Polymerization initiator composition

[Detailed Description of the Invention]

Generally an epoxy resin is used for various uses which need a highly efficient material. Hardening of an epoxy resin is performed by the 2 liquid system based on introducing a usually active amine content compound or carboxylic anhydride into resin. By this system, it is required to mix an ingredient completely, and also cure time takes several hours. A Bremstedt acid catalyst is used for another catalyst used to stiffen an epoxy resin by a 1 liquid system into the form of an amine complex like boron trifluoride ―mono ethyl amine. Emitted if Bremstedt acid is heated, hardening takes place within 1~8 hours, and needs 160degreeC or the temperature beyond it. Therefore, this 1 liquid type epoxy constituent is not applicable to covering of a device sensitive to heat like elaborate electronic parts. Since it is lost by evaporation between hardening, the epoxy monomer which has a low-boiling point cannot be used. Photosensitive aromatic diazonium salt of a certain kind can be used for hardening of an epoxy resin as indicated by U.S. Pat. No. 3703296 of Schlesinger. When photodegradation of this aromatic diazonium salt is carried out, it can emit the Bremstedt acid catalyst which can start the rapid polymerization of an epoxy resin on that occasion. However, even if this 1 liquid type epoxy resin mixture can provide the constituent hardened quickly, in order to make hardening in a dark place into the minimum during preservation of a mixture, it must use stabilizer. Even if it makes it such, gelling of a mixture may take place in the state where there is no light. Nitrogen is emitted during UV hardening and a defect arises on a film. Generally diazonium salt is unstable with heat, and since decomposition may start one after another, it becomes harmful to use the substance of these. Another catalyst system is indicated to U.S. Pat. No. 4138255 of Crivello. It uses radiosensitivity aromatic series onium salt of a following formula. [ (R) _a(R¹)_b(R²)_cX]⁺_d[MQ_e]^-(e-f)(The univalent aromatic series organic group of inside R of a formula is R.)¹The univalent organic fatty series machine chosen from Is alkyl, cycloalkyl, and substitution Alkyl, R²The Many value organic group which forms alicyclic or condensed ring structure chosen from the Is an aliphatic machine and the aromatic series machine, a fellows element and M which were chosen from sulfur, selenium, and tellurium X -- halogen and a of the integer of 0~1 and a+b+c are [ the integer of 0~3, and b / the integer of 0~2, and c ] equal [ metal or metalloid, and Q ] to the valence of 3 or X -- d=e-f Integer e of 2~7 is larger than f at the valence of f=M, and a certain catalyst of these is activated for the integer to 8 by radiant energy usually like an electron beam or ultraviolet rays. Although there was a system which can be used in this way, other polymerization initiators were studied. In these, it can be activated with heat and the initiator activated only at high temperature is also stably contained especially in room temperature. The present invention relates to the constituent for using it in the polymerization of an epoxy resin. This constituent contains the polymerization initiator which is radiosensitivity sulfonium or iodonium salt of a Bremstedt acid polymerization catalyst. An initiator is mixed with a peroxide compound. When it mixes at the epoxy resin and room temperature of hardenability, the above-mentioned constituent is still inactive. However, if it heats, a peroxide compound will work and the Bremstedt acid catalyst for the polymerization of resin will be emitted from an initiator. Therefore, since a polymerization reaction is inhibited or it is activated, temperature can be used. The polymerization initiator of the present invention is radiosensitivity onium salt which has a following formula. [R_aX]⁺_b[C]_-b(R is a univalent organic aromatic series machine each among a formula, X is chosen from the group which comprises sulfur and iodine, C is a Bremstedt acid polymerization catalyst, a is equal to (valence number of X)-1, and b is equal to the valence number of c) The above-mentioned polymerization initiator is mixed with the peroxide compound of a quantity effective in activating this. In an aromatic series suitable for R in the above-mentioned formula, it is C._(6-13)There is a heterocyclic machine like hydrocarbon groups (phenyl, a trill, Naff Chill, anthryl, etc.) or pyridyl, and a full frill. These aromatic series machines are C._(1-8)Alkoxy ,C_(1-8)It may be replaced by 1~4 univalent bases containing Alkyl, nitroglycerine, halogen, and a hydroxyl group. Although different intermediary Stomach of R basis is also good in the above-mentioned salt, it is usually the same. C in the above-mentioned formula is a Bremstedt acid catalyst for the polymerization of an epoxy resin. It is known well and is mainly the metal of changes or rare earth, or a halogenation thing of metalloid. As a typical example, he is BF.₄^-PF₆^-FeCl₄^-SnCl₆^-BiCl₄^-2AlF₆^-3GaCl₄^-InF₄^-TiF₆^-2And ZrF₆^-Have. Especially a desirable thing is AsF.₆^-And SbF₆^-It comes out. Onium salt of the present invention is known well. This is J.W.Knapcayk. And J.Org-Chem.35 of J.Am.Chem.Soc.91 of W.E.McEwen, 145(1969);A.L.Maycock, and G.A.Berchtold, No.8, U.S. Pat. No. 2807648 of 2532(1970);H.M.Pitt, E.Groethals And it can manufacture by J.Am.Chem.Soc.51 of Bul.Soc.Chem.Bleg.73 of P.DeBadzctzky, 546(1964);H.M.Leicester, and F.W.Berstrom, and the method shown in 3587 (1927). This initiator is strong acid negative ion (for example, Cl).^-HSO₄^-Or NO₃^-Onium salt and a strong base positive ion (for example, Na)⁺Or NH₄⁺It can manufacture with the combination of Bremstedt acid chloride. Therefore, an initiator can also be manufactured in the polymerizing epoxy resin constituent. The present invention constituent must also contain the peroxide compound effective in activating a polymerization catalyst. Usually, organic peroxide, such as perbenzoic acid butyl and dicumyl peroxide, is used. As for these peroxides, it is desirable for at least 50, more preferably 100degreeC to be substantially stable. Therefore, the existence is secured, when it is applied to a higher temperature and a polymerization is induced. The quantity of the peroxide in this constituent will not be limited especially if enough to activate a polymerization initiator. Usually, at least 10% of the weight preferably of an initiator and 20 % of the weight are used. As for what is [ more ] than the weight of an initiator, being avoided is common although the case where it is generally superfluous is desirable. The constituent of the present invention is usually further mixed with this, when not generated within a hardenability epoxy resin. mixture -- a small portion of thermal activation -- it carries out in front. A mixture may be stored during the considerable period before actual activation and use, after mixing, since it is stable. the present invention -- therefore, there is an epoxy substance of a monomer, a dimer, oligomer, or the amount of polymers containing one piece or many epoxy functional groups in a hardenability epoxy resin suitable for using it. For example, the reaction of bisphenol A (4 and 4' ―Isopropylidene phenol) and epichlorohydrin, Or the resin generated by the reaction of low-molecular quantity phenol formaldehyde resins (novolac resin) and epichlorohydrin can be used together with independent or the epoxy content compound as reactive diluent, and can be used. Diluents, such as phenyl glycidyl ether, 4 ―Vinyl cyclohexene dioxide, limonene dioxide, 1, 2 ―Cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, and allyl glycidyl ether, can be added as a viscosity controlling agent. The range of these compounds can be extended to what contains the amount substance of polymers containing an epoxy group in an end or a chain. As an example of these compounds, there is a vinyl copolymer which contains glycidyl acrylate or methacrylate as one of the Comonomer. There are epoxy Siloxane resin, epoxy polyurethane, and epoxy polyester in the kind of others of the epoxy content polymer which will be easy to harden if the above-mentioned catalyst is used. These polymers usually have an epoxy functional group at the end of a chain. Epoxy Siloxane resin and a manufacturing method for the same are indicated to J.Am.Chem.Soc.81 of E.P.Plueddemann and G.Fanger, and 632-5 (1959) in more detail. Epoxy resins are amine and carboxylic acid as indicated in this literature, It can also denature with the standard method of many like a reaction with Thiol, phenol, alcohol, etc., It is shown in U.S. Pat. No. 2935488, No. 3235620, No. 3369055, No. 3379653, No. 3398211, No. 3403199, No. 3563350, No. 3567797, No. 3677995, etc. The example of others of the epoxy resin which can be used is Encyclopedia of Polymer Science and. It is shown in Technology, Vo1.6, 1967, Interscience issue, New York, and p.209~271. The quantity in particular of the hardenability epoxy resin used with the initiator of the present invention and the mixture of a peroxide is not limited, but changes over the wide range. However, it is preferred to use 1~15% of initiator of the weight of resin. A perfect polymerization can be performed, without making an excessive initiator useless, if it is this quantity. In the constituent of this invention, various ingredients which do not participate in a polymerization reaction may further be added. There are dye, paints, and a viscosity controlling agent in these, and a bulking agent is the most important. Especially since a bulking agent increases the quantity of the volume of an epoxy output effectively, it is desirable. Generally a conventional bulking agent is used at 10~100% of the weight of a rate of an epoxy resin. The bulking agent of powder aluminum metal may be used as a desirable example. In the case of this aluminum bulking agent, a present invention constituent can be used as plastic Body solder. Application and use of a present invention constituent can be performed easily. The intermediary of this constituent is also good in what kind of form. Usually, it is the powder mixture been smooth, for example. In addition, the liquefied carrier of a solvent or others is contained and it can also be made the range from a paste to varnish with the quantity. Therefore, in 25 degreeC, about 1~100000-cm P of viscosity can be shown. However, the constituent in which an intermediary also contains a hardenability epoxy resin in what kind of form is first applied at the place where hardening output is desired, and the time. Some of uses to which this constituent is applied are accompanied by very various environment. For example, it is used for manufacturing protection, an ornament or pre-insulation, ink, sealant, adhesives, a print tape, etc. As a thin film or covering, it is applied to the base in which many different Noodle are possible usually first in these cases. This constituent is completely stable, unless it is activated. (so -- in about 50~100 degreeC -- or -- less than it -- it is based on) each initiator and peroxide -- a polymerization and hardening hardly take place. Next, what is necessary is just to heat this constituent more than specific activation temperature or it to begin a reaction. Then, a polymerization starts. however -- usually -- an activated point -- at least 25, preferably at least 50degreeC -- a high temperature is actually used. If it carries out like this, a rate of polymerization will be promoted greatly. As mentioned above, a specific combination of the initiator and peroxide in a present invention constituent has character respectively characteristic about the cure rate in activation temperature and a higher temperature. Since combination has change in this way, very desirable tolerance level is permitted in the time of using the present invention to a specific base, and a specific manufacturing process. For example, the desirable example of the other present invention has manufacture of a mica tape laminate object. In the conventional manufacturing method, what resin is made into high temperature for for a long time (there are many cases of 1 hour at about 100 degreeC) is required before lamination and hardening. In a present invention constituent, it succeeds in maintenance of such exposure easily, and final hardening / polymerization is obtained by raising temperature to for example, 150 degreeC continuously. The present invention will be more completely understood by the following example. An example is for explaining an invention and is not for limiting the range. As long as there is no special statement in particular, all rates are based on weight. Example 1 3, 4 ―Epoxy cyclohexyl methyl 3, 100 g of 4 ―Epoxy cyclohexane carboxylic acid (ERL-4221 of Union Carbide), 50% hexafluoro antimonic acid triphenylsulfonium indication agent 4g in propylene carbonate and the mixture of 0.6 g of dicumyl peroxide are adjusted. It puts on the oven which put about 10 g of this mixture into aluminum weighing A cup next, and Set(ed) to 150 degreeC. Resin was gelled in about 30 minutes, and it became hard and it fully hardened it in 3.5 hours. By contrast, most control samples of resin containing either hexafluoro antimonic acid triphenylsulfonium or dicumyl peroxide are inactivity under the same conditions, and Oh. It did not gel, even 2 hours after setting to 150 degreeC. This result shows the common operation of a present invention ingredient. Example 2 The quantity of initiator (50% hexafluoro antimonic acid triphenylsulfonium in propylene carbonate) and perbenzoic acid t ―Butyl is changed into the sample containing 100 g of epoxy resins of Example 1, and it mixes in it. Subsequently, a sample is stiffened under the conditions shown in Table 1, and it is made gel.

[Table]

Comparison of the result of sample No.1~3 shows that the concentration of an initiator/peroxide seldom affects a rate of polymerization. However, the importance of temperature becomes clear from comparison of sample No.3~5. The constituent is comparatively stable at below 100 degreeC. However, if temperature is raised to 150 degreeC, it will be activated and a polymerization reaction will progress quickly. Example 3 The blend of 828]40 g of 60g of epoxy resin [ of Example 1 ], and bisphenol A diglycidyl ether epoxy resin [ShellChemical (Shell Chemical) make Epon, It mixes with 4g of initiators (50% hexafluoro antimonic acid triphenylsulfonium in propylene carbonate), and 1 g of t ―Butyl peroxide. It heats with a sunlight gel tester until it gels this mixture sample. In 150 degreeC, gel time is 4 hours in 135degreeC for 22.3 minutes. Next, a sample is put on the oven of 60 degreeC and is aged for 32 hours. In the meantime, the rise of viscosity is not seen. Next, when it heats to 150 degreeC, a sample shows the gel time for 26.3 minutes. These results show the storage stability of the present invention constituent strongly. Even after aging promotion was carried out at high temperature for a long time, a sample hardly lost activity. Example 4 71.4% Hexafluor acid diphenyliodonium initiator 2.8g and 1 g of perbenzoic acid t ―Butyl in propylene carbonate are used instead, and operation of Example 1 is repeated. In 150 degreeC, gel time is 4.8 minutes, and it is Oh. Example 5 Operation of Example 4 is repeated, using 100 g of diglycidyl ether (Epon 826) of bisphenol A as an epoxy resin. In this sample, the gel time in 150 degreeC is 3.5 minutes. Example 6 4.04 g of Hexafluor acid diphenyliodonium (inside of phenylene carbonate 71.4%) and 2 g of perbenzoic acid t ―Butyl are contained, ERL-4221 Into a mixture (76.13 g and hydroxyl group end stop butadiene acrylonitrile copolymer [Goodyear (goodyear) HTBN] 19.06g), Powder aluminum [Alcoa (Alcoa)101] 167 g is mixed and plastic Body solder is manufactured. By 25 degreeC, for at least nine months, this solder is stable and, on the other hand, it gels it within 5.9 minutes in 150 degreeC. When by contrast Hexafluor acid diphenyliodonium / Copper salt is used together, it is stable for a maximum of about five months. If the art which the above-mentioned and others are good and was known is taken into consideration, it is clear for many improvement and change of the present invention to be possible. So, it will be understood that it can change in each example of this invention. These all go into the range whose intention the present invention specified to this application claim has.