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WO2006088069A1 - Composition d’une resine monocomposant thermodurcissable - Google Patents

Composition d’une resine monocomposant thermodurcissable Download PDF

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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
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WIPO (PCT)
Prior art keywords
compound
component
ring
resin composition
thiirane
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2006/302680
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English (en)
Japanese (ja)
Inventor
Manabu Kirino
Maki Takayama
Manabu Inoue
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThreeBond Co Ltd
Original Assignee
ThreeBond 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/ja
Priority claimed from JP2005215202A external-priority patent/JP4883264B2/ja
Application filed by ThreeBond Co Ltd filed Critical ThreeBond Co Ltd
Priority to KR1020077018549A priority Critical patent/KR101235933B1/ko
Priority to CN200680005105XA priority patent/CN101120036B/zh
Publication of WO2006088069A1 publication Critical patent/WO2006088069A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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.

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  • 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

L’invention concerne une composition d’une résine monocomposant thermodurcissable comprenant : (1) un composé, ou un mélange de composés, contenant au moins un élément choisi parmi un composé ayant deux cycles thiirane ou plus dans chacune de ses molécules (A), un composé ayant à la fois un cycle thiirane et un cycle oxiranne dans chacune de ses molécules (B) et un composé ayant un ou plusieurs cycles oxiranne et ne contenant aucun cycle thiirane dans chacune de ses molécules (C), le rapport cycles oxiranne/cycles thiirane contenus étant compris entre 40/60 et 10/90 ; (2) un composé thiol ayant un ou plusieurs groupes thiol dans chacune de ses molécules ; et (3) un accélérateur de durcissement à chaleur latente ; ainsi qu’éventuellement (4) un composé acide et/ou un ester d’acide borique ; et (5) des microparticules de caoutchouc acrylique de type noyau/coquille. Cette composition peut être utilisée dans diverses utilisations, telles que le collage, le scellage, le coulage, le moulage, la peinture, le revêtement, etc., excelle en ce qui concerne l’aptitude à durcir rapidement à basse température par rapport à une composition classique d’une résine monocomposant thermodurcissable de type épisulfure, et présente une excellente stabilité lors du stockage.
PCT/JP2006/302680 2005-02-17 2006-02-09 Composition d’une resine monocomposant thermodurcissable Ceased WO2006088069A1 (fr)

Priority Applications (2)

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KR1020077018549A KR101235933B1 (ko) 2005-02-17 2006-02-09 가열 경화형 일액성 수지 조성물
CN200680005105XA CN101120036B (zh) 2005-02-17 2006-02-09 加热固化型单组分性树脂组合物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005-039929 2005-02-17
JP2005039929A JP4826708B2 (ja) 2005-02-17 2005-02-17 加熱硬化型一液性樹脂組成物
JP2005-215202 2005-07-26
JP2005215202A JP4883264B2 (ja) 2005-07-26 2005-07-26 加熱硬化型一液性樹脂組成物

Publications (1)

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WO2006088069A1 true WO2006088069A1 (fr) 2006-08-24

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JP2016108467A (ja) * 2014-12-08 2016-06-20 旭化成ケミカルズ株式会社 樹脂組成物の製造方法、樹脂組成物、硬化性樹脂組成物、硬化物、プリプレグ、及び繊維強化プラスチック
JP2017193630A (ja) * 2016-04-20 2017-10-26 積水化学工業株式会社 硬化性樹脂組成物

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JP5732389B2 (ja) * 2009-06-15 2015-06-10 味の素株式会社 樹脂組成物及び有機電解液電池
KR102043160B1 (ko) * 2017-12-20 2019-11-12 이아이씨티코리아 주식회사 저온 속경화 에폭시 수지 조성물
KR102242440B1 (ko) 2019-11-25 2021-04-20 주식회사 케이씨씨 접착제 조성물
JP7582501B2 (ja) * 2021-10-01 2024-11-13 株式会社レゾナック 熱硬化性組成物及びその硬化物、光融解性組成物、並びに構造体の製造方法

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JPH06211970A (ja) * 1992-10-22 1994-08-02 Ajinomoto Co Inc エポキシ樹脂組成物
JPH06211969A (ja) * 1992-10-22 1994-08-02 Ajinomoto Co Inc エポキシ樹脂組成物
WO2000046317A1 (fr) * 1999-02-08 2000-08-10 The Yokohama Rubber Co., Ltd. Compositions resineuses
JP2000230112A (ja) * 1999-02-12 2000-08-22 Ajinomoto Co Inc 導電性樹脂組成物
JP2001270976A (ja) * 1999-04-13 2001-10-02 Hitachi Chem Co Ltd 封止用エポキシ樹脂組成物及び電子部品装置
JP2002015621A (ja) * 2000-06-29 2002-01-18 Toshiba Corp 電気絶縁材料及びその製造方法

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JPH06211970A (ja) * 1992-10-22 1994-08-02 Ajinomoto Co Inc エポキシ樹脂組成物
JPH06211969A (ja) * 1992-10-22 1994-08-02 Ajinomoto Co Inc エポキシ樹脂組成物
WO2000046317A1 (fr) * 1999-02-08 2000-08-10 The Yokohama Rubber Co., Ltd. Compositions resineuses
JP2000230112A (ja) * 1999-02-12 2000-08-22 Ajinomoto Co Inc 導電性樹脂組成物
JP2001270976A (ja) * 1999-04-13 2001-10-02 Hitachi Chem Co Ltd 封止用エポキシ樹脂組成物及び電子部品装置
JP2002015621A (ja) * 2000-06-29 2002-01-18 Toshiba Corp 電気絶縁材料及びその製造方法

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Publication number Priority date Publication date Assignee Title
JP2016108467A (ja) * 2014-12-08 2016-06-20 旭化成ケミカルズ株式会社 樹脂組成物の製造方法、樹脂組成物、硬化性樹脂組成物、硬化物、プリプレグ、及び繊維強化プラスチック
JP2017193630A (ja) * 2016-04-20 2017-10-26 積水化学工業株式会社 硬化性樹脂組成物

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KR101235933B1 (ko) 2013-02-21
KR20070103025A (ko) 2007-10-22
CN101120036B (zh) 2012-06-27

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