Thermosetting resin composition

[Detailed Description of the Invention]

Lord or Rotary background The present invention relates to a thermosetting resin composition useful as Vehicle, such as a paint, adhesives, and printer's ink. The thermosetting resin composition which consists of an acrylic resin, polyester resin, an epoxy resin, etc. which have a hydroxyl group, and melamine resin is widely used in the paint field. While the resin composition of these melamine resin curing systems carries out only . which contains the proton donor, for example, rose toluenesulfonic acid, as a catalyst of a hardening reaction, the system containing free acid tends to gel resin, and generally it is hard to make the cold cure nature and storage stability of a constituent compatible. Then, although using as a catalyst the compound which blocked sulfonic acid with amine etc. was proposed, the hardenability and storage stability were not a thing which can not necessarily be satisfied. The vinyl-base polymer which has alkoxy silyl combination in a side chain, the polyhydroxy compound, and the hardening resin constituent include the curing catalyst are indicated by JP,63-33512,B. If it is in such a system, Self condensation reaction ROSi - of alkoxysilane + -SiOR +llzO -* -54-0-Si+2ROH and Co-condensation reaction ROSi - of alkoxysilane and a hydroxyl group +HO-C- -> -Si-0-C-+ROH It is thought that hardening takes place. considering it as the self condensation of these, and the catalyst of Co-condensation reaction conventionally -- coming out Buchir amine, Dibutyl amine, and 1 Amine, such as - Buchir amine and ethylene diamine Tetra-iso Bloomville titanate, tetrabuthyl titanate, octylic acid tin, lead octylate, octylic acid zinc, octylic acid calcium, and a jib -- acidic compounds, such as metal-containing compounds, such as Tiruzuji acetate, dibutyltin Dioctate, and dibutyltin dilaurate, p1 toluenesulfonic acid, and trichloroacetic acid, were used. However, a system including such a catalyst cannot be stored in stability for a long period of time, including a catalyst so that he can also understand normal temperature hardening also from a possible thing. Therefore, when prolonged storage stability is desired, the measure against blending a catalyst just before use as 2 liquid, decreasing the amount of catalysts, or blocking with amine or acid of the time volatility of hardening etc. is required. However, when it is 2 liquid, there is a problem in workability, and there are restrictions of having to use it within pot lives, Since the fall of film performance and perfect blocking are difficult for other measures, sufficient storage stability is not acquired, amine or acid to block volatilizes, it colors, and there is a problem of generating a nasty smell. JP,58-37003,A -- said -- to Showa 58-37004, it cleaves thermally, and the sulfonium salt type cationic polymerization initiator which generates a Carbonium cation is indicated. These artificers newly developed recently the kinky thread Zinc salt cationic polymerization initiator which cleaves thermally in a similar manner. Refer to Japanese Patent Application No. 62-255388. Although these initiators are developed by the cationic polymerization reaction for the purpose of use Learning in the Carbonium cation which cleaves thermally and is generated, When OH compound existed in the system of reaction which uses these initiators, it considered using the proton which the cation generated by cleavage reacts with a hydroxyl group, and generates as melamine resin or a crosslinking reaction catalyst of an alkoxysilane compound. the above-mentioned sulfonium and a loquat -- unless Zinc salt cleaves thermally and reacts to OH basis, a proton is emitted, it is Nay's and the crosslinking reaction of melamine resin or an alkoxysilane compound does not occur on substance below to the cleavage temperature. Therefore, such a thermosetting resin composition that has criticality storage stability if it cleaves thermally and a Carbonium cation is used is obtained. Main raw group Nominating public (a) Film formation resin containing at least two hydroxyl groups per molecule, 0)) It is 5 at a solid content weight ratio to the above-mentioned hydroxyl group content resin. 0/5 It is 0.01 thru/or 10% of the weight of a formula of the total quantity of the above-mentioned hydroxyl group content resin and melamine resin at melamine resin and (c) solid content weight ratio of the quantity which is 0~95/5. or (The inside of a formula, R., R., and R and R4 are hydrogen, halogen, and Alkyl.) Alkoxy , 2 fatty tuna, amino , alkylamino, hydroxy , cyano, They are alkoxy power Lebonyl, Culver Moyle, or alkanoyl, h is As, Sb, B, or P, X is halogen, n is 4 when h is B, and in other cases, it is 6. A thermosetting resin composition containing kinky thread Zinc salt and/or sulfonium ' salt is provided. In other fields, it is the present invention, (a) Silicon resin containing at least two alkoxy silyl combination per molecule, (b) it is related with a thermosetting resin composition by which the pyridinium salt and/or sulfonium salt of 0.01 thru/or IO% of the weight of above-mentioned silicon resin of a formula (the numerals in a formula are the above -- the same 6 When.) being included as an amount ratio of solid content. Or silicon resin in which the present invention contains at least two alkoxy silyl combination per one molecule (a), (b) resin containing at least two hydroxyl groups per molecule of quantity which becomes the 0.1~10 number of hydroxyl groups per alkoxysilane combination of the above-mentioned silicon resin, and the amount of (c) solid content -- 0.01 thru/or 10% of the weight of the formula of the above-mentioned silicon resin and the above-mentioned hydroxyl group content resin total quantity -- or (the sign in a formula is the same as the above.) -- it is related with a thermosetting resin composition containing kinky thread Zinc salt and/or sulfonium salt. Although the constituent of the present invention is not hardened on substance below to the cleavage temperature of the above-mentioned kinky thread Zinc salt or sulfonium salt, it has the feature with which a hardening reaction advances in criticality by heating more than the temperature. Therefore, the storage stability of the constituent is farther [ than a constituent including an old catalyst ] excellent. Detailed playing 1 Roofing ■ . System containing melamine resin The film-forming resin which uses melamine resin as a hardening agent is widely used in the paint field. Those examples are polyester resin, poly lactone resin, an epoxy resin, an acrylic resin, etc. Polyester resin is obtained by the condensation reaction of polyvalent carboxylic acid, or its acid anhydride and polyhydric alcohol, and resin containing the hydroxy group can be used for it in the end of a polyester chain, and/or the middle. Poly lactone resin of a hydroxyl group end can also be used. As an epoxy resin, an epoxide machine and the resin which has a hydroxy group in the molecule chain middle are mentioned to ends, such as a screw phenol type epoxy resin and/or a novolac type epoxy resin. The acrylic resin which has a hydroxyl group is hydroxy group content 7 Nomar, such as acrylic acid (meta) 2-hydroxyethyl, (Meta) Methyl acrylate, acrylic acid (meta) Buchir, isobutyl acrylate (meta), (Meta) Alkyl acrylate, such as acrylic acid 2-ethylhexyl (meta); it is obtained by making other monomers, such as styrene, its derivative, acrylonitrile (meta), and acetic acid vinyl, copolymerize by a usual state method. Melamine resin is triazine compounds, such as melamine, Penzog anamine, or acetoguanamine, Formaldehyde is made to react and it is obtained by a case by etherifying the methylol group of a condensation product partially or completely by low-grade alkanol like methanol and butanol. The thermosetting resin composition by the combination of the coat fabrication resin which has a hydroxyl group, and melamine resin is common knowledge in the paint field, and is a constituent of the present invention, Except for using the kinky thread Zinc salt / sulfonium salt of the above-mentioned heat cleavage nature as a catalyst of a hardening reaction, it may be the same as a publicly known thermosetting melamine resin hardening type constituent. The ratio of coat formation resin and melamine resin which have a hydroxyl group is weight, and is 5. 0/5 The rate of 0~95/5 may be sufficient. The above-mentioned kinky thread Zinc salt / sulfonium salt are preferably blended 0.05~5.0% of the weight 0.01~10% of the weight to resin solid content. If these loadings are not much small, hardenability will fall, and if superfluous, a bad influence will be produced in respect of appearance, such as coloring of a hardened material and a waterproof fall, and physical properties. The constituent can contain additive agents, such as paints and a bulking agent, according to the use. ■ . -- the system using the self condensation or Co-condensation reaction of an alkoxy silyl group -- Alcokey Sisil There is the following in the classic example of silicon resin containing at least two alkoxy silyl combination per a molecule of silicon which enters. (1) Alkoxy 1 Le The monomer which has an alkoxy silyl group and an ethylenic double bond in a bitter taste 1 Le molecule attaches an alkoxy group content acrylics polymer or a copolymer by an independent polymerization or copolymerization with other polymerization monomers. To. The 1st class of such a monomer is general formula R CHz=C-COO(c} lz) X. -Si(R') - (OR'): It is alkoxy silyl Alkyl ester of acrylic acid or methacrylic acid denoted by l-l1. In inside R of a formula, Alkyl and Ro of one or more integers, R', and I?" are 0, 1, or 2 hydrogen or methyl, and X. As an example of these concrete compounds, it is gamma. - Meta-Cloyl oxib mouth Building trimethoxysilane, T 1 meta-Cloyl oxib mouth Building methyldimethoxysilane, gamma-meta-Cloyl oxib mouth bilge methyl methoxysilane, T-meta-Cloyl oxyp mouth Biltriethoxysilane, gamma-meta-Cloyl oxyp mouth Building methyldiethoxysilane, T-meta-Cloyl oxyp mouth Bildt Liv mouth Boxysilane and gamma-meta-Cloyl oxyp mouth pill methyl -- a jib -- Roboxysilane, There are T-meta-Acrolege methyl Brovoxysilane, T-meta-Cloyl oxib mouth Billy butoxysilane, T-meta-Cloyl oxyp mouth Bill Methyl dibutoxysilane, gamma-meta-Cloyl oxib mouth bilge methyl butoxysilane, etc. The 2nd class is an accretionary prism with acrylic acid (meta), epoxy group content alkoxysilane, for example, T-Glycidoxib mouth Building trimethoxysilane, or delta1 (3, 4-EPO Kishishiku mouth hexyl) ethyltrimethoxysilane. The 3rd class is [ the hydroxyalkyl ester of acrylic acid (meta), such as acrylic acid (meta) 2-hydroxyethyl, acrylic acid (meta) hydronalium Kishibu mouth building, and acrylic acid (meta) 4-hydroxy butyl, and ] a general formula. OCN(cHz) XSi (R'), (OR''), and the compound of 1, for example, T-iso Cyanatube mouth Building trimethoxysilane, It is an accretionary prism with T-isocyanate Bropil methyl dimethoxysilane, gamma-isocyanate pro Biltriethoxysilane, gamma-isocyanate pro Building methyldiethoxysilane, etc. The last class is [ metaglycidyl acrylate (meta) ester and ] amino group content alkoxysilane, For example, gamma-friend knob Robville trimethoxysilane, T 1 friend knob Robville triethoxysilane, It is an accretionary prism with N1(2-aminoethyl)-3-amino pro Building methyldimethoxysilane, N1(2-aminoethyl)-3 1 friend knob Robville trimethoxysilane, T-friend knob mouth bilge methylethoxy Silane, T-friend knob Robville methyldiethoxysilane, etc. As as copolymerizable a monomer as alkoxy silyl group content acrylics monomer -, there are various acrylic ester (meta), styrene, acrylic acid (meta), acrylonitrile (meta), acryl amide (meta), VCM/PVC, acetic acid vinyl, etc. (2) Si 1 Cong epoxy" To The amine machine content alkoxysilane compound quoted immediately before can be used in order to manufacture an alkoxy silyl group content modified epoxy resin by an addition reaction with an epoxy group similarly. (3) Si Cong Polyester The polyester resin which has an isolation power Ruboxil machine can denature by the same epoxy group content alkoxysilane used for an addition reaction with acrylic acid (meta), in order to manufacture the acrylics monomer which Inclusion an alkoxy silyl group, and it can be used as silicon denaturation polyester resin. The polyester resin which has an isolation hydroxyl group denatures by the same isocyanate machine content alkoxysilane that carries out an addition reaction to acrylic acid hydroxyalkyl ester in order to manufacture an alkoxy silyl group content acrylics monomer (meta), It can be considered as silicon denaturation polyester resin. Water Asahi Blood-growing Blood Plate As resin containing at least two hydroxyl groups per molecule, hydroxyl group content polyester resin, hydroxyl group end poly lactone resin, an epoxy resin, and a hydroxyl group content acrylic resin are classic examples. Polyester resin is obtained by the condensation reaction of polyvalent carboxylic acid, or its acid anhydride and polyhydric alcohol, and resin containing the hydroxy group can be used for it in the end of a polyester chain, and/or the middle. Poly lactone resin of a hydroxyl group end can also be used. As an epoxy resin, an epoxy side machine and the resin which has a hydroxy group in the molecule chain middle are mentioned to ends, such as a screw phenol type epoxy resin and/or a novolac type epoxy resin. The acrylic resins which have a hydroxyl group are hydroxy group content monomers, such as acrylic acid (meta) 2-hydroxyethyl, (Meta) Methyl acrylate, butyl acrylate (meta), isobutyl acrylate (meta), (Meta) Alkyl acrylate, such as acrylic acid 2-ethylhexyl (meta); it is obtained by making other monomers, such as styrene, its derivative, Acry (meta) mouth nitril, and acetic acid vinyl, copolymerize by a usual state method. On Farmer ■ Victim ■ Burned down The thermosetting resin composition of the present invention using the self condensation reaction of an alkoxy silyl group uses the above-mentioned silicon resin, and the above-mentioned pyridinium salt/sulfonium salt as an essential ingredient. If it is in the thermosetting resin composition of the present invention using Co-condensation reaction of an alkoxy silyl group and a hydroxyl group, Per alkoxy silyl combination of the above-mentioned silicon resin, the above-mentioned hydroxyl group Inclusion resin of quantity which becomes the 0.1~10 number of hydroxyl groups, and the above-mentioned kinky thread Zinc salt / sulfonium salt are essential ingredients. in any case, the above-mentioned kinky thread Zinc salt / sulfonium salt receive resin solid content -- 0.01~10 % of the weight . -- preferably it is blended 0.05~5.0% of the weight. If these loadings are not much small, hardenability will fall, and if superfluous, Bad customer will be produced in respect of appearance, such as coloring of a hardened material and a waterproof fall, and physical properties. The constituent can contain an additive agent and solvents, such as paints and a bulking agent, according to the use. Although the constituent of the present invention is not hardened, therefore its storage stability is good at below the cleavage temperature of the above-mentioned kinky thread Zinc salt / sulfonium salt, it hardens, when heating to the temperature more than cleavage temperature. Although cure time is based also on temperature, generally it is less than 1 hour. An example illustrates the present invention below. It is based on weight the inside of an example "part", and"%." ■ . Example of manufacture Example 1 of Human manufacture of poly Esour '' 36 copies of hexahydrophthalic acid, 42 copies of Trimethi roll propane, 50 copies of neo bench Lugri calls, and 56 copies of 1.6-hexandiol are taught and heated to the reaction vessel provided with a heating device, a stirring machine, the flowing-back device, the mist separator, the rectifying tower, and the thermometer. Materials dissolve, if stirring becomes possible, stirring will be started, and it is 2. 1 It Temperature rising to 0"C. 2 1 The condensation water Raise the temperature(ed) and generated at constant temperature over 2 hours from 0'C to 230 *C is distilled off out of a system. If 230 degreeC is reached, temperature will be kept constant as it is, and if acid values 1 and 0 are reached, it will cool. 153 copies of after-cooling isophthalic acid is added, and it Temperature rising to 190 *C again. 190 Distill off the condensation water Raise the temperature(ed) and generated at fixed speed over 3 hours from *C to 210 *C out of a system. 210 If *C is reached, three copies of xylene will be added to a reaction vessel, and switch to the condensation under solvent existence, and cool by acid value 5.0. 190 copies of xylene was added after cooling, and polyester resin solution (A) was obtained. Beam of bitter taste 1 Le 18 Example 2 of manufacture To the reaction vessel provided with a stirring machine, a thermometer, a reflux condenser, N2 gas introducing pipe, and dropping Ro 1 A, After teaching 90 copies of Solvesso 100 and Temperature rising(ing) N2 gas to introductory A stone 160 *C, 23.2 copies of methacrylic acid 2-hydroxyethyl, 35.65 copies of acrylic acid n-butyl, and methyl methacrylate 4 0.1 Uniform dropping of the mixture of five copies, 1.0 copy of methacrylic acid, and ten copies of ter t-Petit Barber Oxygen- 2-ethylhexanoate was carried out by dropping Ro 1 A. Uniform dropping of the mixture of ten copies of xylene and one copy of ter t-Petit Barber Oxygen- 2-ethylhexanoate was carried out in 30 minutes after [ of the after / the end of dropping / of a mixture ] 1 hour. After 2-hour maturing after the end of dropping, it cooled and obtained the acrylic resin (A). Yuyu [ this ] l Kadogawa few Hill Example 3 of manufacture To the reaction vessel provided with a A bottle machine, a thermometer, a reflux condenser, N2 gas introducing pipe, and dropping Ro 1 A, Uniform dropping of the mixture of 50 copies of gamma-meta-Cloyl oxyp mouth pill trimethoxysilane and four copies of ter t-Buchir peroxy 2-ethylhexanoate was carried out from dropping Ro 1 A in 3 hours after teaching 45 copies of xylene and Temperature rising(ing) N2 gas to introductory A stone 130 *C. After 30-minute keeping warm after the end of dropping of a mixture and the inside of the system of reaction were cooled to 90 *C, and uniform dropping of the mixture of one copy of tert-Petit Barber Oxygen- 2-ethylhexanoate and five copies of xylene was carried out from dropping Ro 1 A under keeping warm in 1 hour. After 2-hour riping by 90 *C after the end of dropping, it cooled and obtained the silicon resin solution (A). Example 4 of manufacture To the reaction vessel provided with a stirring machine, the thermometer, the reflux condenser, N2 gas introducing pipe, and the dropping funnel, 45 copies of xylene was taught, and uniform dropping of the mixture of four copies of 50 copies of gamma-meta-Cloyl oxyp mouth Building methyldimethoxysilane and tert-Petit Barber Oxygen- 2-ethylhexanoate was carried out from the dropping funnel in 3 hours after Temperature rising(ing) to 130 *C, introducing N2 gas. After 30-minute keeping warm after the end of dropping of a mixture and the inside of the system of reaction were cooled to 90''C, and uniform dropping of the mixture of one copy of tert-Petit Barber Oxygen- 2-ethylhexanoate and five copies of xylene was carried out from the dropping funnel under keeping warm in 1 hour. After 2-hour riping by 90 degreeC after the end of dropping, it cooled and obtained the silicon resin solution (B). Example 5 of manufacture To the reaction vessel provided with a stirring machine, a thermometer, a reflux condenser, N2 gas introducing pipe, and dropping Ro 1 A, 45 copies of xylene was taught, and uniform dropping of the mixture of 50 copies of gamma-Metacloth yloxy Propyl dimethyl methoxysilane and four copies of tert-Petit Barber Oxygen- 2-ethylhexanoate was carried out from the dropping funnel in 3 hours after Temperature rising(ing) to 130 *C, introducing N2 gas. After 30-minute keeping warm after the end of dropping of a mixture and the inside of the system of reaction were cooled to 90 *C, and uniform dropping of the mixture of one copy of tert-Buchir peroxy 2-ethylhexanoate and five copies of xylene was carried out from dropping Ro 1 A under keeping warm in 1 hour. After 2-hour riping by 90 *C after the end of dropping, it cooled and obtained the silicon resin solution (c). Example 6 of manufacture To the reaction vessel provided with a stirring machine, a thermometer, a reflux condenser, N2 gas introducing pipe, and dropping Ro 1 A, 45 copies of xylene was taught, and uniform dropping of the mixture of 50 copies of gamma-meta-Cloyl oxyp mouth pill triethoxysilane and four copies of ter t-Petit Barber Oxy 2-ethylhexanoate was carried out from the dropping funnel in 3 hours after Temperature rising(ing) to 130 *C, introducing N2 gas. After 30-minute keeping warm after the end of dropping of a mixture and the inside of the system of reaction were cooled to 90 *C, and uniform dropping of the mixture of one copy of ter t-Petit Barber Oxy 2-ethylhexanoate and five copies of xylene was carried out from dropping Ro 1 A under keeping warm in 1 hour. After 2-hour riping by 90 *C after the end of dropping, it cooled and obtained silicon resin solution CD. Example 7 of manufacture To the reaction vessel provided with a stirring machine, a thermometer, a reflux condenser, N2 gas introducing pipe, and dropping Ro 1 A, After Temperature rising(ing) to 130 degreeC, teaching 45 copies of xylene and introducing N2 gas, Uniform dropping of the mixture of 25 copies of T-meta-Cloyl oxib mouth Biltriethoxysilane, 25 copies of methyl methacrylate, and four copies of tert-Petit Barber Oxygen- 2-ethylhexanoate was carried out from the dropping funnel in 3 hours. After 30-minute keeping warm after the end of dropping of a mixture and the inside of the system of reaction were cooled to 90 *C, and uniform dropping of the mixture of one copy of ter t-Petit Barber Oxy 2-ethylhexanoate and five copies of xylene was carried out from dropping Ro 1 A under keeping warm in 1 hour. After 2-hour riping by 90 *C after the end of dropping, it cooled and obtained the silicon resin solution (E). Example 8 of manufacture 100 copies of polyester resin solution (A) is taught to the reaction vessel provided with the A bottle machine, the temperature needle, and the reflux condenser, 100 After Temperature rising(ing) to *C, add 0.2 copies of dibutyltin dilaurate, and it is KBM-9007 (product made from Shin-etsu chemicals ■: structure 20CN(cHz) ssi (OCR3) x) 1. Uniform dropping of the zero copy was carried out in 30 minutes from dropping Ro 1 A. After 1-hour maturing, it cooled and obtained silicon resin solution CF. The absorption resulting from the NGO machine of 1720 cm-' in IR Sextract of the obtained resin solution had disappeared. Example 9 of manufacture 100 copies of bisphenol A diglycidyl ether taught the reaction vessel provided with the stirring machine, the thermometer, and the reflux condenser, and uniform dropping of 100 copies of T-friend knob Robville trimethoxysilane was carried out from dropping mouth-A in 1 hour after Temperature rising(ing) to 150 *C. After 1-hour maturing, it cooled and obtained the silicon resin solution (G). ■ . Melamine resin curing system example D To Braxel 308 (3 organic-functions poly by Daicel turnip Lolactonborg all . molecular weight 860) 70 copy, Cymel 303 (melamine resin by Mitsui Toatsu Chemicals, Inc.) 30 copy and two copies of 4-methylbenzyl 4-cyano kinky thread Jinium hexafluoroantimonate are added, and it mixes, It applied to the tin sheet, burned by 140 *C, and obtained the hardening coat. The hardening reactivity and the storage stability examination of the mixed-solution were done on the conditions shown in Table 1, and the result shown in Table 1 was obtained. Example 2 To Braxel 308 (product made by Daicel 3 organic-functions polycaprolactone Boriol, molecular weight 860) 70 copy, Cymel 303 (melamine resin by Mitsui Toatsu Chemicals, Inc.) 30 copy and two copies of 4-chloro Benzyl- 2-methyl kinky thread Jinium hexafluoroantimonate are added, and it mixes, It applied to the tin sheet, burned by 140 *C, and obtained the hardening coat. It inquired like Example l below. Example 3 To Braxel 308 (product made by Daicel 3 organic-functions poly power Bloraktoboriol . molecule 1860) 50 copy, two copies of Xafluoro phosphate is added to Cymel 303 (melamine resin by Mitsui Toatsu Chemicals, Inc.) 50 copy, 2, and 4-Dichlo mouth Benji Lu 2-methyl kinky thread Jinium, and it mixes, It applied to the tin sheet, burned by 140 *C, and obtained the hardening coat. It inquired like Example 1 below. Example 4 To polyester resin A solid content 90, 0.1 copy of Xaflu mouth phosphate was added to Cymel 303 (melamine resin by Mitsui Toatsu Chemicals, Inc.) 10 copy, and 2-methylbenzyl 2-methyl kinky thread Jinium, and it mixed, applied to the tin sheet, burned by 140 *C, and obtained the hardening coat. It inquired like Example 1 below. Example 5 To polyester resin A solid content 60, by making you van 203E (melamine resin by Mitsui Toatsu Chemicals, Inc.) into resin solid content, 40 copies and two copies of 2.4-dimethylbenzyl 2-chloro kinky thread Jinium tetrafluoroborate are added, and it mixes, It applied to the tin sheet, burned by 140 *C, and obtained the hardening coat. It inquired like Example 1 below. Example 6 To polyester resin A solid content 70, 30 copies and seven copies of 4-methoxybenzyl 3-chloro Viridiimu Tetrafluo mouth borate were added, and it mixed by having made you van 20SE (melamine resin by Mitsui Toatsu Chemicals, Inc.) into resin solid content, applied to the tin sheet, burned by 140 *C, and obtained the hardening coat. It inquired like Example l below. Example 7 To acrylic resin A solid content 90, Cymel 303 (melamine resin by Mitsui Toatsu Chemicals, Inc.) 10 copy and two copies of Ben Giroud 2-methyl kinky thread Jinium hexafluoroantimonate were added, and it mixed, applied to the tin sheet, burned by 140 *C, and obtained the hardening coat. It inquired like Example l below. Example day To acrylic resin A solid content 60, two copies of Xaflu mouth phosphate was added to 40 copies and 2-chloro Benzyl- 2-cyano kinky thread Jinium, and it mixed by having made you van 20SE (melamine resin by Mitsui Toatsu Chemicals, Inc.) into resin solid content, applied to the tin sheet, burned by 140 *C, and obtained the hardening coat. It inquired like Example 1 below. Example 9 To acrylic resin A solid content 70, by making you van 20SE (melamine resin by Mitsui Toatsu Chemicals, Inc.) into resin solid content, 30 copies and 0.5 copies of 4-methoxybenzyl 4 chloro kinky thread Jinium hexafluoroantimonate are added, and it mixes, It applied to the tin sheet, burned by 140 *C, and obtained the hardening coat. It inquired like Example 1 below. Comparative example 1 To Braxel 308 (product made by Daicel 3 organic-functions poly power Bloraktoboriol, and molecule ffi860) 70 copy, Cymel 303 (melamine resin by Mitsui Toatsu Chemicals, Inc.) 30 copy and two copies of P-1 Ruenfsrón acid triethyl amine salt are added, and it mixes, It applies to a tin sheet and is 1. 4 It burned by 0"C and obtained the hardening coat. The storage stability examination of the hardening reactivity, and Mixed and Liquid mixture was done on the conditions shown in Table 1, and the result shown in Table 1 was obtained. Comparative example 2 polyester tree rIVA adding Cymel 303 (melamine resin by Mitsui Toatsu Chemicals, Inc.) 10 copy, and two copies of p-Dodecyl benzene Sulfon acid viridin salt, and mixing to solid content 90, -- tin -- it applied temporarily, burned by 140 *C, and obtained the hardening coat. It inquired like Example 1 below. Comparative example 3 You van 203E (melamine resin by Mitsui Toatsu Chemicals, Inc.) is made into resin solid content to acrylic resin A solid content 60, and they are 40 copies and J. Two copies of 1-torr nth Ruhuon acid viridin salt was added, and it mixed, applied to the tin sheet, burned by 140 *C, and obtained the hardening coat. It inquired like Example 1 below. Table 1. Characteristic hardening reactivity 1 of mixed-solution and hardening coat>> Storage stability 2>> O O O O O O O O O O O O O O O O O O Hardening reactivity 1>> Storage stability 2>> Comparative example 0 O O △ x x 1) Coat appearance O after a MEK rubbing test (100 round trips): Abnormality [ in a coat ] nothing, and O:some coat dissolution 2△: Coat nebula, viscosity change (two weeks) O by a x:coat dissolution 240"C sealing system : thickening nothing O: They are thickening and delta:thickening slightly, x: They are 100 copies about the Co-condensation system example 10 acrylic resin (A) of an after [ two weeks ] gelling ■. alkoxy silyl group, and a hydroxyl group, 30.7 copies, five copies of methanol, and 2.62 copies of Benji Lu 4'-cyano pyridinium hexafluoroantimonate are mixed for silicon resin 1'A, One after applying the mixed-solution uniformly on a steel plate and setting it for 2 hours 4 It burned for 30 minutes by 0'C, and obtained the hardening coat. The hardening reaction of the coat and the storage stability examination of the mixed-solution were done on the conditions shown in Table 2, and the result shown in Table 2 was obtained. Example 11 They are 28.9 copies about 100 copies and silicon resin CB in an acrylic resin (A), One after mixing five copies of methanol, and 2.58 copies of 2-chloro Benzyl- 4-cyano kinky thread Jinium hexafluoroantimonate, applying the mixed-solution uniformly on a steel plate and setting for 2 hours 4 It burned for 30 minutes by 0'C, and obtained the hardening coat. It inquired like Example 10 below. Example 12 They are 26.9 copies about 100 copies and silicon resin (c) in an acrylic resin (A), 2.54 copies of five copies of methanol, 2, and 4-Dichlo mouth Benji Lu 4''-cyano kinky thread Jinium hexafluoroantimonate was mixed, and after applying the mixed-solution uniformly on the steel plate and setting it for 2 hours, it burned for 30 minutes by 140 *C, and obtained the hardening coat. It inquired like Example 10 below. Example 13 They are 36.2 copies about 100 copies and silicon resin CD in an acrylic resin (A.), Five copies of methanol and 2.72 copies of 2-methylbenzyl 2'-cyano kinky thread Jinium hexafluoroantimonate were mixed, and after applying the mixed-solution uniformly on the steel plate and setting it for 2 hours, it burned for 30 minutes by 140 *C, and obtained the hardening coat. It inquired like Example 10 below. Example 14 They are 43.4 copies about 100 copies and silicon resin (E) in an acrylic resin [A], Five copies of methanol and 2.87 copies of 4-nitrobenzyl 2 *-methyl kinky thread Jinium hexafluoroantimonate were mixed, and after applying the mixed-solution uniformly on the steel plate and setting it for 2 hours, it burned for 30 minutes by 140 *C, and obtained the hardening coat. It inquired like Example 10 below. Example 15 They are 30 copies about 100 copies and silicon resin (F) in polyester resin [A], 2.87 copies of five copies of methanol and 2-methylbenzyl 4 *-Fluorobillidiumum hexafluoro mouth phosphate was mixed, and after applying the mixed-solution uniformly on the steel plate and setting it for 2 hours, it burned for 30 minutes by 140 *C, and obtained the hardening coat. It inquired like Example 10 below. Example 16 They are 100 copies and silicon resin (they are 18 copies about GE) about polyester resin (A). mixing 2.87 copies of Xaflu mouth phosphate to five copies of methanol, and 4-methoxybenzyl kinky thread Jinium -- the mixed-solution -- a steel plate top -- uniform - after applying and setting for 2 hours, it burned for 30 minutes by 140 degreeC, and obtained the hardening coat. It inquired like Example 10 below. Comparative example 4 100 copies were mixed for the acrylic resin (A), and 30.9 copies and five copies of methanol were mixed for silicon resin (A), and after applying the mixed-solution uniformly on the steel plate and setting it for 2 hours, it burned for 30 minutes by 140 degreeC, and obtained the hardening coat. They are line Cow and comparative example 5 about the same examination as Example 10 below. 100 copies, silicon resin (A.) L30.9 copy, 2.62 copies of Dodecyl Bunsen Sulfone acid, and five copies of methanol were mixed for the acrylic resin (A), and after applying the mixed-solution uniformly on the steel plate and setting it for 2 hours, it burned for 30 minutes by 140 *C, and obtained the hardening coat. The same examination as Example 10 was performed below. (Following space) Table 2. The characteristic of mixed-solution and hardening coat 10 11 12 13 14. 1.5 16 Hardening Reactivity 1O O O O O O O Storage Stability 2>> O O O O O O OX O O x 1) Coat appearance O after a MEK rubbing test (100 round trips) : abnormality in coat nothing, O; the some coat dissolution, △: Coat nebula x: It is viscosity change (two weeks) O:thickening nothing at a coat dissolution 2 room-temperature sealing system. O: It is gelling ■5 slightly at the time of adding a car to a train, the gelling after [ of △: ] two weeks, and x:combination. Self condensation system example 17 of an alkoxy silyl group 100 copies, five copies of methanol, and two copies of 2-chloro Benzyl- 4 *-cyano kinky thread Jinium hexafluoroantimonate are mixed for a silicon resin solution (A), After applying the mixed-solution uniformly on the steel plate and setting it for 2 hours, it burned for 30 minutes by 140 *C, and obtained the hardening film. It inquired like Example 10 below. Example 18 Instead of the silicon resin solution (A), the hardening film was obtained like Example construction 7 except using a silicon resin solution (c). The same examination as Example 10 was performed below. Example 19 Instead of the silicon resin solution (A), the hardening film was obtained like Example 17 except using a silicon resin solution (F). The same examination as Example construction 0 was performed below. Comparative example 6 100 copies and five copies of methanol were mixed for silicon resin (A), and after applying the mixed-solution uniformly on the steel plate and setting it for 2 hours, it burned for 30 minutes by 140 *C, and obtained the hardening film. Comparative example 7 100 copies, two copies of Dodecylbenzel sulfonic acid, and five copies of methanol were mixed for silicon resin [A], and the hardening film was obtained like comparative example 3 below. The same examination as Example 10 was performed below. Table 2. The characteristic of mixed-solution and hardening coat Hardening reactivity O O O Storage stability O O O x O O x Applicant for a patent Nippon Paint Co., Ltd.