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WO2013073363A1 - Composition thermodurcissable - Google Patents

Composition thermodurcissable Download PDF

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Publication number
WO2013073363A1
WO2013073363A1 PCT/JP2012/078031 JP2012078031W WO2013073363A1 WO 2013073363 A1 WO2013073363 A1 WO 2013073363A1 JP 2012078031 W JP2012078031 W JP 2012078031W WO 2013073363 A1 WO2013073363 A1 WO 2013073363A1
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Prior art keywords
component
meth
group
acrylate
acrylic
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PCT/JP2012/078031
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English (en)
Japanese (ja)
Inventor
奈央 有田
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ThreeBond Co Ltd
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ThreeBond Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups

Definitions

  • thermosetting composition colored in the (meth) acrylic resin is related with thermosetting property provided by the organic peroxide.
  • Japanese Patent Application Laid-Open No. 2006-193650 describes an invention that suppresses coloring of a colorless composition by combining a phenol-based antioxidant and a sulfur-based antioxidant in a vinyl polymer having a (meth) acryl group. However, it does not describe what kind of effect is exerted on the colored composition, and has not been verified.
  • thermosetting (meth) acrylic resin colored red or blue with a colorant is exposed to a 150 ° C. or 120 ° C. atmosphere as a high temperature endurance test, discoloration occurs abruptly and the initial coloration It was difficult to maintain a stable state.
  • a first embodiment of the present invention is a thermosetting composition containing components (A) to (E)
  • Component Antioxidant having thioether skeleton (E) component: Dye or organic pigment
  • Second of the present invention the component (B) is 0.1 to 10 parts by mass, the component (C) is 0.1 to 5 parts by mass, and the component (D) is 0.1 parts per 100 parts by mass of the component (A).
  • the thermosetting composition according to (1) which is contained by 5 to 5 parts by mass and the component (E) is contained by 0.001 to 0.05 parts by mass.
  • thermosetting composition according to either (1) or (2), wherein the component (B) is an organic peroxide containing the structure of the general formula 2. It is.
  • the invention's effect In the present invention, when a high temperature durability test at 100 to 150 ° C. is performed, the yellowing degree is low, and the initially colored color is difficult to change. Further, the physical properties are stable, and a thermosetting composition suitable for an adhesive or a sealant is made possible.
  • the component (A) that can be used in the present invention is a compound having a (meth) acryl group.
  • (meth) acryl is a generic name including acryl and methacryl.
  • the component (A) has a reactive (meth) acryl group, and the (meth) acryl group may be present in either the side chain and / or the terminal of the molecule.
  • an oligomer having a (meth) acrylic group a so-called urethane-modified (meth) acrylic oligomer (or a urethane acrylate oligomer) obtained by synthesizing a polyfunctional isocyanate, a compound having a (meth) acrylic group, and a hydroxyl group in a polyhydric polyol. .).
  • the polyhydric polyol may have various skeletons, and various things such as an ethylene oxide skeleton, a polyester skeleton, a polyether skeleton, a polybutadiene skeleton, and a hydrogenated polybutadiene skeleton can be used.
  • oligomers having (meth) acrylic groups include epoxy-modified (meth) acrylic oligomers in which (meth) acrylic acid is added to bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenol novolac resins. (Or also referred to as epoxy acrylate oligomer).
  • these oligomers having a (meth) acryl group may be used alone or as a mixture of two or more.
  • the oligomer having a (meth) acryl group may be a compound (for example, a monomer or an oligomer) having a skeleton obtained by copolymerizing a compound having a vinyl group and having a (meth) acryl group.
  • a (meth) acrylic monomer is preferable, and various compounds can be used.
  • the (meth) acrylic monomer is a general term for monomers having an acrylic group or a methacrylic group.
  • Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (meth) acrylic acid-t-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acryl
  • polymerization can be carried out by selecting from the (meth) acrylic monomer, but it is preferable to select a (meth) acrylic monomer having a hydrocarbon group.
  • the oligomer having the (meth) acryl group may be used alone or as a mixture of two or more kinds.
  • the oligomer is a compound whose main skeleton is made of a polymer of (meth) acrylic monomers and has one (meth) acrylic group in the molecule.
  • the component (A) has a reactive (meth) acrylic group and may be present in any of the side chain and / or terminal of the molecule. From the viewpoint of rubber elasticity and flexibility, It is preferably present at the end of the main skeleton.
  • the weight average molecular weight of the oligomer is preferably 10,000 to 50,000. If the weight average molecular weight is less than 10,000, the elasticity of the cured product tends to be hardly exhibited, and cracks occur in the cured product in a high temperature durability test. On the other hand, when the weight average molecular weight exceeds 50,000, the viscosity becomes too high, and stringing occurs when the thermosetting composition is applied. Examples of the method for measuring the weight average molecular weight in the present invention include GPC, light scattering, viscosity measurement, and mass spectrometry (TOFMASS and the like), and the weight average molecular weight is measured by GPC.
  • the component (A) according to the present invention can be obtained by various polymerization methods, and the method is not particularly limited, but a radical polymerization method is preferable from the viewpoint of versatility of the monomer and ease of reaction control.
  • a radical polymerization method is preferable from the viewpoint of versatility of the monomer and ease of reaction control.
  • controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable.
  • the method for introducing the (meth) acrylic group includes (1) a vinyl polymer having a hydroxyl group at the terminal and a chlorine-containing, bromine- or hydroxyl-containing polymer ( (2) a method based on a reaction with a (meth) acrylate compound, (2) a method based on a reaction between a vinyl polymer having a halogen group at the terminal and an alkali metal ion or quaternary ammonium ion-containing (meth) acrylate compound, (3) at the terminal
  • Examples thereof include a method obtained by reacting a vinyl polymer having a hydroxyl group with a diisocyanate compound and reacting a residual isocyanate group with a hydroxyl group-containing (meth) acrylate.
  • Oil resistance can be improved by using, as the component (A), an oligomer having a skeleton obtained by copolymerizing a compound having a vinyl group and having a (meth) acryl group.
  • the main skeleton is a polymer of a (meth) acryl monomer having at least one reactive (meth) acryl group in the molecule, although it may be present at either the side chain and / or the terminal of the molecule, it is most preferably present at the terminal of the main skeleton from the viewpoint of rubber elasticity and flexibility.
  • a (meth) acrylic monomer can be included as the (A) component, and the (A) component according to the present invention may be a compound having a (meth) acrylic group, A (meth) acryl monomer alone, an oligomer having a (meth) acryl group alone, or a mixture thereof may be used. Furthermore, it is preferable that the said (A) component mixes the said oligomer and the said monomer in order to adjust the viscosity of a composition and to improve workability
  • the (meth) acryl monomer is a low molecular weight (meth) acryl compound having one (meth) acryl group in one molecule and having a molecular weight of less than 1,000.
  • Preferred (meth) acrylic monomers are (meth) acrylic monomers having a hydroxyl group in the molecule and / or (meth) acrylic monomers having a saturated alicyclic structure.
  • Specific examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl.
  • Examples include succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and the like. Most preferably, it includes 2-hydroxypropyl methacrylate and / or 2-hydroxyethyl methacrylate, but is not limited thereto.
  • Specific examples of the (meth) acrylic monomer having a saturated alicyclic structure include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, adamantanyl (meth) acrylate, and the like.
  • a (meth) acrylic monomer having an isobornyl skeleton and / or a dicyclopentanyl skeleton.
  • the addition ratio of the (meth) acrylic oligomer and the (meth) acrylic monomer is preferably 100: 0 to 60:40.
  • the (meth) acrylic monomer may be a single monomer or a mixture of two or more.
  • the preferred component (A) according to the present invention preferably contains at least one selected from the group consisting of a urethane acrylate oligomer, an epoxy acrylate oligomer, an oligomer having a (meth) acryl group, and a (meth) acryl monomer.
  • Examples of the component (B) that can be used in the present invention include organic peroxides having a structure represented by the following general formula 1.
  • R 1 to R 8 in the general formula 1 may be the same or different and each represents a chain, branched or cyclic hydrocarbon group, and / or any two of R 1 to R 8 have an alicyclic structure. It may be formed. Particularly preferred is a structure in which R 4 and R 5 have a cyclohexane ring as shown in the following general formula 2 in which an alicyclic structure is formed. Further, the cyclohexane ring of the general formula 2 may be substituted with R a to R c .
  • organic peroxide examples include 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (T-butylperoxy) -2-methylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, n-butyl-4,4-di (t- Examples thereof include, but are not limited to, butylperoxy) valerate and 2,2-di (4,4-di (t-butylperoxy) cyclohexane) propane.
  • the product name corresponds to the Perhexa series manufactured by NOF Corporation.
  • the organic peroxide may be a single substance or a mixture of two or more kinds.
  • R 1 to R 8 are each independently a chain, branched or cyclic hydrocarbon group, and any two of R 1 to R 8 may form an alicyclic structure.
  • R 1 to R 3 and R 6 to R 8 are each independently a chain, branched or cyclic hydrocarbon group, and any two of R 1 to R 8 form an alicyclic structure.
  • R a to R c are each independently a hydrogen atom, a halogen atom, or a substituent of an alkyl group having 1 to 20 carbon atoms.
  • the chain or cyclic hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms or a carboxylic acid ester group having 1 to 20 carbon atoms.
  • alkyl group examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, 1,3-dimethylbutyl, 1-isopropylpropyl, 1,2-dimethyl Butyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group 3-methyl-1-isopropylbut
  • ester group examples include monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, methyl pentanoate, ethyl pentanoate and pentanoic acid. And propyl, butyl pentanoate, t-butyl pentanoate and the like.
  • a cycloalkylene group is preferably, cyclopropylene group, cyclobutylene Group, cyclopentylene group, cyclohexylene group, cycloheptalene group, cyclooctalene group and the like are preferable.
  • component (B) it is preferable that 0.1 to 10 parts by mass of component (B) is added to 100 parts by mass of component (A).
  • the amount of the component (B) is less than 0.1 parts by mass, the heat curability may be lowered, and when the amount is more than 10 parts by mass, the storage stability may be deteriorated.
  • the component (C) that can be used in the present invention is an antioxidant having a phenol skeleton.
  • the antioxidant having the phenol skeleton is not limited as long as it has an effect of preventing the cured product of the thermosetting composition from being oxidized, but preferably has a phenol group as represented by the general formula 3.
  • the component (C) is mainly composed of hydrogen, carbon and oxygen, and preferably does not contain phosphorus or sulfur.
  • R 9 to R 10 each independently represents any of a methyl group, an ethyl group, a propyl group, and a butyl group.
  • Specific examples of the antioxidant having a phenol skeleton include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, mono (or di or tri) ( ⁇ -methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amyl Hydroquinone, triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) prop
  • Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all of these are manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), ADK STAB AO-30, AO-40, AO-50, AO-60, AO-616, AO-635, AO-658, AO-80, AO-15, AO- 18, 328, AO-37 (all manufactured by ADEKA Corporation), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX -109 , IRGANOX-1222, IRGANOX-1330, (all manufactured by both BASF Co.) IRGANOX-245, IR
  • a monoacrylate phenolic antioxidant can also be used as the component (C).
  • Specific examples include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name Sumilizer GM), 2,4-di-t-amyl. Examples include, but are not limited to, -6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name: Sumilizer GS).
  • the said component (C) may be individual, or 2 or more types of mixtures may be sufficient as it.
  • the component (D) that can be used in the present invention is an antioxidant having a thioether skeleton.
  • the antioxidant having the thioether skeleton is not limited as long as it has an effect of preventing the cured product of the thermosetting composition from being oxidized. It preferably has a thioether group.
  • component (D) includes ADEKA STAB AO-23, AO-412S, and AO-503 manufactured by ADEKA Corporation, and IRGANOX 1726, 1520L as compounds having both Formula 3 and Formula 4. However, it is not limited to these. In addition, the said component (D) may be individual, or 2 or more types of mixtures may be sufficient as it.
  • the component (E) that can be used in the present invention is a colorant such as a dye or an organic pigment.
  • the dye here is a colored substance that is mainly used for coloring by being dissolved in a solvent, and the pigment is a substance that is mainly dispersed and colored in a specific medium.
  • the component (E) is preferably compatible and dispersed in the resin, and does not include an inorganic pigment that is colored by the color of the inorganic filler itself.
  • Specific examples of the component (E) include, but are not limited to, basic dyes, direct dyes, acid dyes, azo pigments, polycyclic pigments, lake pigments, and the like.
  • the main types of azo pigments include monoazo pigments, diazo pigments, and condensed diazo pigments.
  • polycyclic pigments are isoindolinone, quinophthalone, anthraquinone (for example, 1,4-bis (butylamino) -9,10-anthraquinone, 1- (methylamino) anthraquinone, oil-soluble anthraquinone dye, etc.) , Anthrone, xanthene, diketopyrrolopyrrole, perylene, anthraquinone (anthrone), quinacridone, indigoid, quinacridone, perinone, indigoid, dioxazine, xanthene, triphenylmethane (for example, oil-soluble triphenylmethane dye), phthalocyanine (for example, , Phthalocyanine blue, etc.), azomethine, metal naphthenate (eg, copper naphthenate), dicyclohexyl phthalate pigment (eg, dicyclohexyl phthal
  • component (E) Specific product names of component (E) include Yellow SSG, Yellow 93, Yellow GE, Yellow 3G, Yellow 185, Yellow 54, Orange S, Orange R, Orange 826N, Scarlet 3, manufactured by Chuo Gosei Chemical Co., Ltd. Red TR-71, Red RC, Red 6B, Pink 330, Brown SGN, Brown PB, Blue BOM, Blue BA, Blue 94, Blue 8B, Violet MVB, Green 201, Green GB, lack 430B Black 109, Black 141, etc., OIL BLACK 803, OIL BRAC manufactured by Orient Chemical Industry Co., Ltd.
  • OIL BLACK 860 OIL BLACK BS, OIL BLACK HBB, OIL BLACK NO5, OIL BLUE 2N, OIL BLUE 613, OIL BLUE 630, OIL BLUE 650M, OIL BROWN BB, OILGREEN 30IL OIL ORANGE PS, OIL PINK 312, OIL RED 330, OIL RED 5B, OIL RED OG, OIL RED RR, OIL SCARLET 308, OIL SCARLET 318, OIL VIOLET LOW ILO LOW ILO LOW ILO LOW ILO LOW ILO LOW ILO LOW ILO LOW ILO LOW ILO LOW ILO LOW ILO LOW ILO LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW LOW
  • component (C) and 0.1 to 5 parts by mass of component (D) are added to 100 parts by mass of component (A).
  • the ratio of the component (C) to the component (D) is preferably 1: 1 to 3: 1. If the amount is higher than the upper limit values of the components (C) and (D), the heat curability tends to be reduced. If the amount is lower than the lower limit value, it is difficult to suppress discoloration of the cured product. Further, 0.001 to 0.05 parts by mass of component (E) is preferably added to 100 parts by mass of component (A).
  • the addition amount of the component (E) is an element that determines the shade of the color, so that it does not particularly affect the physical characteristics, but the addition of the addition amount is suitable as a hue. If photocurability is imparted, if the color is too dark, the photocurability tends to be reduced, and it is preferably less than 0.05 parts by mass. On the other hand, when it is less than 0.001, it is difficult to be colored.
  • antioxidants are known, and specific examples include phosphorus and nitroxides. Although an anti-aging agent is not necessarily required, conventionally known antioxidants and light stabilizers can be appropriately used.
  • phosphorus antioxidants include Irgafos 38, Irgafos 168, Irgafos P-EPQ (all of which are manufactured by Ciba Geigy Japan).
  • nitroxide antioxidants include cyclic hydroxyamines such as 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical
  • cyclic hydroxyamines such as 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical
  • the nitroxy free radicals from are illustrated.
  • an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.
  • nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like.
  • a stable free radical such as a galvinoxyl free radical may be used.
  • a filler can be added for the purpose of adjusting the viscosity.
  • fumed silica with an alkyl group added to the surface Since silanol remains on the surface of fumed silica, it is hydrophilic in an untreated state.
  • fumed silica having 2 or more carbon atoms and having a linear alkyl group added thereto is preferable.
  • Specific product names include NKC130 and R805 manufactured by Nippon Aerosil Co., Ltd.
  • There are many types of surface treatment of fumed silica but treatments other than alkyl groups tend to settle during long-term storage after being dispersed in the thermosetting composition.
  • a photoinitiator may be added to impart photocurability.
  • Specific examples include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3 -Bromoacetophenone, 2,2-diethoxyacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 2,4,6-trimethylbenzophenone, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl)) Phenyl) propanone), 4-allylacetophenone, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-methylbenzophenone, 4-chloro-4'-benzene Dilbenzophenone, 2-hydroxy-2-
  • the photoinitiator may be used in combination with a light stabilizer.
  • the light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name SANOL). ) And the like. The effect is further exhibited by the combined use, and the heat resistance may be particularly improved.
  • Tinuvin C353, Tinuvin B75 (all of which are manufactured by Ciba Geigy Japan) or the like in which an antioxidant and a light stabilizer are mixed in advance may be used.
  • thermosetting composition of the present invention has various organic fillers, inorganic fillers, additives, anti-aging agents, plasticizers, in order to adjust the properties and physical properties so that the characteristics of the present invention are not impaired. You may mix
  • thermosetting composition of the present invention can be cured by heating after being applied to a seal part, a potting part, etc., it can be used for a site that cannot be handled only by photocuring. Moreover, since this invention has heat resistance and oil resistance, it can be used also for the components which are always exposed to high temperature and oil scattering among in-vehicle electronic components. Specific examples of automotive electronic components that require extreme durability include oil pressure switches, air flow meters, cam position sensors, water temperature sensors, crank position sensors, intake air temperature sensors, vehicle speed sensors, and other vehicles that require bonding. It can be used for assembling electrical and electronic parts.
  • a compound having a main skeleton composed of a polymer of (meth) acrylic monomers and having at least two (meth) acrylic groups in the molecule was produced as follows. Using cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand and diethyl-2,5-dibromoadipate as an initiator, n-butyl acrylate was polymerized, and 300 g of this polymer was added to N, N-dimethylacetamide ( 300 mL), added with 5.3 g of potassium acrylate, stirred under heating in a nitrogen atmosphere at 70 ° C.
  • polymer 1 poly (n-butyl acrylate) having an acrylic group at both ends (hereinafter referred to as polymer 1). ) was obtained.
  • N N-dimethylacetamide in the mixed solution was distilled off under reduced pressure, toluene was added to the residue, and insoluble matter was removed by filtration. Toluene in the filtrate was distilled off under reduced pressure to purify the polymer 1.
  • the polymer 1 after purification had a weight average molecular weight of 32308, a degree of dispersion of 1.36, and an average number of terminal acrylic groups of 2.0 (that is, the rate of introduction of acrylic groups at the terminals was 100%).
  • the aforementioned “number average molecular weight” and “dispersity (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, two GPC columns packed with polystyrene cross-linked gel (shodex GPC K-802.5; manufactured by Showa Denko KK) (shodex GPCK-804; manufactured by Showa Denko KK) are used in series. Chloroform was used as the GPC solvent.
  • thermosetting composition [Examples 1 to 12, Comparative Examples 1 to 11]
  • a thermosetting composition is described as a composition.
  • the transmittance of the cured product is measured by “UV-VISABLE SPECTROTOPOMETER UV-1600” manufactured by Shimadzu Corporation.
  • the cured product is set in a measuring machine that has been subjected to base correction in advance, and the transmittance in the range of 300 nm to 800 nm is measured.
  • Standard illuminant D65 is used for the measurement.
  • a tristimulus value consisting of X, Y, and Z is calculated from the transmittance, and “yellowness (YI)” is calculated based on the tristimulus value from Equation 1.
  • Yellowness ( ⁇ YI) is calculated from YI: yellowness after exposure and YI0: initial yellowness.
  • the composition is left in a hot air drying oven set at 130 ° C. for 1 hour to produce a cured product, and after returning to room temperature, the yellowness is measured. For details, follow the JIS K 7373 yellowness calculation method.
  • Examples 1 to 10 have a yellowing degree of less than 40 after 240 hours.
  • Comparative Examples 1 to 11 the yellowing degree exceeds 40 after 240 hours.
  • Comparative Examples 6 to 8 are compositions lacking the component (C) and / or the component (D), but the degree of yellowing was not sufficient even when the component (B) was used.
  • Table 3 shows the yellowing degree when the component (A) is changed. Since it is difficult to confirm the difference in a very severe test of 150 ° C. atmosphere, Table 3 is confirmed in a 120 ° C. atmosphere lower than 150 ° C. Even in that case, when Examples 1, 11, and 12 were compared with Comparative Example 1, a difference in yellowing degree was observed after 1000 hours, which was less than 40 in the examples.
  • Example 1 Comparative Example 1, Comparative Example 8, and Comparative Example 11, physical properties were measured for hardness, tensile shear strength, elongation rate, and shear bond strength. As a durability test, a heat resistance confirmation test was conducted. Table 4 summarizes the initial measurement results and the rate of change in physical properties after the high temperature durability test.
  • the thickness of the composition is set to 2 mm, and left for 1 hour in a hot-air drying oven set at 130 ° C. to prepare a sheet-like cured product.
  • a test piece is made by punching with No. 3 dumbbell. Fix both ends of the test piece to the chuck so that the long axis of the test piece and the center of the chuck are aligned.
  • the test piece is pulled at a pulling speed of 50 mm / min, and the maximum load is measured.
  • the strength at the maximum load is defined as “tensile strength (MPa)”, and the strength of the cured product itself is quantified. Details follow JIS K 6850.
  • the tensile shear strength is preferably 2.0 MPa or more.
  • the thickness of the composition is set to 2 mm, and left for 1 hour in a hot-air drying oven set at 130 ° C. to prepare a sheet-like cured product.
  • a test piece is made by punching with a No. 3 dumbbell, and marked lines at intervals of 25 mm are written on the test piece.
  • the sample is fixed to the chuck with the same capacity as the measurement of the tensile shear strength and pulled until the test piece is cut under the condition of a tensile speed of 500 mm / min. Since the test piece extends during measurement and the interval between the marked lines increases, the interval between the marked lines is measured with a caliper until the test piece is cut.
  • the elongation ratio is defined as “elongation rate (%)”, which is used as an index of flexibility of the cured product itself. In order to follow expansion and contraction, the elongation is preferably 100% or more.
  • a resin is applied to the tip of 10 mm of 1.6 mm ⁇ 25 mm ⁇ 100 mm (SPCC, SD) and bonded so that the bonding area becomes 25 mm ⁇ 10 mm, and then fixed with a fixing jig for 1 hour in a 130 ° C. atmosphere Let it stand and cure to make a test piece. Fix both ends of the test piece to the chuck so that the long axis of the test piece and the center line of the chuck are in a straight line so that the load passes correctly on the line.
  • the strength at the maximum load is defined as “shear adhesive strength (MPa)” and is used as an index of the adhesive force to the adherend. Details follow JIS K 6850.
  • the shear bond strength is preferably 5.0 MPa or more.
  • High temperature durability test A cured product or a test piece having a plurality of hardnesses, tensile strengths, elongation rates, and shear bond strengths created at the initial measurement is prepared. A part is measured as an initial value, and the remaining part is left in a hot air drying oven set at 120 ° C. for 240 hours at maximum. A cured product or a test piece is taken out and allowed to stand until it reaches room temperature, and then the measurement is performed. In the high temperature endurance test, it is preferable that the absolute value of the change rate falls within 30%.
  • Table 4 confirms whether the physical characteristics are maintained. In all items, the measured values and the rate of change are stable in Example 1, and Comparative Examples 1, 8, and 11 are inferior to Example 1 in any item. When used as a potting agent, sealant, etc., it is also necessary to satisfy stable physical properties.
  • potable electronic parts potting agents and sealants used for parts that are constantly exposed to high temperatures are required to have heat resistance. Since the present invention has heat resistance, it should be used for all on-vehicle electronic components such as oil pressure switches, air flow meters, cam position sensors, water temperature sensors, crank position sensors, intake air temperature sensors, and vehicle speed sensors. Can do. As a feature of the present invention, since the color of the cured product hardly changes even after being exposed to high temperature, it is difficult to cause a defect in appearance as a part.

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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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)

Abstract

[Problème] Quand une résine (méth)acrylique thermodurcissable qui a été colorée en rouge, en bleu, ou analogue par un agent colorant est exposée à une atmosphère de 150°C ou une atmosphère de 120°C en tant que test de durabilité à température élevée, une décoloration rapide a lieu, et il est difficile de maintenir de manière stable la coloration initiale. [Solution] L'invention concerne une composition thermodurcissable comprenant les composants (A) à (E). Composant (A): un composé ayant un groupe (méth)acrylique. Composant (B): un peroxyde organique incluant la structure de formule générale (1). (Dans la formule générale (1), R1 à R8 sont chacun indépendamment un groupe hydrocarboné linéaire, ramifié ou cyclique, et n'importe lesquels de deux des R1 à R8 peuvent former une structure alicyclique.) Composant (C): un antioxydant ayant un squelette de phénol. Composant (D): un antioxydant ayant un squelette de thioéther. Composant (E): un colorant ou pigment organique.
PCT/JP2012/078031 2011-11-17 2012-10-30 Composition thermodurcissable Ceased WO2013073363A1 (fr)

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JP2011251834A JP5861824B2 (ja) 2011-11-17 2011-11-17 熱硬化性組成物

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EP3192778A4 (fr) * 2014-09-11 2018-04-18 Sekisui Chemical Co., Ltd. Couche intermédiaire pour verre feuilleté et verre feuilleté
JP2020097670A (ja) * 2018-12-17 2020-06-25 株式会社Adeka 組成物、これを含有する接着剤、その硬化物およびその製造方法

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CN113621174A (zh) * 2015-03-25 2021-11-09 阿科玛股份有限公司 有色有机过氧化物组合物
CN108350105B (zh) * 2015-11-26 2020-10-13 三键有限公司 热固化性组合物及使用其的导电性粘接剂

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JP2020097670A (ja) * 2018-12-17 2020-06-25 株式会社Adeka 組成物、これを含有する接着剤、その硬化物およびその製造方法
JP7304152B2 (ja) 2018-12-17 2023-07-06 株式会社Adeka 組成物、その硬化物およびその製造方法

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