CN1213386A - Photocurable putty for repairing sheet metal - Google Patents
Photocurable putty for repairing sheet metal Download PDFInfo
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- CN1213386A CN1213386A CN 97192906 CN97192906A CN1213386A CN 1213386 A CN1213386 A CN 1213386A CN 97192906 CN97192906 CN 97192906 CN 97192906 A CN97192906 A CN 97192906A CN 1213386 A CN1213386 A CN 1213386A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
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Abstract
To provide a photocurable one-pack type putty for repairing sheet metal, which cures rapidly by harmless visible light. A photocurable putty for repairing sheet metal comprising: (a) 100 parts by weight (33.3 to 73.5% by weight based on the total amount of the components (a) to (c)) of a bisphenol A type epoxy di(meth)acrylate; (b) 1 to 100 parts by weight (0.7 to 33.3% by weight based on the total amount of the components (a) to (c)) of a photopolymerizable (meth)acrylate; (c) 35 to 100 parts (25.7 to 33.3% by weight based on the total amount of the components (a) to (c)) by weight of a photopolymerizable urethane oligomer having two or more (meth)acryloyloxy groups per molecule; and (d) 0.01 to 10 parts by weight of alpha-diketone as a photoinitiator, 0.01 to 10 parts by weight of tertiary amine as a photosensitizer and 0.01 to 5 parts by weight of an onium salt as a photoreaction accelerator, each amount being based on 100 parts by weight of the total amount of the components (a) to (c).
Description
The present invention relates to be used for the Photocurable putty of repairing sheet metal.More particularly, the present invention relates to be used to repair the thin type putty of executing of the indenture below 3mm.
The putty that is used for the repairing car metal sheet generally is two-component-type, need before using host be mixed with solidifying agent.Curing reaction begins by mixing in two-component-type putty, therefore, must take host and the solidifying agent and the uniform mixing of predetermined amount, and, must promptly in gel time, use the mixed putty of gained with spatula.
Because the speed of curing reaction is subjected to the remarkably influenced of envrionment temperature, the gel time of putty, working life and wear-resisting time also are subjected to the influence of envrionment temperature and change according to envrionment temperature.Therefore, the shortcoming that is produced is the required operating time of repairing sheet metal to look season and noticeable change.
For example, common osculant putty needs 6-8 minute working life and 20-30 minute wear-resisting time at 200 ℃, and many putty (polyputty) then need more set time.Such time limitation is a very big burden in the process of repairing sheet metal.
The present invention can solve above-mentioned common problem, the purpose of this invention is to provide a kind of Photocurable putty repairing sheet metal, one-pack type that is used for, and its available harmless visible light solidifies rapidly.
The present invention reaches purpose of the present invention by a kind of Photocurable putty that is used for repairing sheet metal is provided, and this Photocurable putty comprises:
(a) bisphenol type epoxy two (methyl) acrylate (epoxy di (meth) acrylate) of 100 weight parts (, being 33.3-73.5 weight %) in the total amount of component (a)-(c);
(b) the phtotpolymerizable methacrylic ester of 1-100 weight part (, being 0.7-33.3 weight %) in the total amount of component (a)-(c);
(c) the phtotpolymerizable oligourethane of two or more methacryloxies is arranged in the molecule of 35-100 weight part (in the total amount of component (a)-(c), being 25.7-33.3 weight %);
(d) the 0.01-10 weight part as the α-diketone of light trigger, 0.01-10 weight part as the tertiary amine of photosensitizers and the salt as the photoresponse accelerator of 0.01-5 weight part, the amount of each component is 100 weight parts in the total amount of component (a)-(c).
The invention provides a kind of one-pack type Photocurable putty that is used for repairing sheet metal, its available harmless visible light solidifies rapidly.When light-cured resin of the present invention was used as the putty of repairing car metal sheet, light-cured resin was an one-pack type, can promptly solidify and adhere to by the utmost point by radiation of visible light.Therefore, compare with putty in the past, its practicality is good, and the repairing time shortens.
Photocurable putty of the present invention contains one or more bisphenol type epoxy two (methyl) acrylate monomers.
Its example comprises and is selected from 2,2-two (4-(methacryloxy oxyethyl group) phenyl) propane, 2,2-two (4-(methacryloxy polyethoxye) phenyl) propane, 2,2-two (4-(acryloxy diethoxy) phenyl) propane, dihydroxyphenyl propane 2-glycidyl two (methyl) acrylate (bisphenolA diglycidyl dimethacrylate), 2,2-two (4-(the methacryloxy hydroxypropyl gathers propoxy-) phenyl) propane etc. or their mixture.
Dihydroxyphenyl propane 2-glycidyl two (methyl) acrylate preferably, the second-order transition temperature of this monomeric homopolymer is about 170 ℃, because the curing putty of gained has excellent abrasive, flexible and thermotolerance." second-order transition temperature " speech is meant when measuring sample with Measurement of Dynamic Viscoelasticity device (" RSA-II " that Leometrix company produces) with three-point bending pattern and frequency 1Hz, the temperature when tangent δ reaches maximum." putty " speech be meant be in thixotroping and viscosity (for example, be 1,000-2,000,000cps) state, but be flowable materials before curing.And " curing putty " can not the mobile same substance after being meant curing.
The usage quantity of bisphenol type epoxy two (methyl) acrylate accounts for the 33-73.5% of polymerisable monomer and oligopolymer (being said components (a)-(c)) total amount.When bisphenol type epoxy two (methyl) acrylate during less than 33 weight parts, the modulus of solidifying putty diminishes its ability to cure variation.And when bisphenol type epoxy two (methyl) acrylate surpasses 73.5 weight parts, then the quantitative change of oligourethane get less, the poor adhesion on cated metal plate sections to be repaired.
Any photocuring or phtotpolymerizable methacrylate monomer or its combination can be used in the present invention.The example of useful methacrylate monomer comprises glycidyl methacrylate, benzyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, tert-butyl acrylate etc.
Preferably have the methacrylate monomer of polar group (as hydroxyl, phosphate group or carboxyl), its ability that sticks on the metal sheet of curing putty that obtains because using such monomer has improvement.
Example with methacrylate monomer of hydroxyl comprises methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, methacrylic acid hydroxy butyl ester, the own ester of hydroxyethyl methacrylate, hydroxyethyl methacrylate monooctyl ester etc.
The second-order transition temperature that preferred methacrylate monomer is this monomeric homopolymer is about 55 ℃ hydroxyethyl methylacrylate, preferably with itself and dihydroxyphenyl propane 2-glycidyl two (methyl) acrylic ester copolymer, the generation second-order transition temperature is 70-150 ℃ a multipolymer, for example, second-order transition temperature is dihydroxyphenyl propane 2-glycidyl two (methyl) acrylate-hydroxyethyl methylacrylate (70: 30) (" 3000M " that Japanese Kyoei Co., Ltd. produces) of 115 ℃.
Example with methacrylate monomer of phosphate group comprises the product of those commodity " KAYAMER PM-1 " by name that Japanese Nippon Kayaku Co., Ltd. produces, " KAYAMER PM-2 " and " KAYAMER PM-21 " etc.Use has the methacrylate monomer of phosphate group, also can improve gained and solidify the adhesive power of putty on metal sheet.
The methacrylic ester that preferably has phosphate group is that Nippon Kayaku Co., Ltd. produces " KAYAMER PM-21 ".Because " KAYAMER PM-21 " methacrylate monomer is long-chain compound, gained solidifies putty and still keeps flexible and the adhesive power of putty on metal sheet, and can further improve and the adhesion of staying the old coating of waiting to repair part.
When use had the methacrylate monomer of phosphate group, other polymerisable monomers and oligopolymer (i.e. (a) and (c)) did not preferably have hydroxyl or glycidyl.If have phosphate group and hydroxyl and/or glycidyl simultaneously in putty, then these groups can react and cause putty to solidify, thereby reduce the package stability of putty.
Both there be not hydroxyl not have the example of bisphenol type epoxy two (methyl) acrylate of glycidyl to comprise 2 yet, 2-two (4-(methacryloxy oxyethyl group) phenyl) propane, 2,2-two (4-(methacryloxy diethoxy) phenyl) propane, 2,2-two (4-(methacryloxy polyethoxye) phenyl) propane etc.Preferably 2,2-two (4-(methacryloxy oxyethyl group) phenyl) propane, the second-order transition temperature of this monomeric homopolymer is about 160 ℃.
Example with methacrylate monomer of carboxyl comprises vinylformic acid, phthalic acid, methacrylic acid list hydroxyl ethyl ester, hydroxy-butanedioic acid Beta-methyl acryloxy ethyl ester etc.
Putty of the present invention also contains the phtotpolymerizable oligourethane that two or more methacryloxies are arranged in the molecule.In automotive coating, two-component-type acrylic acid or the like-carbamate coating composition generally is used to repair purposes, and acrylic acid or the like-trimeric cyanamide or alkyd-trimeric cyanamide coating composition is used for new car.Therefore, by in putty, mixing the oligourethane fragment, can obtain the binding property between the residual coating on putty and the metal plate sections to be repaired.
In polymerisable monomer and oligopolymer total amount is 100 weight parts, and the usage quantity of oligourethane is the 14.9-49.8 weight part, is preferably the 20-40 weight part.When the amount of oligourethane during, remain in the poor adhesion between the old coating of waiting to repair part and the curing putty less than 14.9 weight parts.And when the amount of carbamate surpassed 49.8 weight parts, the modulus of then solidifying putty was lower, thereby can cause the wear resistance of the curing putty that generates to descend.
Be preferably, use the combination of high molecular and low-molecular-weight oligourethane in the present invention.Because the high molecular oligourethane is a long-chain compound, it is flexible that gained solidifies putty, and putty further improves the adhesive power of metal sheet and coating.On the other hand, the low molecular weight carbamate oligopolymer can increase the cross-linking density that solidifies putty, improves its high-temperature behavior.
The number-average molecular weight of high molecular oligourethane is not less than 5000, is preferably 8000-10000.When the number-average molecular weight of high molecular oligourethane less than 5000 the time, gained solidifies the flexible poor of putty.
The example of useful high molecular carbamate comprises that commodity are called the oligourethane of the UV curing type carbamate-acrylate of " UX-2201 ", " UX-3301 " and " UX-7101 " (Japanese Nippon Kayaku company product) and commodity " UA-4000 " by name (Japanese Shin-nakamura KCC product).Preferred oligourethane is " UA-4000 ", and its molecular weight is about 8000.
In the present invention, be 100 weight parts in the total amount of polymerizable oligomers, the usage quantity of high molecular oligourethane is the 4-100 weight part, is the 50-70 weight part preferably.When the amount of high molecular oligourethane among the present invention during, remain in old coating and the adhesive power decline of solidifying between the putty that metal sheet waits to repair part less than 40 weight parts.
The number-average molecular weight of low molecular weight carbamate oligopolymer is no more than 1500, and being preferably its number-average molecular weight is 1000-1500.
That the example of useful low molecular weight carbamate oligopolymer comprises is that Japanese Shin-nakamura KCC produces, the NK oligourethane of commodity " U-6HA ", " U～324A " by name, " UA-122P " and " UA-5201 ".Preferred low molecular weight carbamate oligopolymer is the carbamate prepolymer (its molecular weight is about 1100) of difunctionality polycarbonate diol modification of commodity " UA-122P " by name and the four sense oligourethanes that commodity are called " U-4HA ", and the both is a Japanese Shin-nakamura KCC product.
Total amount in polymerizable oligomers is 100 weight parts, and the usage quantity of low molecular weight carbamate oligopolymer is the 0-60 weight part, is the 30-50 weight part preferably.When the amount of low molecular weight carbamate oligopolymer surpasses 60 weight parts, the quantitative change of high molecular oligourethane gets less, solidify the flexible variation of putty, cause solidifying putty with the coating that remains on the metal sheet zone to be repaired between adhesive power decline.
Putty of the present invention also can contain the known various photopolymerization catalyzer of those skilled in the art.In putty of the present invention, preferably have light trigger, photosensitizers and photoresponse accelerator at least to obtain good light solidified.
Preferred light trigger is α-diketone, the especially preferred α-diketone of maximum absorption wavelength in visible-range.
Its example comprises biacetyl, acetylbenzene formyl radical, benzil, camphorquinone, Alpha-Naphthyl, p, p '-benzil of dimethoxy, 2,3-diacetylmethane, 1,2-phenanthrenequione, 1,4-phenanthrenequione, 3,4-phenanthrenequione, 9,10-phenanthrenequione and naphthoquinones or their mixture.Preferred camphorquinone.
Total amount in polymerisable monomer and oligopolymer is 100 weight parts, and the usage quantity of α-diketone is the 0.01-10 weight part, is the 0.1-5 weight part preferably.When the amount of α-diketone during less than 0.01 weight part, light-initiated efficient is low, almost can not be practical.And when the amount of α-diketone surpassed 10 weight parts, then package stability was poor.
In the case, the photosensitizers that is fit to share with α-diketone is a tertiary amine.
The example of useful tertiary amine comprises and is selected from N, accelerine, N, N-Diethyl Aniline, N, the N-dimethyl-to monomethylaniline, 4-dimethyl ethyl aminobenzoate, N, N-dihydroxy ethyl aniline, triethylamine and N, a kind of in the mixture of N-dimethylhexylamine and they.Preferred tertiary amine is the compound that aryl is directly replaced by N, for example the 4-dimethyl ethyl aminobenzoate.
Total amount in polymerisable monomer and oligopolymer is 100 weight parts, and the usage quantity of tertiary amine is the 0.01-10 weight part, is the 0.1-5 weight part preferably.When the amount of tertiary amine during less than 0.01 weight part, light-initiated efficient is low, almost can not be practical.And when the amount of tertiary amine surpassed 10 weight parts, then package stability was poor.
Preferred photoresponse accelerator is a salt.
The example of useful photoresponse accelerator comprises and is selected from a kind of in hexafluoro-antimonic acid triphenylsulfonium, phosphofluoric acid triphenylsulfonium and phosphofluoric acid phenylbenzene iodine or their mixture.
Total amount in polymerisable monomer and oligopolymer is 100 weight parts, and the usage quantity of salt is the 0.01-5 weight part, is the 0.1-1 weight part preferably.When the amount of salt during less than 0.01 weight part, light-initiated efficient is low, almost can not be practical.And when the amount of salt surpassed 5 weight parts, then package stability was poor.
Putty of the present invention can contain the filler that does not suppress light transmissive.The filler that preferably has high light transmissive.Use filler in order that improve shock resistance, give putty with thixotropy and mill capacity with prevent the putty cure shrinkage.
The example of useful filler comprises inorganic little hollow sphere filler, zinc oxide ultra-fine particle, titanium oxide ultra-fine grain, barium sulfate ultra-fine grain etc.The Ball-type packing of preferably little hollow, the glass envelope that they are made up of the borsyl lime glass, for example, " the Glass Bubbles " that 3M company produces.The median size of such glass envelope is the 10-100/ micron, is the 40-80/ micron preferably.
Total amount in polymerisable monomer and oligopolymer is 100 weight parts, and the usage quantity of glass envelope is the 5-20 weight part, is the 10-15 weight part preferably.When the amount of glass bag surpassed 20 weight parts, the elongation variation of gained putty was solidified the putty surface irregularity.And, then can not get suppressing the effect of cure shrinkage when glass envelope during less than 5 weight parts.
In addition, putty of the present invention can contain the zinc oxide ultra-fine particle that median size is about 0.02 micron, has high transmissibility, thereby can produce good spreadability, and it is fine and closely woven to repair surface texturisation.The addition of zinc oxide is generally the 0.1-20 weight part, is the 5-10 weight part preferably.
Putty of the present invention can contain thixotropic agent.Use thixotropic agent controlling flowability and spreadability, and can prevent the filler deposition.
The example of useful thixotropic agent comprises high-purity anhydrous silicon-dioxide, and the interaction of the silanol group that it can be by particle surface is given putty with thixotropy.Be preferably silicon-dioxide ultra-fine grain that handle through hydrophobicity on the surface, that particle diameter is about 7-30nm.When using the superfine silicon dioxide particle of surface process hydrophobicity processing, can prevent the glass envelope deposition.The commercially available product of such silicon-dioxide has the product of the commodity " Aerogy " by name that Japanese Nippon Aerogyl Co., Ltd. produces.
Total amount in polymerisable monomer and oligopolymer is 100 weight parts, and the usage quantity of thixotropic agent is the 0.1-10 weight part, is the 5-8 weight part preferably.When the amount of thixotropic agent during, can not prevent the filler deposition less than 0.1 weight part.And when the amount of thixotropic agent surpassed 10 weight parts, then therefore the mobile variation of putty, was difficult to apply putty with spatula.
Can in putty of the present invention, add silane coupling agent to improve binding property to metal.For example, be 100 weight parts in the total amount of polymerisable monomer and oligopolymer, can add about 0.1-5 weight part, be the γ-methacryloxypropyl trimethoxy silicomethane of 0.5-1.0 weight part preferably.
Said components such as bisphenol type epoxy two (methyl) acrylate, (methyl) acrylate, oligourethane, photopolymerization catalyzer, filler, thixotropic agent and any other component can be mixed to obtain putty of the present invention with the known appropriate method of those skilled in the art.For example, above-mentioned all components is mediated, removed bubble with the vacuum stirring device simultaneously.
When repairing sheet metal, gained putty is coated in part to be repaired.The putty thickness of primary coating preferably is not more than 3mm.When thickness surpassed 3mm, light transmissive was relatively poor, thereby may need many times to be cured and putty may solidify not exclusively.
Then, by irradiation putty coating is solidified.Consider the security of work, preferably use visible light.Used visible wavelength depends on kind, oligopolymer and the photopolymerization catalyzer of polymerisable monomer.General optimal wavelength is at the visible light of 300-1200nm (especially 400-500nm).
The example of launching the irradiating source of these light comprises halogen lamp, xenon lamp, tungsten lamp, carbon arc light modulation, luminescent lamp, mercury lamp etc.Irradiation distance is generally 10-30cm, and irradiation time was generally 1-10 minute.Can use sunlight as light source.
Grind curing putty with those skilled in the art's known method, form patched surface.
Embodiment
The following examples illustrate the present invention in further detail, but should not think the qualification to protection domain of the present invention.In the following embodiments, " part " by weight, except as otherwise noted.Embodiment 1
With 42 parts of dihydroxyphenyl propane 2-glycidyls two (methyl) acrylate, 18 parts of hydroxyethyl methylacrylates, 20 parts of oligourethanes " UA4000 " (Japanese Shin-nakamura KCC product), 0.25 part of camphorquinone, 0.25 part of 4-dimethyl ethyl aminobenzoate, 0.25 part of phosphofluoric acid tripropyl sulfonium, 15 parts of median sizes glass envelope and 7 parts of Aerogyl of 40 microns
TMR972 silicon-dioxide joins in the container, and mixture is evenly mediated, and removes bubble with the vacuum stirring device simultaneously, preparation putty.
Slightly grind the steel plate (" SPCC-SB " of thick 0.7mm with abrasive material (about #80), Japan NipponTest Panel Kogyo Co., Ltd. product), and with the washing composition that is exclusively used in painted surface " Silicon Off " (Japanese Nippon Paint Co., Ltd. product) except that degreasing.The thick putty of coating 1mm on steel plate.Then, shone 5 minutes from the distance of 20cm, be cured with two halogen spot (360W).
The mill capacity and the adhesive power on metal sheet and coating of putty with set time of following method calibrating putty, after solidifying.The results are shown in Table 1.Set time
By mode same as described above, shine the putty (1mm thick) that apply from the distance of 20cm at 5 ℃, 25 ℃ and 35 ℃ with two halogen spot (360W), measure the time that the putty completely solidified is required.The mill capacity test
Under the load of 500g, usefulness crosscut trier and tungsten pin are standardized following on curing putty.With the surfaceness trier three position finding scratch depth and get the averaging of income value and estimate.Fusible test to metal sheet and coating
Use 2.5cm * 10cm and thick respectively for the anti-rust metal plate " Excelite " of 0.8mm with by on this metal sheet, using cated plate " SPCC-SB " (both are Nippon Test Panel Kogyo Co., Ltd. product) that two-component-type acrylic acid or the like-carbamate coating composition obtains as test board.
By mode same as described above, on the surface of each test board, form 2.5cm * 2.5cm and thickly be the curing putty of 1mm.Then, the surface adhesion that will solidify putty with epoxy adhesive is through handling equally, have on the identical shaped test board surface.
Then, rip with the speed of 5mm/min being formed with the test board that solidifies putty and another test board that sticks to above-mentioned curing putty layer surface above it with " Tensilon " device that Olientic company produces, and measure the adhesion strength of putty.Embodiment 2
By preparing with the same way as described in the embodiment 1 and estimating putty, different is that the oligourethane of producing with 20 parts of Shin-nakamura KCCs " U-4HA " replaces oligourethane " UA122P ".The results are shown in Table 1.Embodiment 3
By and same way as described in the embodiment 1 preparation and estimate putty, different is, uses " UA122P " and has used 40 parts of oligourethanes " UA4000 ".The results are shown in Table 1.Embodiment 4
By preparing with the same way as described in the embodiment 1 and evaluation putty, different is, with 40 part 2,2-two (4-(methacryloxy oxyethyl group) phenyl) propane (" BPE-1 " that Shin-nakamura KCC produces) replaces dihydroxyphenyl propane 2-glycidyl two (methyl) acrylate and replaces hydroxyethyl methylacrylate with 18 parts of methacrylic esters (" PM-21 " that Nippon Kayaku Co., Ltd. produces) with phosphate group.The results are shown in Table 1.Comparative example 1
Use the commercially available multiple putty of two-component-type (" SU putty " that Japanese Kansai Paint Co., Ltd. produces).Host contains vibrin and as the styrene monomer of main component.Solidifying agent is a superoxide.Take by weighing 100 parts of hosts and 2 parts of solidifying agent, use the spatula uniform mixing.
On two kinds of test boards that make by mode same as described above, apply the thick putty of 1mm respectively.Then, the putty that applied is left standstill be cured.During curing, the temperature of test board is maintained 5 ℃, 25 ℃ and 35 ℃ respectively, and measure the time that the putty completely solidified is required.
By with the wear resistance of same way as described in the embodiment 1 test solidified putty with to the binding property of metal sheet and coating.The results are shown in Table 1.Comparative example 2
By preparing with the same way as described in the comparative example 1 and estimating putty, different is to replace " the SU putty " of Kansai Paint Co., Ltd. production with " Plastaner " of Nippon Paint Co., Ltd. production.The results are shown in Table 1.
Table 1
| Set time | (branch) | Wear resistance (micron) | Binding property (kgf/cm 2) | |||
| ????5℃ | ????25℃ | ????35℃ | Steel 1 | Coating 2 | ||
| Embodiment 1 | ????5 | ????5 | ????5 | ????178 | ????35 | ????＞43 |
| Embodiment 2 | ????5 | ????5 | ????5 | ????165 | ????30 | ????＞33 |
| Embodiment 3 | ????5 | ????5 | ????5 | ????162 | ????30 | ????＞38 |
| Embodiment 4 | ????5 | ????5 | ????5 | ????183 | ????36 | ????＞40 |
| Comparative example 1 | ????100 | ????30 | ????10 | ????128 | ????43 | ????＞40 |
| Comparative example 2 | ????75 | ????20 | ????8 | ????163 | ????35 | ????＞38 |
1The anti-rust metal plate
2Cated plate
In embodiment 1-4, do not change with envrionment temperature set time, all shorter, is 5 minutes.In addition, the wear resistance of putty is also good.And the commercially available putty of comparative example 1 and 2, set time is longer, and changes with envrionment temperature, thus its poor practicability.
Claims (5)
1. be used for the Photocurable putty of repairing sheet metal, it comprises:
(a) bisphenol type epoxy two (methyl) acrylate of 100 weight parts (, being 33.3-73.5 weight %) in the total amount of component (a)-(c);
(b) the phtotpolymerizable methacrylic ester of 1-100 weight part (, being 0.7-33.3 weight %) in the total amount of component (a)-(c);
(c) the phtotpolymerizable oligourethane of two or more methacryloxies is arranged in the molecule of 35-100 weight part (in the total amount of component (a)-(c), being 25.7-33.3 weight %);
(d) the 0.01-10 weight part as the α-diketone of light trigger, 0.01-10 weight part as the tertiary amine of photosensitizers and the salt as the photoresponse accelerator of 0.01-5 weight part, each amount is 100 weight part meters based on total amount of component (a)-(c).
2. the Photocurable putty that is used for repairing sheet metal as claimed in claim 1 is characterized in that, described oligourethane comprises:
(ⅰ) 40-100 weight part molecular weight is at the high molecular oligourethane more than 5000; With
(ⅱ) 0-60 weight part molecular weight is at the low molecular weight carbamate oligopolymer below 1500, and each amount is in the component (c) of 100 weight parts.
3. the Photocurable putty that is used for repairing sheet metal as claimed in claim 1, its feature is that also it also comprises:
(e) the 5-20 weight part has the filler of high light transmissive; With
(f) 0.1-10 weight part thixotropic agent, each amount is 100 weight part meters based on the total amount of component (a)-(c).
4. the Photocurable putty that is used for repairing sheet metal as claimed in claim 3 is characterized in that, described filler by the borsyl lime glass form, median size is the glass envelope of 10-100 micron.
5. the Photocurable putty that is used for repairing sheet metal as claimed in claim 3 is characterized in that, described thixotropic agent is the silicon-dioxide fine particle that handle through hydrophobicity on the surface, and there is silanol on its surface, and median size is the 7-30 nanometer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53059/96 | 1996-03-11 | ||
| JP5305996A JPH09241533A (en) | 1996-03-11 | 1996-03-11 | Photocurable putty for sheet metal repair |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1213386A true CN1213386A (en) | 1999-04-07 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97192906 Pending CN1213386A (en) | 1996-03-11 | 1997-03-06 | Photocurable putty for repairing sheet metal |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0886660A1 (en) |
| JP (1) | JPH09241533A (en) |
| CN (1) | CN1213386A (en) |
| BR (1) | BR9708026A (en) |
| CA (1) | CA2247434A1 (en) |
| WO (1) | WO1997033928A1 (en) |
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|---|---|---|---|---|
| CN100410058C (en) * | 2006-05-24 | 2008-08-13 | 太原理工大学 | Resin base composite material parts quick forming method |
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| JP2007284626A (en) * | 2006-04-19 | 2007-11-01 | Daicel Value Coating Ltd | Resin composition curable with actinic energy ray and film coated with the composition |
| EP2069441A1 (en) * | 2006-08-18 | 2009-06-17 | E.I. Du Pont De Nemours And Company | Uv curable putty compositions |
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| US4357219A (en) * | 1980-06-27 | 1982-11-02 | Westinghouse Electric Corp. | Solventless UV cured thermosetting cement coat |
| DE3620254C2 (en) * | 1985-06-18 | 1994-05-05 | Canon Kk | By blasting with effective energy curable resin mixture |
| US5128391A (en) * | 1988-02-24 | 1992-07-07 | Borden, Inc. | Extensible and pasteurizable radiation curable coating for metal containing organofunctional silane adhesion promoter |
| DE69009837T2 (en) * | 1989-04-19 | 1994-10-13 | Nat Starch Chem Invest | Adhesive / sealant composition and method of using it. |
-
1996
- 1996-03-11 JP JP5305996A patent/JPH09241533A/en active Pending
-
1997
- 1997-03-06 EP EP97916134A patent/EP0886660A1/en not_active Ceased
- 1997-03-06 BR BR9708026A patent/BR9708026A/en unknown
- 1997-03-06 CA CA 2247434 patent/CA2247434A1/en not_active Abandoned
- 1997-03-06 CN CN 97192906 patent/CN1213386A/en active Pending
- 1997-03-06 WO PCT/US1997/004554 patent/WO1997033928A1/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410058C (en) * | 2006-05-24 | 2008-08-13 | 太原理工大学 | Resin base composite material parts quick forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997033928A1 (en) | 1997-09-18 |
| EP0886660A1 (en) | 1998-12-30 |
| BR9708026A (en) | 1999-07-27 |
| JPH09241533A (en) | 1997-09-16 |
| CA2247434A1 (en) | 1997-09-18 |
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