technical area
The present invention relates to a stereoisomer of an epoxy compound, a curable composition containing it, and a cured product obtained by curing the curable composition.
background engineering
Curable compositions containing epoxy compounds are used as surface protective films, interlayer insulators, protective insulating films for printed alignment substrates, fiber-reinforced composites for semiconductor devices, and organic thin-film devices (eg, electronic devices). electroluminescent organics and organic thin films). . - thin film solar cells). Among these epoxy compounds, epoxy compounds having an aromatic ring are used to obtain a cured product excellent in heat resistance and the like.
However, aromatic compounds cause few problems in electronic materials applications as described above because they generally have high electron density and high dielectric constant. Furthermore, recent advances in the miniaturization and high performance of electronic devices are accompanied by increased performance requirements for the various materials used. For example, as signals become faster and of higher frequency, materials with low electrical energy loss are required, that is, materials with excellent dielectric properties. Therefore, the alicyclic diamine compound, which does not have an aromatic ring, has attracted attention in recent years. Furthermore, the cured products of curable compositions used in the above applications are required to have high heat resistance.
Among these epoxy compounds, epoxy compounds having an alicyclic skeleton are known to provide cured products such as excellent heat resistance. For example, Patent Document 1 describes an epoxy compound having an alicyclic skeleton with a specific structure, and a resin excellent in heat resistance and the like can be obtained.
Among these epoxy compounds, it is known that an epoxy compound having two or more alicyclic skeletons in the molecule can provide a cured product excellent in heat resistance, transparency and the like. E.g. Patent Document 2 describes a curable composition containing a diepoxybicyclohexyl compound.
On the other hand, in recent years, as described above, components with higher heat resistance have been required in the fields of surface protective films, interlayer insulating films, and protective insulating films for printed substrates of semiconductor devices and organic devices of thin film. Furthermore, as described above, materials with excellent dielectric properties are required in electronic materials. Therefore, the conventional epoxy compound proposed in Patent Document 2 has room for further improvements from the viewpoint of heat resistance, dielectric properties and the like of a cured product.
reference to the state of the art patent documents
- Patent document 1: JP-A nr. S49-126658
- Patent Document 2: JP-A No. 2008-31424
Content of the invention The problem to be solved by the present invention
The present inventors have now discovered that a mixture of stereoisomers of an epoxy compound containing a stereoisomer with a specific structure above a certain ratio can significantly increase the yield of a cured product obtained by curing a curable composition containing the compound. epoxy. Heat resistance and dielectric properties. mix.
Therefore, an object of the present invention is to provide a stereoisomer of an epoxy compound which, when contained in a curable composition, can improve heat resistance and dielectric properties of a cured product. Another object of the present invention is to provide a curable composition for obtaining a cured product with excellent dielectric and heat resistance properties.
means to solve problems
Accordingly, the present invention includes the following inventions:
[1] Stereoisomers of epoxy compounds represented by the following formula (1):
Stereoisomers represented by formula (2):
Among them, in formula (1),
R1a R18each independently selected from the group consisting of hydrogen, alkyl, and alkoxy, and
Among them, in formula (2),
R1a R18are the same as formula (1).
[2] The stereoisomer according to [1], where R1a R18It's all hydrogen.
[3] A mixture of stereoisomers of the compound represented by the above formula (1),
where the amount of stereoisomer according to [1] or
[2] 60 mol% or more with respect to the total amount of the mixture of stereoisomers.
[4] A curable composition containing the stereoisomer described in [1] or [2] or the mixture described in [3].
[5] The curable composition according to [4], further comprising at least one selected from the group consisting of a curing agent, a thermal cationic polymerization initiator and a photocationic polymerization initiator.
[6] The curable composition according to [5], wherein the hardener is at least one selected from acid anhydride compounds and anionic compounds.
[7] The curable composition according to [6], wherein the anionic compound is at least one selected from the group consisting of amine compounds, phenolic compounds, thiol compounds, and latent curing agents. agent.
[8] The curable composition according to any of [4] to [7], further comprising a curing accelerator.
[9] The curable composition of [8], wherein the cure accelerator is an imidazole-based cure accelerator.
[10] The curable composition according to any of [4] to [9], which further contains an epoxy compound, an oxetane compound and a vinyl group other than the compound represented by the formula (1). At least one of the group consisting of compounds. ether.
[11] A cured product obtained by curing the curable composition according to any of [4] to [10].
[12] A method of producing a cured product, comprising the step of curing the curable composition described in any of [4] to [10].
invention effect
In accordance with the present invention, a stereoisomer or a mixture of stereoisomers can be provided which is useful for producing a cured product with excellent heat resistance and dielectric properties. In other words, according to the present invention, the stereoisomer represented by the above formula (2) or the stereoisomer mixture of the compound represented by the formula (1) contains the stereoisomer represented by the formula (2) in a specific ratio or More stereoisomers can be used as agents to improve heat resistance and dielectric properties. Furthermore, according to the present invention, a curable composition can be provided to obtain a cured product with excellent dielectric and heat resistance properties.
Detailed description of the invention definition
The terms "part", "%" and the like are based on mass unless otherwise specified in this document. As used herein, the term "epoxy equivalent" is defined as the mass of an epoxy compound having 1 equivalent of an epoxy group. Here, in the case of a mixture of m types (m is an integer greater than 2) of epoxy compounds, the epoxy equivalent of the mixture is expressed as:
The epoxy equivalent of an epoxy compound can be measured based on JISK7236.
Stereoisomers of epoxy compounds.
In an embodiment of the present invention, the stereoisomer of the epoxy compound is a stereoisomer of the epoxy compound represented by the following formula (1), and the stereoisomer is represented by the following formula (2). The stereoisomers represented by the following formula (2) may be contained in the curable composition.
I form (1), R1a R18Each is independently selected from the group consisting of hydrogen, alkyl, and alkoxy.
Yo formula (2), R1a R18Each is independently selected from the group consisting of hydrogen, alkyl, and alkoxy.
In one embodiment of the present invention, in the epoxy compound of the present invention or the stereoisomer of the present invention, R1a R18in the above formula (1) or (2), each independently selected from the group consisting of hydrogen, alkyl, and alkoxy. Among them, hydrogen is particularly preferred.
The number of carbons in the alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group may be linear or branched.
Examples of straight chain alkyl groups include methyl, ethyl, n-propyl, and n-butyl.
Examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl, and tert-butyl.
The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 4.
The alkyl group that is part of the alkoxy group may be a straight or branched chain alkyl group.
Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.
In a preferred embodiment of the present invention, R1a R18in the above formula (1) and/or (2) are all hydrogen.
In a preferred embodiment of the present invention, R1a R18Same as R in the above formula (2)1a R18in formula (1) above.
In an embodiment of the present invention, the stereoisomer mixture of the compound represented by the above formula (1) is a mixture in which the amount of the stereoisomer represented by the above formula (2) is 60 mol% or more based on the Total amount. mixture of stereoisomers. It is preferably 70 mol% or more, more preferably it is 75 mol% or more.
In other embodiments of the present invention, the mixture of stereoisomers of the compound represented by formula (1) above is at least one of the stereoisomers of the compound represented by formula (1) above represented by formula (2) above A mixture of stereoisomers, wherein, in a gas chromatogram obtained by analysis of the mixture by gas chromatography under the following analytical conditions, the ratio of the peak area of the largest peak to the sum of the peak areas derived from the stereoisomers of the compound is 60% or more, represented by formula (1), and the peak of the largest peak is within the retention time range of 29.80 to 30.30 minutes. The mixture of the present invention is a mixture containing at least one stereoisomer represented by the above formula (2) among the stereoisomers of the compound represented by the above formula (1), wherein the gas chromatogram obtained by analyzing the mixture by gas chromatography under the analysis conditions shown below, the ratio of the maximum peak area to a peak within the retention time range of 29.90 to 30.30 minutes and the sum of the peak areas within the time range retention from 29.80 to 30.50 minutes 60% or more.
(Analysis conditions)
Chromatographic column: HP-5MS (Agilent Technologies, Inc.), length: 30.0 m, inner diameter: 320 μm, film thickness: 250 μm
Liquid phase: (5%-fenil)-methylpolysiloxane
Carrier gas: N2
Tight flow: 5.2ml/min
Split Ratio: 60:1
Sample inlet temperature: 200°C.
Detector temperature: 250°C.
Column heating conditions: 50°C (5 minutes), 50-150°C (5°C/min), 150-250°C (10°C/min), 250°C (10 minutes)
In other embodiments of the present invention, the mixture of stereoisomers of the compound represented by formula (1) above is at least one of the stereoisomers of the compound represented by formula (1) above represented by formula (2) above A a mixture of stereoisomers, ie a stereoisomer derived from the compound represented by the formula (1), is a gas chromatogram obtained by subjecting the mixture to gas chromatographic analysis under the above analytical conditions.
In another embodiment of the present invention, the ratio of the peak area of the largest peak of the mixture of stereoisomers of the compound represented by the above formula (1) and the sum of the peak areas derived from the stereoisomers is 60% or more. . The content of the compound represented by the formula (1) contained in the mixture in the gas chromatogram obtained by gas chromatography analysis under the above analysis conditions. The peak area ratio of the largest peak is preferably 62% or more, more preferably 65% or more, even more preferably 70% or more, even more preferably 75% or more. The peak of the largest peak occurs in the retention time interval of 29.80 to 30.30.
In another embodiment of the present invention, the mixture is a mixture comprising at least one stereoisomer represented by the above formula (2) among the stereoisomers of the compound represented by the above formula (1), wherein gas chromatography on the gases obtained by analyzing the mixture under the above analysis conditions is the peak area of the largest peak with a peak within the retention time range of 29.90 to 30.30 minutes relative to the sum of the peak areas within the retention time range of 29.80 minutes The percentage at 30.50 minutes is 60% or more. The peak area ratio of the largest peak is preferably 65% or more, more preferably 70% or more, even more preferably 75% or more.
In an embodiment of the present invention, the stereoisomer corresponding to the largest peak in the mixture of stereoisomers of the compound represented by formula (1) above is preferably represented by formula (2) above.
Process for preparing stereoisomers of epoxy compounds.
The method for producing the stereoisomer represented by the formula (2), which is a stereoisomer of the epoxy compound represented by the formula (1), will be described in detail.
The stereoisomer represented by the formula (2) can be obtained by a method including the step of reacting a compound represented by the following formula (3) with a peroxyacid:
where R1a R18Each is independently selected from the group consisting of hydrogen, alkyl, and alkoxy.
R1a R18In the above, the formula (3) is the same as that described in the formula (1).
In an embodiment of the present invention, the stereoisomer represented by the above formula (2) can be obtained by reacting the compound represented by the above formula (3) with peroxyacids such as hydrogen peroxide, peroxyacid, peracetic acid, perbenzoic acid, etc. . synthesize
In an embodiment of the present invention, the compound represented by the above formula (3) can be synthesized by the Diels-Alder reaction of butadiene and dicyclopentadiene.
In an embodiment of the present invention, when hydrogen peroxide is used as the peroxyacid, the preparation of the stereoisomer represented by the above formula (2) is preferably carried out in the presence of a catalyst and/or a surfactant, more preferably in the presence of. catalysts and surfactants.
Examples of catalysts include tungsten compounds, phosphates, phosphonates, and salts thereof.
Tungsten compounds are not particularly limited as long as they can generate tungsten anions in water and catalyze the epoxidation reaction of carbon-carbon double bonds with hydrogen peroxide. Examples include tungsten acid, tungsten trioxide, tungsten trisulfide, tungsten hexachloride, phosphotungstic acid, silicotungstic acid, etc.; tungstates such as ammonium tungstate, potassium tungstate, sodium tungstate and calcium tungstate. Among them, tungstic acid, tungstic trioxide, phosphotungstic acid and sodium tungstate are preferred, and sodium tungstate dihydrate is more preferable. These tungsten compounds can be used singly or in combination of two or more.
Phosphates, phosphonates and salts thereof are not particularly limited as long as they can catalyze the epoxidation reaction of carbon-carbon double bonds with hydrogen peroxide. Examples of phosphoric acid include phosphoric acid, polyphosphoric acid, pyrophosphate, hexametaphosphate, hypophosphite, phosphoric acid, dodecylphosphoric acid, 2-ethylhexylphosphoric acid, and the like. Examples of phosphates include sodium phosphate, potassium phosphate, ammonium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, sodium polyphosphate, sodium hexametaphosphate, hexametaphosphate sodium hexametaphosphate, sodium hexametaphosphate pyrophosphate, disodium dihydrogen pyrophosphate, sodium hypophosphite pyrophosphate, and sodium phosphite. Examples of phosphonic acids include methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid, t-butylphosphonic acid, phenylphosphonic acid, 4-methoxybenzenephosphonic acid, 1-aminophosphonic acid, 4-aminophosphonic acid, 1- aminophosphonic acid, 1-bis(phosphonic acid), nitrilotris(methylenephosphonic acid), etc. Examples of phosphonates include sodium phenylphosphonate and the like. Among them, phosphoric acid, phenylphosphonic acid, phosphoric acid, hypophosphoric acid, 2-ethylhexylphosphoric acid, laurylphosphoric acid, sodium dihydrogen phosphate, etc., among them, phenylphosphonic acid is preferred. In the present invention, one or a combination of two or more selected from the group consisting of the aforementioned phosphates, phosphonates and salts thereof may be used.
The amount of the catalyst used is usually 0.0001 to 20 mol%, preferably 0.01 to 10 mol%, based on 1 mol of the compound of formula (3). When the catalyst is a combination of several catalysts, the amount of catalyst used refers to the total amount.
Examples of surfactants include ionic surfactants. Examples of ionic surfactants include cationic surfactants and anionic surfactants. Examples of cationic surfactants include quaternary ammonium salts, nitrogen ring-containing quaternary ammonium salts, quaternary phosphonium salts and quaternary sulfonium salts, and quaternary ammonium salts are particularly preferred. Examples of quaternary ammonium cations include benzyltrimethylammonium, benzyltributylammonium, benzyltrimethylammonium, lauryldimethylbenzylammonium, tetramethylammonium, tetrapropylammonium, tetrabutylammonium, tetrahexylammonium, tetraoctylammonium, dimethylammonium, dimethylammonium, dimethylammonium, dimethylammonium, dimethylammonium, dimethylammonium, dimethylammonium, dipropylammonium, diole yldimethylammonium, lauryltrimethylammonium, distearyldimethylammonium, stearyltrimethylammonium , dioctadecyldimethylammonium, behenyldimethylammonium, cetyltrimethylammonium, trioctylmethylammonium, cetyldimethylethylammonium, cetyltrimethylammonium, and lauryldimethylethylammonium. Preferred quaternary ammonium salts are cetyltrimethylammonium methylsulfate, trioctylmethylmethylsulfate, and didecyldimethylmethylsulfate. The amount of surfactant to be used is 0.0001 to 10 mol%, usually relative to 1 mol of compounds of formula (3). 0.01 to 10 mol% is preferable.
In an embodiment of the present invention, crystallization and purification can further increase the proportion of the stereoisomer represented by formula (2) above in the mixture. More specifically, the proportion of the stereoisomer represented by the above formula (2) can be increased by dissolving the mixture in isopropanol, cooling to -10°C, crystallizing and then filtering followed by drying the resulting residue.
In one embodiment of the present invention, crystallization and purification can further increase the peak area ratio of the largest peak with a peak within the retention time range of 29.90 to 30.30 on the gas chromatogram. obtained by gas chromatographic analysis. previous analysis conditions. More specifically, the peak area ratio of the largest peak can be increased by dissolving the mixture in isopropanol, cooling to -10 °C, crystallizing, and then filtering and drying the resulting residue.
curable composition
In an embodiment of the present invention, the curable composition contains a mixture of stereoisomers of the compound represented by the above formula (2) or a stereoisomer of the compound represented by the above formula (1).
The curable composition may contain a stereoisomer represented by the above formula (2) or a mixture of stereoisomers of the compound represented by the above formula (1), so as to more effectively impart heat resistance and/or dielectric properties to the cured product. From one point of view, other components (for example, hardener, thermal cationic polymerization initiator, photocationic polymerization initiator, curing accelerator, epoxy compound other than the compound represented by the above formula (1), oxygen heterocycle, etc. combination butane and vinyl ether compounds).
Components that can be included in the curable composition will be described in detail below.
Stereoisomers of the compound represented by formula (2) or a mixture of stereoisomers of the compound represented by formula (1)
The stereoisomers or mixtures of stereoisomers of the compound represented by the formula (2) are as described above.
In an embodiment of the present invention, the mixing ratio of the mixture of stereoisomers of the compound represented by the formula (1) in the curable composition is preferably 5 to 100 parts by mass of the total curable composition. It is 99 to 99 parts by mass, more preferably 10 to 80 parts by mass, more preferably 15 to 40 parts by mass. In other embodiments of the present invention, with respect to 100 mass parts of the total amount of the curable composition, the mixing ratio of the stereoisomer represented by the formula (2) in the curable composition is preferably 5 to 80 mass parts. , more preferably it is the range of 10-50 parts by mass, more preferably it is the range of 12-40 parts by mass. When the stereoisomer of the compound represented by the formula (2) or the stereoisomer mixture of the compound represented by the formula (1) is contained within this range, a cured product with more excellent dielectric and heat resistance properties can be obtained.
In an embodiment of the present invention, the curable composition contains a stereoisomer or a mixture of stereoisomers of the compound represented by the formula (2) of the present invention and an acid anhydride compound, or the curable composition of the present invention contains stereoisomers represented by formula (2) or mixtures of stereoisomers of the compounds represented by formula (1), compositions of acid anhydride compounds and curing accelerators, stereoisomers or mixtures of formula (2) The epoxy equivalent of the stereoisomer of the compound of formula (1 ) content in the composition is preferably 70 to 600 g/equiv., more preferably 70 to 400 g/equiv. and even more preferably from 85 to 300 g/eq. equiv., even more preferably from 90 to 300 g/equiv., and even more preferably from 90 to 200 g/equiv.
hardener
In one embodiment of the present invention, the hardener that can be included in the curable composition can be, for example, an anhydride compound or an anionic compound (eg, an amine compound, a phenol-type compound, or a latent curing agent), preferably anhydride compounds or phenolic compounds.
anhydrides
As the acid anhydride compound contained in the curable composition of the present invention, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, methylcarbon hydride, cyclohexane anhydride , cyclohydride, cyclohexane tetracarboxy anhydride Lico Anhydride, Horse Maleic Anhydride, Phthalic Anhydride, Dodecenylsuccinic Anhydride, Octenylsuccinic Anhydride, Pyromellitic Acid, Trimellitic Anhydride, Alkylstyrene-Maleic Anhydride Copolymer, Hydrochloric Anhydride, Polyazelaic Anhydride, Dibenzophene Tetracarboxylic Anhydride na, ethyl acetate-trimellitaglycol, bistoacetate , bisto-tri melaglycol, e , benzophenone-tetracarboxylic acid, polyadipic anhydride, polysebacic anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, high anhydride, norbornane-2,3-dicarboxylic anhydride, etc.
Among them, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride or combinations thereof are preferred because when they are combined with a stereoisomer represented by formula (2) or a stereoisomer represented by formula (2) when the mixture of isomers is combined, resistance to heat of the cured product can be further improved. 1) The present invention. The curable composition according to the present invention may contain one or two or more of the above-mentioned acid anhydride compounds.
From the viewpoint of heat resistance of the cured product, the amount of the curing agent when the curable composition of the present invention does not contain an epoxy compound other than the compound represented by the formula (1) above is described below, in based on the amount contained in the curable composition The epoxy equivalent of the stereoisomer of formula (2) according to the present invention or the mixture of stereoisomers of the compound of formula (1) is preferably 0.5~1.5 equivalents (anhydride equivalents of acid), more preferably 0.6~1.2 equivalents, more preferably 0.8 to 1.2 equivalents. The amount of the curing agent, when the curable composition of the present invention contains epoxy compounds other than the compound represented by the above formula (1), is based on 1 epoxy equivalent of the mixture of stereoisomers of formula (2) of the stereoisomer of the The compound of the formula (1) and the epoxy compound of the epoxy compound, except for the compound represented by the above formula (1), contained in the curable composition is preferably 0.5 to 1.5 equivalents (acid anhydride equivalent ), more preferably, it is 0.6 to 1.2 equivalents, and it is even more preferred that it is 0.8 to 1.2 equivalents. The mixing ratio of the curing agent in the curable composition is preferably in the range of 10 to 80 mass parts, more preferably in the range of 20 to 60 mass parts, based on 100 mass parts of the total amount of the compound. curable. material. composition. A lot of.
Curing agents other than acid anhydride compounds
Examples of the curing agent that can be contained in the curable composition of the present invention include anionic compounds such as amine compounds and phenolic compounds, latent hardeners and the like, in addition to acid anhydride compounds.
Eksempler på aminforbindelser indbefatter polyoxyethylenediamine, polyoxypropylenediamine, polyoxybutylenediamine, polyoxyethylenetriamine, polyoxybutylenetriamine, polyoxypentylenetriamine, diethylenetetramine Amine, tetraethylenepentamine, m-xylylenediamine, trimethylhexamethylenediamine, 2-methylisethylamino, cyclopropylamino, cyclopropylamino, cycloprop ilamino, cyclopropylamino, cyclopropylamino, cyclopropylamino, cyclopropylamino, cyclopropylamino, cyclopropylamino, cyclopropylamino , , bis (4-aminocyclohexyl)methane, norbornandiamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfona, N-aminoethylpiperazine, etc.
Algunos fenolforbindelsen er de novolakressiner kontendende et xylylenskelet, novolakressiner kontendende y dicyclopentadienskelet, novolakressiner kontendende et biphenylskelet, novolakressiner kontendende et terpenskelet, bisfenol A novolaca, bisfenol S nolovaca, bisfenol S novolaca, bisfenol engen bisfenol, bisfenol. , bisphenol Z novolac, tetramethylbisphenol A novolac, tetramethylbisphenol F novolac, dimethylbisphenol F novolac, tetramethylbisphenol S novolac, dimethylbisphenol novolac S, tetramethyl-4,4'-biphenol novolac, trihydroxyfenilmethane novolac, trihydroxyfenilmethane novolac, novolaca de somfatter, hidroquinonnovolac, pirogallolnovolac, diisopropylidennovolac, 1,1-di-4-hidroxifenilfluorennovolac, fenolisereda polibutadienenovolac, fenolnovolac, cresolnovolac, etilfenolnovolac, butylocvolacolnovolac, butyl-ocvolacolnovolac, etc.
Examples of latent curing agents include dicyandiamide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, ketimine, imidazole compounds, hydrazide compound, amine adduct latent curing agent.
The curable composition according to the present invention may contain one or two or more of the above-mentioned curing agents.
From the viewpoint of heat resistance of the cured product, the mixing ratio of the hardener in the curable composition is preferably in the range of 10 to 80 parts by mass, more preferably 20 to 60 parts by mass based on 100 parts. by mass of the total amount of the curable composition within the range of parts by mass.
thermal cationic polymerization initiator
In one embodiment of the present invention, cationic polymerization initiators that may be included in the curable composition include thermal cationic polymerization initiators (initiators capable of generating cationic active species using thermal energy) and photocationic polymerization initiators (capable of generating cationic active species ). starter species). Active substances irradiated with beams of light or electrons). The stereoisomer of formula (2) or the compound of formula (1) can be combined with a mixture or stereoisomer of a thermal cationic polymerization initiator to further improve the heat resistance of the cured product.
Examples of thermal cationic polymerization initiators include (i) thermal cationic polymerization initiators based on aromatic sulfonium salts; (ii) thermal cationic polymerization initiators based on phosphonium salts; (iii) thermal cationic polymerization initiators based on quaternary ammonium salts; (iv) ) cationic thermal polymerization initiators based on aluminum complex, (v) cationic thermal polymerization initiators based on aromatic iodonium salt, (vi) cationic thermal polymerization initiators based on aromatic diazonium salt and (vii ) pyridinium-based thermal cationic polymerization initiators.
(i) Examples of thermal cationic polymerization initiators for aromatic sulfonium salt systems include (2-ethoxi-1-metil-2-oxoetilo)metil-2-naphthilsulfoniohexafluorantimonsyresal, 4-(methoxycarbonyloxy)fenilbencilmetilsulfoniohexafluorantimonato, 4-metildifluoro-antimonio, 4-methyldifluoro- antimonatoxi 4-hidroxifenil(o-metilbencil)metilhexafluorantimonio, 4-hidroxifenil(a-naphthilmetil)metilhexafluorantimonio, difenil-4-(fenilthio)fenilhexafluorantimonio, trifenilhexafluorantimonio, bis[2-4-(4-ylhidroxiethoxi)fenilhidroxiethoxi)fenilsulfonilo], etc. , (2-etoxi-1-metil-2-oxoetil)metil-2-naphthalenilsulfoniohexafluorofosfato, 4-acetoxifenilbencilmetilsulfoniohexafluorofosfato, 4-hidroxifenil(o-metilbencil)metilsulfoniohexafluorofosfato, 4-metil-(hidroxifenil)-sulfofenilmetil-a-hexafluorofosfato, difenilo - 4-(fenilthio)fenilsulfoniohexafluorfosfato, bis[4-(4-(4-(2-hidroxietoxi)fenilsulfo)fenil]svovl -(difeniltio)fenil] )metilsulfoniohexafluorarsenato etc., (2-ethoxi-1-metil-2-oxoethyl )metil-2-naftilsulfoniotetrafluorborato, 4-hidroxifenil(o-metilbencilbencil)metilsulfoniotetrafluorborato, 4-hidroxifenilbencilmetilsulfoniotetrafeniltio-4-( )fenilsulfoniotetrafluorborato, tetrafluoroborato, trifenilsulfonio tetrafluorborato de sockel, bis[4-(4-(2-hydroxyethoxy))fenilsulfoniotetrafluorborato ]sulfidbistetrafluorborato, triflato de 4-hidroxifenil(o-metilbencil)metilsulfonio, triflato de sampal, triflato, etc. -4-(feniltio)benzene Trifluorometanosulfonato de sulfonio, 4 -hidroxifenil (α-naphthilmetil)metilsulfoniobis(trifluorometilsulfon)imid, bis(trifluorometilsulfon)imid, sakke 4-hidroxibenceno Benzilmetilsulfoniumbis(trifluorometilsulfon)imid, (1-2- -2-oxoethyl ) metil-2-naphthylthiotetrakis (pentafluorofenil) Borat, 4 -(methoxycarbonyloxy) fenilbenzilmetilthiotetrakis (pentafluorofenil) Borat, 4-hidroxifenil (α-naphthilmetilsulfonyletra (p-hidroxifenil (α-naphthylmetilmetilsulfoniumtalina (p-hydroxyfenil) metilmetilmetilsulfoniumt. Ylmetilmetilmetil) Borat, 4-hidroxifenilbencilmetilsulfonium tetrakis (Pentafluorofenil) Borat, exemplar komplekte tetrakis (pentafenil ) borat sämke trifenilsulfonio tetrakis (pentafluorfenil) borato, bis[4-(bis(4-(2-hidroxietoxi))fenilsulfo)fenil]thiotetrakis(pentafluorofenil) )borato og bis[4-(difenil]sulfo)fenthiotetrakis(pentafluorofenil)borato .
(ii) Examples of phosphonium-type salt thermal cationic polymerization initiators include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
(iii) Examples of quaternary ammonium salt type thermal cationic polymerization initiators include N,N-dimethyl-N-benzylaniline hexafluoroantimonato, diethyl-N-benzylaniline antetrafluoroborato, N,N-dimethyl-N-benzylpyridine hexafluoroantimonato, N,N-dimethyl-N-(4-methoxybenzyl )pyridine hexafluoroantimonate, N,N-diethylbase-N-(4-methoxybenzyl)toluidine hexafluoroantimonate, dimethyl-N-(4-methoxybenzyl)toluidine hexafluoroantimonate, etc.
(iv) Examples of aluminum complex thermal cationic polymerization initiators include aluminum carboxylate, aluminum alkoxide, aluminum chloride, aluminum acetoacetate (alkoxy) chelate, aluminum acetoacetyl, aluminum ethylacetoacetate.
(v) Eksempler på termiske kationiske polymerizationinitiatorer til aromatiske iodoniumsaltsystemer omfatter phenylyodoniumhexafluorantimonate, diphenyloniodoniumtetrafluoroborate, diphenyloniodoniumtetrakis(pentafluorphenyl)borate, diphenyloniodoniumhexafluorophosphate, bis hexafluorphosphate, bis(dodecylbenzenobase)yodo niotetrafluorborate, bis(dodecylphenyl)yodonium tetrakis(pentafluorphenyl)borate, 4-methylphenyl-4- (1-methylethyl)phenyl jodhexafluorphosphate, 4-methylphenyl-4-(1-methylethyl)phenylodohexafluorantimonate, 4-methyl)phenyl-4-methyl(1-methyl)yoditetrafluorborate, 4-methylphenyl-4-(1-methylethyl)phenylyodidtrakis( pentafluorphenyl)borate and lignendo.
(vi) Examples of thermal cationic polymerization initiators based on aromatic diazonium salts include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate and phenyldiazonium tetrafluoroborate.
(vii) Eksempler på pyridinbaserede termiske kationiske polymerization initiator instead of 1-phenylazo-2-cyanopyridinehexafluorophosphate, 1-phenylazo-2-cyanopyridinehexafluoroantimonate, 1-benzopyridine Nitrogen-2-cyanopyridin-methyl-2-cyanopyridin-methyl-1-cyanopyridin- methyl-2-cyanopyridine, hexafluorophosphate, 1-(naphthylmethyl)-2-cyanopyridinehexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridinetetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinetetrakis(pentafluorophenyl)borate osv.
The thermal cationic polymerization initiators can be used alone or in combination of two or more of them.
In the curable composition of the present invention, epoxy compounds other than the compound represented by the formula (1) described below, the oxetane compound described below and the vinyl ether described below are not included. cationic polymerization initiator in the curable composition according to the invention in proportion to 100 mass parts of the stereoisomer or mixture of stereoisomers of the compound of formula (2) according to the present invention contained in the curable composition, preferably 0.1 to 15 parts by mass or more. It is preferably 0.3 to 7 parts by mass. The curable composition of the present invention contains one or more cationic thermal polymerization initiators selected from epoxy compounds and oxetane compounds other than the compound represented by the above formula (1). With respect to the total of the stereoisomer of formula (2) contained in the curable composition or mixture of the compound of formula (1) according to the present invention, the oxetane compound and the vinyl ether stereoisomer 100 parts by mass, vinyl ether is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 7 parts by mass. If the amount of the cationic thermal polymerization initiator is within the above numerical range, the heat resistance of the cured product can be further improved.
More preferably, the cationic thermal polymerization initiator contained in the curable composition of the present invention is selected from cationic thermal polymerization initiators based on aromatic sulfonium salts, cationic thermal polymerization initiators based on aromatic iodonium salts and initiators of thermal cationic polymerization of aluminum complexes. Cationic polymerization initiator. More preferably, the thermal cationic polymerization initiator contained in the curable composition of the present invention is a thermal cationic polymerization initiator based on an aromatic sulfonium salt.
photocationic polymerization initiator
In an embodiment of the present invention, examples of the photocationic polymerization initiator contained in the curable composition of the present invention include initiators that generate cationic species or Lewis acids upon irradiation with active energy rays such as visible light and ultraviolet rays. X-rays, X-rays or electron beams initiate the polymerization of cationically polymerizable compounds. As the cationic photopolymerization initiator contained in the curable composition of the present invention, compounds such as onium salts, metallocene complexes and iron-allene complexes can be used. Examples of onium salts that can be used include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic phosphonium salts, and aromatic selenium salts. Examples of its counterion that can be used include anions such as CF3so3−blast furnace4−, FP6−arsenfluoride6−y SbF6−Among them, the aromatic sulfonium salt-based photocationic polymerization initiator also has ultraviolet absorption in the wavelength range of 300 nm or more, has excellent curability, and can provide good mechanical strength and adhesive force. The curable composition of the present invention may contain two or more photocationic polymerization initiators.
Examples of aromatic sulfonium salts include difenil-4-(fenilthio)fenilsulfoniohexafluorofosfato, 4,4'-bis(difenilthio)difenilsulfidbhexafluorofosfato, 4,4'-bis[bis(p-hidroxietoxi)fenilfluorthio]fenilsulfo-7-difenilsulfo-7 [ bis(p-toluene)sulfo]-2-isopropyltioxantonhexafluorantimonato, 7-[di(p-toluene)sulfo]-2-isopropyltioxantontetrakis(pentafluorfenil)borato, 4-fenilcarbonyl-4'-difenilsulfo-di-fenilsulfo 4-(p-tert-butilfenilcarbonyl)-4'-difenilsulfidohexafluorantimonato de difenilo, 4-(p-tert-butilfenilcarbonyl)-4'-di(p-toluyl)sulfonio-difenilsulfidotetrakis(pentafluorfenil)borato, difenilsulfontio-(fenilsulfontio)hexafluorantimonato , trifenilsulfoniohexafluorantimonattrifluorometansulfonat, bis[4-(difenilsulfo)fenil]sulfidbis-hexafluorantimonat, (4-methyloxyphenyl)difenilsulfoniohexafluorantimonat etc.
Examples of aromatic iodonium salts include difeniliyodonio tetrakis(pentafluorophenyl)borato, difeniliyodonio hexafluorofosfato, difeniliyodonio hexafluoroantimonato, bis(4-nonylbenzene)hexafluorophosphatilo)iodoniofenilodonilosal, (4-antifluorodonilosal, (4-antifluorodonilo) t-butylfenil)iodoniohexafluorofosfato and the like.
Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium tetrafluoroborate and 4-chlorobenzenediazonium hexafluorophosphate.
Examples of aromatic phosphonium salts include benzyltriphenylphosphonium hexafluoroantimonate and the like.
Examples of aromatic selenium salts include triphenylselenohexafluorophosphate and the like.
Examples of Iron-Allene Complexes include Xylene-CyclopentaDeryyl Iron(II) Hexafluoroantimonate, Cumene-CyclopentaDeryyl Iron(II) Hexafluorophosphate AND Xylene-CyclopentaDeadene Iron(II) Hexafluorophosphate Irmonyl hexafluorodienyl hexafluorodienyl hexafluorodienyl hexafluorophobia. (trifluoromethylsulfonyl) methanuro.
The amount of the photocationic polymerization initiator when the curable composition of this invention does not contain the compound represented by the formula (1) mentioned below, the oxetane compound mentioned below and epoxy compounds other than vinyl ether. As will be described later, it is preferably 0.01 to 20 mass parts, more preferably 0.1 to 5 mass parts based on 100 mass parts of the stereoisomer or mixture of stereoisomers of the compound of formula (2) according to the present invention contained in the dough pieces of hardenable composition. In the curable composition of the present invention, when the curable composition of the present invention contains one or more compounds selected from epoxy and oxetane compounds other than the compound represented by the above formula (1), the amount of photocationic polymerization initiator and vinyl ether, in relation to the stereoisomer of formula (2) contained in the curable composition or the stereoisomer of the compound of formula (1) according to the present invention, the oxygen heterocycle. A total of 100 mass parts of the mixture of the butane compound and vinyl ether is preferably 0.01 to 20 mass parts, more preferably 0.1 to 5 mass parts. When the amount of the photocationic polymerization initiator is within this numerical range, the heat resistance of the cured product can be further improved.
heal accelerator
According to one embodiment of the present invention, the curing accelerator contained in the curable composition, e.g. triphenylphosphine, triphenylbenzyltetraphenylborate, tetrabutyldiethylphosphine-dithiophosphine, tetraphenylphosphine bromide, tetrabutylphosphine bromide, tetra-fluoro-tetra-boron-tetra-boron-tetraphen-butyl, ate, methyltriphenylbromide, ethyltriphenylbromide chloride, ethyltriphenylodide, ethyltriphenylacetic acid, methyltri-n-butyldimethylphosphoric acid, n -butyltriphenylbromide, benzyltriphenylchloride, tetraphenyltetraphenylphosphines and their, such as quaternary boron salt 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzo-2-phenylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl)-2 - ethyl-4-methylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2-benzeneimidazoline, 2,3-dihydro-1H-pyrrolo[1,2-a] benzimidazole and other imidazoles, tris(dimethylaminomethyl)phenol and other tertiary amines, tetrabutylammonium bromide and its quaternary salts, superbasic organic compounds such as 1,8-diazabicyclo(5,4,0)nonen-5, zinc octoate, zinc laurate , zinc stearate, examples of which include organometallic chelates Substances such as tin octoate, etc., organometallic chelates such as benzoylacetonate zinc chelate, dibenzoylmethane zinc chelate, ethyl acetoacetate zinc chelate, tetra-dithionate n-butylsulfonium-o,o-diethyl, etc.
Among them, imidazole curing accelerators are more preferred, and 2-methyl-imidazole, 2-phenyl-imidazole and 2-ethyl-4-methylimidazole are more preferred because they can be stereoisomerized by the formula (2) Combination of the present invention or a mixture of stereoisomers of the compound of formula (1) can further improve the heat resistance of the cured product.
The curable composition of the present invention may contain one or two or more curing accelerators as described above.
From the viewpoint of heat resistance of the cured product, the amount of the curing accelerator when the curable composition of the present invention does not contain an epoxy compound other than the compound represented by the following formula (1) is based on the curable composition containing the stereoisomer or the mixture of stereoisomers of the compound of formula (2) according to this invention is preferably 0.01-10 mass parts relative to 100 mass parts, more preferably it is 0.05-8 mass parts . More preferably, it is 0.1 to 6 parts by mass. When the curable composition of the present invention contains epoxy compounds other than the compound represented by the above formula (1), with respect to a total of 100 mass parts of the stereoisomers of formula (2) or formula (2), accelerating curing . The amount is preferably 0.01 to 10 parts by mass of the mixture of the stereoisomer of the compound of the formula (1) of the present invention and the epoxy compound other than the compound represented by the formula (1) contained in the curable composition, plus preferably 0.05 to 10 parts by mass. 8 parts by mass, more preferably 0.1 to 6 parts by mass.
Epoxy compounds other than the compound represented by the above formula (1)
In an embodiment of the present invention, the curable composition may contain other epoxy compounds (hereinafter sometimes referred to as "other epoxy compounds"), other than the compound represented by formula (1) above, depending on the application. Examples of other epoxy compounds include glycidyl ether epoxides, glycidyl ester epoxides, glycidylamine epoxides, cycloaliphatic epoxides and other epoxides and their oligomers and polymers, and tetraphenylethylene epoxy resin. The polymer can be epoxy resins such as glycidyl ether epoxide, glycidyl ester epoxide, glycidyl amine epoxide, alicyclic epoxide, etc., preferably bisphenol A, bisphenol F, bisphenol glycidyl ether epoxy resins such as AD and bisphenol S. more preferably bisphenol A epoxy resin.
Some epoxides of glycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol S diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether bisphenol A, bisphenol A diglycidyl ether, bisphenol S dihydroxyphenol A ether, glycidyl ether, tylcresol triglycidyl ether, tris(hydroxyphenyl) methan triglycidyl ether, dinaphthalentriol Triglycidyl ether, novolac glycidyl ether, cresol novolac glycidyl ether, novolac glycidyl ether indeholdende xylene skeleton, novolac glycidyl ether indeholdende dicyclopentadien skeleton skeleton skeleton, novolac skeletal ether terpenphenol glycidyl ether, bisphenol A phenolglycidyl ether, bisphenol S phenol glycidyl ether, bisphenol AP phenol glycidyl ether, bisphenol E phenol glycidyl ether, bisphenol Z phenol glycidyl ether, tetramethylphenol bisfenglycol A methylphenol bisfen glycol A glycidyl ether, dimethylbisphenol F phenolglycidyl ether, tetramethylbisphenol S phenolglycidyl ether, dimethylbisphenol S phenolglycidyl ether, tetramethyl-4,4'-biphenol phenolglycidyl ether, trihydroxyphenylmethane phenolglycidyl ether, resorcinolphenolic glycidyl ether, hydroxypropylglycidyl ether, hydropropylglycidylglycidyl glycidyl ether, novolac, glycidyl ether ill of 1 ,1-di-4-hydroxyphenyl fluorene, phenoliseret polybutadiene novolac glycidyl ether, ethylphenol novolac glycidyl ether, glycidylphenol novolac glycidyl ether, octylphenol novolac glycidyl ether, såsom hydrogenated glycidol novolac, naphthol glycid novolac glycidyl ether, ethylene glycol diglycidyl ether , propylene glycol diglycidyl ether, butandiold diglycidyl ether, 1,6-hexandioldiglycidyl ether, cyclohexandioldiglycidyl ether og polyethylene glycol diglycidyl ether, hvorafeksempler indbefatter glycidyl ether af triglycol ether, såsom polypropylene glycol ether, f. , glycerintriglycidyl ether, pentaerythritol, tetraglycidyl ether, sorbitol hexaglycidyl ether, polyglycerolpolyglycidyl ether or andre polyoler Glycidyl ether, triglycidylisocyanurate osv.
Examples of glycidyl ester type epoxy resins include glycidyl methacrylate, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, cyclohexane glycidyl esters of carboxylic acids such as diglycidyl dicarboxylate and trityl triglycidyl acid, and ester type glycides. Mentioned.
Some glycidylamine-type epoxides, such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, N,N,N',N'-tetraglycidyldiaminodiphenyl Methane, N,N,N',N'-tetraglycidyldiaminodiphenylsulfone, N,N,N ' or g N'-tetraglycidyldiethyldiphenylmethane, bis(N,N-Diglycidylaminocyclohexyl)methane (hydrogenated from N,N,N',N'-tetraglycidyldiaminodiphenylmethane), N,N,N',N'-tetraglycidyl-1,3-(bisetraglycidyl- 1,3-(bis))cyclohexane (N,N,N',N'-tetraglycidylxylyldiaminehydrogen product), triglycidyl-p-aminophenol, N-glycidyl-4-glycidyloxypyrrolidone and andreglycidylheterocycloamine.
As cycloaliphatic epoxides, e.g. vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl)ether, ethylene glycol bicyclooxydicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3',4'-epoxylatocyclohexane,3',4'-epoxylatocyclohexane 4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 3,4-epoxy-3-methylhexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, methylenebis(3,4-epoxycyclohexane), (3,3',4,4'-diepoxy)bicyclohexyl, 1,2 - bis(hydroxymethylepoxy-(2-oxyethynyl)cyclohexane)-1-butanol adduct, tetrahydroindene diepoxide, etc. As mentioned above, the curable composition of this invention may contain 1 type or 2 or more types of epoxy compounds, except the compound represented by the formula (1).
As described above, from the viewpoint of heat resistance of the cured product, the amount of the epoxy compound other than the compound represented by the above formula (1) is preferably in the following range of 1 to 90 parts by mass with respect to to a total of 100 parts by mass of the parts of the curable composition, more preferably in the range of 5 to 85 parts by mass.
In a preferred embodiment of the present invention, the epoxy compound other than the compound represented by the above formula (1) contained in the curable composition of the present invention is selected from glycidyl ether epoxide, glycidyl ester epoxide, alicyclic family of epoxides, tetraphenylethane epoxides. glycidyl ether resins and epoxy resins.
active diluent
In one embodiment of the present invention, the curable composition may further include a reactive diluent to have a lower viscosity. Examples of reactive diluents include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl ethers of C12-13 mixed alcohols, and 1,2-epoxy-4-vinylcyclohexane. The curable composition may contain one or two or more reactive diluents as described above. The mixing ratio of the reactive diluent can be appropriately adjusted so that the curable composition containing the reactive diluent has the desired viscosity.
oxetane compounds
In one embodiment of the present invention, the curable composition may comprise an oxetane compound. Examples of oxetane compounds include 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 3-ethyl-3-(phenoxymethyl)oxyhetidine, bis[(3-ethyl-3-oxetanyl)methyl] ether, 3-ethyl-3-(cyclohexyloxymethyl)oxetane, novolakoxygen Hetidine, 1,3-bis[(3-ethyloxetan-3-yl)]methoxybenzene, oxetanyl silicate, bis[1-ethyl(3-oxy-heterobutyl) ]-methyl ether, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3)-oxetanylmethyl)diphenolate, trimethylolpropanetrimethylolpropane (3-ethyl-3-oxetanylmethyl)ether, pentaerythritoltetrakis(3-ethyl-3-oxetanylmethyl)ether and oxetane novolak type. The curable composition according to the present invention may contain one or two or more oxetane compounds as described above.
From the viewpoint of heat resistance of the cured product, the content of the oxetane compound in the curable composition of the present invention is preferably in the range of 1 to 90 mass parts with respect to 100 mass parts of the amount total curable composition. The parts by mass are more preferably in the range of 5 to 85 parts by mass.
vinyl ether compound
According to one embodiment of the present invention, the curable composition may comprise a vinyl ether compound. Examples of vinyl ether compounds include monofunctional vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether, such as butanediol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether, pentavinyl trivinyl ether, pentaeryth ritol tetravinyl ether, vinyl ether, glycol divinyl ether, diethylene glycol divinyl ether, hydroxyethyl vinyl ether, cyclohexane dimethanol, monovinyl ether, cyclohexanediol monovinyl ether, 9-hydroxynonyl vinyl ether, propylene glycol monovinyl ether, neopentyl glycol monovinyl ether, neopentyl glycol monovin yl ether, dimethylene, Glycol monovinyl ether, dimethylene propane monovinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, diethylene glycol monovinyl ether, tetraethylvinyl groups with hydroxyl groups such as glycol monovinyl ether, tricyclodecanediol monovinyl ether, tricyclodecandimethanol monovinyl ether, acrylic acid 2 -(2- Vinyloxyethoxy)ethyl compounds, etc., such as vinyl ethers, have various functional groups, such as 2-(2-vinyloxyethoxy)ethyl methacrylate. The curable composition of the present invention may contain one or two or more vinyl ether compounds as described above.
From the viewpoint of heat resistance of the cured product, the content of the vinyl ether compound in the curable composition of the present invention is preferably in the range of 1 to 90 mass parts with respect to 100 mass parts of the total amount of the curable composition, more preferably the range of 5-85 parts by mass.
hydroxyl compounds
In one embodiment of the present invention, the curable composition may further comprise a compound with a hydroxyl group. By containing a compound with a hydroxyl group in the curable composition, the curing reaction can be slowed down. Examples of compounds with a hydroxyl group include ethylene glycol, diethylene glycol, and glycerin. The curable composition of the present invention may contain one or two or more of the compounds having a hydroxyl group.
From the viewpoint of heat resistance of the cured product, the content of the compound having a hydroxyl group in the curable composition of the present invention is preferably in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the total. amount. amount of the curable composition. 10 parts by mass, more preferably in the range of 0.2 to 8 parts by mass.
solvent/other
In one embodiment of the present invention, the curable composition may further comprise a solvent. Examples of solvents include methyl ethyl ketone, ethyl acetate, toluene, methanol, and ethanol.
In one embodiment of the present invention, the curable composition may contain various additives without degrading the properties. Examples of additives include fillers, silane coupling agents, release agents, dyes, flame retardants, antioxidants, light stabilizers and plasticizers, defoaming agents, light stabilizers, colorants such as pigments and dyes, plasticizers, pH adjusters , anticoloring agents, mattifying. deodorants, weathering agents, antistatic agents, thread wear reducing agents, lubricants and ion exchangers.
Production of hardenable compositions.
In an embodiment of the present invention, the components further contained in the curable composition and the method of preparing the curable composition in preparing the curable composition can be appropriately selected based on common knowledge generally known to those skilled in the art. .
In a preferred embodiment of the invention, the method for preparing the curable composition allows the preparation of the curable composition, for example, by kneading or mixing the stereoisomers of formula (2) or the stereoisomers of the compound of formula (1). A mixture of the present invention as described above, and optionally the components as described above, and other components added as appropriate.
The method of kneading or mixing is not particularly limited and, for example, mixing or kneading machines such as planetary mixers, twin-screw extruders, heat rollers and kneading machines can be used for mixing.
Cured product and manufacturing method thereof.
In an embodiment of the present invention, the cured product is obtained by curing the above curable composition of the present invention. The curing method of the curable composition is not particularly limited and can be carried out by heating or light irradiation as necessary.
When the curable composition is cured by heating, the curable composition is preferably heated several times in view of the high reactivity of the epoxy compound. This allows the curing reaction to proceed sufficiently. For example, the curing reaction can be carried out by heating at 90 to 110°C for 10 to 150 minutes for the first time and heating at 140 to 160°C for 10 to 400 minutes for the second time. For example, the curing reaction can be carried out by heating at 100-130°C for 10-150 minutes for the first time, heating at 140-160°C for 10-150 minutes for the second time, and heating at 170-200°C. c. °C for the third time. 60-180 minutes, the fourth heating at 210-250°C for 10-150 minutes. For example, the curing reaction can be carried out by heating at 100-130°C for 10-150 minutes for the first time, heating at 140-200°C for 10-150 minutes for the second time, and heating at 210-250°C. c. °C for the third time. 10 to 150 minutes. For example, the curing reaction can be carried out by heating at 80-100°C for 10-150 minutes for the first time, heating at 110-120°C for 10-150 minutes for the second time, and heating at 130-140°C. c. °C for the third time. 60-180 minutes, fourth heating at 150-170°C for 10-150 minutes, fifth heating at 180-200°C for 60-180 minutes, sixth heating at 210-230°C for 60-240 minutes. For example, the curing reaction can be carried out by heating at 100-110°C for 10-150 minutes for the first time, heating at 120-150°C for 10-150 minutes for the second time, and heating at 160-150°C. c. 220°C. °C for the third time. 10-150 minutes, the fourth heating at 230-250°C for 10-150 minutes. However, the curing reaction is not limited to this and is preferably carried out by appropriately changing the amount of the epoxy compound, the properties of other compounds contained in the curable composition and the like.
When active energy rays such as visible light, ultraviolet rays, X-rays and electron beams are irradiated to cure the curable composition, the type and conditions of the active energy rays used are preferably changed appropriately according to the composition of the composition. curable composition. In one embodiment, it is preferred to irradiate ultraviolet rays such that the cumulative amount of light represented by the product of the radiation intensity and the radiation time is 10 to 5000 mJ/cm2.2The active species from a photocationic polymerization initiator can be fully formed if the photoaccumulative amount of a curable composition is in said numerical range. It can also increase productivity.
hardened properties
In one embodiment of the present invention, the heat resistance of the cured product can be assessed by measuring the glass transition temperature. From the viewpoint of imparting heat resistance, the glass transition temperature is preferably higher.
The glass transition temperature can be measured by differential scanning calorimetry (DSC).
DSC-based glass transition temperature measurement can be easily performed using a commercially available differential scanning calorimeter (eg, product name: DSC7020, manufactured by Hitachi High-Tech Science Corporation).
The glass transition temperature of the cured product of the present invention as measured by DSC may be 140°C or higher, preferably 150°C or higher, more preferably 170°C or higher. The upper limit is not particularly limited, but is preferably 400°C or less.
In one embodiment of the present invention, the dielectric properties of the cured product can be evaluated by measuring at least one selected from a dielectric constant and a dielectric loss factor (tan 5). From the viewpoint of reducing energy loss, the dielectric constant and the dielectric loss tangent are preferably lower.
The dielectric constant and dielectric loss factor of the cured product can be measured using the resonant cavity perturbation method.
Measurement of dielectric constant and dielectric loss factor can be easily performed using a commercially available measurement resonator (for example, ADMS01Nc1, manufactured by AET, Inc.) and analyzer (for example, Vector Network Analyzer MS46122B, manufactured by Anritsu Corporation).
The dielectric constant of the cured product of the present invention is preferably 2.50 to 2.72 at 10 GHz.
The dielectric loss tangent of the cured product of the present invention at 10 GHz may be 0.0150 or less, preferably 0.0140 or less, more preferably 0.0120 or less. The lower limit is not particularly limited, but is preferably 0.0050 or more.
In a preferred embodiment of the invention comprising a stereoisomer of formula (2) or a stereoisomer of a compound of formula (1) as compared to a curable composition that does not comprise a stereoisomer of formula (2) The curable composition of the mixture ( as described above) or the mixture of stereoisomers of the compound of formula (1) as described above may have improved dielectric and heat resistance properties.
Use of hardened product.
Since the use of a curable composition and/or cured product can specifically enumerate the coating material on substrates such as metal, resin film, glass, paper, wood; Semiconductor device and organic film device (such as organic electroluminescence device and organic thin film solar cell) surface protection film; hard coating; antifouling film, antireflection film and other coatings; adhesives; pressure sensitive adhesives; lenses, prisms, filters, imaging materials, lens arrays, various optical components such as sealing materials for optical semiconductor devices, reflective materials, sealing materials for semiconductor devices, optical waveguides, light guide plates, plates light diffusion elements, diffraction elements and optical adhesives. Casting materials; intermediate layer insulators; protective insulating films against printed substrates; fiber reinforced composites; and the like.
Example
The present invention will be described in more detail below with reference to examples, but it is not limited to these examples.
Production Example 1: Production of epoxy compound (A-1)
Add 40.0 g of diene compound represented by formula (4), 40.0 g of toluene, 1.44 g of sodium tungstate dihydrate, 1.0 g of hexadecyl to the reactor equipped with thermometer, stirrer, reflux tube and dropper device Trimethylammonium methylsulfate, 0.64 g phenato78-phosphonato-phosphonatyl. g of anhydrous sodium sulfate and 39.2 g of 45% hydrogen peroxide were reacted at 30°C for 11 hours.
After the reaction, wash once with 15 g of a 10% aqueous sodium carbonate solution, once with 15 g of a 10% aqueous sodium sulfite solution, and three times with 20 g of a saturated aqueous solution. of sodium sulfate for liquid separation. The organic layer, after washing and separating, was distilled under reduced pressure with a rotary evaporator (60°C, 50 hPa), and 53 g of the obtained crude product was added to 90 g of isopropanol to dissolve. Then, the solution was cooled to -10°C to crystallize and filtered, followed by drying the residue to obtain 33.3 g of white crystals (epoxy compound (A-1) represented by formula (5)).
The obtained epoxy compound (A-1) was analyzed by gas chromatography (GC). Specifically, the analysis was performed under the following conditions.
[Analysis conditions]
Measurement equipment: Intuvo 9000 GC System (Agilent Technologies, Inc.)
Chromatographic column: HP-5MS (Agilent Technologies, Inc.), length: 30.0 m, inner diameter: 320 μm, film thickness: 250 μm
Liquid phase: (5%-fenil)-methylpolysiloxane
Carrier gas: N2
Tight flow: 5.2ml/min
Split Ratio: 60:1
Sample inlet temperature: 200°C.
Detector temperature: 250°C.
Column heating conditions: 50°C (5 minutes), 50-150°C (5°C/min), 150-250°C (10°C/min), 250°C (10 minutes)
GC analysis showed that the ratio of the primary isomer peak among the peaks derived from the compound represented by the formula (5)(A-1) was 77%.
Preparation Example 2: Further purification of the epoxy compound (A-1)
Further, the obtained epoxy compound (A-1) was repeatedly recrystallized from isopropanol to obtain a sample in which the maximum ratio of the primary isomer was increased to 96%. The samples obtained were1thousand13C-NMR spectroscopy followed by 2D NMR (NOESY). Specifically, the analysis was performed under the following conditions.
[Measuring ratio1MRI]
Measuring equipment: AVANCE II 800US2 (User)
Disolvente: CDCl3
Pulse angle: 90° pulse
Sample concentration: 10% by mass
Total time: 4 times
[Measuring ratio13MRI]
Measuring equipment: AVANCE II 800US2 (User)
Disolvente: CDCl3
Pulse angle: 30° pulse
Sample concentration: 10% by mass
Total time: 32
(1Preparation Example 2) The collection of 1H-NMR samples of the obtained sample
1RMN H (800 MHz, CDCI3) 5 (ppm) 1,298 (d, 1 H), 1,502 (m, 2H), 1,681 (d, 1 H), 1,738 (m, 2H), 1,812 (m, 1 H), 1,912 (q, 1 H) , 1.986 (m 2, 2H), 2.109 (m, 2H), 2.364 (m, 1H), 2.434 (m, 1H), 3.102 (m, 2H), 3.297 (d, 1H), 3.518 (t, 1H) .
(13Preparation Example 2) The 13 C-NMR spectrogram of the obtained sample
13CNMR (800 MHz, CDCI3) δ (ppm) 27.236、27.426、27.949、30.289、31.170、37.695、44.649、45.103、47.037、47.875、47.875、47.875、47.8 75、47.875 41,61.612.
The configurational analysis of the sample was carried out by two-dimensional NMR (NOESY method), and the peak structure of the major isomer of the compound (A-1) was confirmed to be the structure of the following formula (6).
The compounds and the like used in the following examples and comparative examples are as follows.
The component (A) used is the following:
(A-1): the epoxy compound obtained by the method described in Production Example 1 (hereinafter also referred to simply as "epoxy compound (A-1)");
(A-2): liquid bisphenol A epoxy resin (trade name: YD-128, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
(A-3): Tetraphenylethane epoxy resin (trade name: jER1031S, manufactured by Mitsubishi Chemical Corporation)
(A-4): Cycloaliphatic epoxy (trade name: CELLOXIDE 2021P, manufactured by Daicel Corporation)
The component (B) used was the following:
(B-1): 4-methylhexahydrophthalic anhydride and a mixture of hexahydrophthalic anhydride (trade name: MH-700, manufactured by Shin Nippon Chemical Co., Ltd.)
The component (C) used is the following:
(C-1): 2-ethyl-4-methylimidazole (trade name: 2E4MZ, manufactured by Shikoku Chemical Co., Ltd.)
Example 1-2, Comparative Example 1-4: Preparation and Evaluation of the Curable Composition Containing the Epoxy Compound (A-1) (1) Preparation of curable composition and cured product Example 1
Curing acceleration 50 mass parts of epoxy compound (A-1), 50 mass parts of epoxy compound (A-2), 0.9 equivalents of acid anhydride compound (B-1) to 1 equivalents of component (A ) and 0.2 mass parts of Agent (C-1) were mixed for the production of a curable composition. The obtained curable composition was heated at 100°C for 2 hours in a hot air circulation oven and then heated at 150°C for 5 hours to obtain a cured product. Table 1 summarizes the measurement results.
Comparative example 1 and 2
A curable composition and its cured product were prepared in the same manner as in Example 1, except that the composition of the curable composition was changed as shown in Table 1 below.
Example 2
A curable composition and a cured product thereof were prepared in the same manner as in Example 1, except that the composition of the curable composition was changed as shown in Table 2 below.
Comparative Examples 3 and 4
A curable composition and its cured product were prepared in the same manner as in Example 1, except that the composition of the curable composition was changed as shown in Table 2 below.
(2) Appraisal of physical property
This was judged as the heat resistance of the cured product using a differential scanning calorimeter (product name: DSC7020, manufactured by Hitachi High-Tech Science Corporation). Here, the glass transition temperature is based on the "midpoint glass transition temperature: Tmilligrams” Described in JIS K7121, “Test method for transition temperature of plastics. Tables 1 and 2 summarize the measurement results.
The dielectric constant and the dielectric loss factor were measured under the following conditions. Tables 1 and 2 summarize the measurement results.
-
- Test method: cavity resonator disturbance method (according to JIS C2565 standard)
- Measurement Topics: Dielectric Constant and Dielectric Loss Factor
- Sample shape: 3mm × 80mm × 1mm
- Measurement conditions: Frequency 10 GHz
- Measurement temperature: 23°C.
- Number of measurements: n=3 (3 test tubes are made of the same cured product and the average of the measured values for each test tube)
- measurement equipment:
- Meter Resonator: ADMS01Nc1, manufactured by AET, Inc.
- Analyzer: Vector Network Analyzer MS46122B, manufactured by Anritsu Corporation
The above results show that the cured products of the curable compositions in the examples of the present invention show excellent heat resistance and excellent dielectric properties.