WO2006088069A1 - Thermosetting one-component resin composition - Google Patents

Thermosetting one-component resin composition Download PDF

Info

Publication number
WO2006088069A1
WO2006088069A1 PCT/JP2006/302680 JP2006302680W WO2006088069A1 WO 2006088069 A1 WO2006088069 A1 WO 2006088069A1 JP 2006302680 W JP2006302680 W JP 2006302680W WO 2006088069 A1 WO2006088069 A1 WO 2006088069A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
component
ring
resin composition
thiirane
Prior art date
Application number
PCT/JP2006/302680
Other languages
French (fr)
Japanese (ja)
Inventor
Manabu Kirino
Maki Takayama
Manabu Inoue
Original Assignee
Three Bond Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2005039929A external-priority patent/JP4826708B2/en
Priority claimed from JP2005215202A external-priority patent/JP4883264B2/en
Application filed by Three Bond Co., Ltd. filed Critical Three Bond Co., Ltd.
Priority to CN200680005105XA priority Critical patent/CN101120036B/en
Priority to KR1020077018549A priority patent/KR101235933B1/en
Publication of WO2006088069A1 publication Critical patent/WO2006088069A1/en

Links

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
    • C08G59/66—Mercaptans
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C08G75/08—Polythioethers from cyclic thioethers from thiiranes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to a one-part resin composition that is excellent in rapid curability by heating at a low temperature and has good storage stability (storage stability).
  • episulfide resin A compound having a thiirane ring in which all or some of the enzyme atoms of the oxysilane ring of the epoxy resin are replaced with sulfur atoms is known as episulfide resin.
  • Episulfide resins are known to have characteristics such as excellent low-temperature curability with epoxy resin compared to epoxy resins, good water resistance, high refractive index, and flame retardancy.
  • most of the conventional episulfide-based compositions are two-component type, requiring complicated steps such as weighing, mixing, and defoaming the resin component and the curing agent component immediately before actual use.
  • the usable period after mixing is limited and there is a possibility of mixing errors, it has the disadvantage of being inferior in workability and reliability.
  • JP-A-50-124952, JP-A-11-140161, and JP-A-2002-173533 show an episulfide resin composition that is faster curing at low temperature than an epoxy resin composition.
  • these compositions are two-component and have the above-mentioned problems in workability and reliability.
  • the above-mentioned two-component composition problem is solved by using a so-called latent curing agent that does not react with episulfide resin at room temperature but shows reactivity by stimulation such as heating. It is known that a one-component composition can be obtained.
  • Japanese Patent Application Laid-Open No. 4-202523 describes a specific example in which a resin containing an episulfide resin is made into one component using a carboxylic acid-containing compound and a thermal latent catalyst as a curing agent.
  • thermosetting type one-component resin composition using an episulfide resin by using a latent hardener.
  • a latent hardener there is no specific example describing which curing agent is used and how much it can achieve good low temperature fast curing and storage stability.
  • the object of the present invention is to be used for various applications such as adhesion, sealing, casting, molding, painting, coating, etc., and it can be cured at lower temperature and faster than conventional episulfide-based thermosetting one-component resin compositions.
  • An object of the present invention is to provide an episulfide-containing heat-curable one-component resin composition having excellent and good storage stability.
  • a further object of the present invention is that the liquid is excellent in rapid curability by heating at a low temperature, has high adhesive force, does not cause separation and uncuring at the time of heat curing, and has good storage stability (storage stability). It is in providing a conductive resin composition.
  • the present invention provides, firstly, (A) a compound containing two or more thiirane rings in the molecule, (B) a compound containing one or more thiirane rings and one or more oxsilane rings in the molecule, and (C ) The ratio of the compound containing one or more oxilan rings in the molecule and no thiirane ring, and the ratio of oxilan ring Z thiirane ring (ie the ratio of the number of oxilan rings to the content of Z thiirane rings)
  • the second aspect of the present invention is a hydrogenated bisphenol type epoxy compound obtained by hydrogenating a carbon-carbon unsaturated bond of an aromatic ring of an epoxy compound having a bisphenol skeleton.
  • a first thermosetting one-component resin composition comprising a compound containing a thiirane ring in which all or some of the oxygen atoms of the oxysilane ring of the hydrogenated bisphenol type epoxy compound are substituted with sulfur atoms. is there.
  • the present invention provides a compound in which the compound (C) has two or more oxosilane rings.
  • the first or second heat-curable one-component resin composition is provided.
  • the present invention provides the heat-curable one-component resin composition according to any one of the first to third, wherein the ratio of the (1) component oxolan ring and thiirane ring is 40/60 to 90 ° 90.
  • the present invention is the heat-curable one-component resin composition according to any one of the first to fourth, further comprising (4) an acidic compound Opop Z or a borate ester.
  • the present invention is the heat-curable one-component resin composition according to any one of the first to fifth, further comprising (5) core-seal type acrylic rubber fine particles.
  • the blending ratio of each component is (1) 100 parts by weight of the component, (3) 0.1 to 30 parts by weight of the component, and (4) 0.01 to 10 parts by weight of the component.
  • Parts, (5) component is 1 to 50 parts by weight, and (2) the amount of the component is (1) the thiol equivalent ratio with respect to the total of thiirane ring and oxysilane ring in the component is 0.01 to A sixth heat-curable one-component resin composition of 0.5.
  • the present invention provides the heat-curable one-component resin composition according to any one of the first to seventh, wherein (3) the thermal latent curing accelerator is a solid-dispersed amine acid-based latent curing accelerator. It is a thing.
  • the ninth aspect of the present invention is the eighth thermosetting one-part resin composition, wherein the solid dispersion type amine adduct system latent curing accelerator is a thermal latent curing accelerator of urea type adduct system.
  • the present invention relates to (5) a rubbery polymer having a glass transition point of 10 ° C. or less at the core portion of the core-shell type acrylic rubber fine particles, and the shell portion has a glass transition point of 70 ° C. or more.
  • the heat-curable one-component resin composition according to any one of the sixth to ninth glass-like polymers.
  • the present invention is a resin composition obtained by curing the heat-curable one-component resin composition according to any one of the first to tenth.
  • thermosetting resin composition of the present invention is one-part, has good storage stability, is rapidly cured at low heating temperature, and has a tough and excellent physical property. Can be used as adhesive, casting, molding, painting, coating material, etc.
  • composition comprising the components (5) and (6) is further excellent in low-temperature fast curability, has high adhesive strength, does not cause separation and uncuring during heat curing, and is stable in storage (storage stable). The effect that it is more excellent in property. '
  • the compound (A) containing a thiirane ring used in the present invention may be a compound containing two or more thiirane rings in the molecule.
  • the compound (B) containing a thiirane ring may be a compound containing at least one thiirane ring and one oxilan ring in the molecule.
  • the compound (A) or (B) containing the thiirane ring may have a functional group other than the oxysilane ring and the thiirane ring. Specific examples thereof include a hydroxyl group, a vinyl group, an acetal group, an ester group, a carbonyl group, an amide group, and an alkoxysilyl group.
  • the compound (A) or (B) containing the thiirane ring may be used alone or in admixture of two or more.
  • the thiirane ring-containing compound used in the present invention is produced by various methods. Examples include thermal hydrolysis of hydroxymercaptan, treatment with 1,2-chlorothiol with a weak alkaline solution, treatment with ethylenically unsaturated ethers such as sulfur or polysulfide dialkyl.
  • a method for obtaining a thiirane ring-containing compound by replacing all or part of oxygen atoms in the epoxy ring with sulfur atoms using an epoxy compound as a raw material is already known.
  • Such compounds are also called episulfide or episulfide resin.
  • thiirane ring-containing compound examples include, for example, 2, 2-bis (4-(2,3-epitipropoxy) phenyl) propane, bis (4-(2,3 -epitipropoxy) phenyl) methane, 1,6-di (2,3-epitipropoxy) naphthalene, 1, 1, 1-tris (4- (2,3-Epiciopropoxy) phenyl) ethane, 2,2-bis (4 (2,3-Epiciopropoxy) cyclohexyl) propane, bis ( 4-(2,3-epeticopropoxy) hexyl) methane, 1, 1, 1 tris (4- (2, 3-epeticopropoxy) cyclohexinole) ethane, 1, 5 -2,3-Epithiocyclohexenole of pentanediol, and di (3,4-epoxyoctyl) ether of 1,6-hexanediol.
  • a compound having both a thiirane ring and an oxysilane ring in one molecule used in the present invention A compound having both a thiirane ring and an oxysilane ring in one molecule used in the present invention
  • (B) can be obtained by adjusting the amount of episulfide reagent used or the reaction conditions when an epoxy compound is used as a raw material to synthesize an episulfide resin by exchanging oxygen atoms in the epoxy ring with sulfur atoms. . It can also be obtained by mixing the partial episulfide obtained by separation by various purification methods with the total episulfide.
  • the thiirane ring-containing compound more preferably used in the present invention is a hydrogenation of a carbon-carbon unsaturated bond of an aromatic ring of an epoxy compound having a bisphenol skeleton as disclosed in JP-A-2000-351 829.
  • the composition using this compound is particularly excellent in curability, workability and storage stability.
  • the compound (C) that contains one or more oxosilane rings and does not contain a thiirane ring in the molecule used in the present invention is generally called an epoxy compound.
  • Specific examples include diglycidyl ethers derived from bisphenol A and epichlorohydrin and derivatives thereof, diglycidyl ethers derived from bisphenol F and epichlorohydrin, and derivatives thereof, so-called epibis type liquid epoxy.
  • Resin aliphatic ⁇ Glycidille derived from aromatic alcohol and epichlorohydrin Glycidyl ester derived from polybasic acid and epichlorohydrin, and derivatives thereof, hydrogenated bisphenol A and glycidyl ether derived from epichlorohydrin, 3,4 epoxies 6-methinoresic hexinoremethino Rhee 3, 4-oxyloxy 6-methinorexane hexanoyl hexoxylate, bulesic hexacene xylide, bis (3,4-epoxy 1-methylcyclohexylmethyl) adipate and other cyclic cyclic epoxies, and the like Derivatives, 5, 5'-dimethylhydantoin-type epoxy resin, triglycidyl isocyanate, substituted epoxy derived from isoptylene, y -glycidoxypropyltrimethoxysilane and other compounds containing an alkoxys
  • Examples of commercially available epoxy resin products include Epicoat 828, 1 001, 801, 806, 807, 152, 604, 630, 871, YX8000, ⁇ 8034, ⁇ 4000, and Card Yura ⁇ 10 manufactured by Japan Epoxy Resin Co., Ltd.
  • Examples include, but are not limited to, KBM 403 and KBE402 manufactured by the company. These may be used alone or in combination of two or more.
  • each component of the above (A) to (C) may have a functional group other than the oxosilane ring and the thiirane ring.
  • functional groups include a hydroxyl group, a vinyl group, an acetal group, an ester group, a carbonyl group, an amide group, and an alkoxysilyl group.
  • the compounds represented by (A) to (C) in the yarn composition of the present invention are compounds (A) containing two or more thiirane rings in the molecule, or both a thiirane ring and an oxysilane ring in the molecule.
  • Compound (B) containing one or more, or one or more of compounds (C) having an oxysilane ring in the molecule and not containing a thiirane ring, and the ratio of the oxysilane ring / thiirane ring Is 80 / 20-0Zl 00 or a mixture of said compounds.
  • the proportion of the thiirane ring is smaller than this range, it is impossible to develop fast curing while maintaining sufficient storage stability.
  • the ratio of the content is more preferably 40 to 0 to 100, more preferably 40 to 100 to 98, and still more preferably 40/60 to 290.
  • the presence of a small amount of a compound containing an oxysilane ring improves the solubility of the latent curing agent, resulting in an improvement in the curing rate.
  • the thiol compound used in the present invention may be a thiol compound having one or more thiol groups in the molecule. Specific examples include 3-methoxyptyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, trimethylolpropane tristhiopropionate, pentaerythritol.
  • Examples of commercially available thiol compound products are Epomate QX 1 1, QX 12, Epicure QX30, QX40, QX6 manufactured by Japan Epoxy Resin Co., Ltd.
  • More preferable thiol compounds are those having as few basic impurities as possible from the viewpoint of storage stability. From the viewpoint of heat resistance of the cured product, a thiol compound having 2 or more functional groups and a thiol compound containing an aromatic ring in the molecule are more preferable.
  • the blending amount of the thiol compound (2) in the composition of the present invention is not particularly limited, but is preferably based on the total of thiirane ring and opoxysilane rings in the resin component described in (1) above.
  • the thiol equivalent ratio can be added in the range of 0.005 to 1.5, more preferably 0.01 to 0.5. More preferably, when the ratio of oxysilane ring to thiirane ring is 80 20 to 50 50, the thiol equivalent ratio is in the range of 0.5 to 1.4 with respect to the total of thiirane ring and opioxylan ring.
  • the thiol equivalent ratio is in the range of 0.01 to 0.7 with respect to the total of thiirane ring and oxsilane ring.
  • the thiol compound is added within the above range, the curing rate and storage stability can be further improved, and a composition excellent in the balance of strength and heat resistance of the cured product can be obtained.
  • the heat latent curing accelerator used in the present invention is a compound that does not have an activity with respect to an epoxy resin at room temperature, and is activated by dissolution, decomposition, transition reaction, etc. when heated, and functions as an accelerator.
  • Examples include, but are not limited to, imidazole compounds that are solid at room temperature and derivatives thereof, salts of various amines and acids, and solid dispersion type amine adduct-based latent curing accelerators.
  • examples of solid dispersion type amine adduct latent curing accelerators include reaction products of amine compounds and epoxy compounds (amine-epoxy adducts) reaction products of amine compounds and isocyanate compounds or urea compounds.
  • thermal latent curing accelerators solid dispersion type amine adduct type latent curing agents are preferred, and urea type adduct type thermal latent curing agents are more preferred.
  • the composition of the present invention exhibits an excellent effect on the low curing temperature and storage stability.
  • the blending amount of these thermal latent curing agents is not particularly limited, but is preferably added in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the resin component (1). When there are few hardening accelerators, hardening will be slow, and when too much, storage stability will worsen.
  • thermal latent curing accelerator examples include imidazole compounds 2 PZ, 2 PHZ, 2 P4MHZ, C 1 7 Z, 2M Z-A, 2E4MZ- CNS, manufactured by Shikoku Kasei Kogyo Co., Ltd. 2 MA— OK, Ajinomoto Fine Techno Co., Ltd. MIKIYUA PN23, PN31, PN40 J, PN— H, MY 24, MY_H, Asahi Denka Co., Ltd.
  • acid compound opium Z or boric acid esters to the composition containing (1) to (3) as a main component.
  • the acidic compound used here is a liquid or solid organic acid or inorganic acid at room temperature. Examples include, but are not limited to, sulfuric acid, acetic acid, adipic acid, tartaric acid, fumaric acid, barbituric acid, boric acid, phosphoric acid, phosphoric acid ester, pyrogallol, phenolic resin, carboxylic acid anhydride, and the like. . These acidic substances have the effect of further improving the storage stability of the composition in the storage state.
  • boric acid esters used in the present invention are liquid or solid boric acid esters at room temperature.
  • These (4) acidic compound opborate esters may be used alone or in admixture of two or more. Further, a mixture obtained by mixing these acidic substances and epoxy resins into a master batch may be added as a storage stability improver.
  • storage stability improvers include, but are not limited to, commercially available products such as Cure Duct L 1 07 N manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • the blending amount of these acidic substances opiborate is not particularly limited, but is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the fat component of (1). It is added in the range of.
  • the storage stability is further improved by the additive, but if the amount added is too large, the curability decreases.
  • core-shell type acrylic rubber fine particles used in the present invention are fine particles which are polymers having different properties in the core portion and the shell portion of the particles. Many examples of such materials are exemplified, but core-seal fine particles comprising a rubbery polymer core and a glassy polymer shell are preferred.
  • the core-shell structured particles have “elasticity” in the core portion and “hardness” in the shell portion, and do not dissolve in the liquid resin.
  • the addition of the core-shell type acrylic rubber fine particles can impart high temperature, low adhesive strength and thermal shock resistance at low temperature after curing, and can suppress uncured separation.
  • the core part is produced by polymerizing a polymerizable monomer.
  • this polymerizable monomer examples include n-propyl (meth) atelate, n-butyl (meth) attareido , 2-methylhexyl (meth) acrylate, n-decyl (meth) acrylate (meth) acrylate monomers, styrene, vinyl toluene, QJ-methyl styrene and other aromatic bur compounds, acrylonitrile, Cyanide butyl compounds such as metatalilonitrile, vinylidene cyanide, 2-hydroxykistil (meth) attalylate, 3-hydroxyoxypuccinole (meth) acrylate, 2-hydroxy chinenolev fumarate, hydroxy Shibutino Levinino Leetenore, Monobutino Remareate, Butoki Shetinore Metatalylate, etc.
  • ethylene glycol di (meth) acrylate butylene glycol di (meth) acrylate, trimethylolpropane di (meta Acrylate Trimethylo Rep Reactive groups such as Pantry (meth) acrylate, Hexanediol ⁇ / Di (meth) acrylate, Hexanediol tri (meth) acrylate, Rigocetyl (meth) acrylate, Oligoethylene tri (meth) acrylate Cross-linkable monomers having two or more of them, aromatic dibule monomers such as dibenzenebenzene, triallyl trimellitic acid, triallyl isocyanate, etc., which can be used by selecting one or two or more different .
  • the core portion must be a rubbery polymer at room temperature (eg, 25 ° C.). More preferably, the obtained polymer has a glass transition point of 110 ° C. or lower.
  • a second polymerization is performed in which the polymer particles thus obtained are used as a core, and a polymer monomer is further polymerized to form a shell made of a polymer having glass properties at room temperature.
  • the polymerizable monomer used in this case can be selected from the same polymerizable monomers for obtaining the core.
  • the shell portion must be a glassy polymer at room temperature (eg, 25 ° C.).
  • the glass transition point of the obtained polymer is preferably 70 ° C. or higher. This can be determined by the molecular weight, molecular shape, crosslinking density, etc. of the polymer obtained when the selected polymerizable monomer is copolymerized.
  • Preferred examples of the polymerizable monomer used as the shell material include alkyl groups having 1 to 4 carbon atoms in the alkyl group such as ethyl (meth) acrylate, n-butyl acrylate, methyl methacrylate, butyl methacrylate, etc. ) Atarirate.
  • alkyl groups having 1 to 4 carbon atoms in the alkyl group such as ethyl (meth) acrylate, n-butyl acrylate, methyl methacrylate, butyl methacrylate, etc. ) Atarirate.
  • ethyl (meth) acrylate ethyl (meth) acrylate
  • n-butyl acrylate methyl methacrylate
  • butyl methacrylate etc.
  • methyl methacrylate is particularly preferable.
  • the particle diameter of these core seal type acryl rubber fine particles is preferably in the range of 0.05 ⁇ m to 10 m. If it is less than 0.05 m, high adhesive strength cannot be obtained, and if it exceeds 10 ⁇ m, the toughness of the cured product (the balance of the sea-island structure is lost) cannot be obtained.
  • core-shell type acryl rubber fine particles for example, F 3 51 manufactured by Nippon Zeon Co., Ltd., Metaprene S manufactured by Mitsubishi Rayon Co., Ltd., and Staffoil manufactured by Ganz Kasei Co., Ltd. (both are trade names) are commercially available.
  • the core shell type acryl rubber fine particles are not limited to these.
  • the core acryl type rubber fine particles are contained in such an amount that gives good properties to the cured adhesive composition. Specifically, it is used in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the total of (1) components. If the amount is less than 1 part by weight, sufficient reduction in adhesion force and separation uncured measures cannot be obtained, and if it exceeds 50 parts by weight, workability tends to deteriorate due to decrease in adhesion force and increase in viscosity.
  • inorganic materials such as pigments, dyes and other colorants, calcium carbonate, tanorek, silica, alumina, aluminum hydroxide and the like are used as long as the characteristics of the present invention are not impaired.
  • Additives such as fillers, flame retardants, organic fillers, plasticizers, antioxidants, antifoaming agents, force pulling agents, leveling agents, and rheo-mouth ji control agents may be blended in appropriate amounts.
  • the cured resin obtained by heat-curing the composition of the present invention is tough and has excellent characteristics, and can be used as an adhesive, casting, molding, painting, coating material and the like. Also,
  • the heat-curable one-part resin composition of the present invention is one-part, has good storage stability, rapidly cures at a low heating temperature, and forms a cured product that exhibits toughness and excellent physical properties. It is useful for bonding, casting, molding, painting, coating materials, etc. with excellent workability and reliability.
  • Compound B Hydrogenated bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
  • KBM 403 ⁇ -glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.
  • YX 8000 Hydrogenated bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
  • Thiocol L P—3 Polysulfide polymer of terminal thiol manufactured by Toray Fine Chemical Co., Ltd.
  • Polythiocol QE—340M Trifunctional aliphatic polythiol manufactured by Toray Fine Chemical Co., Ltd.
  • PETG Pentaerystole tetrakistide colloid made by Sakai Chemical Co., Ltd.
  • FXR-1080 Latent curing agent FUJI CURE manufactured by Fuji Chemical Industry Co., Ltd.
  • Triethyl borate Reagents from Tokyo Chemical Industry Co., Ltd.
  • Atarise' DOO BPF- 307 Nippon Shokubai Co., Ltd. core-shell Akurirugo arm microparticle dispersion epoxy resin (a rubber component content of 16 wt 0/0) The case where it was destroyed in a damaged state was marked as brittle (X), and the case where it was not strong was marked as strong ( ⁇ ).
  • the amount of the rubber fine particle component added (parts by weight) to the total amount of 100 parts by weight of the liquid components in the resin component (1).
  • the composition is dropped into the center of the slide glass so that it becomes a hemisphere with a diameter of 1 mm, and another glass slide is overlaid and fixed with a pinch or the like. After standing for 2 minutes, it was cured for 30 minutes in a thermostatic bath set at 80 ° C., and it was observed whether separation of uncured resin components occurred at the outer peripheral edge of the cured composition.
  • Epicoat 807 Bisphenol F type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
  • F 351 Core shell type acryl rubber fine particles manufactured by Nippon Zeon Co., Ltd.
  • the thiirane ring content in the resin component (1) was calculated by the following formula.
  • each composition was dropped on a glass slide so as to form a hemisphere, and placed in a hot air circulation type constant temperature drying oven set at 80 ° C, and the composition gelled (touch with a stirring bar etc.). The time until no fluid flows) was measured.
  • each composition was dropped on a glass slide so as to form a hemisphere and placed in a hot air circulating constant temperature drying oven set at 80 ° C to cure the composition (touch the cured product with your finger). The time until the surface tack was eliminated) was measured.
  • Example l After observing the state of the cured composition after the shear bond strength test, the cured product was shattered. From Example l, the curing time at 80 ° C. is obtained by adding a thiol compound and a thermal latent curing accelerator to a resin component having a content ratio of oxolan ring Z thiirane ring of 100. Thus, a composition excellent in low-temperature fast curability and storage stability having a storage stability of not more than 30 minutes and a storage stability of 7 days or longer at 40 ° C. was obtained.
  • the ratio of the content of the oxolan ring Z thiirane ring is 100, a blend of an acid compound and a boric acid ester in a resin component, a thiol compound, and a thermal latent curing accelerator As a result, a composition having excellent storage stability was obtained while maintaining the low temperature fast curability.
  • Example 5 in the case of a resin component in which the ratio of the content of oxolan ring / thiirane ring is 80/20 to 0/100, the curing time at 80 ° C. is 30 minutes or less, and 40 ° In C, a composition having a storage stability of 7 days or more and excellent low-temperature fast curing property and storage stability was obtained.
  • Example 5 it can be seen that there is no particular problem even if an inorganic filler is further added.
  • Example 20 Example 21 Example 22 Example 23 Resin Component (1) Compound A 100 100 100 100 100 100 Epicure QX40
  • Examples 1 6 to 23 are examples in which the type of thiol compound is changed.
  • the composition has excellent low-temperature fast curing and storage stability, with a curing time at 80 ° C of 30 minutes or less and storage stability of 40 days or more at 40 ° C. You can see that you can get things.
  • Example 24 Difficult example 24 rows 25 Example 26 Example 27
  • Example 28 Compound A 96 96 96 98 98 Resin component (1) KBM403 4 4 4 4
  • Examples 2 4 to 3 2 are examples in which the type and amount of the thermal latent curing accelerator or acidic compound / boric acid ester compound were changed. From these results, a composition having an excellent curing temperature at low temperature and storage stability, having a curing time at 80 ° C of 30 minutes or less and storage stability at 40 ° C of 7 days or more. It can be seen that
  • a resin component in which the content ratio of the oxosilane ring Z thiirane ring in the mixture of the resin component (1) is in the range of 40/6 to 10Z90, a thiol compound, a thermal latent curing accelerator, By blending fine acryl rubber fine particles and acidic compounds, it has a high shear bond strength of 15 ⁇ a or more, the curing time at 80 ° C is within 15 minutes, and at _20 ° C for more than 3 months Thus, a rosin composition having a storage stability of no segregation uncured was obtained.
  • Examples 39 and 40 it can be seen that if the content of the thiirane ring in the mixture of the resin component (1) is less than 60, rapid curability within 15 minutes cannot be achieved at 80 ° C.
  • Examples 40 and 44 when the content of the thiirane ring in the mixture of the resin component (1) is greater than 90, high shear bond strength of 15 MPa or more and good storage stability of 3 months or more cannot be achieved. I understand. Further, in Examples 41 to 44, it is found that when the core-shell type acryl rubber fine particles are not contained, separation uncured occurs.
  • Examples 45 to 47 even when the kind of the core-shell type acryl rubber fine particles is changed, it has a high shear bond strength of 15 MPa or more, a curing time at 80 ° C. is within 30 minutes, and A resin composition having a storage stability of 3 months or more at ° C and free from separation and hardening was obtained.
  • Example 48 even when the type of the core seal type acrylic rubber fine particles was changed, if the content of the thiirane ring in the mixture of the resin components (1) and (2) was greater than 90, a high shear adhesion of 15 MPa or more was obtained. It can be seen that strength and good storage stability over 3 months cannot be achieved.
  • the present invention is excellent in workability and reliability, and can be used as adhesion, sealing, casting, molding, coating, coating material, etc. in transportation equipment, electrical equipment, electronic equipment industry, etc., especially at low heating temperature It is useful as an adhesive and sealant for mounting, assembling, and electronic parts that require fast curing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A thermosetting one-component resin composition comprising: (1) a compound, or mixture of compound, containing at least one of a compound having two or more thiirane rings in each molecule thereof (A), a compound having both of a thiirane ring and an oxirane ring in each molecule thereof (B) and a compound having one or more oxirane rings and containing no thiirane ring in each molecule thereof (C), wherein the ratio of oxirane rings/thiirane rings contained is in the range of 40/60 to 10/90; (2) a thiol compound having one or more thiol group in each molecule thereof; and (3) a heat-latent curing accelerator; optionally together with (4) an acid compound and/or a boric acid ester; and (5) core/shell type acrylic rubber microparticles. This composition can be used in various usages, such as bonding, sealing, casting, molding, painting, coating, etc., excelling in low-temperature rapid curability as compared with that of conventional episulfide thermosetting one-component resin composition, and has excellent storage stability.

Description

明 細 書  Specification
加熱硬化型一液性樹脂組成物 Heat-curing one-part resin composition
技術分野 Technical field
本発明は低温での加熱による速硬化性に優れ、 かつ貯蔵安定性 （保存安定性） が 良好である一液性樹脂組成物に関するものである。  The present invention relates to a one-part resin composition that is excellent in rapid curability by heating at a low temperature and has good storage stability (storage stability).
背景技術 Background art
エポキシ樹脂の持つォキシラン環の酵素原子の全てまたは一部を硫黄原子に置き 換えたチイラン環を有する化合物はェピスルフィド榭脂として知られている。 ェピ スルフィド樹脂はエポキシ樹脂に比ベアミン化合物との低温硬化性に優れる、 耐水 性が良い、 屈折率が高い、 難燃性を有する等の特徴があることが知られている。 し かしながら従来のェピスルフィド系組成物の大部分 二液型であり、 実際の烤用直 前に樹脂成分と硬化剤成分を計量、 混合、 脱泡するなどの煩雑な工程が必要であり、 また混合後の使用可能期間が限られており、 混合ミスなどの可能性もあるため、 作 業性、 信頼性に劣るという欠点があった。 例えば特開昭 50- 124952号公報、 特開平 11— 140161号公報、 特開 2002— 173533号公報には、 ェポ キシ榭脂系組成物より低温速硬化であるェピスルフィド榭脂系組成物が示されてい るが、 これらの組成は二液性であり前述のような作業性 ·信頼性上の問題を抱えて いる。  A compound having a thiirane ring in which all or some of the enzyme atoms of the oxysilane ring of the epoxy resin are replaced with sulfur atoms is known as episulfide resin. Episulfide resins are known to have characteristics such as excellent low-temperature curability with epoxy resin compared to epoxy resins, good water resistance, high refractive index, and flame retardancy. However, most of the conventional episulfide-based compositions are two-component type, requiring complicated steps such as weighing, mixing, and defoaming the resin component and the curing agent component immediately before actual use. In addition, since the usable period after mixing is limited and there is a possibility of mixing errors, it has the disadvantage of being inferior in workability and reliability. For example, JP-A-50-124952, JP-A-11-140161, and JP-A-2002-173533 show an episulfide resin composition that is faster curing at low temperature than an epoxy resin composition. However, these compositions are two-component and have the above-mentioned problems in workability and reliability.
この問題を解決する手法として、 常温ではェピスルフィ ド樹脂と反応せず、 加熱 等の刺激によって反応性を示す、 いわゆる潜在性硬化剤を用いることによって前述 のような二液型組成物の問題を解決した一液型組成物を得ることができることが知 られている。 例えば特開平 4— 202523号公報にはェピスルフィド樹脂を含む 樹脂に硬化剤としてカルボン酸含有化合物と熱潜在性触媒を用いて一液化した具体 例が記載されている。 しかしながらこの組成物は硬化時間 （焼付時間） に 140°C で 30分を要するため、 より低温 ·短時間の加熱条件で硬化可能なェビスルフィ ド 系加熱硬化型一液性組成物が望まれている。 特開 2004— 142133号公報に はェピスルフィド榭脂を含む樹脂に硬化剤としてフエノールやジシアンジアミ ドを 添加した具体例が記載されているが、 貯蔵安定性については記載がなく、 また硬化 温度も 170°Cを要し低温速硬化性を示すものではない。 特許 3253919号公 報、 特許 3540926号公報、 特開 2001— 342253号公報には潜在性硬 化剤を用いることでェピスルフィ ド樹脂を用 、た加熱硬化型一液性樹脂組成物が可 能であるとされているが、 具体的にどの硬化剤をどの程度用いれば良好な低温速硬 化性と貯蔵安定性が得られるか具体的事例が記載されていない。 As a method to solve this problem, the above-mentioned two-component composition problem is solved by using a so-called latent curing agent that does not react with episulfide resin at room temperature but shows reactivity by stimulation such as heating. It is known that a one-component composition can be obtained. For example, Japanese Patent Application Laid-Open No. 4-202523 describes a specific example in which a resin containing an episulfide resin is made into one component using a carboxylic acid-containing compound and a thermal latent catalyst as a curing agent. However, since this composition requires a curing time (baking time) of 30 minutes at 140 ° C, an Ebisulfide-based thermosetting one-component composition that can be cured under lower temperature and shorter heating conditions is desired. . Japanese Patent Application Laid-Open No. 2004-142133 describes a specific example in which phenol or dicyandiamide is added as a curing agent to a resin containing episulfide resin, but there is no description about storage stability, and curing is not possible. The temperature also requires 170 ° C and does not exhibit low temperature rapid curability. Patent No. 3253919, Patent No. 3540926, and Japanese Patent Application Laid-Open No. 2001-342253 can use a thermosetting type one-component resin composition using an episulfide resin by using a latent hardener. However, there is no specific example describing which curing agent is used and how much it can achieve good low temperature fast curing and storage stability.
発明の開示 Disclosure of the invention
発明の目的 Object of the invention
本発明の目的は、 接着、 封止、 注型、 成型、 塗装、 コーティング等様々な用途に 使用が可能であり、 従来のェピスルフィ ド系加熱硬化型一液性樹脂組成物より低温 速硬化性に優れ、 かつ良好な貯蔵安定性を有するェピスルフィド含有加熱硬化型一 液性樹脂組成物を提供することにある。  The object of the present invention is to be used for various applications such as adhesion, sealing, casting, molding, painting, coating, etc., and it can be cured at lower temperature and faster than conventional episulfide-based thermosetting one-component resin compositions. An object of the present invention is to provide an episulfide-containing heat-curable one-component resin composition having excellent and good storage stability.
本発明の更なる目的は、 低温での加熱による速硬化性に優れ、 高接着力を有し、 加熱硬化時に分離未硬化を起こさない、 貯蔵安定性 （保存安定性） が良好である一 液性樹脂組成物を提供することにある。  A further object of the present invention is that the liquid is excellent in rapid curability by heating at a low temperature, has high adhesive force, does not cause separation and uncuring at the time of heat curing, and has good storage stability (storage stability). It is in providing a conductive resin composition.
発明の要約 Summary of invention
本発明は、 第 1に、 （A) 分子内に 2つ以上のチイラン環を含む化合物、 （B) 分子内に 1つ以上のチイラン環と 1つ以上のォキシラン環とを含む化合物および (C) 分子内に 1つ以上のォキシラン環を含み、 チイラン環を含まない化合物から なる群から選ばれ、 かつォキシラン環 Zチイラン環の割合 （即ちォキシラン環の含 有数 Zチイラン環の含有数の比） が 80Z20〜0/100である化合物もしくは 混合物、 （2) 分子内にチオール基を 1つ以上有するチオール化合物、 および ( 3 ) 熱潜在性硬化促進剤を必須成分とする加熱硬化型一液性樹脂組成物である。 本発明は、 第 2に、 前記化合物 （Α) または/および （Β) 1 ビスフエノール 骨格を有するエポキシ化合物の芳香環の炭素一炭素不飽和結合を水素化した水添ビ スフエノール型エポキシ化合物であって、 かつ、 水添ビスフエノール型エポキシ化 合物のォキシラン環の酸素原子の全てまたは一部を硫黄原子に置換したチイラン環 を含む化合物からなる第 1の加熱硬化型一液性樹脂組成物である。  The present invention provides, firstly, (A) a compound containing two or more thiirane rings in the molecule, (B) a compound containing one or more thiirane rings and one or more oxsilane rings in the molecule, and (C ) The ratio of the compound containing one or more oxilan rings in the molecule and no thiirane ring, and the ratio of oxilan ring Z thiirane ring (ie the ratio of the number of oxilan rings to the content of Z thiirane rings) A compound or mixture in which 80Z20 to 0/100, (2) a thiol compound having one or more thiol groups in the molecule, and (3) a thermosetting one-component resin comprising a thermal latent curing accelerator as an essential component It is a composition. The second aspect of the present invention is a hydrogenated bisphenol type epoxy compound obtained by hydrogenating a carbon-carbon unsaturated bond of an aromatic ring of an epoxy compound having a bisphenol skeleton. And a first thermosetting one-component resin composition comprising a compound containing a thiirane ring in which all or some of the oxygen atoms of the oxysilane ring of the hydrogenated bisphenol type epoxy compound are substituted with sulfur atoms. is there.
本発明は、 第 3に、 前記化合物 （C) が 2つ以上のォキシラン環を有する化合物 である第 1または第 2の加熱硬化型一液性樹脂組成物である。 Thirdly, the present invention provides a compound in which the compound (C) has two or more oxosilane rings. The first or second heat-curable one-component resin composition.
本発明は、 第 4に、 前記 （1) 成分のォキシラン環 チイラン環の割合が 40/ 60〜10ノ90である第 1〜第 3のいずれかの加熱硬化型一液性樹脂組成物であ る。  Fourthly, the present invention provides the heat-curable one-component resin composition according to any one of the first to third, wherein the ratio of the (1) component oxolan ring and thiirane ring is 40/60 to 90 ° 90. The
本発明は、 第 5に、 さらに （4) 酸性化合物おょぴ Zまたはホウ酸エステルを含 有する第 1〜第 4のいずれかの加熱硬化型一液性樹脂組成物である。  Fifth, the present invention is the heat-curable one-component resin composition according to any one of the first to fourth, further comprising (4) an acidic compound Opop Z or a borate ester.
本発明は、 第 6に、 さらに （5) コアシヱル型アクリルゴム微粒子を含有する第 1〜第 5のいずれかの加熱硬化型一液性樹脂組成物である。  Sixthly, the present invention is the heat-curable one-component resin composition according to any one of the first to fifth, further comprising (5) core-seal type acrylic rubber fine particles.
本発明は、 第 7に、 各成分の配合割合が、 （1) 成分 100重量部に対して、 (3) 成分が 0. 1〜30重量部、 (4) 成分が 0. 01〜10重量部、 （5) 成 分が 1〜50重量部であり、 かつ、 （2) 成分の量が （1) 成分中のチイラン環お よびォキシラン環の合計に対してチオール当量比で 0. 01〜0. 5である第 6の 加熱硬化型一液性樹脂組成物である。  In the present invention, seventhly, the blending ratio of each component is (1) 100 parts by weight of the component, (3) 0.1 to 30 parts by weight of the component, and (4) 0.01 to 10 parts by weight of the component. Parts, (5) component is 1 to 50 parts by weight, and (2) the amount of the component is (1) the thiol equivalent ratio with respect to the total of thiirane ring and oxysilane ring in the component is 0.01 to A sixth heat-curable one-component resin composition of 0.5.
本発明は、 第 8に、 前記 （3) 熱潜在性硬化促進剤が、 固体分散型アミンァダク ト系潜在性硬化促進剤である第 1〜第 7のいずれかの加熱硬化型一液性樹脂組成物 である。  Eighthly, the present invention provides the heat-curable one-component resin composition according to any one of the first to seventh, wherein (3) the thermal latent curing accelerator is a solid-dispersed amine acid-based latent curing accelerator. It is a thing.
本発明は、 第 9に、 固体分散型アミンァダクト系潜在性硬化促進剤が、 尿素型ァ ダクト系の熱潜在性硬化促進剤である第 8の加熱硬化型一液性樹脂組成物である。 本発明は、 第 10に、 前記 （5) コアシェル型アクリルゴム微粒子のコア部分の ガラス転移点が一 10°C以下のゴム状ポリマーであって、 かつシェル部分がガラス 転移点が 70 °C以上のガラス状ポリマーである第 6〜第 9のいずれかの加熱硬化型 一液性樹脂組成物である。  The ninth aspect of the present invention is the eighth thermosetting one-part resin composition, wherein the solid dispersion type amine adduct system latent curing accelerator is a thermal latent curing accelerator of urea type adduct system. Tenthly, the present invention relates to (5) a rubbery polymer having a glass transition point of 10 ° C. or less at the core portion of the core-shell type acrylic rubber fine particles, and the shell portion has a glass transition point of 70 ° C. or more. The heat-curable one-component resin composition according to any one of the sixth to ninth glass-like polymers.
本発明は、 第 1 1に、 第 1〜第 10のいずれかの加熱硬化型一液性樹脂組成物を 硬化処理することによって得られる樹脂組成物である。  The present invention, first, is a resin composition obtained by curing the heat-curable one-component resin composition according to any one of the first to tenth.
発明の効果 The invention's effect
本発明の加熱硬化型樹脂組成物は一液性であり、 貯蔵安定性が良好で、 低い加熱 温度により急速に硬化し強靭で優れた物性を.示す硬化物を形成するため、 作業性と 信頼性に優れた接着、 注型、 成型、 塗装、 コーティン材等としての使用が可能であ る。 The thermosetting resin composition of the present invention is one-part, has good storage stability, is rapidly cured at low heating temperature, and has a tough and excellent physical property. Can be used as adhesive, casting, molding, painting, coating material, etc. The
特に前記 （5) および （6) 成分を配合した組成物は、 さらに低温速硬化性に優 れ、 高接着力を有し、 加熱硬化時に分離未硬化を起こさず、 かつ貯蔵安定性 （保存 安定性） に一層優れているという効果を示す。 '  In particular, the composition comprising the components (5) and (6) is further excellent in low-temperature fast curability, has high adhesive strength, does not cause separation and uncuring during heat curing, and is stable in storage (storage stable). The effect that it is more excellent in property. '
発明の実施の形態 BEST MODE FOR CARRYING OUT THE INVENTION
以下に、 本発明について詳細に説明する。  The present invention is described in detail below.
(1) チイラン環を含む榭脂成分  (1) Oil component containing thiirane ring
本発明に使用されるチイラン環を含む化合物 （A) は、 分子内に 2つ以上のチイ ラン環を含む化合物であれば良い。 また、 チイラン環を含む化合物 （B) は、 分子 内にチイラン環とォキシラン環の両方を 1つ以上含む化合物であれば良い。 なお、 前記チイラン環を含む化合物 （A) または （B) は、 ォキシラン環とチイラン環以 外の官能基を有していても良い。 その具体例としては例えばヒドロキシル基、 ビニ ル基、 ァセタール基、 エステル基、 カルボニル基、 アミ ド基、 アルコキシシリル基 等である。 さらに、 前記チイラン環を含む化合物 （A) または （B) は、 それぞれ 単独、 あるいは 2種以上を混合して使用することができる。  The compound (A) containing a thiirane ring used in the present invention may be a compound containing two or more thiirane rings in the molecule. Further, the compound (B) containing a thiirane ring may be a compound containing at least one thiirane ring and one oxilan ring in the molecule. In addition, the compound (A) or (B) containing the thiirane ring may have a functional group other than the oxysilane ring and the thiirane ring. Specific examples thereof include a hydroxyl group, a vinyl group, an acetal group, an ester group, a carbonyl group, an amide group, and an alkoxysilyl group. Furthermore, the compound (A) or (B) containing the thiirane ring may be used alone or in admixture of two or more.
本発明に使用されるチイラン環含有化合物は各種方法で製造される。 例えばヒド ロキシメルカプタンの熱加水分解、 1， 2—クロロチオールの弱アルカリ溶液での 処理、 エチレン性不飽和エーテルの硫黄またはポリサルフィドジアルキルのような 化合物との処理が挙げられる。  The thiirane ring-containing compound used in the present invention is produced by various methods. Examples include thermal hydrolysis of hydroxymercaptan, treatment with 1,2-chlorothiol with a weak alkaline solution, treatment with ethylenically unsaturated ethers such as sulfur or polysulfide dialkyl.
また、 エポキシ化合物を原料としてエポキシ環中の酸素原子の全部あるいは一部 を硫黄原子に置換してチイラン環含有化合物を得る方法は既に知られている。 この ような化合物はェピスルフィ ド、 またはェピスルフィ ド樹脂とも呼ばれる。 例示す ると、 J. P o l ym. S c i . P o l ym. P h y s . ， 1 7， 329 (1 97 9) に記載のエポキシ化合物とチォシアン酸塩を用いる方法や、 J. O r g. Ch em. , 26， 3467 (1 96 1) に記載のエポキシ化合物とチォ尿素を用いる 方法、 特開 2000— 351 829号公報、 特開 2001— 342253号公報に 示される方法等が挙げられるがこれらに限定されるものではない。  In addition, a method for obtaining a thiirane ring-containing compound by replacing all or part of oxygen atoms in the epoxy ring with sulfur atoms using an epoxy compound as a raw material is already known. Such compounds are also called episulfide or episulfide resin. For example, a method using an epoxy compound and thiocyanate described in J. Pol ym. S ci. Pol ym. Ph s., 17, 329 (1997), J. Org Chem., 26, 3467 (1 96 1), a method using an epoxy compound and thiourea, a method disclosed in JP 2000-351 829 A, and JP 2001-342253 A, etc. It is not limited to these.
以上に詳述した、 チイラン環含有化合物の具体例としては、 例えば 2, 2—ビス (4 - (2, 3ーェピチォプロポキシ) フェニル) プロパン、 ビス (4 - (2, 3 —ェピチォプロポキシ） フエニル） メタン、 1， 6—ジ （2, 3—ェピチォプロボ キシ） ナフタレン、 1, 1, 1ートリス一 (4 - (2， 3—ェピチォプロポキシ） フエニル) ェタン、 2 , 2 -ビス (4一 (2, 3—ェピチォプロポキシ） シクロへ キシル） プロパン、 ビス (4 - (2, 3ーェピチォプロボキシ) シク口へキシル) メタン、 1 , 1, 1ートリス一 (4 - (2, 3ーェピチォプロポキシ) シクロへキ シノレ） ェタン、 1， 5—ペンタンジォーノレの 2， 3—ェピチオシクロへキシノレ） ェ 一テル、 1， 6—へキサンジオールのジ (3, 4ーェポチォォクチル) エーテル等 が挙げられるが、 これらに限定されるものではない。 Specific examples of the thiirane ring-containing compound described in detail above include, for example, 2, 2-bis (4-(2,3-epitipropoxy) phenyl) propane, bis (4-(2,3 -epitipropoxy) phenyl) methane, 1,6-di (2,3-epitipropoxy) naphthalene, 1, 1, 1-tris (4- (2,3-Epiciopropoxy) phenyl) ethane, 2,2-bis (4 (2,3-Epiciopropoxy) cyclohexyl) propane, bis ( 4-(2,3-epeticopropoxy) hexyl) methane, 1, 1, 1 tris (4- (2, 3-epeticopropoxy) cyclohexinole) ethane, 1, 5 -2,3-Epithiocyclohexenole of pentanediol, and di (3,4-epoxyoctyl) ether of 1,6-hexanediol. It is not something.
本発明に使用される 1分子中にチイラン環とォキシラン環の両方を持つ化合物 A compound having both a thiirane ring and an oxysilane ring in one molecule used in the present invention
(B) は、 エポキシ化合物を原料としてエポキシ環中の酸素原子を硫黄原子に交換 してェピスルフィ ド樹脂を合成するときに、 ェピスルフィド化試薬の使用量或いは 反応条件を調整することによって得ることができる。 また、 各種精製方法で分離し て得た部分ェピスルフィド化物を全ェピスルフィド化物と混合しても得ることがで さる。 (B) can be obtained by adjusting the amount of episulfide reagent used or the reaction conditions when an epoxy compound is used as a raw material to synthesize an episulfide resin by exchanging oxygen atoms in the epoxy ring with sulfur atoms. . It can also be obtained by mixing the partial episulfide obtained by separation by various purification methods with the total episulfide.
本発明においてより好ましく使用されるチイラン環含有化合物は、 特開 2000 -351 829号公報に示されるような、 ビスフエノール骨格を有するエポキシ化 合物の芳香環の炭素一炭素不飽和結合を水素化 （水添） した、 水素化ビスフエノー ルェポキシ榭脂が有するォキシラン環の酸素原子の全てまたは一部を硫黄原子に置 換したチイラン環を含む化合物、 特に水素化ビスフエノール A骨格を含むチイラン 環含有化合物であり、 この化合物を用いた組成物は特に硬化性、 作業性と貯蔵安定 性に優れる。  The thiirane ring-containing compound more preferably used in the present invention is a hydrogenation of a carbon-carbon unsaturated bond of an aromatic ring of an epoxy compound having a bisphenol skeleton as disclosed in JP-A-2000-351 829. (Hydrogenated) compounds containing thiirane rings in which all or part of the oxygen atoms of the oxysilane ring of hydrogenated bisphenol epoxy resin have been replaced with sulfur atoms, particularly thiirane ring-containing compounds containing hydrogenated bisphenol A skeleton The composition using this compound is particularly excellent in curability, workability and storage stability.
本発明に使用される分子内に 1つ以上のォキシラン環を含有し、 チイラン環を含 まない化合物 （C) は、 一般的にエポキシ化合物と呼ばれるものである。 その具体 例としてはビスフエノール Aとェピクロルヒドリンから誘導されるジグリシジルェ 一テル、 およびその誘導体、 ビスフエノール Fとェピクロルヒ ドリンから誘導され るジグリシジルエーテル、 およびその誘導体等の所謂ェピービス型液状エポキシ樹 脂、 脂肪族 ·芳香族アルコールとェピクロルヒドリンから誘導されるグリシジルェ 一テル、 多塩基酸とェピクロルヒ ドリンから誘導されるグリシジルエステル、 およ びその誘導体、 水添ビスフヱノール Aとェピクロルヒ ドリンから誘導されるグリシ ジルエーテル、 3， 4一エポキシ一 6—メチノレシク口へキシノレメチノレー 3 , 4ーェ ポキシ一 6—メチノレシク口へキサン力ノレボキシレート、 ビュルシク口へキセン才キ サイ ド、 ビス （3， 4—エポキシ一 6—メチルシクロへキシルメチル） アジペート 等の脂肪族環状エポキシ、 およびその誘導体、 5, 5 ' —ジメチルヒダントイン型 エポキシ樹脂.、 トリグリシジルイソシァネート、 イソプチレンから誘導される置換 型エポキシ、 y—グリシドキシプロピルトリメ トキシシランなどの分子内にアルコ キシシリル基を含む化合物等が拳げられるがこれらに限定されるものではない。 市販されているェポキシ榭脂製品としては例えばジャパンェポキシレジン株式会 社製のェピコート 828、 1 001、 801、 806、 807、 1 52、 604、 630、 871、 YX8000、 ΥΧ8034、 ΥΧ4000、 カージユラ Ε 10 Ρ、 大日本インキ工業株式会社製のェピクロン 830、 835 L V, HP 4032 D、 703、 720、 726、 HP 820、 旭電化工業株式会社製の E P 4100、 EP4000、 EP4080、 EP 4085、 EP4088、 EPU6、 EPR4 023、 EPR 1 309、 EP49— 20、 ナガセケムテックス株式会社製デナコ —ル EX41 1、 EX 3 14、 EX201、 EX21 2、 EX252、 EX 1 1 1、 EX 146、 EX 72 1、 信越化学工業株式会社製 K BM 403、 KBE402等 が挙げられるがこれらに限定されるものではない。 これらは、 それぞれ単独で用い ることも、 また二種以上を混合して用いても良い。 The compound (C) that contains one or more oxosilane rings and does not contain a thiirane ring in the molecule used in the present invention is generally called an epoxy compound. Specific examples include diglycidyl ethers derived from bisphenol A and epichlorohydrin and derivatives thereof, diglycidyl ethers derived from bisphenol F and epichlorohydrin, and derivatives thereof, so-called epibis type liquid epoxy. Resin, aliphatic · Glycidille derived from aromatic alcohol and epichlorohydrin Glycidyl ester derived from polybasic acid and epichlorohydrin, and derivatives thereof, hydrogenated bisphenol A and glycidyl ether derived from epichlorohydrin, 3,4 epoxies 6-methinoresic hexinoremethino Rhee 3, 4-oxyloxy 6-methinorexane hexanoyl hexoxylate, bulesic hexacene xylide, bis (3,4-epoxy 1-methylcyclohexylmethyl) adipate and other cyclic cyclic epoxies, and the like Derivatives, 5, 5'-dimethylhydantoin-type epoxy resin, triglycidyl isocyanate, substituted epoxy derived from isoptylene, y -glycidoxypropyltrimethoxysilane and other compounds containing an alkoxysilyl group in the molecule You can fist, but you ’re limited to these Not. Examples of commercially available epoxy resin products include Epicoat 828, 1 001, 801, 806, 807, 152, 604, 630, 871, YX8000, ΥΧ8034, ΥΧ4000, and Card Yura Ε10 manufactured by Japan Epoxy Resin Co., Ltd. Epiclon 830, 835 LV, HP 4032 D, 703, 720, 726, HP 820, manufactured by Dainippon Ink Industries, Ltd., EP 4100, EP4000, EP4080, EP 4085, EP4088, EPU6, manufactured by Asahi Denka Kogyo Co., Ltd. EPR4 023, EPR 1 309, EP49—20, Nagase ChemteX Corporation Denacoll — EX41 1, EX 3 14, EX201, EX21 2, EX252, EX 1 1 1, EX 146, EX 72 1, Shin-Etsu Chemical Co., Ltd. Examples include, but are not limited to, KBM 403 and KBE402 manufactured by the company. These may be used alone or in combination of two or more.
なお、 上記した （A) 〜 （C) の各成分は、 ォキシラン環とチイラン環以外の官 能基を有しても良い。 このような官能基の例としては、 ヒ ドロキシル基、 ビニル基、 ァセタール基、 エステル基、 カルボニル基、 アミ ド基、 アルコキシシリル基等があ る。  In addition, each component of the above (A) to (C) may have a functional group other than the oxosilane ring and the thiirane ring. Examples of such functional groups include a hydroxyl group, a vinyl group, an acetal group, an ester group, a carbonyl group, an amide group, and an alkoxysilyl group.
本発明の糸且成物における （A) 〜 （C) で示される化合物は、 分子内に 2つ以上 のチイラン環を含む化合物 （A) 、 または分子内にチイラン環とォキシラン環の両 方を 1つ以上含む化合物 （B) 、 または分子内にォキシラン環を有し、 チイラン環 を含まない化合物 （C) のうち 1種以上を含み、 ォキシラン環/チイラン環の割合 が 80/20〜0Zl 00である前記化合物もしくは前記化合物の混合物である。 チイラン環の割合がこの範囲より小さくなると、 充分な貯蔵安定性を保ちつつ速硬 化性を発現することができない。 より好ましい含有数の割合は、 ォキシラン環 Ζチ ィラン環の割合が 60 40〜0ノ 100であり、 より好ましくは 40ノ60〜1 0Ζ98であり、 更に好ましくは 40/60〜2 90である。 ォキシラン環を含 む化合物が少量存在すると潜在性硬化剤の溶解性が向上し結果的に硬化速度により 向上する。 The compounds represented by (A) to (C) in the yarn composition of the present invention are compounds (A) containing two or more thiirane rings in the molecule, or both a thiirane ring and an oxysilane ring in the molecule. Compound (B) containing one or more, or one or more of compounds (C) having an oxysilane ring in the molecule and not containing a thiirane ring, and the ratio of the oxysilane ring / thiirane ring Is 80 / 20-0Zl 00 or a mixture of said compounds. When the proportion of the thiirane ring is smaller than this range, it is impossible to develop fast curing while maintaining sufficient storage stability. The ratio of the content is more preferably 40 to 0 to 100, more preferably 40 to 100 to 98, and still more preferably 40/60 to 290. The presence of a small amount of a compound containing an oxysilane ring improves the solubility of the latent curing agent, resulting in an improvement in the curing rate.
(2) チオール化合物  (2) Thiol compounds
本発明に使用されるチオール化合物は、 分子内にチオール基を 1つ以上有するチ オール化合物であれば良い。 具体的に例示すると、 3—メ トキシプチル 3—メルカ プトプロピオネート、 2—ェチルへキシル 3—メルカプトプロピオネート、 トリデ シル 3—メルカプトプロピオネート、 トリメチロールプロパントリスチォプロピオ ネート、 ペンタエリストールテトテキスチォプロピオネート、 メチルチオグリコレ 一ト、 2—ェチルへキシルチオグリコレート、 エチレングリコールビスチォダルコ レート、 1， 4—プタンジォ一/レビスチォグリコレート、 トリメチローノレプロパン トリスチォグリコレート、 ペンタエリストールテトラキスチォグリコレート、 ジ (2—メノレカプトェチル） エーテル、 1一ブタンチォーノレ、 1—へキサンチオール、 シクロへキシノレメノレカブタン、 1, 4—ブタンジチォ一ノレ、 3—メ カプト 2—プ タノール、 γ—メルカプトプロピルトリメ トキシシラン、 ベンゼンチオール、 ベン ジルメルカプタン、 1, 3， 5—トリメルカプトメチルベンゼン、 1， 3, 5—ト リメルカプトメチルー 2, 4, 6 _トリメチルベンゼン、 末端チオール基含有ポリ エーテル、 末端チオール基含有ポリチォエーテル、 エポキシ化合物と硫化水素との 反応によって得られるチオール化合物、 ポリチオール化合物とエポキシ化合物との 反応によって得られる末端チオール基を有するチオール化合物等が挙げられるがこ れらに限定されるものではない。  The thiol compound used in the present invention may be a thiol compound having one or more thiol groups in the molecule. Specific examples include 3-methoxyptyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, trimethylolpropane tristhiopropionate, pentaerythritol. Stoltetotextiopropionate, Methylthioglycolate, 2-Ethylhexylthioglycolate, Ethylene glycol bisthiodalcolate, 1,4-Ptandio / Lebisthioglycolate, Trimethylololepropane Tristhioglycolate , Pentaerythroletetrakisthioglycolate, di (2-menolecaptoethyl) ether, 1-butanthionole, 1-hexanethiol, cyclohexenoremenolecabutane, 1,4-butanedithionole, 3-mecapto 2-Panol, γ-Me Lucaptopropyltrimethoxysilane, benzenethiol, benzylmercaptan, 1,3,5-trimercaptomethylbenzene, 1,3,5-trimercaptomethyl-2,4,6_trimethylbenzene, terminal thiol group-containing polyether Terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound and hydrogen sulfide, thiol compound having terminal thiol group obtained by reaction of polythiol compound and epoxy compound, etc. It is not limited.
市販されているチオールィ匕合物の製品としては、 例えばジャパンエポキシレジン株 式会社製のェポメート QX 1 1、 QX 12、 ェピキュア QX30、 QX40、 QX6 Examples of commercially available thiol compound products are Epomate QX 1 1, QX 12, Epicure QX30, QX40, QX6 manufactured by Japan Epoxy Resin Co., Ltd.
0、 QX900、 カプキュア CP 3— 800、 淀化学株式会社製の O T G、 EGTG、 TMTG、 PETG、 3— MPA、 TMTP、 PETP、 東レファインケミカル株式 会社製チォコール LP— 2、 LP— 3、 ポリチオール QE— 340M、 信越化学工業 株式会 ¾ ΚΒΜ803等が挙げられるがこれらに限定されるものではない。 これら は、 それぞれ単独で用いることも、 また二種以上を混合して用いても良い。 0, QX900, Capcure CP 3-800, OTG, EGTG, Sakai Chemical Co., Ltd. TMTG, PETG, 3-MPA, TMTP, PETP, Toray Fine Chemical Co., Ltd. Thiokol LP-2, LP-3, Polythiol QE-340M, Shin-Etsu Chemical Co., Ltd. Absent. These may be used alone or in admixture of two or more.
より好ましいチオール化合物は、 貯蔵安定性の面からは塩基性不純物の極力少な いものである。 また硬化物の耐熱性の面からは官能基数が 2以上のチオール化合物 および分子内に芳香環を含むチオール化合物がより好ましい。  More preferable thiol compounds are those having as few basic impurities as possible from the viewpoint of storage stability. From the viewpoint of heat resistance of the cured product, a thiol compound having 2 or more functional groups and a thiol compound containing an aromatic ring in the molecule are more preferable.
本発明の組成物におけるチオール化合物 （2) の配合量については、 特に範囲を 限定するものではないが、 好ましくは前記 （1) 記載の樹脂成分におけるチイラン 環おょぴォキシラン環の合計に対してチオール当量比で 0. 005〜1. 5、 より 好ましくは 0. 01〜0. 5の範囲内で加えることができる。 さらに好ましくはォ キシラン環 Ζチイラン環の割合が 80 20〜50ノ50の場合は、 チイラン環お ょぴォキシラン環の合計に対してチオール当量比で 0. 5〜1. 4の範囲、 ォキシ ラン環 Ζチイラン環の割合が 50/50を超え 0Z100までの場合はチイラン環 およびォキシラン環の合計に対してチオール当量比で 0. 01〜0. 7の範囲であ る。 上記の範囲内でチオール化合物を加えると、 より硬化速度、 貯蔵安定性が向上 でき、 また、 硬化物の強度や耐熱性のバランスに優れた組成物を得ることができる。  The blending amount of the thiol compound (2) in the composition of the present invention is not particularly limited, but is preferably based on the total of thiirane ring and opoxysilane rings in the resin component described in (1) above. The thiol equivalent ratio can be added in the range of 0.005 to 1.5, more preferably 0.01 to 0.5. More preferably, when the ratio of oxysilane ring to thiirane ring is 80 20 to 50 50, the thiol equivalent ratio is in the range of 0.5 to 1.4 with respect to the total of thiirane ring and opioxylan ring. When the ratio of ring thiirane ring exceeds 50/50 and reaches 0Z100, the thiol equivalent ratio is in the range of 0.01 to 0.7 with respect to the total of thiirane ring and oxsilane ring. When the thiol compound is added within the above range, the curing rate and storage stability can be further improved, and a composition excellent in the balance of strength and heat resistance of the cured product can be obtained.
(3) 熱潜在性硬化促進剤  (3) Thermal latent curing accelerator
本発明に使用される熱潜在性硬化促進剤とは、 室温ではエポキシ樹脂に対し活性 を持たず、 加熱することにより溶解、 分解、 転移反応などにより活性化し促進剤と して機能する化合物である。 例えば室温で固体のイミダゾール化合物およびその誘 導体、 各種ァミンと酸との塩、 固体分散型アミンァダクト系潜在性硬化促進剤等が 挙げられるがこれらに限定されるものではない。 さらに、 固体分散型アミンァダク ト系潜在性硬化促進剤の例としては、 ァミン化合物とエポキシ化合物との反応生成 物 (ァミン一エポキシァダクト系) ゃァミン化合物とイソシァネート化合物または 尿素化合物との反応生成物 （尿素型ァダクト系） 、 等が挙げられるがこれらに限定 されるものではない。 これらの熱潜在性硬化促進剤のうち好ましくは固体分散型ァ ミンァダクト系潜在性硬化剤、 より好ましくは尿素型ァダクト系の熱潜在性硬化剤 が、 本発明の組成物の低い硬化温度と貯蔵安定性に優れた効果を発揮する。 これら 熱潜在性硬化剤の配合量については特に範囲を限定するものではないが、 好ましく は前記 （1) の樹脂成分 100重量部に対し 0. 1〜30重量部の範囲で添加され る。 硬化促進剤が少ないと硬化が遅く、 多すぎると貯蔵安定性が悪くなる。 The heat latent curing accelerator used in the present invention is a compound that does not have an activity with respect to an epoxy resin at room temperature, and is activated by dissolution, decomposition, transition reaction, etc. when heated, and functions as an accelerator. . Examples include, but are not limited to, imidazole compounds that are solid at room temperature and derivatives thereof, salts of various amines and acids, and solid dispersion type amine adduct-based latent curing accelerators. In addition, examples of solid dispersion type amine adduct latent curing accelerators include reaction products of amine compounds and epoxy compounds (amine-epoxy adducts) reaction products of amine compounds and isocyanate compounds or urea compounds. (Urea-type adduct system) and the like, but are not limited thereto. Of these thermal latent curing accelerators, solid dispersion type amine adduct type latent curing agents are preferred, and urea type adduct type thermal latent curing agents are more preferred. However, the composition of the present invention exhibits an excellent effect on the low curing temperature and storage stability. The blending amount of these thermal latent curing agents is not particularly limited, but is preferably added in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the resin component (1). When there are few hardening accelerators, hardening will be slow, and when too much, storage stability will worsen.
前記熱潜在性硬化促進剤で市販されている製品としては、 例えば四国化成工業株 式会社製のィミダゾール化合物 2 P Z、 2 PHZ、 2 P4MHZ、 C 1 7 Z、 2M Z— A、 2E4MZ— CNS、 2 MA— O K、 味の素ファインテクノ株式会社製ァ ミキユア PN23、 PN31、 PN40 J、 PN— H、 MY 24、 MY_H、 旭電 化株式会社製 EH— 3293 S、 EH_3366 S、 EH— 36 1 5 S、 EH— 4 070 S、 EH— 4342 S、 EH— 373 1 S、 旭化成ケミカルズ株式会社製ノ バキュア HX— 3742、 HX- 3721、 富士化成工業株式会社製 F X E— 10 00、 FXR— 1030、 FXR— 1080、 F X R— 1 1 10などが挙げられる がこれらに限定されるものではない。  Examples of products marketed as the thermal latent curing accelerator include imidazole compounds 2 PZ, 2 PHZ, 2 P4MHZ, C 1 7 Z, 2M Z-A, 2E4MZ- CNS, manufactured by Shikoku Kasei Kogyo Co., Ltd. 2 MA— OK, Ajinomoto Fine Techno Co., Ltd. MIKIYUA PN23, PN31, PN40 J, PN— H, MY 24, MY_H, Asahi Denka Co., Ltd. EH— 3293 S, EH_3366 S, EH— 36 1 5 S, EH— 4 070 S, EH— 4342 S, EH— 373 1 S, Asahi Kasei Chemicals Corporation NOVACURE HX— 3742, HX-3721, Fuji Chemical Industry Co., Ltd. FXE—1000, FXR—1030, FXR—1080 FXR— 1 1 10 and the like, but are not limited to these.
(4) 酸性化合物 Zホウ酸エステル  (4) Acidic compound Z borate
本発明では、 前記 （1) 〜 (3)·を主成分とする組成物に、 さらに （4) 酸性化 合物おょぴ Zまたはホウ酸エステル類を添加することが可能であり、 好ましい。 こ こで用いられる酸性化合物は、 室温で液状または固体の有機酸、 または無機酸であ る。 例えば硫酸、 酢酸、 アジピン酸、 酒石酸、 フマル酸、 バルビツール酸、 ホウ酸、 リン酸、 リン酸エステル、 ピロガロール、 フ ノール樹脂、 カルボン酸無水物等が 挙げられるがこれらに限定されるものではない。 これら酸性物質は組成物の保存状 態での貯蔵安定性をさらに向上させる効果がある。  In the present invention, it is possible to further add (4) acid compound opium Z or boric acid esters to the composition containing (1) to (3) as a main component. The acidic compound used here is a liquid or solid organic acid or inorganic acid at room temperature. Examples include, but are not limited to, sulfuric acid, acetic acid, adipic acid, tartaric acid, fumaric acid, barbituric acid, boric acid, phosphoric acid, phosphoric acid ester, pyrogallol, phenolic resin, carboxylic acid anhydride, and the like. . These acidic substances have the effect of further improving the storage stability of the composition in the storage state.
また、 本発明に使用されるホウ酸エステル類は、 室温で液状または固体のホウ酸 エステルである。 例えばトリメチルボレート、 トリェチルポレート、 トリー n—プ 口ピルボレート、 トリイソプロピルボレート、 トリー n—ブチルポレート、 トリぺ ンチルボレート、 トリアリノレポレート、 トリへキシルボレート、 トリシクロへキシ ルポレート、 トリオクチルポレート、 トリノニルボレート、 トリデシルポレート、 トリ ドデシノレボレート、 トリへキサデシノレボレート、 トリォクタデシノレボレート、 トリス （2—ェチルへキシロキシ） ボラン、 ビス （1， 4， 7, 1 0—テトラォキ サウンデルシル） （1， 4， 7 , 1 0， 1 3—ペンタォキサテトラデシル) ( 1 , 4 , 7—トリオキサウンデルシル） ボラン、 トリベンジルボレート、 トリフエニル ボレート、 トリ一 o—トリボレート、 トリー m—トリルポレート、 トリエタノール ァミンポレート等が挙げられるがこれに限定されるものではない。 これらのホウ酸 エステルは硬化促進剤表面と反応し硬化促進剤表面の塩基性をプロックする役割を 果たし組成物の保存状態での貯蔵安定性をさらに向上させる効果がある。 Further, the boric acid esters used in the present invention are liquid or solid boric acid esters at room temperature. For example, trimethylborate, triethylporate, tri-n-pyroborate, triisopropylborate, tri-n-butylporate, tripentylborate, trialinoreporate, trihexylborate, tricyclohexylporate, trioctylporate, trinonylborate, Tridecylporate, tridodecinoreborate, trihexadecinoreborate, trioctadecinoreborate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10) -tetraoxy (Soundelsil) (1, 4, 7, 10, 13-pentaoxatetradecyl) (1, 4, 7, 7-trioxaundersyl) Borane, tribenzyl borate, triphenyl borate, tri-o-triborate, tree m —Tolylporate, triethanolamine porate and the like are exemplified, but not limited thereto. These boric acid esters react with the surface of the curing accelerator to block the basicity of the surface of the curing accelerator, and have the effect of further improving the storage stability of the composition in the storage state.
これら （4 ) 酸性化合物おょぴホウ酸エステル類は、 それぞれ単独でも、 2種以 上を混合して使用しても良い。 またこれら酸性物質とエポキシ樹脂等を混合しマス ターバッチ化したものを保存安定性向上剤として添カ卩しても良い。 このような保存 安定性向上剤としては市販されている製品としては例えば四国化成工業株式会社製 キュアダクト L一 0 7 N等が挙げられるがこれに限定されるものではない。 これら 酸性物質おょぴホウ酸エステルの配合量については特に範囲を限定するものではな いが、 好ましくは （1 ) の榭脂成分 1 0 0重量部に対し 0 . 0 1〜1 0重量部の範 囲で添加される。 添カ卩により貯蔵安定性がさらに向上するが、 添加量が多すぎると 硬化性が低下する。  These (4) acidic compound opborate esters may be used alone or in admixture of two or more. Further, a mixture obtained by mixing these acidic substances and epoxy resins into a master batch may be added as a storage stability improver. Examples of such storage stability improvers include, but are not limited to, commercially available products such as Cure Duct L 1 07 N manufactured by Shikoku Kasei Kogyo Co., Ltd. The blending amount of these acidic substances opiborate is not particularly limited, but is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the fat component of (1). It is added in the range of. The storage stability is further improved by the additive, but if the amount added is too large, the curability decreases.
( 5 ) コアシェル型アクリルゴム微粒子  (5) Core-shell type acrylic rubber fine particles
本発明では、 前記 （1 ) 〜 （3 ) 成分、 さらに好ましくは （1 ) 〜 （4 ) 成分に 加え、 さらに （5 ) コアシェル型アクリルゴム微粒子を添加することが好ましい。 本発明で使用されるコアシヱル型アクリルゴム微粒子とは、 粒子のコアの部分と シェルの部分が異なる性質を持つ重合体である微粒子である。 このようなものとし ては多数例示されるが、 ゴム状ポリマーのコアとガラス状ポリマーのシェルからな るコアシヱル系微粒子が好ましい。 このコアシェル構造粒子は、 コア部に 「弾力 性」 を有しシェル部に 「硬質性」 を有すもので、 液状樹脂中で溶解しないものであ る。 本発明においては、 コアシェル型アクリルゴム微粒子の添加により、 硬化後の 低温での高レ、接着強さおよび耐熱衝撃性を付与し、 分離未硬化を抑制できる。 本発明で使用される好ましいコアシェル型アクリルゴム微粒子の製造においては、 まず、 コア部分を重合性モノマーを重合させることにより製造する。 この重合性モノ マーの例として n—プロピル （メタ） アタリレート、 n—ブチル （メタ） アタリレー ト、 2—ェチルへキシル (メタ） アタリレート、 n—デシル (メタ) アタリレートな どの （メタ） アタリレート系モノマー、 スチレン、 ビニルトルエン、 QJ—メチルスチ レンなどの芳香族ビュル系化合物、 アクリロニトリル、 メタタリロニトリルなどのシ アン化ビュル化合物、 シアン化ビニリデン、 2—ヒ ドロキシェチル (メタ) アタリ レ ート、 3—ヒ ドロキシプチノレ （メタ） アタリレート、 2—ヒ ドロキシェチノレフマレー ト、 ヒ ドロキシブチノレビニノレエーテノレ、 モノブチノレマレエート、 ブトキシェチノレメタ タリレートなどが挙げられさらに、 エチレングリコールジ （メタ） アタリレート、 ブ チレングリコールジ （メタ） アタリ レート、 トリメチロールプロパンジ (メタ） ァク リ レート トリメチローノレプロパントリ （メタ） アタリ レート、 へキサンジオー^/ジ (メタ) アタリレート、 へキサンジオールトリ (メタ) アタリ レート、 才リゴェチレ ンジ （メタ） アタリレート、 オリゴエチレントリ （メタ） アタリレートなどの反応性 基を 2個以上有する架橋性モノマー、 ジビエルベンゼンなどの芳香族ジビュルモノマ 一、 トリメリット酸トリアリル、 トリアリルイソシァネレートなどがあげられ、 これ らは 1種または異なる 2種以上を選択し使用できる。 In the present invention, in addition to the components (1) to (3), more preferably the components (1) to (4), it is preferable to further add (5) core-shell type acrylic rubber fine particles. The core-seal type acrylic rubber fine particles used in the present invention are fine particles which are polymers having different properties in the core portion and the shell portion of the particles. Many examples of such materials are exemplified, but core-seal fine particles comprising a rubbery polymer core and a glassy polymer shell are preferred. The core-shell structured particles have “elasticity” in the core portion and “hardness” in the shell portion, and do not dissolve in the liquid resin. In the present invention, the addition of the core-shell type acrylic rubber fine particles can impart high temperature, low adhesive strength and thermal shock resistance at low temperature after curing, and can suppress uncured separation. In the production of the preferred core-shell type acrylic rubber fine particles used in the present invention, first, the core part is produced by polymerizing a polymerizable monomer. Examples of this polymerizable monomer include n-propyl (meth) atelate, n-butyl (meth) attareido , 2-methylhexyl (meth) acrylate, n-decyl (meth) acrylate (meth) acrylate monomers, styrene, vinyl toluene, QJ-methyl styrene and other aromatic bur compounds, acrylonitrile, Cyanide butyl compounds such as metatalilonitrile, vinylidene cyanide, 2-hydroxykistil (meth) attalylate, 3-hydroxyoxypuccinole (meth) acrylate, 2-hydroxy chinenolev fumarate, hydroxy Shibutino Levinino Leetenore, Monobutino Remareate, Butoki Shetinore Metatalylate, etc. In addition, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, trimethylolpropane di (meta Acrylate Trimethylo Rep Reactive groups such as Pantry (meth) acrylate, Hexanediol ^ / Di (meth) acrylate, Hexanediol tri (meth) acrylate, Rigocetyl (meth) acrylate, Oligoethylene tri (meth) acrylate Cross-linkable monomers having two or more of them, aromatic dibule monomers such as dibenzenebenzene, triallyl trimellitic acid, triallyl isocyanate, etc., which can be used by selecting one or two or more different .
前記の重合性モノマーを重合させた重合体の分子量、 分子形状、 架橋密度により、 ゴム性状は変化する。 本発明ではコア部分は室温 （例えば 2 5 °C) でゴム状ポリマ 一でなければならない。 さらに好ましくは得られる重合体のガラス転移点が一 1 0 °C以下となることが好ましい。  The rubber properties change depending on the molecular weight, molecular shape, and crosslinking density of the polymer obtained by polymerizing the polymerizable monomer. In the present invention, the core portion must be a rubbery polymer at room temperature (eg, 25 ° C.). More preferably, the obtained polymer has a glass transition point of 110 ° C. or lower.
次に、 このようにして得られた重合体粒子をコアとし、 さらに、 重合体モノマーを 重合させて、 室温でガラス性状を有する重合体からなるシェルを形成させる第 2回目 の重合を行う。 この際用いられる重合性モノマーとしては、 前記のコアを得るための 重合性モノマーと同じものから選択し使用することができる。 ただし、 本発明では、 シェル部分は室温 （例えば 2 5 °C) でガラス状ポリマーでなければならない。 好まし くは、 得られる重合体のガラス転移点が 7 0 °C以上であることが好ましい。 これは、 選択した重合性モノマーを共重合させたときに得られる重合体の分子量、 分子形状、 架橋密度などにより決定することができる。 室温でガラス状でない場合には、 ラジカ ル重合が可能な液状樹脂中に本重合体粒子を混合してシール剤組成物とした場合、 粒 子が、 ラジカル重合性モノマーにより膨潤してしまい、 保存中に経時的に粘度が増加 し、 ゲル化してしまう。 すなわち、 貯蔵安定性が不十分になる。 Next, a second polymerization is performed in which the polymer particles thus obtained are used as a core, and a polymer monomer is further polymerized to form a shell made of a polymer having glass properties at room temperature. The polymerizable monomer used in this case can be selected from the same polymerizable monomers for obtaining the core. However, in the present invention, the shell portion must be a glassy polymer at room temperature (eg, 25 ° C.). The glass transition point of the obtained polymer is preferably 70 ° C. or higher. This can be determined by the molecular weight, molecular shape, crosslinking density, etc. of the polymer obtained when the selected polymerizable monomer is copolymerized. When it is not glassy at room temperature, when the polymer particles are mixed in a liquid resin capable of radical polymerization to form a sealant composition, the particles are swollen by the radical polymerizable monomer and stored. Viscosity increases over time during And gelled. That is, storage stability becomes insufficient.
シェル材として使用される重合性モノマーの好ましい例は、 ェチル （メタ） ァク リ レート、 n—ブチルァクリ レート、 メチルメタクリ レート、 プチルメタクリ レー ト、 などのアルキル基の炭素数が 1〜4の （メタ） アタリレートが挙げられる。 こ れらは 1種用いてもよいし、 2種以上を組み合わせて用いてもよいが、 これらの中 で特にメチルメタクリレートが好適である。  Preferred examples of the polymerizable monomer used as the shell material include alkyl groups having 1 to 4 carbon atoms in the alkyl group such as ethyl (meth) acrylate, n-butyl acrylate, methyl methacrylate, butyl methacrylate, etc. ) Atarirate. One of these may be used, or two or more may be used in combination. Among these, methyl methacrylate is particularly preferable.
また、 これらのコアシヱル型ァクリルゴム微粒子の粒径は 0 . 0 5 μ m〜 1 0 mの範囲が好ましい。 0 . 0 5 i mより小さいと高い接着強さが得られず、 1 0 μ mを超えると硬化物の強靭性 （海島構造のバランスが崩れる） が得られない。 このようなコアシェル型ァクリルゴム微粒子としては、 例えば日本ゼオン社製の F 3 5 1や三菱レイヨン社製のメタプレン Sやガンツ化成社製のスタフイロィドな ど （何れも商標名） が市販されている。 他にコアシヱル型アクリルゴム微粒子をェ ポキシ樹脂中に均一分散させた、 日本触媒製のァクリセット B P F— 3 0 7なども 市販されている。 ただしコアシェル型ァクリルゴム微粒子はこれらに限定されるも のではない。  The particle diameter of these core seal type acryl rubber fine particles is preferably in the range of 0.05 μm to 10 m. If it is less than 0.05 m, high adhesive strength cannot be obtained, and if it exceeds 10 μm, the toughness of the cured product (the balance of the sea-island structure is lost) cannot be obtained. As such core-shell type acryl rubber fine particles, for example, F 3 51 manufactured by Nippon Zeon Co., Ltd., Metaprene S manufactured by Mitsubishi Rayon Co., Ltd., and Staffoil manufactured by Ganz Kasei Co., Ltd. (both are trade names) are commercially available. In addition, Akaship BPF-3070 manufactured by Nippon Shokubai Co., Ltd., in which core-seal acrylic rubber fine particles are uniformly dispersed in an epoxy resin, is also commercially available. However, the core shell type acryl rubber fine particles are not limited to these.
コアシ ル型ァクリルゴム微粒子は硬化後の接着剤組成物に良好な特性を与える ような量で含まれる。 具体的には （1 ) 成分の合計 1 0 0重量部に対し 1〜5 0重 量部の範囲で用いる。 1重量部より少ないと接着力の低下および分離未硬化対策が 充分に得られず、 5 0重量部より多いと接着力の低下および粘度の増大により作業 性が悪化する傾向がある。  The core acryl type rubber fine particles are contained in such an amount that gives good properties to the cured adhesive composition. Specifically, it is used in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the total of (1) components. If the amount is less than 1 part by weight, sufficient reduction in adhesion force and separation uncured measures cannot be obtained, and if it exceeds 50 parts by weight, workability tends to deteriorate due to decrease in adhesion force and increase in viscosity.
本発明の加熱硬化型一液性樹脂組成物には、 本発明の特性を損なわない範囲にお いて顔料、 染料などの着色剤、 炭酸カルシウム、 タノレク、 シリカ、 アルミナ、 水酸 化アルミニウム等の無機充填剤、 難燃剤、 有機充填剤、 可塑剤、 酸化防止剤、 消泡 剤、 力ップリング剤、 レベリング剤、 レオ口ジーコントロール剤等の添加剤を適量 配合しても良い。 これらの添加により、 より樹脂強度 ·接着強さ ·難燃性 ·熱伝導 性、 作業性等に優れた組成物およびその硬化物が得られる。  In the heat-curable one-part resin composition of the present invention, inorganic materials such as pigments, dyes and other colorants, calcium carbonate, tanorek, silica, alumina, aluminum hydroxide and the like are used as long as the characteristics of the present invention are not impaired. Additives such as fillers, flame retardants, organic fillers, plasticizers, antioxidants, antifoaming agents, force pulling agents, leveling agents, and rheo-mouth ji control agents may be blended in appropriate amounts. By these additions, a composition excellent in resin strength, adhesive strength, flame retardancy, thermal conductivity, workability and the like and a cured product thereof can be obtained.
本発明の組成物を加熱硬化処理して得られる樹脂硬化物は強靭で優れた特性を有 し接着、 注型、 成型、 塗装、 コーティング材等としての使用が可能である。 また、 本発明の加熱硬化型一液性樹脂組成物は、 一液性であり、 貯蔵安定性が良好で、 低 い加熱温度により急速に硬化し強靭で優れた物性を示す硬化物を形成するため、 作 業性と信頼性に優れた接着、 注型、 成型、 塗装、 コーティング材等として有用であ る。 The cured resin obtained by heat-curing the composition of the present invention is tough and has excellent characteristics, and can be used as an adhesive, casting, molding, painting, coating material and the like. Also, The heat-curable one-part resin composition of the present invention is one-part, has good storage stability, rapidly cures at a low heating temperature, and forms a cured product that exhibits toughness and excellent physical properties. It is useful for bonding, casting, molding, painting, coating materials, etc. with excellent workability and reliability.
実施例 Example
以下に実施例によって本発明について具体的に説明するが、 本発明は以下の実施 例により制約されるものではない。 また、 下記の表中の配合割合は特に断りのない 限り重量基準である。  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the following examples. Further, the blending ratios in the following table are based on weight unless otherwise specified.
実施例で使用した材料：  Materials used in the examples:
実施例に使用した材料は下記のとおりである。  The materials used in the examples are as follows.
•化合物 A： ジャパンエポキシレジン株式会社製 水素化ビスフエノール A型ェ ポキシ榭脂の 1 0 0 %ェピスルフィ ド化品  • Compound A: Hydrogenated bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
•化合物 B ： ジャパンエポキシレジン株式会社製 水素化ビスフヱノール A型ェ ポキシ榭脂の 8 0 %ェピスルフィ ド化品  • Compound B: Hydrogenated bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
•化合物 C ： ジャパンエポキシレジン株式会社製 水素化ビスフエノール A型ェ ポキシ樹脂の 5 0 %ェピスルフィ ド化品  • Compound C: Hydrogenated bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
• Y L 7 0 0 0 : ジャパンエポキシレジン株式会社製 ビスフエノール A型ェポ キシ樹脂の 1 0 0 %ェピスルブイ ド化品  • Y L 7 0 0 0: Bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
• Y L 7 1 5 0 ：ジャパンエポキシレジン株式会社製 ビスフエノール A型ェポ キシ榭脂の 2 0 %ェピスルフィド化品  • Y L 7 1 5 0: Bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
•ェピクロン 8 3 5 L V :大日本ィンキ工業株式会社製 ビスフヱノール型ェポ キシ樹脂  • Epiclon 8 3 5 L V: Bisphenol type epoxy resin manufactured by Dainippon Ink Industries, Ltd.
•カージユラ E 1 0 P ： ジャパンエポキシレジン株式会社製 3級飽和モノカル ボン酸のモノグリシジノレエーテノレ  • Cardiula E 10 P: Japan Epoxy Resin Co., Ltd., Class 3 saturated monocarboxylic acid monoglycidino enotenole
•デナコール E X 1 4 6 ：ナガセケムテックス株式会社製 p—ターシャリーブ チノレフェニノレグリシジンエーテノレ  • Denacol E X 1 4 6: Nagase ChemteX Corporation p-tertiary chinorepheninoreglycidin etherenole
• K B M 4 0 3 ：信越化学工業株式会社製 γ—グリシドキシプロピルトリメ ト キシシラン • YX 8000 ： ジャパンエポキシレジン株式会社製 水素化ビスフエノール A 型エポキシ樹脂 • KBM 403: γ-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. • YX 8000: Hydrogenated bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
攀ェピキュア QX 30 ： ジャパンエポキシレジン株式会社製 3官能脂肪族ポリ チォーノレ 攀 epicure QX 30 ： Trifunctional aliphatic polythionole manufactured by Japan Epoxy Resin Co., Ltd.
•ェピキュア QX40 ： ジャパンエポキシレジン株式会社製 4官能脂肪族ポリ チオール  • Epicure QX40: Tetrafunctional aliphatic polythiol manufactured by Japan Epoxy Resin Co., Ltd.
•ェピキュア QX60 ： ジャパンエポキシレジン株式会社製 6官能脂肪族ポリ チオール  • Epicure QX60: 6-functional aliphatic polythiol manufactured by Japan Epoxy Resin Co., Ltd.
•チォコール L P— 3 ： 東レファインケミカル株式会社製 末端チオールのポリ サルフアイ ドポリマー  • Thiocol L P—3: Polysulfide polymer of terminal thiol manufactured by Toray Fine Chemical Co., Ltd.
•ポリチォコール QE— 340M：東レファインケミカル株式会社製 3官能脂 肪族ポリチオール • Polythiocol QE—340M: Trifunctional aliphatic polythiol manufactured by Toray Fine Chemical Co., Ltd.
• PETG ：淀化学株式会社製 ペンタエリストールテトラキスチォダリコレー 卜  • PETG: Pentaerystole tetrakistide colloid made by Sakai Chemical Co., Ltd.
*ジ （2—メルカプトェチル） エーテル：東京化成工業株式会試薬  * Di (2-mercaptoethyl) ether: Reagent for Tokyo Chemical Industry Co., Ltd.
• 3—メ トキシブチル 3—メルカプトプロピオネート ：東京化成工業株式会社試 薬  • 3-Methoxybutyl 3-Mercaptopropionate: Tokyo Chemical Industry Co., Ltd.
•ベンジルメルカブタン：東京化成工業株式会社試薬  • Benzyl mercabtan: Reagents of Tokyo Chemical Industry Co., Ltd.
• PN31 ：味の素ファインテクノ株式会社製 潜在性硬化剤ァミキユア •MY 24 ：味の素フアインテクノ株式会社製 潜在性硬化剤ァミキユア - • FXE- 1000 ：富士化成工業株式会社製 潜在性硬化剤フジキュア • PN31: Latent curing agent Amichia made by Ajinomoto Fine Techno Co., Ltd. • MY 24: Latent curing agent Amichiure made by Ajinomoto Fine Techno Co., Ltd. • • FXE-1000: Latent curing agent Fuji Cure, made by Fuji Kasei Kogyo Co., Ltd.
• FXR- 1080 ：富士化成工業株式会社製 潜在性硬化剤フジキュア • FXR-1080: Latent curing agent FUJI CURE manufactured by Fuji Chemical Industry Co., Ltd.
*バルビツール酸、 ホウ酸、 クェン酸：東京化成工業株式会社試薬 * Barbituric acid, boric acid, citrate: Reagents from Tokyo Chemical Industry Co., Ltd.
• トリェチルボレート ：東京化成工業株式会社試薬 • Triethyl borate: Reagents from Tokyo Chemical Industry Co., Ltd.
• L-07N：四国化成工業株式会社製キュアダクト （有機酸系保存性向上剤） *タルク ： ソブエ レー株式会社製 平均粒子径 7. 0 μ m品  • L-07N: Cure duct manufactured by Shikoku Kasei Kogyo Co., Ltd. (Organic acid preservative improver) * Talc: Average particle size 7.0 μm
•アタリセッ ト BPF— 307 ： 日本触媒株式会社製 コアシェル型アクリルゴ ム微粒子分散エポキシ樹脂 （ゴム成分含有率 16重量0 /0) た状態で破壌されている場合を脆い （X ) 、 そうでない場合を強靭 （〇） とした。 • Atarise' DOO BPF- 307: Nippon Shokubai Co., Ltd. core-shell Akurirugo arm microparticle dispersion epoxy resin (a rubber component content of 16 wt 0/0) The case where it was destroyed in a damaged state was marked as brittle (X), and the case where it was not strong was marked as strong (〇).
[一 2 0 °C貯蔵安定性]  [Storage stability at 1-20 ° C]
各組成物を 5 0 m lガラス瓶に約 3 0 m l入れ密栓し、 一 2 0 °Cに設定した保冷 庫にて貯蔵、 2 5 °Cにおける粘度が初期の 2倍になるまでの時間を求めた。  About 30 ml of each composition was placed in a 50 ml glass bottle, sealed, and stored in a cool box set at 120 ° C. The time until the viscosity at 25 ° C doubled the initial value was determined. .
[ゴム微粒子添加量]  [Addition amount of rubber fine particles]
樹脂成分 （1 ) 中の液状成分の合計 1 0 0重量部に対する、 ゴム微粒子成分の添 加量 （重量部） とした。  The amount of the rubber fine particle component added (parts by weight) to the total amount of 100 parts by weight of the liquid components in the resin component (1).
[分離未硬化]  [Separated uncured]
スライドガラスの中央に組成物を直径 1 mmの半球状になるように滴下し、 もう 一枚のスライドガラスを重ね合わせ、 ピンチ等で固定する。 2分静置した後 8 0 °C に設定した恒温槽にて 3 0分硬化させ、 硬化した組成物の外周端部に未硬化の樹脂 成分の分離が発生するかを観察した。  The composition is dropped into the center of the slide glass so that it becomes a hemisphere with a diameter of 1 mm, and another glass slide is overlaid and fixed with a pinch or the like. After standing for 2 minutes, it was cured for 30 minutes in a thermostatic bath set at 80 ° C., and it was observed whether separation of uncured resin components occurred at the outer peripheral edge of the cured composition.
(実施例：！〜 3 2およぴ比較例 1〜 4 )  (Example:! ~ 3 2 and Comparative Examples 1 ~ 4)
下表 （表 1〜表 4 ) に示す通りの重量比で材料を混合撹拌し、 実施例 1〜 3 2お よび比較例 1〜4の各試料 （組成物） を得て、 評価検討を行った。  The materials were mixed and stirred at the weight ratios shown in the following table (Table 1 to Table 4) to obtain each sample (composition) of Examples 1 to 3 2 and Comparative Examples 1 to 4, and the evaluation was conducted. It was.
評価結果も表 1〜表 4に示す。  The evaluation results are also shown in Tables 1 to 4.
表 1  table 1
細列 1 難例 2 実施例 3 実施例 4 比較例 1 比較例 2 化合物 A 100 100 100 80 100 100 樹脂成分（1)  Fine row 1 Difficult example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Compound A 100 100 100 80 100 100 Resin component (1)
YL7000 20  YL7000 20
チオール化合物（2) ェピキュア QX30 5 1 5 5 10 熱潜在性硬化促進剤（3) FXR- 1080 5 10 10 10 10  Thiol compounds (2) Epicure QX30 5 1 5 5 10 Thermal latent curing accelerator (3) FXR- 1080 5 10 10 10 10
酸化化合物 (4) L-07N 1 1 1 1  Oxidized compound (4) L-07N 1 1 1 1
チイラン環含有率 (％) 100 100 100 100 100 100 Thiilanic ring content (%) 100 100 100 100 100 100
80°Cゲルタイム（分） 10 9 9 8.5 15 120以上80 ° C gel time (min) 10 9 9 8.5 15 120 or more
80°C硬化時間（分） 18 18 14 15 40 120以上80 ° C curing time (min) 18 18 14 15 40 120 or more
40°C貯蔵安定性（日） 2 15以上 15以上 10 15以上 15以上 15 Storage stability at 40 ° C (day) 2 15 or more 15 or more 10 15 or more 15 or more 15
•ェピコート 807 ： ジャパンエポキシレジン株式会社製 ビスフエノール F型 エポキシ樹脂 • Epicoat 807: Bisphenol F type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.
• F 351 ： 日本ゼオン株式会社製 コアシェル型ァクリルゴム微粒子  • F 351: Core shell type acryl rubber fine particles manufactured by Nippon Zeon Co., Ltd.
実施例で行った評価：  Evaluation performed in the examples:
実施例で各試料 （組成物） について行つた評価項目および評価方法は下記のとお りである。  The evaluation items and evaluation methods performed for each sample (composition) in the examples are as follows.
[チイラン環含有率]  [Thiirane ring content]
樹脂成分 （1) 中のチイラン環含有率を次式の計算により求めた。  The thiirane ring content in the resin component (1) was calculated by the following formula.
チイラン環含有率 （％) =樹脂成分 （1) のォキシラン当量 Thialan ring content (%) = xylan equivalent of resin component (1)
(樹脂成分 （1) のチイラン当量 +樹脂成分 （1) のォキシラン当量） X I 00 [80°Cゲルタイム]  (Thiirane equivalent of resin component (1) + oxysilane equivalent of resin component (1)) X I 00 [80 ° C gel time]
各組成物 0. 1 gをスライドガラス上に半球状になるように滴下し、 80°Cに設 定した温風循環式恒温乾燥炉に投入し組成物がゲル化 （撹拌棒などで触れても流動 しなくなる状態） までの時間を測定した。  0.1 g of each composition was dropped on a glass slide so as to form a hemisphere, and placed in a hot air circulation type constant temperature drying oven set at 80 ° C, and the composition gelled (touch with a stirring bar etc.). The time until no fluid flows) was measured.
[ 80 °C硬化時間]  [80 ° C curing time]
各組成物 0. 1 gをスライドガラス上に半球状になるように滴下し、 80°Cに設 定した温風循環式恒温乾燥炉に投入し組成物が硬化 （硬化物を指で触れて表面のタ ックがなくなった状態） するまでの時間を測定した。  0.1 g of each composition was dropped on a glass slide so as to form a hemisphere and placed in a hot air circulating constant temperature drying oven set at 80 ° C to cure the composition (touch the cured product with your finger). The time until the surface tack was eliminated) was measured.
[40°C貯蔵安定性]  [40 ° C storage stability]
各糸且成物を 2 Omlガラス瓶に約 10ml入れ密栓し、 40°Cに設定した温風循 環式恒温乾燥炉にて貯蔵、 40°Cにおいてゲル化する （組成物が撹拌棒を用いて手 でかき混ぜられなくなる状態） までの日数を求めた。  About 10 ml of each threaded product is put into a 2 Oml glass bottle, tightly stoppered, stored in a hot air circulating thermostatic oven set at 40 ° C, and gelled at 40 ° C. The number of days until the hand cannot be stirred is determined.
[せん断接着強さ]  [Shear bond strength]
1. 6 X 2 5 X 1 0 Ommの S PCC-S D鋼板 2枚を 1 Ommオーバーラップ した面に組成物を塗布し貼り合わせ、 80°Cに設定した恒温層にて 30分硬化させ た後 25 °Cにて万能引張試験機にて引っ張り速度 1 OmmZm i n. にて測定した。  1. Two 6 x 25 x 10 Omm SPCC-SD steel plates were coated and bonded to the 1 Omm overlap surface and cured for 30 minutes in an isothermal layer set at 80 ° C. After that, it was measured at 25 ° C with a universal tensile testing machine at a pulling speed of 1 OmmZm i n.
[硬化物脆さ]  [Hardened material brittleness]
'前記せん断接着強さ試験後の組成物硬化物の状態を観察し、 硬化物が粉々に砕け 実施例 lからは、 ォキシラン環 Zチイラン環の含有数の割合が 1 0 0である樹脂 成分に、 チオール化合物と、 熱潜在性硬化促進剤を配合することにより、 8 0 °Cに おける硬化時間が 3 0分以下であり、 かつ、 4 0 °Cにおいて 7日以上の貯蔵安定性 を有する、 低温速硬化性と貯蔵安定性に優れた組成物が得られた。 'After observing the state of the cured composition after the shear bond strength test, the cured product was shattered. From Example l, the curing time at 80 ° C. is obtained by adding a thiol compound and a thermal latent curing accelerator to a resin component having a content ratio of oxolan ring Z thiirane ring of 100. Thus, a composition excellent in low-temperature fast curability and storage stability having a storage stability of not more than 30 minutes and a storage stability of 7 days or longer at 40 ° C. was obtained.
実施例 2〜4からは、 ォキシラン環 Zチイラン環の含有数の割合が 1 0 0である 榭脂成分と、 チオール化合物と、 熱潜在性硬化促進剤に、 酸性化合物、 ホウ酸エス テルを配合することにより、 低温速硬化性を維持しながら更に貯蔵安定性に優れた 組成物が得られた。  From Examples 2 to 4, the ratio of the content of the oxolan ring Z thiirane ring is 100, a blend of an acid compound and a boric acid ester in a resin component, a thiol compound, and a thermal latent curing accelerator As a result, a composition having excellent storage stability was obtained while maintaining the low temperature fast curability.
比較例 1、 2からは、 チオール化合物、 または、 熱潜在性硬化促進剤を含有しな い場合、 所望の低温速硬化性を得ることが出来ないことが分かる。 表 2  From Comparative Examples 1 and 2, it can be seen that when a thiol compound or a thermal latent curing accelerator is not contained, the desired low-temperature rapid curability cannot be obtained. Table 2
魏例 5難例 6細列 7難例 8難例 9細列 10難例 11 化合物 A 90 95 95 95 95 94 化合物 B 10 100 化合物 C  魏 Example 5 Difficult Case 6 Fine Row 7 Difficult Case 8 Difficult Case 9 Fine Row 10 Difficult Case 11 Compound A 90 95 95 95 95 94 Compound B 10 100 Compound C
YL7150  YL7150
樹脂成分 (1) ェピクロン/ 835LV 5 6  Resin component (1) Epiclon / 835LV 5 6
カージユラ E10P 5  Card Yura E10P 5
デナコール EX146 5  Denacor EX146 5
KBM403 5 3  KBM403 5 3
YX8000  YX8000
チオール化合物（2) ェピキュア QX30 5 5 5 5 5 5 5 熱潜在性硬化促進剤（3) FXR- 1080 10 10 10 10 10 10 10 酸性化合物 (4) L-07N 1 1 1 1 1 1 1 無機充填剤 タルク 50  Thiol compound (2) Epicure QX30 5 5 5 5 5 5 5 Thermal latent curing accelerator (3) FXR- 1080 10 10 10 10 10 10 10 Acidic compound (4) L-07N 1 1 1 1 1 1 1 Inorganic filling Agent Talc 50
チイラン環含有率 (％) 98 93 96 95 95 93 80 Thiilanic ring content (%) 98 93 96 95 95 93 80
80°Cゲルタイム (分) 8 6 8.5 7 7.5 6.5 4.580 ° C Gel time (min) 8 6 8.5 7 7.5 6.5 4.5
80°C硬化時間（分） 15 13 13 13 13 13 1080 ° C curing time (min) 15 13 13 13 13 13 10
40。C貯蔵安定性（日） 15以上 15以上 15以上 15以上 15以上 15以上 15以上 表 2続き 40. C Storage stability (day) 15 or more 15 or more 15 or more 15 or more 15 or more 15 or more 15 or more Table 2 continued
Figure imgf000020_0001
実施例 5〜 15からは、 ォキシラン環/チイラン環の含有数の割合が 80/20 〜0/100である樹脂成分の場合、 80°Cにおける硬化時間が 30分以下であり、 かつ、 40°Cにおいて 7日以上の貯蔵安定性を有する、 低温速硬化性と貯蔵安定性 に優れた組成物が得られた。 また実施例 5は、 さらに無機充填剤を配合しても特に 問題ないことが分かる。
Figure imgf000020_0001
From Examples 5 to 15, in the case of a resin component in which the ratio of the content of oxolan ring / thiirane ring is 80/20 to 0/100, the curing time at 80 ° C. is 30 minutes or less, and 40 ° In C, a composition having a storage stability of 7 days or more and excellent low-temperature fast curing property and storage stability was obtained. In Example 5, it can be seen that there is no particular problem even if an inorganic filler is further added.
比較例 3、 4からは、 ォキシラン環ノチイラン環の含有数の割合が 80/20〜 0/100の範囲を外れると、 低温速硬化性と貯蔵安定性を両立することが出来な いことが分かる。 表 3 From Comparative Examples 3 and 4, it can be seen that if the content ratio of the oxysilane ring notirane ring is out of the range of 80/20 to 0/100, it is impossible to achieve both low-temperature fast curability and storage stability. . Table 3
麵列 16雞例 17雄例 18難例 19 樹脂成分（1) 化合物 A 100 100 100 100 ェピキュア QX40 5  Row 16 16 cases 17 male cases 18 difficult cases 19 Resin component (1) Compound A 100 100 100 100 Epicure QX40 5
ェピキュア QX60 5  Epicure QX60 5
LP- 3 5  LP- 3 5
QE-340M 5 チオール化合物（2)  QE-340M 5 Thiol Compound (2)
PETG  PETG
ジ（2—メルカプトェチル）エーテル  Di (2-mercaptoethyl) ether
3—メトキシブチル 3—メルカプトプロピオ一ネート  3-Methoxybutyl 3-mercaptopropionate
ベンジルメルカプタン  Benzyl mercaptan
熱潜在性硬化促進剤（3) FXR- 1080 8 8 8 8 酸性化合物 (4) L-07N 1 1 1 1 チイラン環含有率（％) 100 100 100 100Thermal latent curing accelerator (3) FXR- 1080 8 8 8 8 Acidic compound (4) L-07N 1 1 1 1 Thiilan ring content (%) 100 100 100 100
80°Cゲルタイム（分） 11 11 11 1080 ° C gel time (min) 11 11 11 10
80°C硬化時間（分） 18 18 18 • 1980 ° C curing time (min) 18 18 18 • 19
40°C貯蔵安定性（日） 15以上 15以上 15以上 11 表 3の続き Storage stability at 40 ° C (day) 15 or more 15 or more 15 or more 11 Continuation of Table 3
雞例 20難例 21難例 22実施例 23 樹脂成分（1) 化合物 A 100 100 100 100 ェピキュア QX40  Example 20 Example 21 Example 22 Example 23 Resin Component (1) Compound A 100 100 100 100 Epicure QX40
ェピキュア QX60  Epicure QX60
LP-3  LP-3
QE-340M  QE-340M
チオール化合物（2)  Thiol compounds (2)
PETG 3  PETG 3
ジ（2—メルカプトェチル）エーテル 3  Di (2-mercaptoethyl) ether 3
3 -メトキシブチル 3-メルカプトプロピオ一ネート 4  3-Methoxybutyl 3-mercaptopropionate 4
ベンジルメルカプタン 4 熱潜在性硬化促進剤（3) FXR-1080 8 8 8 8 酸性化合物（4) L-07N 1 1 1 1 チイラン環含有率（％) 100 100 100 100 Benzyl mercaptan 4 Thermal latent curing accelerator (3) FXR-1080 8 8 8 8 Acidic compound (4) L-07N 1 1 1 1 Thiirane ring content (%) 100 100 100 100
80°Cゲルタイム（分） 12 10 10 1180 ° C gel time (min) 12 10 10 11
80°C硬化時間（分） 18 18 18 1880 ° C curing time (min) 18 18 18 18
40°C貯蔵安定性（日） 15以上 15以上 15以上 15以上 実施例 1 6〜2 3は、 チオール化合物の種類を変えた場合の実施例である。 いず れの場合も 8 0 °Cにおける硬化時間が 3 0分以下であり、 かつ、 4 0 °Cにおいて 7 日以上の貯蔵安定性を有する、 低温速硬化性と貯蔵安定性に優れた組成物が得られ ることが分かる。 Storage stability at 40 ° C (day) 15 or more 15 or more 15 or more 15 or more Examples 1 6 to 23 are examples in which the type of thiol compound is changed. In all cases, the composition has excellent low-temperature fast curing and storage stability, with a curing time at 80 ° C of 30 minutes or less and storage stability of 40 days or more at 40 ° C. You can see that you can get things.
表 4  Table 4
難例 24麵列 25実施例 26 例 27実施例 28 化合物 A 96 96 96 98 98 樹脂成分（1) KBM403 4 4 4  Difficult example 24 rows 25 Example 26 Example 27 Example 28 Compound A 96 96 96 98 98 Resin component (1) KBM403 4 4 4
EX146 2 2 チオール化合物（2) ェピキュア QX40 6 6 6 5 5  EX146 2 2 Thiol compounds (2) Epicure QX40 6 6 6 5 5
PN31 6  PN31 6
MY24 10  MY24 10
熱潜在性硬化促進剤（3) Thermal latent curing accelerator (3)
FXE- 1000 7  FXE- 1000 7
FX - 1080 8 8 ノ ノレビッ一ノレ酸 0.6  FX-1080 8 8 Norebinorenoic acid 0.6
ホウ酸 0.6 酸性化合物（4) クェン酸  Boric acid 0.6 Acidic compound (4) Quenic acid
トリェチルポレート  Torytilpole
L-07N 2 1 1  L-07N 2 1 1
チイラン環含有率（％) 96 96 96 98 98 Thiilan ring content (%) 96 96 96 98 98
80°Cゲルタイム（分） 10 14 10 7 780 ° C gel time (min) 10 14 10 7 7
80°C硬化時間（分） 18 20 14 13 1380 ° C curing time (min) 18 20 14 13 13
40°C貯蔵安定性（日） 8 10 14 9 11 表 4続き Storage stability at 40 ° C (day) 8 10 14 9 11 Table 4 continued
Figure imgf000023_0001
Figure imgf000023_0001
実施例 2 4〜3 2は、 熱潜在性硬化促進剤または酸性化合物 ·ホウ酸エステル化 合物の種類 ·量を変えた場合の実施例である。 これらの結果から 8 0 °Cにおける硬 化時間が 3 0分以下であり、 かつ、 4 0 °Cにおいて 7日以上の貯蔵安定性を有する、 低温速硬化性と貯蔵安定性に優れた組成物が得られることが分かる。  Examples 2 4 to 3 2 are examples in which the type and amount of the thermal latent curing accelerator or acidic compound / boric acid ester compound were changed. From these results, a composition having an excellent curing temperature at low temperature and storage stability, having a curing time at 80 ° C of 30 minutes or less and storage stability at 40 ° C of 7 days or more. It can be seen that
(実施例 3 3〜 4 0およぴ比較例 5〜： 1 2 )  (Examples 3 to 40 and Comparative Examples 5 to: 1 2)
下表 （表 5 ) に示す通りの重量比で材料を混合撹拌し、 実施例 3 3〜 4 0および 比較例 5〜 1 2の各試料 （組成物） を得た。 得られた各試料 （組成物） の評価を行 つた。 その結果を表 5にあわせて示す。 表 5 The materials were mixed and stirred at a weight ratio as shown in the following table (Table 5) to obtain each sample (composition) of Examples 33 to 40 and Comparative Examples 5 to 12. Each sample (composition) obtained was evaluated. The results are also shown in Table 5. Table 5
Figure imgf000024_0001
Figure imgf000024_0001
表 5続き Table 5 continued
Figure imgf000025_0001
Figure imgf000025_0001
実施例 33〜 38は、 樹脂成分 （1) の混合物のォキシラン環 Zチイラン環の含 有数の割合が 40/60〜10Z90の範囲にある樹脂成分に、 チオール化合物、 熱潜在性硬化促進剤、 コァシ ル型ァクリルゴム微粒子、 酸性化合物を配合するこ とにより、 15ΜΡ a以上の高いせん断接着強さを有し、 80°Cにおける硬化時間 が 15分以内であり、 かつ、 _ 20°Cにおいて 3ヶ月以上の貯蔵安定性を有し、 分 離未硬化の発生しなレ、榭脂組成物が得られた。 In Examples 33 to 38, a resin component in which the content ratio of the oxosilane ring Z thiirane ring in the mixture of the resin component (1) is in the range of 40/6 to 10Z90, a thiol compound, a thermal latent curing accelerator, By blending fine acryl rubber fine particles and acidic compounds, it has a high shear bond strength of 15ΜΡa or more, the curing time at 80 ° C is within 15 minutes, and at _20 ° C for more than 3 months Thus, a rosin composition having a storage stability of no segregation uncured was obtained.
実施例 39および 40では、 榭脂成分 （1) の混合物のチイラン環の含有率が 6 0より小さいと、 80°Cで 15分以内の速硬化性が達成できないことがわかる。 実 施例 40および 44では、 樹脂成分 （1) の混合物のチイラン環の含有率が 90よ り大きいと、 15MP a以上の高いせん断接着強さと 3ヶ月以上の良好な貯蔵安定 性を達成できないことがわかる。 また、 実施例 41〜44では、 コアシェル型ァク リルゴム微粒子を含まない場合、 分離未硬化が発生してしまうことがわかる。 実施例 45〜47では、 コアシェル型ァクリルゴム微粒子の種類を変えた場合で も、 15MP a以上の高いせん断接着強さを有し、 80°Cにおける硬化時間が 30 分以内であり、 かつ、 一 20°Cにおいて 3ヶ月以上の貯蔵安定性を有し、 分離未硬 化の発生しない樹脂組成物が得られた。  In Examples 39 and 40, it can be seen that if the content of the thiirane ring in the mixture of the resin component (1) is less than 60, rapid curability within 15 minutes cannot be achieved at 80 ° C. In Examples 40 and 44, when the content of the thiirane ring in the mixture of the resin component (1) is greater than 90, high shear bond strength of 15 MPa or more and good storage stability of 3 months or more cannot be achieved. I understand. Further, in Examples 41 to 44, it is found that when the core-shell type acryl rubber fine particles are not contained, separation uncured occurs. In Examples 45 to 47, even when the kind of the core-shell type acryl rubber fine particles is changed, it has a high shear bond strength of 15 MPa or more, a curing time at 80 ° C. is within 30 minutes, and A resin composition having a storage stability of 3 months or more at ° C and free from separation and hardening was obtained.
実施例 48では、 コアシヱル型アクリルゴム微粒子の種類を変えた場合でも、 榭 脂成分 （1) と （2) の混合物のチイラン環の含有率が 90より大きいと、 15M P a以上の高いせん断接着強さと 3ヶ月以上の良好な貯蔵安定性を達成できないこ とがわかる。  In Example 48, even when the type of the core seal type acrylic rubber fine particles was changed, if the content of the thiirane ring in the mixture of the resin components (1) and (2) was greater than 90, a high shear adhesion of 15 MPa or more was obtained. It can be seen that strength and good storage stability over 3 months cannot be achieved.
産業上の利用可能性 Industrial applicability
本発明は作業性と信頼性に優れ、 輸送機器、 電機機器、 電子機器産業等の接着、 封止、 注型、 成型、 塗装、 コーティング材等としての使用が可能であり、 特に低い 加熱温度での速硬化性が要求される電子部品の実装 ·組立用の接着剤 ·封止剤とし て有用である。  The present invention is excellent in workability and reliability, and can be used as adhesion, sealing, casting, molding, coating, coating material, etc. in transportation equipment, electrical equipment, electronic equipment industry, etc., especially at low heating temperature It is useful as an adhesive and sealant for mounting, assembling, and electronic parts that require fast curing.

Claims

請求の範囲 The scope of the claims
1. (A) 分子内に 2つ以上のチイラン環を含む化合物、 （B) 分子内に 1っ以 上のチイラン環と 1つ以上のォキシラン環とを含む化合物おょぴ （C) 分子 内に 1つ以上のォキシラン環を含み、 チイラン環を含まない化合物からなる 群から選ばれ、 かつォキシラン環 Zチイラン環の割合が 80/20-0/1 00である化合物もしくは混合物、 （2) 分子内にチオール基を 1つ以上有 するチオール化合物および （3) 熱潜在性硬化促進剤を必須成分とする加熱 硬化型一液性樹脂組成物。  1. (A) A compound containing two or more thiirane rings in the molecule, (B) A compound containing one or more thiirane rings and one or more oxsilane rings in the molecule (C) Intramolecular A compound or mixture selected from the group consisting of compounds containing at least one oxilan ring and no thiirane ring, and the ratio of oxilan ring Z thiirane ring is 80 / 20-0 / 100, (2) molecule A thiol compound having one or more thiol groups therein, and (3) a heat-curable one-component resin composition comprising a thermal latent curing accelerator as an essential component.
2. 前記化合物 （A) または/および （B) 力 ビスフエノール骨格を有するェ ポキシ化合物の芳香環の炭素一炭素不飽和結合を水素化した水添ビスフエノ ール型エポキシ化合物であって、 かつ、 水添ビスフエノール型エポキシ化合 物のォキシラン環の酸素原子の全てまたは一部を硫黄原子に置換したチイラ ン環を含む化合物からなる請求項 1記載の加熱硬化型一液樹脂組成物。 2. A hydrogenated bisphenol type epoxy compound obtained by hydrogenating a carbon-carbon unsaturated bond of an aromatic ring of an epoxy compound having a bisphenol skeleton, wherein the compound (A) and / or (B) has a force, and 2. The thermosetting one-component resin composition according to claim 1, comprising a compound containing a thirane ring in which all or part of oxygen atoms of the oxysilane ring of the hydrogenated bisphenol type epoxy compound are substituted with sulfur atoms.
3. 前記化合物 （C) が 2つ以上のォキシラン環を有する化合物である請求項 1 または 2記載の加熱硬化型一液性樹脂組成物。 3. The thermosetting one-component resin composition according to claim 1 or 2, wherein the compound (C) is a compound having two or more oxosilane rings.
4. 前記 （1) 成分のォキシラン環ノチイラン環の割合が 40Z60〜10/9 0である請求項 1〜 3のいずれか 1項記載の加熱硬化型一液性樹脂組成物。 4. The thermosetting one-component resin composition according to any one of claims 1 to 3, wherein a ratio of the oxosilane ring notilan ring as the component (1) is 40Z60 to 90/90.
5. さらに、 （4) 酸性化合物おょぴノまたはホウ酸エステルを含有する請求項 1〜 4のいずれか 1項記載の加熱硬化型一液性樹脂組成物。 5. The thermosetting one-component resin composition according to any one of claims 1 to 4, further comprising (4) an acidic compound opino or borate ester.
6. さらに、 (5) コアシェル型アクリルゴム微粒子を含有する請求項 1〜5の いずれか 1項記載の加熱硬化型一液性樹脂組成物。  6. The heat-curable one-component resin composition according to any one of claims 1 to 5, further comprising (5) core-shell type acrylic rubber fine particles.
7. 各成分の配合割合が、 （1) 成分 100重量部に対して、 （3) 成分が 0.  7. The blending ratio of each component is as follows: (1) 100 parts by weight of component (3) 0.
1〜30重量部、 （4) 成分が 0. 01〜10重量部、 （5) 成分が 1〜5 0重量部であり、 かつ、 （2) 成分の量が （1) 成分中のチイラン環および ォキシラン環の合計に対してチオール当量比で 0. 01〜0. 5である請求 項 6記載の加熱硬化型一液性樹脂組成物。  1 to 30 parts by weight, (4) component is 0.01 to 10 parts by weight, (5) component is 1 to 50 parts by weight, and (2) the amount of the component is (1) a thiirane ring in the component The heat-curable one-component resin composition according to claim 6, which has a thiol equivalent ratio of 0.01 to 0.5 with respect to the total of oxsilane rings.
8. 前記 （3) 熱潜在性硬化促進剤が、 固体分散型アミンァダクト系潜在性硬化 促進剤である請求項 1〜 7のいずれか 1項記載の加熱硬化型一液性榭脂組成 物。 8. The heat-curable one-component resin composition according to any one of claims 1 to 7, wherein the (3) thermal latent curing accelerator is a solid dispersion type amine adduct type latent curing accelerator. object.
9 . 固体分散型アミンァダクト系潜在性硬化促進剤が、 尿素型ァダクト系の熱潜 在性硬化促進剤である請求項 8記載の加熱硬化型一液性樹脂組成物。  9. The thermosetting one-component resin composition according to claim 8, wherein the solid dispersion type amine adduct type latent curing accelerator is a urea type adduct type thermal latent curing accelerator.
1 0 . 前記 （5 ) コアシェル型アクリルゴム微粒子のコア部分のガラス転移点が一  10 (5) The glass transition point of the core portion of the core-shell type acrylic rubber fine particles is the same.
1 0 °C以下のゴム状ポリマーであって、 かつシェル部分がガラス転移点が 7 0 °C以上のガラス状ポリマーである請求項 6〜 9のいずれか 1項記載の加熱 硬化型一液性榭脂組成物。  The heat-curable one-part liquid according to any one of claims 6 to 9, wherein the polymer is a rubber-like polymer having a temperature of 10 ° C or lower, and the shell portion is a glassy polymer having a glass transition point of 70 ° C or higher. A rosin composition.
1 1 . 請求項 1〜 1 1のいずれか 1項記載の加熱硬化型一液性樹脂組成物を硬化処 理することによって得られる樹脂硬化物。  1 1. A cured resin obtained by curing the thermosetting one-component resin composition according to any one of claims 1 to 11.
PCT/JP2006/302680 2005-02-17 2006-02-09 Thermosetting one-component resin composition WO2006088069A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN200680005105XA CN101120036B (en) 2005-02-17 2006-02-09 Heat-curing type one-pack resin composition
KR1020077018549A KR101235933B1 (en) 2005-02-17 2006-02-09 Thermosetting one-component resin composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005039929A JP4826708B2 (en) 2005-02-17 2005-02-17 Heat-curing one-part resin composition
JP2005-039929 2005-02-17
JP2005-215202 2005-07-26
JP2005215202A JP4883264B2 (en) 2005-07-26 2005-07-26 Heat-curing one-part resin composition

Publications (1)

Publication Number Publication Date
WO2006088069A1 true WO2006088069A1 (en) 2006-08-24

Family

ID=36916471

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/302680 WO2006088069A1 (en) 2005-02-17 2006-02-09 Thermosetting one-component resin composition

Country Status (3)

Country Link
KR (1) KR101235933B1 (en)
CN (1) CN101120036B (en)
WO (1) WO2006088069A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016108467A (en) * 2014-12-08 2016-06-20 旭化成ケミカルズ株式会社 Method for producing resin composition, resin composition, curable resin composition, cured product, prepreg, and fiber-reinforced plastic
JP2017193630A (en) * 2016-04-20 2017-10-26 積水化学工業株式会社 Curable resin composition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010147070A1 (en) * 2009-06-15 2010-12-23 味の素株式会社 Resin composition and organic-electrolyte battery
KR102043160B1 (en) * 2017-12-20 2019-11-12 이아이씨티코리아 주식회사 Low Temperature Curing Epoxy Resin Composition
KR102242440B1 (en) 2019-11-25 2021-04-20 주식회사 케이씨씨 Adhesive composition

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06211970A (en) * 1992-10-22 1994-08-02 Ajinomoto Co Inc Epoxy resin composition
JPH06211969A (en) * 1992-10-22 1994-08-02 Ajinomoto Co Inc Epoxy resin composition
WO2000046317A1 (en) * 1999-02-08 2000-08-10 The Yokohama Rubber Co., Ltd. Resin compositions
JP2000230112A (en) * 1999-02-12 2000-08-22 Ajinomoto Co Inc Electroconductive resin composition
JP2001270976A (en) * 1999-04-13 2001-10-02 Hitachi Chem Co Ltd Epoxy resin composition for sealing and electronic device
JP2002015621A (en) * 2000-06-29 2002-01-18 Toshiba Corp Electrical insulation material and its manufacturing method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030007741A (en) * 2002-11-28 2003-01-23 아지노모토 가부시키가이샤 Conductive resin composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06211970A (en) * 1992-10-22 1994-08-02 Ajinomoto Co Inc Epoxy resin composition
JPH06211969A (en) * 1992-10-22 1994-08-02 Ajinomoto Co Inc Epoxy resin composition
WO2000046317A1 (en) * 1999-02-08 2000-08-10 The Yokohama Rubber Co., Ltd. Resin compositions
JP2000230112A (en) * 1999-02-12 2000-08-22 Ajinomoto Co Inc Electroconductive resin composition
JP2001270976A (en) * 1999-04-13 2001-10-02 Hitachi Chem Co Ltd Epoxy resin composition for sealing and electronic device
JP2002015621A (en) * 2000-06-29 2002-01-18 Toshiba Corp Electrical insulation material and its manufacturing method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016108467A (en) * 2014-12-08 2016-06-20 旭化成ケミカルズ株式会社 Method for producing resin composition, resin composition, curable resin composition, cured product, prepreg, and fiber-reinforced plastic
JP2017193630A (en) * 2016-04-20 2017-10-26 積水化学工業株式会社 Curable resin composition

Also Published As

Publication number Publication date
KR20070103025A (en) 2007-10-22
KR101235933B1 (en) 2013-02-21
CN101120036A (en) 2008-02-06
CN101120036B (en) 2012-06-27

Similar Documents

Publication Publication Date Title
AU2007323759B2 (en) Epoxy resins comprising a cycloaliphatic diamine curing agent
US9315664B2 (en) High Tg epoxy systems for composite applications
JP2016501922A (en) Toughened curable epoxy compositions for high temperature applications
US9334426B2 (en) Latent curing agent and epoxy compositions containing the same
JP2013543012A (en) One-part epoxy resin composition
KR101994355B1 (en) Structural epoxy adhesives composition
JP5441447B2 (en) Insulating paint for electronic parts and electronic parts using the same
JP2007106852A (en) One-component thermosetting flame retardant composition and cured material of the same
WO2006088069A1 (en) Thermosetting one-component resin composition
JP4883264B2 (en) Heat-curing one-part resin composition
CN103052681A (en) Hardener for epoxy resins
JP2016507622A (en) Curable composition with high fracture toughness
JP6161340B2 (en) Bisimidazole compound, epoxy resin curing agent containing the bisimidazole compound, and one-component curable epoxy resin composition containing the epoxy resin curing agent
JP4826708B2 (en) Heat-curing one-part resin composition
JP2021095531A (en) Adhesive composition for automobile structure
JP7217565B1 (en) Resin compositions, adhesives, sealing materials, cured products, semiconductor devices and electronic components
JP7217566B1 (en) Resin compositions, adhesives, sealing materials, cured products and semiconductor devices
JP2003105060A (en) Thermosetting resin composition having vibration-damping properties and adhesive using the same
JP2019056057A (en) Epoxy resin composition and structural member
JP2018184531A (en) Thermosetting epoxy resin composition
WO2024090259A1 (en) Resin composition, adhesive, sealing material, cured product, semiconductor device, and electronic component
WO2023026872A1 (en) Epoxy resin composition
Reynolds et al. High T g epoxy systems for composite applications
JP6161464B2 (en) One-part curable resin composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1020077018549

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 200680005105.X

Country of ref document: CN

Ref document number: 12007501764

Country of ref document: PH

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06713821

Country of ref document: EP

Kind code of ref document: A1