Heat curable compositions

[Detailed Description of the Invention]

The present invention relates to an epoxy resin, cyclic ether, and the organic substance in which a thermosetting positive ion polymerization like phenol formaldehyde resin is possible, and is in this quality of organicity, With a reducing agent like dicyclopentadienyl iron, an aromatic series onium salt initiator like the a-th fellows of an aromatic series or the a-th fellows onium salt is used. The organic substance which the thermosetting constituent of the present invention can (A) positive ion polymerize, It consists of aromatic series onium salt chosen from the group which consists of 0.1 thru/or 15% of the weight of the a-th fellows onium salt, and the a-th fellows onium salt to (B) and (A) to 0.5 thru/or 25% of the weight of a reducing agent, and (C) heat hardening constituent. Aromatic series onium salt can be used as a photoinitiator for stiffening an epoxy resin. Heat hardening can be carried out without an epoxy resin's also using radiant energy if necessary. However, heat hardening of the epoxy resin which uses the above-mentioned aromatic series onium salt is quite slow compared with the case where a source of radiant energy like ultraviolet rays is used. When using aromatic series onium salt together with the reducing agent, it discovered that it reached far and wide only not only in an epoxy resin using aromatic series onium salt, and could obtain quite quickly the hardened material of the organic substance in which various kinds of the positive ion polymerizations of other are possible. The aromatic series onium salt used when carrying out the present invention is a formula. (1) [Y]⁺[J]^-It is alike and is included, inside J of a formula is a non-nucleophilicity counter ion, as it defines in detail suddenly also below, and it is Y, (3) [ (R) _f(R²)_g(R³)_hE] the a-th fellows positive ion of Of aromatic, and (4) [ (R) _i(R⁴)_k(R⁵)_nG] It is the positive ion chosen from the group which consists of the a-th fellows positive ion of Of aromatic, R is a univalent aromatic series organic group among a formula, and it is R.²And R⁴It is the univalent organic fatty series machine chosen from the Is alkyl machine, the cycloalkyl machine, and the substitution Alkyl machine, and is R.³And R⁵It is a Many value organic group which is chosen from Is, a fatty series machine, and an aromatic series machine, and forms heterocycle or fusion ring structure with E or G, and is E, It is the a-th fellows element chosen from N, P, As, Sb, and Bi, and is G, It is the a-th fellows element chosen from S, Se, and Te, and "f" is, It is an integer of 0 thru/or 4, "g" is an integer of 0 thru/or 2, and "h" is, The sum of Then, "f", "g", and "h" is equal to the valence of 4 or E for the integer of 0 thru/or 2, "j" is an integer of 0 thru/or 3, "k" is an integer of 0 thru/or 2, and the sum of "m" of Then, "j", "k", and "m" is [ k ] equal to the valence of 3 or G for the integer of 0 or 1. A basis included by R is an aromatic carbon ring or a heterocyclic machine which has 6 thru/or 20 carbon atoms, is the same or different. Also being able to replace by 1 thru/or 4 univalent bases chosen from an alkoxy group of 1 thru/or 8 carbon numbers, a Alkyl machine of 1 thru/or 8 carbon numbers, a nitro group, a chloro machine, etc., R is more specifically a phenyl group, a chlorophenyl machine, a nitrophenyl group, a methoxypheny machine, and a pyridyl group. R²And R⁴Bases are a Alkyl machine of 1~8 carbon numbers, such as methyl and an ethyl group, and -C.₂H₄OCH₃-CH₂COOC₂H₅-CH₂COCH₃It is a substitution Alkyl machine of etc and defines Q' below. R³And R⁵In a basis, it is a formula. [Formula]

[Formula]

[Formula]

[Formula]

[Formula]

[Formula]

[Formula]

[Formula]

[Formula]

[Formula]

of -- a structure [ like ] is included. Inside of formula and Q' is O (CH),₂it is chosen out of n, N, R, and S, and n is an integer of 1 thru/or 4 -- Z -O- and -S- and [Formula]

Selected from and R' are water. It is chosen out of base, the Alkyl machine of 1~8 carbon numbers, and the aryl group of 6~13 carbon numbers. The non-nucleophilicity counter ion included by J of a formula (1) is MQ._dIt is negative ion and M is metal or metalloid here. Q is a halogen group and d is an integer of 4 thru/or 6. J of a formula (1) is perchloric acid salt and CF.₃SO₃^-C₆H₄SO₃^-The non-nucleophilicity counter ion of etc can also be included. When the substance in which a positive ion polymerization is possible is phenol-formaldehyde resin or other formaldehyde condensation resin like urea, J of a formula (1) is a nitrate and not only an phosphate but Cl.^-Br^-F^-Then is also good at a etc halogen counter ion. Non-nucleophilicity counter ion MQ included by J of a formula (1) as the definition was already given_dThe metal or metalloid included by of M is Sb, Fe, Sn, and Bi, It is metalloid like Actinide, such as a rare earth element like lanthanides, such as aluminum, Ga, In, Ti, Zr, Sc, V, Cr, Mn and a transition metal like Cs, for example, Cd, Pr, and Nd, Th, Pa, U, and Np, B, P, and As. MQ_dThe complex anion boiled and included is BF, for example.^-₄PF^-₆AsF^-₆SbF^-₆FeCl^-₄SnCl^-₆Sbcl⁼₆And BiCl⁼₅It comes out. it is included by the formula (1) and has a positive ion of a formula (3) -- carrying out the a-th fellows onium salt -- for example<img file="JPS6136530B2_D0001.tif" /><img file="JPS6136530B2_D0002.tif" /><img file="JPS6136530B2_D0003.tif" /><img file="JPS6136530B2_D0004.tif" /><img file="JPS6136530B2_D0005.tif" /><img file="JPS6136530B2_D0006.tif" /><img file="JPS6136530B2_D0007.tif" /><img file="JPS6136530B2_D0008.tif" /><img file="JPS6136530B2_D0009.tif" /><img file="JPS6136530B2_D0010.tif" /><img file="JPS6136530B2_D0011.tif" /><img file="JPS6136530B2_D0012.tif" />To list -- things are made. as the a-th fellows onium salt which is included by the formula (1) and has a positive ion of a formula (4) -- for example<img file="JPS6136530B2_D0013.tif" /><img file="JPS6136530B2_D0014.tif" /><img file="JPS6136530B2_D0015.tif" /><img file="JPS6136530B2_D0016.tif" /><img file="JPS6136530B2_D0017.tif" /><img file="JPS6136530B2_D0018.tif" /><img file="JPS6136530B2_D0019.tif" /><img file="JPS6136530B2_D0020.tif" /><img file="JPS6136530B2_D0021.tif" /><img file="JPS6136530B2_D0022.tif" />To list -- things are made. The "epoxy resin" used for explanation of the hardenability constituent of the present invention includes the monomer, the dimer, oligomer, or the polymers epoxy substance containing a single or multiple epoxy functional group. For example, resin obtained by the reaction of bisphenol A (4 and 4'-iso pro Pileddene phenol) and Epichlorohi drine compounds, or the reaction of low-molecular quantity phenol-formaldehyde resin (novolac resin) and Epichlorohi drine compounds, It can be used independently together with the epoxy content compound as a reactant diluent. Phenyl glycidyl ether, 4-vinyl cyclo hexane dioxide, Limonene dioxide, 1 and 2-cyclo Hexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, and a diluent like allyl glycidyl ether may be added as a viscosity property modification agent. The polymeric mass which extends the range of the above-mentioned compound and contains an end or a pendant epoxy group can be included. As an example of the above-mentioned compound, the vinyl copolymer which contains glycidyl acrylate or methacrylate as one of the comonomers can be mentioned. There are EPO Ix- Shiroki Sun resin, epoxy polyurethane, and epoxy polyester as other groups of the epoxy content polymer which can be hardened using the above-mentioned catalyst. These polymer usually has an epoxy functional group at the end of the chain. Epoxy Siloxane resin and a manufacturing method for the same, E, Py, Prudeman, G, and a finger (E. P.Plueddemann and G.Fanger), It is indicated in more detail to Journal of American Chemical Society and 632~635 pages of volume [ 80th ] (1959) (J. Am.Chem.soc.80632-5 (1959)). It is an epoxy resin as indicated in this literature, They are amine and carboxylic acid as clearly shown by U.S. Pat. No. 2935488, No. 3235620,; of; of; of; of; of 3369055 No. 3379653 No. 3398211 No. 3403199 No. 3563850 No. No. 3567797, and No. 3677995, It can also denature by Thiol, phenol, and the typical method of many like a reaction with alcohol. The example of the epoxy resin which can be used is Gencer Equipe Deia of polymer science and technology further, The 6th volume, 1957, Interscience Publishers . New York, 209 - 271 pages (the Encyclopedia of Polymer Science and Technology) It is clearly shown by Vol.6, 1967, Interscience Publishers, New York, and pp.209-271. As another organic matter which can be used for the above-mentioned thermosetting constituent and which can be positive ion polymerized, there are thermosetting formaldehyde resins, cyclic ether, lactone, lactam, cyclic acetal, and vinyl organicity pre polymer. For example, [CH₂=N-CONH₂]_x- H₂O [CH₂=NCONH₂]_xCH₃COOH [CH₂=NCONHCH₂NHCONHCH₂OH]_xof -- urea type resin [ like ] -- and<img file="JPS6136530B2_D0023.tif" /><img file="JPS6136530B2_D0024.tif" />(x and n are one or more integers among a formula.)<img file="JPS6136530B2_D0025.tif" /><img file="JPS6136530B2_D0026.tif" />of -- phenol formaldehyde type resin [ like ] is included by thermosetting organicity condensation resin of the formaldehyde which can be used when carrying out the present invention. Melamine thiourea resin, melamine, or urea aldehyde resin, A joint object with other Carboxy like cresol formaldehyde resins, polyester, alkyd, and polysulfide, hydroxyl, and amino and Mel Caputo content resin can also be used. It is CH as vinyl organicity pre polymer which can be used in order to obtain the constituent which can polymerize the present invention.₂=CH-O-(CH₂-CH₂O)_o-CH=CH₂(n is a positive integer which exceeds 1000 to about 1000 among a formula.) -- 1-2-3-pro pantry vinyl ether, Trimethylol pro pantry vinyl ether, and formula<img file="JPS6136530B2_D0027.tif" />The low-molecular quantity poly butadiene which has 200 thru/or 10000-cm P of viscosity by of pre polymer and 25 degreeC can be mentioned. The product produced by hardening such a constituent can be used for the general use as printer's ink and thermosetting resin. There is cyclic ether convertible into thermoplastics as a still larger category of the organic substance which can be used in order to obtain the constituent which can polymerize. it is clearly shown by patent (U.S.) No. 3673216 of Shurouta (Schroeter) transferred to these people at the above-mentioned cyclic ether, for example -- as An oxo run like oxetane and the tetrahydro franc like 3 and 3-screw chloromethyl oxetane, oxepane, an oxygen content spiro compound, trio Xan, and a dioxo run is included. Cyclic amine like cyclic ester like beta-lactone, for example, propiolactone, which adds cyclic ether, and 1, 3 and 3-Tori Methyl- azetidine, and ORGANO silicon ring formation, for example, a formula<img file="JPS6136530B2_D0028.tif" />(R'' is same or different univalent organic group like a methyl group or a phenyl group among a formula.) m is an integer of 3 thru/or 8. A substance included is also included. Hexamethyl trisiloxane and octamethyl tetra-Siloxane can be mentioned as an example of ORGANO silicon ring formation. The products obtained by the present invention are the amount of polymers, and rubber. In the ring former agent which can be used together with aromatic series onium salt of the present invention, they are Thiophenol, reducing sugar, ascorbic acid, and citric acid (C), for example,₅H₅)₂Fe reaches (C).₇H₁₅CO₂)₂Iron salt (C) like Fe,₇H₁₅CO₂)₂Co and Co₂(CO)₆[ (C)₆H₅)₃P]₂of -- cobalt salt [ like ] -- furthermore (C)₇H₁₅CO₂)₂Sn, [Formula]

etc -- Tin salt Copper salt like Facial expression CuI, CuBr, and CuCl is included. The thermosetting constituent of the present invention is obtained by blending with an effective amount of aromatic series onium salt the organic substance in which a positive ion polymerization is possible, and also making it combine with a ring former agent. When the organic substances in which a positive ion polymerization is possible were an epoxy resin, cyclic ether, Return-like ester, etc., as it mentioned already, the aromatic series onium salt used is shown by the formula (1), and the inside of a formula and J are MQ(s)._dNegative ion or CF₃SO^-₃And C₆H₄SO^-₃It comes out. However, as mentioned already, when the substance in which a positive ion polymerization is possible is formaldehyde condensation resin, as mentioned already, Then is also good [ J ] by a halogenation thing etc. The obtained heat hardening constituent is in the varnish of 1 thru/or 100000 centimeter Poise, or the state of smooth powder in the viscosity of 25 degreeC. Although this hardenability constituent can be used for various kinds of base materials (Substrates) by the usual method and is based on an operating temperature of 25degreeC thru/or 250 degreeC, it can be hardened within 0.5 thru/or 20 minutes, and can be made into print resistance. According to the reducing agent of onium salt, and compatibility with an epoxy resin, before uniting onium salt, organic solvents, such as nitromethane and acetonitrile, can be dissolved or distributed together with a reducing agent. When an epoxy resin is a solid, onium salt can be united by Dry kneading or fusion mixture. If wished, onium salt can also be made to generate on the spot. It is I and It was that it can be made to change sharply since this salt is substance top inactivity unless the ratio to the epoxy resin of onium salt is activated by experience. A desirable result will be obtained if 1 thru/or 15% of the weight of onium salt is used to the weight of a hardenability constituent. A hardenability constituent may contain an inert ingredient like an inorganic bulking agent, dye, paints, an extender, a viscosity regulation agent, processing aid, and an ultraviolet-rays interception agent in the quantity of 100 or less copies of bulking agents per 100 copies of epoxy resins. A hardenability constituent can be used for metal, rubber, a plastic, a cast or a forming film, paper, wood, a woven glass fabric, concrete, and a base material like ceramics. As a use of the hardenability constituent of the present invention, protection, an ornament, insulating coating, Potting material, printer's ink, sealant, adhesives, a molding composition, wire insulation, textiles coating, a lamination, an impregnating tape, and Funis can be mentioned, for example. Limitation gives the following example not a sake, but for explanation so that a person skilled in the art can carry out the present invention easily. All parts are units of weight. Example 1 The mixture of 97 % of the weight of Jigrish gin ether of 3 % of the weight of tetramethylen phenacyl sulfonium hexafluoro arsenate, and Epon(Epon)828, i.e., ShellChemical (Shell Chemical Company) bisphenol A It heated to 150 degreeC in small A bottle. After-heating gelling was not accepted at all for 20 minutes. The same operation as the above was repeated except adding 3% of the weight of p-chlorothiophenol. It is I solved it. that the hardening output which was heated for 5 minutes and been smooth by 150 degreeC is obtained. What will be suitable for the above-mentioned hardenability mixture as an object for enclosure of electronic parts is known among persons skilled in the art. Example 2 As for tetramethylen phenacyl sulfoniumhexafluoroantimonate of three copies, and the uniform mixture of seven copies of Epon 828, it is I solved it. to become the shape of a solid been smooth after heating in small A bottle for 15 minutes by 150 degreeC. Another sample of the above-mentioned mixture was blended with three copies of p-chlorothiophenol per 100 copies of mixtures. As for this blended mixture, it is I solved it. that it hardened in [ 150 degreeC ] 2.5 minutes, and will be smooth. Example 3 The [ of Epon 282 / 97 copies and three copies of tetramethylen Phenicil sulfoniumhexafluoroantimonate ] blend was blended with three copies of Thiophenol. It is I solved it. that the hardened material been smooth 5 minutes afterward by 150 degreeC is obtained. It is Made about another blend by the same operation except using thiosalicylic acid instead of Thiophenol. By 150 degreeC, this mixture was hardened in a similar manner 3 minutes afterward. Example 4 Tetramethylen phenacyl sulfoniumhexafluoroantimonate of three copies and the mixture of 97 copies of Ciba-Geigy alicyclic screw epoxy CY-179 were heated to 150 degreeC. It is I solved it. that the hardened material of a mixture is obtained by 150 degreeC in 3 minutes. Reference example 5 The blend with 97 copies and three copies of diphenyliodonium hexafluoro arsenate of Epon 828 was heated for 30 minutes by 120 degreeC after churning in small A bottle. As for Change which is conspicuous into a mixture, not accepting is I solved it.. The same operation as the above was repeated except blending three copies of p-chlorothiophenol into the above-mentioned mixture. It is I solved it. that the output been smooth into small A bottle after 4 minutes by 120 degreeC is obtained. Example 6 The blend with 97 copies of Ciba-Geigy 179 and three copies of phenacyltriphenyl phosphonium Hexa chloro antimonate was heated to 130 degreein glass small A bottle C. Change which is conspicuous into a mixture in 20 minutes accepts -- having -- and It was. The same operation as the above was repeated except adding three copies of p-chlorothiophenol to this mixture. It is I solved it. that the output been smooth 5 minutes afterward by 130 degreeC is obtained. Reference example 7~9 Ciba-Geigy 0.3 g of 0.3 g of 4 and 4'-dimethyldi phenyliodonium hexafluoro arsenate, ferrocene, 3 iron dodecacarbonyl, and n-octyl Feron was added to the sample of 10 ml of each of screw EPO Xide CY-179. These mixtures were heated in Oil bath and within small A bottle, and the time which hardening took was recorded. Compound With no cure time 4 hours 7 Ferrocene 6 to 7 Minutes 8 3 Iron Dodecacarbonyl 3 Minutes 9 N-Octyl Ferrocene 7 Minutes Independently, under the absence of iodonium salt, under existence of only ferrocene, when CY-179 was heated to 120 degreeC, hardening did not take place after 16-hour heating. Reference example 10-13 The same experiment as the above was repeated except the following cobalt content compound having replaced the iron reducing agent.

[Table]

Reference example 14 The mixture which consists of 94% of 3 % of the weight of 4 and 4-dimethyldi phenyliodonium hexafluoro arsenate, 3 % of the weight of 1st tin [ of octanoic acid ], and CY-179 was heated to 130 degreeC. It hardened within 3 minutes. 3 hours need to be heated for making it harden, when tin octanoate does not exist at 130 degreeC, and it is Oh. Reference example 15 The mixture of 3 % of the weight of 4 and 4'-dimethyldi phenyliodonium hexafluoro arsenate, and 97% of bisphenol A type resin (Ciba Guy Gee Araldite 6060) was heated to 170 degreeC. At this temperature, 1 hour was taken to harden this combination thing. if 3% of the 1st tin of octanoic acid is united with this mixture -- deliquescence -- time decreased in 4.3 minutes. Reference example 16 Ciba-Geigy The blend which consists of 2% of 1st tin [ of octanoic acid ] and chopped glass fiber 20% was blended together by 100 degreeC diphenyliodonium hexafluoro arsenate 2% 76% of Araldite 6060. This mixture was put into the heating metallic mold for 4 minutes by 170 degreeC. Mechanical properties were good and obtained the white molded rod which was excellent in solvent-proof nature. Reference example 17 6% of ascorbic acid was added to 91% of mixture of 4 and 4'-dimethyldi Phenyliliodium hexafluoro arsenate 3% and CY-179. The above-mentioned constituent was hardened by 2 minutes and a half by 130 degreeC. When 6% of ascorbic acid was added only to CY-179, even if heated by 130 degreeC for 1 hour or more, this screw EPO Xide did not harden. Reference example 18 0.5 g of 4 and 4'-dimethyldi phenyliodonium hexafluoro arsenate, A Ciel bisphenol A solid epoxy resin, i.e., 40 g of Epon 1002, The mixture of ascorbic acid 1g and chopped glass fiber 15g was mixed together in Bravender Torque Leo meter (Brabender Torzue Rheometer) by 90 degreeC. One copy of this molding composition was compressed between heating metal plates by 165~170 degreeC. The even forming film which has the outstanding solvent-proof nature was obtained to the hydrocarbon solvent. Reference example 19 Various quantity of ferrocene was added to the sample of CY-179 Naka 4 and 4'-G t-butyl diphenyliodonium hexafluorophosphate 3.24% solution. These samples were heated in glass small A bottle of 130 degreeC, and the time which hardening takes was measured. Ferrocene % cure time 18 210 Seconds 15 240 Seconds 12 275 Seconds 9 570 Seconds Reference example 20 G t-butyl diphenyliodoniumhexafluoroantimonate 3% and ferrocene 6% of the mixture was hardened for 2.75 minutes by 120 degreeC among CY-179. Because of comparison, he is BF in CY-179.₃- The necessity of heating for 30 minutes by 120 degreeC although the same hardening state is acquired when monoethyl amine 3% is used is Oh. It is shown that the above-mentioned example excels the Lewis acid catalyst in those who use the positive ion system of the present invention. Reference example 21 4 and 4'-dimethyldi phenyliodonium hexafluoro arsenate 3% and ferrocene 6% of solution was stored in A pot for seven weeks among CY-179. Solution did not carry out gelling during this period, and did not receive viscosity change, either. Similarly, they are inside of CY-179, and BF.₃- When using the 3% solution of monoethyl amine, it gelled within three days. According to the above-mentioned example, it turns out that advanced pot-lives stability can be acquired in the positive ion system of the present invention compared with A pot ripe which is considerably inferior in a Lewis acid-epoxy mixture. Reference example 22 Ivy which isolates preparatively the solution which consists of 3% of the weight of 4 and 4'-Dimethyl diphenyl- iodonium hexafluoro arsenate among bisphenol A-diglycidyl ether (Ciel Epon), and attaches ten samples. The ferrocene of quantity which is different to each of these samples was added. The time which heats the following Stomach aliquot in glass small A bottle, is heated to 130 degreeC, and hardening takes was measured. Ferrocene % cure time (second) 21 66 18 65 15 75 10 75 9 85 6 95 4 135 3 210 2 220 1 435 0 &gt;144000 Reference example 23 The mixture of the Ciba-Geigy bisphenol A solid epoxy resin containing 1.5 % of the weight of diphenyliodonium hexafluoro arsenate and 3% of Ascoville acid was put into the Mixing ball of a Brabender mixer by 90 degreeC. As directions of hardening, torque and temperature were supervised continuously. Change of what did not take place to viscosity or temperature 45 minutes afterward, either. At this time, temperature was raised quickly and it was referred to as 170 degreeC. Hardening of a rise in heat is Woke up within 6 minutes from Starting so that it may be shown by the rapid rise of torque and temperature. The generated resin was not further able to be fused by the solid-like substance which crosslinked highly. When the mixture of the same ingredient was put into the Mixing ball of a Brabender mixer by 170 degreeC, hardening is Woke up in 45 seconds. Two above-mentioned experiments show the characteristic feature of the redox positive ion system of the present invention of fusing at the temperature of 90 degreeC for a long time, heating after handling Ivy and also to high temperature, and hardening quickly. Reference example 24 The mixture which consists of 94% of 3% of 1st copper [ of bromination ] and CY-179 was heated to 120 degreeC in aluminum A cup 4 and 4'-dimethyldi phenyliodonium hexafluoro arsenate 3%. In 10~12 minutes, a mixture hardens and is the lump and Noodle of non-Melt firmly. Reference example 25 Two copies of diphenyliodonium hexafluoro arsenate and two copies of ferrocenes were added to 46 copies of diethylene glycol Zivinyl ether. This mixture was poured into aluminum A cup and it heated to 100 degreeC. The very quick exothermic polymerization reaction occurred and produced the hard resin which crosslinked. Reference example 26 Two copies of diphenyliodonium perchlorate and three copies of ferrocenes were added to 95 copies of phenol-formaldehyde resin (methylone 11 of a general electrics company). This reaction mixture was heated to 120 degreeC in aluminum A cup. The lump and Noodle which hard crosslinked 5 minutes after gelling this resin. The embodiment of the present invention is as follows. (1) The thermosetting constituent of an application for patent, wherein the organic substance in which a positive ion polymerization is possible is an epoxy resin given in the 1st paragraph of the range. (2) The thermosetting constituent of an application for patent, wherein the organic substance in which a positive ion polymerization is possible is phenol-formaldehyde resin given in the 1st paragraph of the range. (3) The thermosetting constituent of an application for patent, wherein a reducing agent is Thiophenol given in the 1st paragraph of the range.