polyester resins, polyurethane resins, acrylic resins, polyester resins, melamine resins, urethane modified epoxy resins, rubber modified epoxy resins, alkyd modified epoxy resins, etc.
• An epoxy resin is mentioned.
• Examples of the crystalline alcohol include 1,2 cyclohexanediol, 1,3 cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, and trimethylolpropane.
• examples of the other additive include a curing agent for epoxy resin (h3).
• the epoxy resin hardener (h3) is generally used as an epoxy resin hardener in addition to the amine epoxy resin hardener similar to the epoxy resin hardener (H) described above.
• Any curing agent for epoxy resin can be used. Among them, at least selected from the group consisting of acid anhydride type curing agents, phenolic type curing agents, hydrazide type curing agents, and guanidine type curing agents from the viewpoint of adhesive strength, Tg, ease of blending, and the like.
• One kind of epoxy resin hardener is preferred.
• Examples of the acid anhydride-based curing agent include phthalic anhydride, trimellitic anhydride, anhydrous pyromellitic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, benzophenone anhydrous tetracarboxylic acid, anhydrous
• Examples thereof include succinic acid, methyl succinic anhydride, dimethyl succinic anhydride, dichlor succinic anhydride, methyl nadic acid, dodecyl succinic acid, chlorendectaic anhydride, maleic anhydride and the like.
• phenolic curing agents examples include phenol novolac and talezo novolac.
• hydrazide-based curing agent examples include succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide terephthalic acid dihydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenolic propionic acid hydrazide, and the like. And dihydrazide.
• guanidine-based hardeners examples include dicyandiamide, methyldanidine, ethinoreguanidine, propinoreguanidine, butinoleguanidine, dimethylenoguanidine, trimethylguanidine, phenyldagin, diphenylguanine, and toluylguanidine. -Gin etc. are mentioned.
• the epoxy resin hardener (h3) may be the same as the epoxy resin hardener (H) which is the starting material of the core (C), but from the viewpoint of easy blending of the composition, It is preferable to be different.
• the proportion of the other additives in the masterbatch type epoxy resin curing agent composition or the one-component epoxy resin composition described below is usually less than 30% by mass.
• the cyclic borate ester compound can improve the storage stability of the masterbatch type epoxy resin curing agent composition.
• the cyclic borate ester compound means that boron is included in the cyclic structure.
• 2,2′-oxybis (5,5, -dimethyl-1,3,2-oxaborinane) is particularly preferable.
• the cyclic borate ester compound, the masterbatch epoxy ⁇ curing agent composition, or the proportion in one-component epoxy ⁇ composition to be described later is generally from 0.001 to 10 mass 0/0 It is.
• a microcapsule type epoxy resin curing agent is used by using three rolls and the like.
• (e3), or epoxy ⁇ and (e3) a method of dispersing in a highly soluble epoxy ⁇ (G), epoxy ⁇ (e 3), or epoxy ⁇ (e3) and high solubility 'epoxy ⁇
• the shell (S) is formed on the surface of the epoxy resin-hardening curing agent (H) in the fat (G)!
• Examples thereof include a method for obtaining an epoxy resin hardener. The latter is preferable because of high productivity.
• a microcapsule type epoxy resin A method in which an epoxy resin composition in which an oil curing agent is dispersed in an epoxy resin (e3) is added to the epoxy resin composition and dispersed uniformly and mixed, and an epoxy resin curing agent ( H)
• the shell (S) is formed on the surface of the surface !, a microcapsule type epoxy resin hardener, and at the same time a masterbatch type epoxy resin hardener is obtained.
• Examples thereof include a method using a mixed resin of epoxy resin ( ⁇ 3) and highly soluble epoxy resin (G).
• the one-component epoxy resin composition of the present embodiment includes the above masterbatch type epoxy resin curing agent composition and epoxy resin (e4).
• epoxy resin (e4) the same epoxy resin curing agent as the epoxy resin (el) described above can be used.
• polyvalent epoxy compounds can be preferably used.
• the masterbatch type epoxy resin curing agent composition and one-component epoxy resin composition of the present embodiment can have a paste-like or film-like form, and can be used for any application (processed product). ) Available.
• bonding films In particular, in addition to adhesives and Z or bonding paste, bonding films, conductive materials, It is useful as an anisotropic conductive material, insulating material, sealing material, coating material, coating composition, pre-preda, heat conductive material, fuel cell sealing material, and the like.
• the adhesive and Z or bonding paste and bonding film are useful for liquid adhesives, film adhesives, die bonding materials, and the like, for example.
• Examples of the method for producing the film adhesive include methods described in JP-A-62-141083 and JP-A-05-295329. More specifically, a solution is prepared in which solid epoxy resin, liquid epoxy resin, and solid urethane resin are dissolved, mixed, and dispersed in toluene so as to be, for example, 50% by mass. The master-batch type epoxy resin of this embodiment is added to the obtained solution.
• a varnish is prepared by adding and dispersing, for example, 30% by mass of the curing agent composition for the solution.
• this varnish is applied to a polyethylene terephthalate substrate for peeling having a thickness of 50 / z m so that the coating film has a thickness of 30 m after drying the toluene in the varnish.
• By drying toluene in the varnish it is possible to obtain a bonding film that is inactive at room temperature and exhibits adhesiveness by the action of the latent curing agent when heated.
• Examples of the conductive material include a conductive film and a conductive base.
• Examples of anisotropic conductive materials include anisotropic conductive films and anisotropic conductive bases.
• As a manufacturing method thereof for example, there is a method described in JP-A-01-113480. More specifically, for example, in the production of the bonding film described above, the conductive material is anisotropically mixed and dispersed at the time of preparation of the varnish, applied to the substrate for peeling, and then dried. It can be manufactured from Kotoko.
• conductive particles examples include solder particles, nickel particles, nano-sized metal crystals, metal particles coated with other metals, metal particles such as copper and silver inclined particles, and styrene resins, urethane resins, Particles coated with conductive thin film such as gold, nickel, silver, copper, solder, etc. on melamine resin, epoxy resin, acrylic resin, phenolic resin, styrene resin, etc. Is used. In general, conductive particles are spherical fine particles of about 1 to 20 m.
• the base material for forming a film include base materials such as polyester, polyethylene, polyimide, and polytetrafluoroethylene.
• an anisotropic conductive film by applying a varnish solvent containing conductive particles to these substrates and then drying the solvent in the varnish.
• the insulating material there are an insulating adhesive film and an insulating adhesive base.
• an insulating adhesive film that is an insulating material can be obtained.
• an insulating adhesive best can be obtained by blending an insulating filler among the aforementioned fillers into a one-component epoxy resin composition.
• Examples of the sealing material include a solid sealing material, a liquid sealing material, and a film-shaped sealing material.
• the liquid sealing material is useful as an underfill material, a potting material, a dam material or the like.
• a method for producing the sealing material for example, JP-A-5-43661, JP-A-2002-226675 and the like are described. More specifically, a bisphenol A type epoxy resin, an acid anhydride as a curing agent, methylhexahydrophthalic anhydride as a curing agent, and spherical fused silica powder are added and mixed uniformly.
• the encapsulant can be obtained by adding the masterbatch type epoxy resin curing agent composition obtained in the invention and mixing them uniformly.
• Examples of the coating material include an electronic material coating material, an overcoat material for a printed wiring board cover, and a resin composition for interlayer insulation of a printed board.
• Examples of the manufacturing method of the coating material include various methods described in, for example, JP-B-4-6116, JP-B-7-304931, JP-A-8-64960, and JP-A-2003-246838. There is. More specifically, silica and other fillers are selected as a filler, and in addition to bisphenol A type epoxy resin, phenoxy resin, rubber-modified epoxy resin, etc. are blended. Formulate a master-batch epoxy resin hardener composition and prepare a 50% solution in methyl ethyl ketone (MEK).
• MEK methyl ethyl ketone
• Examples of the method for producing the coating composition include methods described in JP-A-11-323247, JP-A-2005-113103, and the like. More specifically, bisphenol A type epoxy resin is blended with titanium dioxide, talc, etc., and a 1: 1 solvent mixture of methyl isoburketone (MIBK) / xylene as a mixed solvent is added, stirred, and mixed to be the main agent. And The masterbatch type epoxy resin curing agent composition of the present embodiment is added to this and dispersed uniformly. By making it, an epoxy coating composition can be obtained.
• MIBK methyl isoburketone
• an epoxy resin composition is impregnated into a reinforcing substrate and heated. There is a way to get it.
• the varnish solvent to be impregnated include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol, and the like. It is preferable that these solvents do not remain in the prepreader.
• the type of the reinforcing base material is not particularly limited, and examples thereof include paper, glass cloth, glass nonwoven fabric, alarm cloth, and liquid crystal polymer.
• the ratio of the composition of the resin composition and the reinforcing base is not particularly limited, but it is usually preferable to prepare so that the composition of the resin in the prepreg is 20 to 80% by mass.
• Examples of methods for producing a heat conductive material include Japanese Patent Laid-Open No. 06-136244 and Japanese Patent Laid-Open No.
• JP-A No. 10-237410 and JP-A No. 2000-3987 There are methods described in JP-A No. 10-237410 and JP-A No. 2000-3987. More specifically, an epoxy resin as a thermosetting resin, a phenol novolac curing agent as a curing agent, and a graphite powder as a heat conductive filler are mixed and kneaded uniformly.
• the master-batch type epoxy resin curing agent composition of the present invention can be blended with this to obtain a heat conductive resin paste.
• a method for producing a fuel cell sealing material there are methods described in JP-A Nos. 2002-332328 and 2004-75954. More specifically, using an artificial graphite material as the conductive material, liquid epoxy resin, biphenyl type epoxy resin, resole type phenol resin, and novolac type phenol resin as the thermosetting resin, Mix the ingredients.
• the masterbatch epoxy resin curing agent composition of the present embodiment is added to the obtained mixture and uniformly dispersed to obtain a fuel cell sealing material molding material composition.
• This molding material composition is compression-molded at a mold temperature of 170 to 190 ° C and a molding pressure of 150 to 300 kgZcm 2 , so that it has excellent practical conductivity, good gas impermeability, and moldability. An excellent fuel cell seal material can be obtained.
• an overcoat material for a flexible wiring board there are methods described in WO00Z64960, JP-A-2006-137838, and the like. More specifically, epoxy resins and carboxyl-modified polybutadienes that react with epoxy resins. Rubber particles and the like are appropriately blended with epoxy resin as a raw material for preparing an overcoat material for a flexible wiring board, and the master one-batch type epoxy resin curing agent composition of the present invention is added as a curing accelerator. And uniformly dispersed to obtain an epoxy resin composition. This epoxy resin composition is dissolved and dispersed in MEK to prepare an overcoat material solution for a flexible wiring board having a solid concentration of 30% by mass.
• the epoxy resin and the amine compound were reacted under the reaction solution concentration and reaction temperature conditions shown in Table 2. Thereafter, by distilling off the solvent under reduced pressure, the bulk of the amine adduct (A) or the amine adduct (A) and the low molecular amine compound (B) as the main components is obtained.
• Curing agents for epoxy resin were h-1 to h-7.
• Table 2 also shows the evaluation results of the obtained bulk epoxy hardeners h-1 to h-7.
• Formulation (equivalent) in the table means the quantitative ratio between the number of moles of epoxy groups of the epoxy resin and the number of moles of the amine compound itself.
• “Resin content” in the table means the total amount of epoxy resin and amine compound.
• a chromatogram (HPLC analysis chart) was obtained by high performance liquid chromatography (HPLC).
• AS-8021 manufactured by Tosohichi Co., Ltd. and detector UV-8020 were used.
• As the column Novapack C-18 manufactured by Millipore was used.
• the detection wavelength was 254 nm.
• a calibration curve for quantifying the content of the low-molecular amine compound (B) was prepared using the solvent used for each formulation. The amount of low molecular weight amine compound (B) was quantified using a rough calibration curve
• the obtained crude epoxy resin was repeatedly subjected to vacuum distillation to obtain highly soluble epoxy resin G-1.
• Table 3 shows the evaluation results of the obtained highly soluble epoxy resin G-1.
• a highly soluble epoxy resin G-2 was obtained in the same manner as in Production Example 2-1, except that 110 g (l mol) of resorcin was used instead of 166 g (l mol) of tert-butylhydroquinone. Table 3 shows the evaluation results for the highly soluble epoxy resin G-2.
• a highly soluble epoxy resin G-3 was obtained in the same manner as in Production Example 2-1, except that no glycidol was added during the reaction.
• Table 3 shows the evaluation results of the obtained highly soluble epoxy resin G-3.
• MS mass spectrometer
• Samples 1 to 10 g were precisely weighed so that the titer was 3 to 7 ml. This was dissolved in 25 ml of ethylene glycol monobutyl ether, further added with 25 ml of 1N KOH propylene glycol solution and boiled for 20 minutes, and then titrated with an aqueous silver nitrate solution.
• the lump-shaped curing agent for epoxy resin (h-1) obtained in Production Example 11 is subjected to coarse pulverization, pulverization and classification under known conditions. For example, first, coarsely pulverize to about 0.1 to 2 mm with a crusher “Koto-Tplex” (manufactured by Hosokawa Micron). Next, the obtained coarsely crushed material is supplied to an air-jet jet mill (Nisshin Engineering Co., Ltd., model CJ25) at a supply amount of 5. OkgZHr, and pulverized at a pulverization pressure of 0.6 MPa-s.
• the pulverized product is classified with an air classifier “Turbo Classifier” (manufactured by Nissin Engineering Co., Ltd.). In this way, pulverization and classification operations are optimally combined.
• a curing agent (H) for epoxy resin having various average particle sizes and small particle size contents shown in Table 4 was obtained.
• 2-methylimidazole was added before pulverization.
• a method of addition a method of melting 100 parts by mass of a block curing agent for epoxy resin (h-1), uniformly mixing 0.9 part by mass of 2-methylimidazole, and cooling to room temperature is used. It was.
• 40 at 40 03 ⁇ 4 40 ° C 3 hours 3 hours 3 hours 3 hours 3 hours 3 hours Shell formation conditions + + 10 + + + +
• Solvent resistance o o ⁇ ⁇ X ⁇ Poxy resin (e 3-1): Bisphenol A type liquid epoxy resin (epoxy equivalent 17
• MR-200 Nippon Polyurethane Polymethylene Phenylene Polyisocyanate
• TD I Tolylene Diisocyanate
• the masterbatch type epoxy resin curing agent composition was repeatedly washed and filtered with xylene until the epoxy resin disappeared, and then washed and filtered with cyclohexane until xylene disappeared. Then, it was vacuum-dried at 40 ° C to determine its mass (separation of microphone mouth capsule type epoxy resin curing agent).
• microcapsule type epoxy The resin hardener was repeatedly washed and filtered with methanol until the epoxy resin hardener disappeared, and the methanol was completely removed and dried at a temperature of 50 ° C or less (microcapsule type epoxy resin). Separation of capsule film from hardener.
• the separated capsule membrane was vacuum-dried at 40 ° C, and 3 g of the obtained capsule membrane sample was pulverized in an agate mortar. Thereafter, 2 mg of the pulverized product was pulverized and mixed with 50 mg of potassium bromide (KBr) powder, and a tablet for FT-IR measurement was prepared using a tablet molding machine. Using this tablet, an infrared spectrum was obtained by FT / IR-410 manufactured by JASCO Corporation. Spectrum Chiya obtained - and DOO, by comparing the standard vector line, bond group in the capsule film (x), (y), and probability of the presence of (z) 0
• 1630 ⁇ 1680cm _ 1 forces having a binding group (X) having an absorption band of the (y) and a (z) Model compound (Ml), which similarly has a binding group (y) having an absorption band of 1680-1725 cm _1 but does not have the binding groups (X) and (z), 1730-1755 cm_
• a model compound (M3) is prepared which has a linking group (z) having an absorption band of 1 but no linking groups (X) and (y).
• the mixture of the model compounds (Ml), (M2), and (M3) which are precisely weighed and mixed at an arbitrary ratio, is pulverized with KBr powder and FT— Prepare a calibration sample tablet for IR measurement.
• the absorption spectrum of the model compound (Ml) from 1630 to 1680 cm _1 and the model compounds (M2) and (M3) were also measured for each of the bonding groups (x), (y), and (z) according to their measured spectra.
• a standard IR spectrum can be created.
• FTZIR-410 manufactured by JASCO Corporation was used.
• the viscosities before and after storing the masterbatch type epoxy resin curing agent at 40 ° C for 2 weeks were measured and evaluated by the viscosity increase ratio.
• the rate of increase in viscosity after storage is 10 times or more or gelation, X, 5 times or more and less than 10 times, ⁇ , 2 times or more and less than 5 times ⁇ , and 2 times or less, ⁇ .
• the viscosity was measured using a BM type viscometer at 25 ° C.
• epoxy resin (e4) 30 parts of the master batch type epoxy resin curing agent was added to the bisphenol A type epoxy resin.
• One-part epoxy resin composition was prepared by mixing with 100 parts of resin (epoxy equivalent 189 gZ equivalent, total chlorine content 1200 ppm; hereinafter referred to as epoxy resin (e4)).
• the temperature rise rate is 5 using a rheometer (Rheo Stress 5600) manufactured by Thermo ELECTORON CORPORATION.
• a viscosity-temperature curve was obtained under the condition of CZmin. Then, a viscosity measurement value at 40 ° C., and a temperature and a viscosity at which the viscosity increase rate becomes a curing start temperature of 20% Zmin or more were measured.
• the viscosity change rate was less than 5% and the curing start temperature was 130 ° C or less. If the starting temperature is 130 ° C or less, ⁇ , if the viscosity increases from 5% to less than 20%, the starting temperature exceeds 130 ° C but 150 ° C or less X, 20% or more
• the thickened product was designated as XX.
• solvent resistance the time to gely using a gely test machine based on JIS C-6521 was measured and evaluated as follows. That is, keep the gel plate at 120 ° C, place a 0.4 ml sample on the plate, and after mixing, mix with a force stirring rod until the yarn stops being pulled, that is, until the gel Measure time (seconds).
• a curing agent for epoxy resin can provide a curing agent composition for epoxy resin that exhibits excellent curability and high long-term storage stability / solvent resistance.
• a large amount of the active hydrogen compound used as a material for forming the shell (S) and a large average particle diameter can contribute to an improvement in solvent resistance.
• the raw materials shown in Table 6 were subjected to known coarse pulverization 'pulverization' classification treatment to obtain epoxy resin hardeners H-6 to H-11.
• 2-methylimidazole was added before pulverization.
• 100 parts by mass of a bulk epoxy resin hardener (h-1) is melted, and 0.9 parts by mass of 2-methylimidazole is uniformly mixed therein and cooled to room temperature. The method was used.
• Properties of the obtained epoxy resin hardeners H-6 to H-11 and average particle diameters are also shown in Table 6. Note that the evaluation methods not particularly specified are the same as in any of the above production examples, examples, or comparative examples.
• Epoxy resin (e 3-2) Bisphenol A type liquid epoxy resin (Epoxy equivalent 1 7
• a Bruker DSX400 (magnetic field: 400 MHz) was used as a nuclear magnetic resonance spectrum measuring apparatus.
• the measurement conditions were as follows: observation measurement nuclide 13C, pulse program CPSELTICS, pulse condition (repetition time 5 seconds, proton 90 degree pulse 5.2 microseconds, contact time 1 millisecond), magic angle spinning 5000 Hz.
• the ratio was 1/10 or less compared to the model compound, it was determined that there was no carbonyl carbon of the carboxylate ester group (no carboxylate ester bond).
• a hardener composition for a masterbatch type epoxy resin was cured using a modified aliphatic amine curing agent while holding the microcapsules for 12 hours at 40 ° C. Thereafter, the composition was completely cured at 120 ° C. for 24 hours.
• An ultrathin sample was prepared from the cured product using a cryoultra microtome, and the thickness of the shell of the microcapsule type curing agent in the epoxy resin was observed and measured by observation with a transmission electron microscope (TEM).
• TEM transmission electron microscope
• the masterbatch type epoxy resin curing agent composition was repeatedly washed and filtered with xylene until the epoxy resin disappeared. Next, the filtrate was distilled off under reduced pressure at 100 ° C or lower to obtain epoxy resin.
• the obtained epoxy resin samples 1 to 10 g were precisely weighed so that the titration amount was 3 to 7 ml. This was dissolved in 25 ml of ethylene glycol monobutyl ether, further added with 25 ml of a 1N KOH propylene glycol solution, boiled for 20 minutes, and titrated with an aqueous silver nitrate solution.
• the viscosities before and after storing the masterbatch type epoxy resin curing agent at 40 ° C for 1 week were measured and evaluated by the viscosity increase ratio.
• the rate of increase in viscosity after storage is 10 times or more or gelation, X, 5 times or more and less than 10 times, ⁇ , 2 times or more and less than 5 times ⁇ , and less than 2 times ⁇
• the viscosity was measured using a BM type viscometer at 25 ° C.
• / 0-c is Ding (viscosity in degrees (! 11? &'5)
• / 0-c +5 is Ding +5 (viscosity in degrees
• pTh is the viscosity (mPa's) at Th (° C)
• p40 is the viscosity (mPa • s) at 40 ° C.
• the curing agent for epoxy can realize a curing agent composition for epoxy resin that exhibits curability with excellent reaction steepness, high storage stability, and storage stability when humidified.
• the raw materials shown in Table 8 were subjected to known crushing, pulverization, and classification treatments, and epoxy resin curing agents H-12 to H-18 were obtained.
• epoxy resin hardener H-12 2-methylimidazole was added before grinding.
• 100 parts by mass of a block curing agent for epoxy resin (h-1) is melted, and 0.9 part by mass of 2-methylimidazole is uniformly mixed therein and cooled to room temperature. It was.
• Properties of the resulting epoxy resin curing agents H-12 to H-18 are shown in Table 8. Note that the evaluation methods not particularly specified are the same as in any of the above production examples, examples, or comparative examples.
• a master batch type epoxy resin curing agent was obtained by using a rheometer (Rheo Stress 5600) manufactured by Thermo ELECTORON CORPORATION to obtain a viscosity-temperature curve with a temperature measurement rate of ⁇ ⁇ ⁇ . 40.
• the measured viscosity of C and the temperature and viscosity at which the rate of increase in viscosity is 20% Zmin or more and the curing start temperature were measured. 40. Compare the viscosity measurement value of C (A) with the viscosity measurement value (B) of the curing start temperature, and calculate the viscosity change rate from the following formula. I tried.
• Viscosity change rate (%) ((A-B) / A) * 100
• the curing agent can realize an epoxy resin curing agent composition that exhibits excellent reaction steepness, high storage stability, solvent resistance, and storage stability when humidified.
• Table 10 shows the evaluation results of the obtained master-batch type epoxy resin curing agent. Note that the evaluation method not particularly specified is the same as any one of the above production examples, examples, and comparative examples.
• Epoxy resin (e 3-3) Bisphenol F-type liquid epoxy resin (SP:
• Master batch type epoxy resin curing agent (F) 30 parts is mixed with epoxy resin (e4) 100 parts to produce a one-part epoxy resin composition.
• epoxy resin (e4) 100 parts to produce a one-part epoxy resin composition.
• the film sample was sandwiched between 1.2 mm thick stainless steel plate (stainless steel plate grade: SUS304) and thermocompression bonded on a 200 ° C hot plate at 30 kgZcm 2 for 20 seconds. After that, we measured the tensile shear bond strength before and after holding for 8 hours at a temperature of 85 ° C and a humidity of 85%. The thing is X.
• the raw materials shown in Table 11 were subjected to known coarse pulverization 'pulverization' classification treatment. Curing agents for epoxy resin, H-20 to H-23, were obtained.
• epoxy resin hardener H-20 2-methylimidazole was added before grinding.
• the addition method is a method of melting 100 parts by mass of hard epoxy hard resin (h-1), mixing 0.9 parts by mass of 2-methylimidazole uniformly, and cooling to room temperature. Was used. Properties of the resulting epoxy resin hardeners H-20 to H-23 are shown in Table 11. Note that the evaluation methods not particularly specified are the same as in any of the above production examples, examples, or comparative examples.
• the epoxy resin hardener (H), epoxy resin (e3-l to e3-2), isocyanate compound and active hydride are mixed in the formulations shown in Tables 12 and 13, and shown in Tables 12 and 13 Shell shape
• the reaction was performed under the growth conditions.
• a highly soluble epoxy resin (Epoxy resin manufactured in Production Examples 2-1 to 2-3 and 3-1 to 3-2) is blended to obtain a master one-batch type epoxy resin curing agent. It was.
• the evaluation results of the obtained masterbatch type epoxy resin curing agent are shown in Tables 12 and 13 together.
• the evaluation method not particularly specified is the same as in any of the above production examples, examples, or comparative examples.
• H- 12 100 100 100 100 100 Epoxy H- 13 100
• Bisphenol A type epoxy resin (AER-2603, manufactured by Asahi Kasei Chemicals Co., Ltd.) 15 parts by mass, phenol novolac resin (trade name “BRG-558” manufactured by Showa Polymer Co., Ltd.), 6 parts by weight, synthetic rubber (Japan) 4 parts by mass were dissolved in 20 parts by mass of a 1: 1 (mass ratio) mixed solvent of methyl ethyl ketone and butylcetone sorb acetate, manufactured by Zeon Corporation, trade name “Nipol 1072”, weight average molecular weight 300,000). This solution was mixed with 74 parts by mass of silver powder, and further kneaded with a three-necked tool.
• Example 16 30 parts by mass of the masterbatch type epoxy resin curing agent obtained in Example 16 was added and further uniformly mixed to obtain a conductive adhesive.
• the obtained conductive adhesive was cast on a polypropylene film having a thickness of 40 m and dried and semi-cured at 80 ° C. for 60 minutes to obtain a conductive film having a conductive adhesive layer having a thickness of 35 m. Obtained.
• the conductive adhesive layer was transferred onto the back of the silicon wafer on a heat block at 80 ° C.
• the silicon wafer was fully diced and a semiconductor chip with a conductive adhesive was bonded and cured to the lead frame on a heat block at 200 ° C for 2 minutes, there was a problem with the conductivity of the chip. There was no.
• Bisphenol A-type epoxy resin (Asahi Kasei Chemicals, AER6097, epoxy equivalent 42500gZeq) 40 parts by mass, phenoxy resin (Toto Kasei, YP-50) 30 parts by mass are dissolved in 30 parts of ethyl acetate.
• a varnish which is a raw material of the directionally conductive film was obtained.
• 30 parts by mass of the master-batch type epoxy resin curing agent composition obtained in Example 16 was used.
• 5 parts by mass of conductive particles (cross-linked polystyrene plated with gold) having a particle diameter of 8 ⁇ m were added and mixed uniformly to obtain a one-part epoxy resin composition.
• the obtained one-component epoxy resin composition was applied onto a polyester film, and ethyl acetate was removed by drying at 70 ° C. to obtain an anisotropic conductive film.
• the obtained anisotropic conductive film was sandwiched between electrodes of an IC chip and a test substrate, and thermocompression bonded on a 200 ° C hot plate at 30 kgZcm 2 for 20 seconds. It was useful as an anisotropic conductive material because the IC chip and the electrodes of the test substrate were joined together and electrical conduction was obtained.
• Bisphenol A-type epoxy resin (Asahi Kasei Chemicals, AER6091, epoxy equivalent 480g / eq) 50 parts by mass, Bisphenol A-type epoxy resin (Asahi Kasei Chemicals AE R2603) 50 parts by mass, micro particles as conductive particles Au-205 (manufactured by Sekisui Chemical Co., Ltd., specific gravity 2.67) After mixing 5 parts by mass, add 30 parts by mass of the hardener composition for masterbatch type epoxy resin obtained in Example 16 and mix evenly. An anisotropic conductive base was obtained. The obtained anisotropic conductive paste was applied on low alkali glass having an indium tin oxide (ITO) electrode.
• ITO indium tin oxide
• TAB Tepe Automated Bonding
• Bisphenol F-type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name “YL98 3U”) 100 parts by mass, 4 parts by mass of dicyandiamide, 100 parts by mass of silica powder, 10 parts by mass of glycidyl ether as diluent And 1 part by mass of an organic phosphate ester (manufactured by Nippon Gyaku Co., Ltd., trade name “PM-2”) was sufficiently mixed and then kneaded with a three-roll.
• YL98 3U Bisphenol F-type epoxy resin
• Example 16 30 parts by mass of the master-batch type epoxy resin curing agent composition obtained in Example 16 was added thereto, and further uniformly mixed, and subjected to vacuum defoaming and centrifugal defoaming treatment for insulation. A sexual best was produced.
• the semiconductor chip was bonded to a resin substrate by heating and curing at 200 ° C. for 1 hour, and it was useful as an insulating paste.
• [0130] [Example of production of insulating film] 180 parts by weight of phenoxy resin (trade name “YP-50” manufactured by Tohto Kasei Co., Ltd.), talezo-novolac type epoxy resin (epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd., product name 3 ⁇ 40 ??) 1020-80 ”) 40 parts by weight, spherical silica (average particle size: 2 m, manufactured by Admatech Co., Ltd., trade name SE-5101) 300 parts by weight, 200 parts by weight of methyl ethyl ketone were prepared and dispersed uniformly. .
• phenoxy resin trade name “YP-50” manufactured by Tohto Kasei Co., Ltd.
• talezo-novolac type epoxy resin epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd., product name 3 ⁇ 40 ??
• spherical silica average particle size:
• Example 16 250 parts by mass of the masterbatch type epoxy resin hardener composition obtained in Example 16 is added and further stirred and mixed to obtain a solution containing the epoxy resin composition.
• the obtained solution was applied onto polyethylene terephthalate that had been subjected to a mold release treatment so that the thickness after drying was 50 m, and was heat-dried in a hot-air circulating drier, for semiconductor adhesion.
• An insulating film was obtained.
• the obtained insulating film for semiconductor bonding is cut into support substrates larger than the 5-inch wafer size, and the resin film is aligned with the electrode part side of the wafer with bump electrodes.
• the insulating base film is sandwiched between the wafers with bump electrodes using a thermo-bonder with the support substrate with release treatment facing up, and heat-pressed in vacuum at 70 ° C, lMPa, and pressurization time of 10 seconds.
• a wafer with adhesive grease is obtained.
• a dicing saw (DISCO, DAD-2H6M)
• the obtained film was useful as an insulating film [Example of production of sealing material]
• Bisphenol A-type epoxy resin (Asahi Kasei Chemicals, AER6091, epoxy equivalent 480g / eq) 50 parts by mass, Bisphenol A-type epoxy resin (AER2603, made by Asahi Kasei Chemicals) 50 parts by mass, anhydrous phthalate as curing agent 40 parts by mass of acid-based HN-2200 (manufactured by Hitachi Chemical Co., Ltd.) and 80 parts by mass of spherical fused silica having an average particle size of 16 ⁇ m were uniformly dispersed and blended. To this, 5 parts by mass of the master-batch type epoxy resin hardener composition obtained in Example 16 is added to obtain an epoxy resin composition.
• the obtained epoxy resin composition was applied to a 1 cm square so as to have a thickness of 60 m on a printed wiring board, and was semi-cured by heating in an oven at 110 ° C. for 10 minutes. After that, place a silicon chip with a thickness of 370 / ⁇ ⁇ on a semi-cured epoxy resin composition and apply a load to keep the bump and chip electrodes in contact with each other at 220 ° C. A complete curing process was performed for a time. Obtained epoxy cake The encapsulant made of the oil composition was useful without any problem in appearance and chip conduction.
• Bisphenol A epoxy resin (Asahi Kasei Chemicals, AER6091, epoxy equivalent 480 gZeq) 50 parts by mass, 30 parts by mass of titanium dioxide, 70 parts by mass of talc, and MIBK / xylene 1: 1 as a mixed solvent 140 parts by mass of a mixed solvent was added, stirred and mixed to obtain the main agent.
• 30 parts by mass of the hardener composition for master-batch type epoxy resin obtained in Example 16 was added and dispersed uniformly to obtain a useful epoxy coating composition.
• Bisphenol A type epoxy resin (AER2603, manufactured by Asahi Kasei Chemicals Co., Ltd.), methyl as a curing agent for epoxy resin, phenol novolac resin (Arakawa Chemical Co., Ltd., trade name “TAMANOR 759”) Ethyl ketone 50% solution 40 parts by mass, scaly graphite powder (Union force—manufactured by Bite, trade name HOPG) 15 parts by mass were stirred until uniform, and then uniformly dispersed with a single three-neck. 15 parts by weight of the hardener composition for master-batch type epoxy resin obtained in Example 16 was added and mixed with sufficient stirring.
• a semiconductor chip (1.5 mm square, thickness 0.8 mm) was mounted on a Cu lead frame and heat cured at 150 ° C. for 30 minutes to obtain a sample for evaluation.
• the thermal conductivity of the obtained sample was measured by a laser flash method.
• the soot was 5 5 10 _3 Cal / cm 'sec' ° C or more and was useful as a heat conductive paste.
• Biphenol type epoxy resin 3, 3 ', 5, 5, -tetramethyl-4,4, -dihydroxybiphenol Nino-Reglycidinoreatenore (manufactured by Japan Epoxy Resin, Epicot YX 4000 (epoxy equivalent 195) 100 parts by mass , Phenol novolac resin (Dainippon Ink, TD-2131) 60 parts by mass, bisphenol A type epoxy resin (Asahi Kasei Chemicals, AER2603) 10 parts by mass, artificial graphite (manufactured by SC Corporation) (Product name SGP, average particle size 75 / zm) 800 parts by mass, Raw materials containing a release agent (calcium stearate) and a lubricant (carnauba wax) were mixed in a mixer.
• Example 16 To this was added 10 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 16, and the mixture was uniformly mixed in a three-necked flask.
• the obtained material was subjected to pressure molding using a mold for a separator material for a fuel cell at a molding pressure of 25 MPa, a molding temperature of 150 ° C., and a molding time of 15 minutes to obtain a sample for evaluation.
• the bending strength of the obtained separator material for fuel cells was measured according to JIS K 7203, it showed a bending strength of 50 MPa.
• the gas permeability was measured by JIS K7126A method using nitrogen gas, the gas permeability was 0.6 cm 3 Zm 2 '24 hours .atm, which was useful as a separator for fuel cells. .
• Epoxy resin modified EPB-13 (epoxy equivalent 70 Og / eq., Viscosity 800P) by the reaction of Nippon Soda polybutadiene dicarboxylic acid resin "C 1000" and bisphenol type epoxy resin.
• maleated modified polybutadiene resin “BN-1015” (acid equivalent: 145 gZeq.)
• Manufactured by Nippon Soda is obtained in Example 16 as a curing accelerator.
• the masterbatch type epoxy resin curing agent composition thus obtained was blended in an amount of 5 parts by mass and 3 parts by mass of JSR “EXR-91” as rubber fine particles.
• an overcoat adhesive solution 200 parts by mass of methyl ethyl ketone (MEK) is added, and the mixture is stirred and mixed with a mixer until uniform to dissolve and disperse to obtain an overcoat adhesive solution.
• MEK methyl ethyl ketone
• an overcoat material sample for a flexible wiring board was obtained.
• the resulting polyimide film was bent at 180 ° C, the occurrence of cracks and the warpage of the polyimide film when treated at 50% humidity and 150 ° C for 8 hours were measured. It was useful as an overcoat material.

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• 2007
  • 2007-01-31 KR KR1020087019075A patent/KR100976303B1/ko active Active
  • 2007-01-31 WO PCT/JP2007/051595 patent/WO2007088889A1/ja not_active Ceased
  • 2007-01-31 CN CN2007800043842A patent/CN101379108B/zh active Active
  • 2007-01-31 US US12/223,523 patent/US7927514B2/en active Active
  • 2007-01-31 CA CA002641409A patent/CA2641409A1/en not_active Abandoned
  • 2007-01-31 EP EP07713755A patent/EP1980580A1/en not_active Withdrawn
  • 2007-01-31 JP JP2007556890A patent/JP5148292B2/ja active Active
  • 2007-02-02 TW TW096103927A patent/TW200734368A/zh unknown

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