CN102134362B - Resin impregnant and manufacturing method of the same - Google Patents
Resin impregnant and manufacturing method of the same Download PDFInfo
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- CN102134362B CN102134362B CN 201010623401 CN201010623401A CN102134362B CN 102134362 B CN102134362 B CN 102134362B CN 201010623401 CN201010623401 CN 201010623401 CN 201010623401 A CN201010623401 A CN 201010623401A CN 102134362 B CN102134362 B CN 102134362B
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Abstract
A resin impregnant and a manufacturing method thereof are provided. A resin impregnant contains the following: an acrylic monomer including 100 parts of first acrylic monomer by weight to provided the softness to a harden material, 40-100 parts of second acrylic monomer by weight to provide rigidity, and 4-20 parts of third acrylic monomer by weight to provide the coherence between monomers; an anti oxidant; a cyanoacrylic acid ester based photo stabilizer; and a surfactant.
Description
Technical field
The present invention relates to resin impregnant, relate in particular to by using water-insoluble monomer, thus when washing can with water sepn, therefore recyclable and resin impregnant that its rate of recovery is high and preparation method thereof.
Background technology
The purpose of using soaker is to fill the space of the material that is made of the casting product that have the space, sintering metal, aluminium alloy etc. to guarantee its resistance to air loss.
The soaker of prior art roughly is divided into mineral-type and several classes is arranged, wherein, mineral-type soaker is to be the water glass class of main component with silicate, and has a few class soaker to comprise anaerobism acrylic resin, thermoset unsaturated ester resinoid and thermoset acrylics resinoid.
Mineral-type soaker solidifies by moisture evaporation, and therefore, its set time is very long, the viscosity height, and the infiltration efficient of dipping synthetics is low.Especially, reduce because solidifying the back volume, the liquid discharging amount is many, and includes low-boiling point material, therefore, is not suitable for bigger pore.In addition, than mineral-type soaker, anaerobism acrylic resin and thermoset unsaturated polyester esters resin, though its set time is short, the infiltration efficient of dipping synthetics is also higher, but its process management complexity, and than the thermoset acrylics resinoid, the infiltration efficient of its set time and dipping synthetics etc. are all slightly inferior.In addition, after the dipping of finishing the pore of material, in the surface cleaning process, because of the washing force that utilizes water a little less than, thereby at the residual dipping composition of material surface, cause easily bad, and, cause can not reuse the waste liquid that stays after the cleaning, thereby increases the cost of technology of liquid waste disposal and cause environmental pollution.
In addition, the precedent of using water-insoluble monomer is arranged also in the prior art in part soaker, but because of need additional input additive in use, thereby cause the problem on technology and the expense, and, exist thermotolerance low, problems such as cured article variable color, thus bring inconvenience to use.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art and a kind of resin impregnant and preparation method thereof is provided, it is low because of viscosity, thereby the infiltration efficient height of dipping synthetics, and because of the thermotolerance height, thereby in high temperature, also can not deform or variable color, in addition, even in water washing process, contact with moisture, also can not cause corrosion or the oxidation of coated article.
Another purpose of the present invention is to provide a kind of resin impregnant and preparation method thereof, and its antioxidant adopts Phosphorus antioxidant, thereby prevents the oxidation of cured article, and its stability is high.
Another purpose of the present invention is to provide a kind of resin impregnant and preparation method thereof, and it uses cyanoacrylate photostabilizer, thereby preparation is easily, and because thermotolerance and antioxidant effect are good, thereby significantly improve the rerum natura of soaker and cured article thereof.
Resin impregnant of the present invention comprises:
Acrylic Acid Monomer comprises to cured article and gives the first soft Acrylic Acid Monomer, gives the second rigid Acrylic Acid Monomer and to the 3rd Acrylic Acid Monomer of giving bonding force between the monomer to cured article;
Antioxidant;
Cyanoacrylate (cyanoacrylate ester) fluid-like state photostabilizer; And
Tensio-active agent.
Above-mentioned second Acrylic Acid Monomer can comprise 40～100 weight parts with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts; And above-mentioned the 3rd Acrylic Acid Monomer can comprise 4～20 weight parts with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts.
Above-mentioned first Acrylic Acid Monomer can comprise at least a material of selecting from the group who is made of isodecyl methacrylate (Isodecylmethacrylate), methacrylic ester (Methacrylic ester), different ten trimethacrylates (Isotridecyl methacrylate), formaldehyde dodecyl acrylate (Dodecyl methacrylate), vinylformic acid tridecyl ester (Tridecyl acrylate) and composition thereof.
Above-mentioned second Acrylic Acid Monomer can comprise from by methacrylic acid benzylester (Benzylmethacrylate), isobornyl acrylate (Isobornyl acrylate), iso-borneol methacrylic ester (isobornyl methacrylate), Jia Jibingxisuanyizhi (Ethyl Methacrylate), 1-butyl methacrylate (1-butyl Methacrylate), Rocryl 410 (Hydroxypropylmethacrylate), N-butyl methacrylate (N-butyl methacrylate), methyl methacrylate (Methyl methacrylate), at least a material of selecting among the group that cyclohexyl methacrylate (Cyclohexyl methacrylate) and composition thereof constitutes.
The 3rd Acrylic Acid Monomer can comprise from by ethylene glycol dimethacrylate (Ethylene glycoldimethacrylate), Diethylene Glycol dimethacrylate (DiEthylene glycol dimethacrylate), Viscoat 295 (Trimethylol propane triacrylate), trimethylolpropane trimethacrylate (Trimethylolpropane trimethacrylate), tri (propylene glycol) diacrylate (Tripropylene glycol diacrylate), at least a material of selecting among the group that trimethylammonium alcohol propane methacrylic ester (Trimethylolpropane methacrylate) and composition thereof constitutes.
Above-mentioned resin impregnant also comprises the tetrapropylene acid mono, and above-mentioned tetrapropylene acid mono can comprise from by by Propenoic acid, 2-methyl, isobutyl ester (Isobutyl methacrylate), 2-ethylhexyl methacrylate (2-ethylhexyl methacrylate), alkyl methacrylate (Alkyl methacrylate), tridecyl methacrylic ester (Tridecyl methacrylate), stearyl alcohol methacrylic ester (Stearylmethacrylate), diethyl amido ethyl-methyl vinylformic acid (Diethylaminoethyl methacrylate), ethylene glycol dimethacrylate (Ethylene glycol dimethacrylate), 1,3-butylene glycol dimethacrylate (1,3-butylene glycol dimethacrylate), 1, the 6-dimethacrylate (1,6-hexanedioldimethacrylate), at least a material of selecting among the group that 2-ethoxyethyl group methacrylic ester (2-ethoxyethyl methacrylate) and composition thereof constitutes.
Above-mentioned tetrapropylene acid mono can comprise 1～4 weight part with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts.
Above-mentioned tensio-active agent can comprise 1～3 weight part with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts; Above-mentioned antioxidant can comprise 0.2～0.8 weight part with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts; And above-mentioned photostabilizer can comprise 1～2 weight part with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts.
Above-mentioned antioxidant can comprise Phosphorus antioxidant.
Above-mentioned resin impregnant also can comprise fire retardant.
Above-mentioned fire retardant can comprise 1～3.5 weight part with respect to 100 weight part aforesaid propylene acid mono.
Above-mentioned fire retardant can comprise from by more than one materials of selecting halogen, Phosphorus and hydroxide metal compound constitutes the group.
Above-mentioned tensio-active agent can comprise the second surface promoting agent of nonionic higher alcohols first surface promoting agent and nonionic fatty acid ester.
Above-mentioned first surface promoting agent can comprise methyl alcohol ethoxylate (Methanol ethoxylate) or Ethanol Ethoxylation thing (Ethanol ethoxylate).
Above-mentioned second surface promoting agent can comprise more than one materials of selecting from the group who is made of oleic acid macrogol ester (Polyethylene glycololeate), the smooth fatty acid ester of sorb (Sorbitan fatty acid ester), polyoxyethylene lipid acid sorbitan ester (Polyoxyethylene sorbitan fatty acid ester).
The weight ratio of above-mentioned first surface promoting agent and above-mentioned second surface promoting agent can be 1: 1～and 1: 3.
Above-mentioned resin impregnant also can comprise fluorescent agent.
Luminous material when above-mentioned fluorescent agent can be irradiation ultraviolet radiation.
Above-mentioned fluorescent agent can comprise from by 7-diethylin-4-methylcoumarin (4-methyl-7-(diethylamino) coumarin), 2.5-two-(the 5-tertiary butyl-2-benzoxazolyl) thiophene (2,2 '-(2,5-thiophenediyl) Bis[5-(1,1-dimethylethyl)]-benzoxazole), 2,2 '-(4,4 '-phenyl vinyl) two-benzoxazoles (2,2 '-more than one materials of selecting among the group that (4,4 '-diphenolvinyl) di-benzoxazole) constitute.
Above-mentioned fluorescent agent can comprise 0.001～0.003 weight part with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts.
Resin impregnant preparation method of the present invention comprises:
The monomer mixing step mixes to cured article and gives the first soft Acrylic Acid Monomer, gives the second rigid Acrylic Acid Monomer and to the 3rd Acrylic Acid Monomer of giving bonding force between the monomer to cured article;
The additive mixing step is dissolved in the aforesaid propylene acid mono mixed solution antioxidant fully, and after mixing stirring cyanoacrylate photostabilizer, adds tensio-active agent.
When adding above-mentioned tensio-active agent, can add fire retardant in the lump.
Above-mentioned tensio-active agent can comprise the second surface promoting agent of nonionic higher alcohols first surface promoting agent and nonionic fatty acid ester.
When adding above-mentioned tensio-active agent, can add fluorescent agent in the lump.
Resin impregnant of the present invention and preparation method thereof, than the soaker that can not reclaim the prior art of use because of use water soluble propene acid mono, its solubleness in water is lower than 5%, thereby separates with washing water in water washing process, and is recyclable.Therefore, not only can prevent the environmental pollution that causes because of waste water, but also can save the wastewater treatment expense.
In addition, because need not to add other material in removal process, therefore, technology is simple, but possesses the function of enough resin impregnants.And, because not producing any taste in the preparation, thereby can improve operating environment.
If add fire retardant, then because weight loss on heating becomes minimum, thereby good heat resistance also can seal micropore in high thermal environment.In addition, if add fluorescent agent, then can after the sealing of finishing micropore, with the naked eye can confirm sealed state.
Description of drawings
Fig. 1 is for comparing one embodiment of the invention and the stable on heating photo of other company's products;
Fig. 2 is for comparing the photo of one embodiment of the invention and other company's product by heating decrements;
Fig. 3 is for comparing the photo of one embodiment of the invention and other company's products solidifying thing states;
Fig. 4 is the photo that uses the resin impregnant irradiation ultraviolet radiation of fluorescent agent to one embodiment of the invention;
Fig. 5 is the washing force state photo with the usage quantity variation of tensio-active agent of the present invention;
Fig. 6 is the photo that uses the resin impregnant irradiation ultraviolet radiation of fluorescent agent to one embodiment of the invention;
Fig. 7 is for using the photo of the resin impregnant irradiation ultraviolet radiation of fluorescent agent to the present invention.
Embodiment
Resin impregnant of the present invention comprises water-insoluble Acrylic Acid Monomer, tensio-active agent, antioxidant and photostabilizer.Meanwhile, can comprise fire retardant and fluorescent agent.
Water-insoluble Acrylic Acid Monomer comprises different types of first Acrylic Acid Monomer, second Acrylic Acid Monomer and the 3rd Acrylic Acid Monomer, and, also optionally comprise the tetrapropylene acid mono.
The effect of first Acrylic Acid Monomer is to give soft with by the bonding force of thing and cured article, can comprise more than at least a in the following monomer of enumerating without limitation.
First Acrylic Acid Monomer: isodecyl methacrylate, methacrylic ester, different ten trimethacrylates, formaldehyde dodecyl acrylate, vinylformic acid tridecyl ester.
The effect of second Acrylic Acid Monomer is rigid to solidifying in giving, and can comprise more than at least a in the following monomer of enumerating without limitation, and preferably, with respect to 100 weight parts, first Acrylic Acid Monomer, comprise 40～100 weight parts.If its content is lower than 40 weight parts, then because can not effectively solidifying cured article, thereby prolong set time, and too high as if proportion, then can not reach the purpose of oily water separation smoothly.
Second Acrylic Acid Monomer: methacrylic acid benzylester, isobornyl acrylate, iso-borneol methacrylic ester, Jia Jibingxisuanyizhi, 1-butyl methacrylate, Rocryl 410, N-butyl methacrylate, methyl methacrylate, cyclohexyl methacrylate.
The effect of the 3rd Acrylic Acid Monomer is the effect of playing linking agent, namely increase the bonding force between the various resins in the dipping cured article so that it is stablized, can comprise more than at least a in the following monomer of enumerating without limitation, and preferably, with respect to 100 weight parts, first Acrylic Acid Monomer, comprise 4～20 weight parts.If its content is lower than 4 weight parts, then will reduce high-temperature heat-resistance, and if its content surpasses 20 weight parts, then reduce rerum natura, cause variable color or produce the crack.
The 3rd Acrylic Acid Monomer: ethylene glycol dimethacrylate, Diethylene Glycol dimethacrylate, Viscoat 295, trimethylolpropane trimethacrylate, tri (propylene glycol) diacrylate, trimethylammonium alcohol propane methacrylic ester.
The tetrapropylene acid mono is the composition that optionally adds, its effect is further to increase bonding force and sealing effectiveness, can comprise more than at least a in the following monomer of enumerating without limitation, and preferably, with respect to 100 weight parts, first Acrylic Acid Monomer, comprise 1～4 weight part.If its content is lower than 1 weight part, then will prolongs set time, and if its content surpasses 4 weight parts, then will increase viscosity and proportion.
Tetrapropylene acid mono: Propenoic acid, 2-methyl, isobutyl ester, 2-ethylhexyl methacrylate, alkyl methacrylate, tridecyl methacrylic ester, stearyl alcohol methacrylic ester, diethyl amido ethyl-methyl vinylformic acid, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-dimethacrylate, 2-ethoxyethyl group methacrylic ester.
In addition, the effect of tensio-active agent is to finish after the dipping, in washing step, removes the residual resin soaker that is attached to the surface.
The content of tensio-active agent is not to be advisable by the content of the rinse water emulsification of resin impregnant, and with respect to 100 weight parts, first Acrylic Acid Monomer, comprise 1～3 weight part, can use nonionic surfactant, cationic surfactant, water-insoluble tensio-active agent etc. without limitation.But, if its content is lower than 1 weight part, then will reduce washing force, and if its content surpasses 3 weight parts, then the mixing because of water-insoluble Acrylic Acid Monomer and rinse water is easier to, and will cause the emulsification of rinse water.
Above-mentioned tensio-active agent can include only a kind of material, but unrestricted.Therefore, preferably, tensio-active agent mixes the second surface promoting agent that uses nonionic higher alcohols first surface promoting agent and nonionic fatty acid ester.
The effect of first surface promoting agent is wash residual in the steeping fluid of dipping parts surface, can use methyl alcohol ethoxylate, Ethanol Ethoxylation thing class etc.; And the second surface promoting agent can use oleic acid macrogol ester, the smooth fatty acid ester of sorb, polyoxyethylene lipid acid sorbitan ester etc.
At this moment, preferably, the weight ratio of first surface promoting agent and second surface promoting agent is 1: 1～1: 3.If the content of first surface promoting agent surpasses above-mentioned standard, then will produce excessive foam, thereby be difficult to be used in the washing procedure.
The effect of antioxidant is to prevent that synthetic resins is subjected to the influence of air, moisture, heat or light etc. that undesirable rerum natura takes place and changes, with respect to 100 weight parts, first Acrylic Acid Monomer, comprise 0.2～0.8 weight part, can use phenols, sulphur class, amine etc., and therein, it is more that phenol antioxidant is used, and, do not limit the use of phenol antioxidant among the present invention yet, but can be by adding Phosphorus antioxidant, not only can prevent variable color, and by improving thermotolerance, improve chemical/physical stability.Spendable Phosphorus antioxidant for example has the antioxidant that comprises phosphite (Phosphite).
The effect of photostabilizer is from hot environment or UV-lamp protection soaker, with respect to 100 weight parts, first Acrylic Acid Monomer, comprises 1～2 weight part.At this moment, preferably, photostabilizer uses the cyanoacrylate photostabilizer, and can comprise the following composition of enumerating without limitation, be dicyanogen methyl isophorone diphenylacrylate ester (Bis cyano-diphenyl-acrylic ester), multi-functional 2-cyanoacrylate (2-cyanoacrylicester), 1,3-pair-[(2 '-cyano group-3 ' 3 '-phenylbenzene propylene anilide) oxygen]-2,2-pair-[(2-cyano group-3 ', 3 '-phenylbenzene propylene anilide) oxygen] methyl) propane (1, the oxy of 3-bis-[(2 '-cyano-3 ' 3 '-diphenylacryloyl)]-2,2-bis-[(2-cyano-3 ', 3 '-diphenyl acryloyl) oxy] methyl) propane).
At this moment, (in 300～370nm) the ultraviolet high absorbing power, possess as the antiacid effect of the advantage of phenols with as the thermostability of the advantage of hindered amines possessing the part the highest to injury tolerance.
In addition, photostabilizer is contained in wherein with the form of liquid photostabilizer, so not only dissolving easily, and because of good heat resistance, its weight loss on heating reduces half, and, can guarantee the stability of under strong sunlight, also not solidifying.
In addition, the effect of fire retardant is in order also to guarantee the micropore sealing function as the most important effect of soaker in high thermal environment, to reduce weight loss on heating to greatest extent, giving thermotolerance.Fire retardant comprises 1～3.5 weight part with respect to the whole Acrylic Acid Monomers of 100 weight parts.If its content is lower than 1 weight part, then do not improve effect, but its content surpasses 3.5 weight parts, also can not get better improving effect.
Above-mentioned fire retardant can use from by more than one materials of selecting halogen, Phosphorus and hydroxide metal compound constitutes the group.Especially, the mixing fire retardant of halogen and phosphorus generates phosphorus and oxyhalogenide, and because of the molecular weight height of Phosphorates phosphorus Halides, thereby its Heavy Weight, and O
2The prevention effect big.But the halogen fire retardant belongs to nearest environmental restraint application, therefore, preferably, uses aluminium hydroxide or the magnesium hydroxide of more environmental protection.
Resin impregnant also can comprise fluorescent agent.The effect of fluorescent agent is that soaker be impregnated in after the micropore, in order to confirm the sealed state of micropore, confirms to dipping part irradiation ultraviolet radiation, with respect to the whole Acrylic Acid Monomers of 100 weight parts, comprises 0.001～0.003 weight part.
At this moment, preferably, employed fluorescent agent can be luminous during for irradiation ultraviolet radiation material, for example, comprise from by 7-diethylin-4-methylcoumarin, 2.5-two-(the 5-tertiary butyl-2-benzoxazolyl) thiophene, 2,2 '-more than one materials of selecting among the group that (4,4 '-phenyl vinyl) two-benzoxazoles constitutes.
In addition, for the solidified nature of stable resin soaker, obtain outstanding thermotolerance and good sealing effectiveness, before using resin impregnant, also can add polymerization starter.Polymerization starter uses water-insoluble azo (azo) class polymerization starter, and with respect to the resin impregnant all wts, comprises 0.1～1 weight %.Spendable azo (azo) class polymerization starter specifically has azobis isobutyronitrile (Azobisisobutyronitrile), 2,2 '-azo is two-isopropyl cyanide (2,2 '-azobis-2-isobutyronitrile), 2,2 '-azo is two-methylbutyronitrile (2,2 '-azobis-2-methylbutyronitrile), 2,2 '-azo two-2,4-methyl pentane nitrile (2,2 '-azobis-2,4-dimethylvaleronitrile), dimethyl-2,2 '-the two isobutyrates of azo (dimethyl-2,2 '-azobis iso butylate) etc.
The resin impregnant that comprises above-mentioned substance is prepared from by the following method:
At first, mix to cured article and give the first soft Acrylic Acid Monomer, give the second rigid Acrylic Acid Monomer and to the 3rd Acrylic Acid Monomer of giving bonding force between the monomer to cured article.
Then, antioxidant is dissolved in the aforesaid propylene acid mono mixed solution fully, and after mixing stirring cyanoacrylate photostabilizer, adds tensio-active agent.As mentioned above, above-mentioned tensio-active agent can comprise the second surface promoting agent of nonionic higher alcohols first surface promoting agent and nonionic fatty acid ester.
In addition, when adding above-mentioned tensio-active agent, can add fire retardant and/or fluorescent agent in the lump.
[embodiment]
＜embodiment 1 〉
Mixing is as the isodecyl methacrylate of the 45g of first Acrylic Acid Monomer, as the cyclohexyl methacrylate of the 45g of second Acrylic Acid Monomer and as the trimethylammonium alcohol propane methacrylic ester of the 8g of the 3rd Acrylic Acid Monomer; Then, in the mixed solution of Acrylic Acid Monomer, make the Phosphorus antioxidant songnox of 0.3g
TM1680-PW (Songwon industry) dissolves fully and after the cyanoacrylate photostabilizer that mixes 0.7g fully stirs, adds the tensio-active agent ISC-100 of 1g
TM(Ilsan chemistry) is with the preparation resin impregnant.
＜embodiment 2 〉
Mixing is as the isodecyl methacrylate of the 50g of first Acrylic Acid Monomer, as the methacrylic acid benzylester of the 38g of second Acrylic Acid Monomer, as the trimethylammonium alcohol propane methacrylic ester of the 8g of the 3rd Acrylic Acid Monomer and as the basic isobutyl acrylate of the 2g of tetrapropylene acid mono; Then, in the mixed solution of Acrylic Acid Monomer, the phenol antioxidant BHT of 0.2g is dissolved fully and after the cyanoacrylate photostabilizer that mixes 0.8g in order to improve thermotolerance fully stirs, add the tensio-active agent ISC-100 of 1g
TM(Ilsan chemistry) is with the preparation resin impregnant.
＜embodiment 3 〉
Mixing is as the isodecyl methacrylate of the 60g of first Acrylic Acid Monomer, as the iso-borneol methacrylic ester of the 32g of second Acrylic Acid Monomer, as the Diethylene Glycol dimethacrylate of the 8g of the 3rd Acrylic Acid Monomer and as the alkyl methacrylate of the 2g of tetrapropylene acid mono; Then, in the mixed solution of Acrylic Acid Monomer, the phenol antioxidant BHT of 0.2g is dissolved fully and after the cyanoacrylate photostabilizer that mixes 0.8g fully stirs, add the tensio-active agent ISC-100 of 1g
TM(Ilsan chemistry) is with the preparation resin impregnant.
＜embodiment 4 〉
Mixing is as the formaldehyde dodecyl acrylate of the 68g of first Acrylic Acid Monomer, as the Rocryl 410 of the 27g of second Acrylic Acid Monomer and as the Diethylene Glycol dimethacrylate of the 3g of the 3rd Acrylic Acid Monomer; Then, in the mixed solution of Acrylic Acid Monomer, make the Phosphorus antioxidant songnox of 0.5g
TM1680-PW (Songwon) dissolves fully and after the cyanoacrylate photostabilizer that mixes 0.5g fully stirs, adds the tensio-active agent ISC-100 of 1g
TM(Ilsan chemistry) is with the preparation resin impregnant.
＜comparative example 1 〉
Mixing is as the isodecyl methacrylate of the 45g of first Acrylic Acid Monomer, as the methacrylic acid benzylester of the 45g of second Acrylic Acid Monomer and as the Diethylene Glycol dimethacrylate of the 8g of the 3rd Acrylic Acid Monomer; Then, in the mixed solution of Acrylic Acid Monomer, the phenol antioxidant BHT of 0.2g is dissolved fully and after the Powdered photostabilizer benzotriazole (Benzotriazole) that mixes 0.8g fully stirs, add tensio-active agent ISC-100
TM(Ilsan chemistry) is with the preparation resin impregnant.
＜comparative example 2 〉
Mixing is as the isodecyl methacrylate of the 50g of first Acrylic Acid Monomer, as the Rocryl 410 of the 40g of second Acrylic Acid Monomer, as the trimethylammonium alcohol propane methacrylic ester of the 5g of the 3rd Acrylic Acid Monomer and as the alkyl methacrylate of the 3g of tetrapropylene acid mono; Then, in the mixed solution of Acrylic Acid Monomer, the phenol antioxidant BHT of 0.4g is dissolved fully and after the Powdered photostabilizer benzotriazole that mixes 0.8g fully stirs, add the tensio-active agent ISC-100 of 1g
TM(Ilsan chemistry) is with the preparation resin impregnant.
Above-described embodiment 1 to 4 and comparative example 1 and 2 arrangements are as shown in table 1 below:
[table 1]
＜experimental example 1 〉
The comparison of embodiment 1 to 4 and comparative example 1 and 2
Utilize above-described embodiment 1 to 4 and comparative example 1 and 2 to measure the thermotolerance of resin impregnant, washing force, stability, oily water separation, weight loss on heating etc., obtain experimental result as shown in table 2:
[table 2]
| |
|
Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| 1) thermotolerance | ◆ | ◇ | ◆ | ◆ | x | x |
| 2) washing force | ◇ | ◇ | ◆ | ◇ | ◇ | x |
| 3) oily water separation | ◆ | ◆ | ◇ | ◆ | ◇ | ◇ |
| 4) weight loss on heating | ◆ | ◇ | ◆ | ◇ | x | x |
◆: good; ◇: good; X: bad
Thermotolerance
At this moment, stable on heating measurement is finished by three kinds of modes, and, if solidify, then be evaluated as " bad "; If variable color takes place, then is evaluated as " well "; And if without any variation, then be evaluated as " good ".Metering system is following three kinds:
1) ultraviolet ray test: utilize ultraviolet radiation device, at the 315nm irradiation ultraviolet radiation; 2) sun exposure test: resin impregnant is placed in the place at the direct projection well lighted; 3) embathe test: in about 60 ℃, embathe.
Washing force
Evaluation to embodiment and comparative example washing force is as follows: if washing out of order, then be evaluated as " bad "; If the washing state is general, then be evaluated as " well "; And if the washing state is good, then be evaluated as " good ".Metering system comprises the steps:
1) metal testing plate be impregnated in after the resin impregnant one minute, take out and placed one minute;
2) be soaked in tap water after 15 seconds, wash up and down for several times with tap water as required;
3) placed one hour after, embrace after the metal testing plate with parchment, with in isobaric ten minutes of book;
4) affirmation sticks to the residue on the parchment.
Oily water separation
Oily water separation is measured by observing the state of embodiment and comparative example and water sepn, if separate stage is bad, then is evaluated as " bad "; If separate stage is general, then be evaluated as " well "; And if separate stage is good, then be evaluated as " good ".
When 1) using beaker: in tap water 85%, add resin impregnant 15% and stir after 30 seconds, place certain hour and also observe separation degree;
When 2) using separating funnel: in tap water 85%, add after resin impregnant 15% and the dandle 10 times, place certain hour and also observe separation degree.
Weight loss on heating
The measurement of weight loss on heating is after the weight of measuring embodiment and comparative example, remeasures weight after 200 ℃ are placed five hours, if weight loss on heating surpasses 20%, then is evaluated as " bad "; If weight loss on heating surpasses 10%, then be evaluated as " well "; And if weight loss on heating is less than 10%, then be evaluated as " good ".Metering system comprises the steps:
1) resin impregnant of getting about 3g solidifies after the 90 ℃/15min, only gets cured article and measures initial weight;
2) in baking box, after the 200 ℃/5hr of heating, measure its weight;
3) calculate 1) and 2) the difference acquisition weight loss on heating (%) of weight.
Stopping property
Characteristic and dipping processing effect in order to test soaker, then carry out following experiment under the standard test condition:
1) preparation of MIL CUP
MIL CUP is the most representative dipping processing test test piece of MIL-I-6869D defined, be that the thickness that has 200～300 pores that connect from inside to outside by special processing is the cup shape aluminium alloy casting product of 0.25 inch (6.35mm), at this, selective permeability is the MILCUP of 1～25cc/sec.
2) withstand voltage test (initial withstand voltage test) after the dipping processing
Apply 5.6kg/cm to the MIL CUP that utilizes the processing of one embodiment of the invention resin impregnant dipping
2The pressure of G also is deposited in the water of normal temperature, whether to confirm MIL CUP seepage.
3) high temperature durability test
To in initial withstand voltage test, confirm as the cup of sealing (not observing the state of seepage fully) fully, put into temperature be set at 200 ± 1 ℃ circulating hot air dryer and every took out in 50 hours cool after, implement the withstand voltage test of above-mentioned condition.Till reach 200 hours heat-up time, whether repeat the seepage of air among the test of above-mentioned initial withstand voltage test and high temperature durability and the record MIL CUP, and, the quantity of seepage and the leakage of unit time (cc/sec) etc. among the MIL CUP as required.
As shown in table 3 with the result that recovery liquid carries out leakage test to the new liquid of soaker according to aforesaid method.
Test-results shows that the new liquid of resin impregnation liquid of the present invention or recovery liquid did not all observe any seepage phenomenon in 200 hours.
[table 3]
＜experimental example 2 〉
Comparison with other company's products
Be its company's product (Ultraseal company, the MX-II that sells on comparing embodiment 1 and the market
TM), the rate of recovery, COD etc. after measurement proterties, smell, proportion, year, moisture, gelation time, thermotolerance, washing force, oily water separation, weight loss on heating, cured article state, the oily water separation.Each is measured the character that reclaims preceding (before the oily water separation) and reclaims the character that back (after the oily water separation) is recovered state to individual test portion in experiment.
Proterties, smell, proportion, viscosity, moisture % and gelation time
The result of experiment proterties, smell, proportion, viscosity, moisture % and gelation time is as shown in table 4:
[table 4]
The measurement of gel time is at first to long 10cm, the glass test tube of diameter 0.8cm is poured the resin impregnant about seventy percent into and is that accurate the measurement inserted after the iron wire, the bed that embathes at 90 ℃ solidifies, and to catch Glass tubing together is raised when carrying on the iron wire time as gel time.
Thermotolerance
1. utilize the ultraviolet investigation result of ultraviolet radiation device irradiation 312nm to be: embodiment 1 is after through three hours, the colour-change of colourless transparent liquid does not still take place, but other company's products are after through 30 minutes, by fluorescence purple yellowing, and through 10 hours after fixing.
The investigation result of 2. placing resin impregnant in the place of direct projection well lighted is: embodiment 1 is after through three hours, the colour-change of colourless transparent liquid does not originally still take place, but other company's products are after through 30 minutes, by fluorescence purple yellowing, and after through about five days, solidify.
3. with 75 ℃ of results that embathe be: embodiment 1 is through 150 minutes after fixing, and other company's products are also through 150 minutes after fixing.
Fig. 1 represents the colour-change photo of appearance in the thermotolerance experiment.
Washing force
The result who measures washing force with the method for explanation in the experimental example 1 is: before oily water separation, the washing force of embodiment 1 and other company's products shows peer-level, but after oily water separation, though the washing force of embodiment 1 is kept original level, but because of the oily water separation of other company's products bad, therefore, aspect washing force, there is not direct comparability.
Oily water separation
The result who measures oily water separation with the method for explanation in the experimental example 1 is: the oily water separation of embodiment 1 is obvious, but other company's product oily water separations are bad.
Weight loss on heating
The result who measures weight loss on heating with the method for explanation in the experimental example 1 is: weight loss on heating is as shown in table 5, and state as shown in Figure 2.Its result shows that all variable color is bigger before and after oily water separation for other company's products, and especially the weight loss on heating after the oily water separation is many, but the heating variable change does not appear in embodiment 1 before and after oily water separation, and its amount is also few.
[table 5]
| |
Other company's products | |
| Before the oily water separation | 5.08 | 11.0 |
| After the oily water separation | 6.05 | 29.98 |
The cured article state
With the state result as shown in Figure 3 who detects by an unaided eye behind embodiment 1 and other company's products solidifyings.Its result shows, embodiment 1 before oily water separation, solidify better and color transparent, and after oily water separation, do not have foam and transparent yet, show good hard state.But other company's products do not solidify before oily water separation fully, and after oily water separation, its solid state is very bad.
The rate of recovery
Rate of recovery measuring result is after the oily water separation of embodiment 1 and other company's products: other company's products are bad because of oily water separation, though get all substances on upper strata so be as the criterion with the interface, top, but also show similar to Example 1 about 75% the rate of recovery, therefore, its result shows the rate of recovery height of embodiment 1.
COD
Mixing water 90 weight % in the resin impregnant 10 weight % of embodiment 1 and other company's products, and get except supernatant liquor (resin impregnant part) lower part (waste water) afterwards, as shown in table 6 according to the result of water pollution technological test method (2009) measure CO D.
[table 6]
| |
Other company's products | |
| COD(ppm) | 18100 | 29400 |
Below, 5 to 12 the present invention will be described in more detail in conjunction with the embodiments.
＜embodiment 5 〉
Mixing is as the isodecyl methacrylate of the 45g of first Acrylic Acid Monomer, as the cyclohexyl methacrylate of the 45g of second Acrylic Acid Monomer and as the trimethylammonium alcohol propane methacrylic ester of the 8g of the 3rd Acrylic Acid Monomer; Then, in the mixed solution of Acrylic Acid Monomer, make the Phosphorus antioxidant songnox of 0.3g
TM1680-PW (Songwon industry) dissolves fully and after the cyanoacrylate photostabilizer that mixes 0.7g fully stirs, adds the tensio-active agent ISC-100 of 1g
TMThe fire retardant SJC-9025 of (Ilsan chemistry) and 2g
TM(Samji Chemteck) is with the preparation resin impregnant.
＜embodiment 6 〉
Mixing is as the isodecyl methacrylate of the 50g of first Acrylic Acid Monomer, as the methacrylic acid benzylester of the 38g of second Acrylic Acid Monomer, as the trimethylammonium alcohol propane methacrylic ester of the 8g of the 3rd Acrylic Acid Monomer and as the basic isobutyl acrylate of the 2g of tetrapropylene acid mono; Then, in the mixed solution of Acrylic Acid Monomer, the phenol antioxidant BHT of 0.2g is dissolved fully and after the cyanoacrylate photostabilizer that mixes 0.8g in order to improve thermotolerance fully stirs, add the tensio-active agent ISC-100 of 1g
TMThe fire retardant SJC-9025 of (Ilsan chemistry) and 2g
TM(Samji Chemteck) is with the preparation resin impregnant.
＜embodiment 7 〉
Mixing is as the isodecyl methacrylate of the 60g of first Acrylic Acid Monomer, as the iso-borneol methacrylic ester of the 32g of second Acrylic Acid Monomer, as the Diethylene Glycol dimethacrylate of the 8g of the 3rd Acrylic Acid Monomer and as the alkyl methacrylate of the 2g of tetrapropylene acid mono; Then, in the mixed solution of Acrylic Acid Monomer, the phenol antioxidant BHT of 0.2g is dissolved fully and after the cyanoacrylate photostabilizer that mixes 0.8g fully stirs, add the tensio-active agent ISC-100 of 1g
TMThe fire retardant FR-300 of (Ilsan chemistry) and 2g
TM(Samji Chemteck) is with the preparation resin impregnant.
＜embodiment 8 〉
Mixing is as the formaldehyde dodecyl acrylate of the 68g of first Acrylic Acid Monomer, as the Rocryl 410 of the 27g of second Acrylic Acid Monomer and as the Diethylene Glycol dimethacrylate of the 3g of the 3rd Acrylic Acid Monomer; Then, in the mixed solution of Acrylic Acid Monomer, make the Phosphorus antioxidant songnox of 0.5g
TM1680-PW (Songwon) dissolves fully and after the cyanoacrylate photostabilizer that mixes 0.5g fully stirs, adds the tensio-active agent ISC-100 of 1g
TMThe fire retardant FR-300 of (Ilsan chemistry) and 2g
TM(Samji Chemteck) is with the preparation resin impregnant.
＜embodiment 9〉to＜embodiment 12 〉
The fluorescent agent 7-diethylin-4-methylcoumarin that respectively adds 0.0015g to embodiment 5 to embodiment 8 prepares the resin impregnant of embodiment 9 to embodiment 12.
Above-described embodiment 5 to 8 and comparative example 1 and 2 arrangements are as shown in table 7 below:
[table 7]
＜experimental example 3 〉
The comparison of embodiment 5 to 8 and comparative example 1 and 2
Utilize above-described embodiment 5 to 8 and comparative example 1 and 2 to measure the thermotolerance of resin impregnant, washing force, stability, oily water separation, weight loss on heating etc., obtain experimental result as shown in table 8:
[table 8]
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 | Comparative example 2 | |
| 1) thermotolerance | ◆ | ◇ | ◆ | ◆ | x | x |
| 2) washing force | ◇ | ◇ | ◆ | ◇ | ◇ | x |
| 3) oily water separation | ◆ | ◆ | ◇ | ◆ | ◇ | ◇ |
| 4) weight loss on heating | ◆ | ◇ | ◆ | ◇ | x | x |
◆: good; ◇: good; X: bad
Thermotolerance
At this moment, stable on heating measurement is finished by three kinds of modes, and, if solidify, then be evaluated as " bad "; If variable color takes place, then is evaluated as " well "; And if without any variation, then be evaluated as " good ".Metering system is following three kinds:
1) ultraviolet ray test: utilize ultraviolet radiation device, at the 315nm irradiation ultraviolet radiation; 2) sun exposure test: resin impregnant is placed in the place at the direct projection well lighted; 3) embathe test: in about 60 ℃, embathe.
Washing force
Evaluation to embodiment and comparative example washing force is as follows: if washing out of order, then be evaluated as " bad "; If the washing state is general, then be evaluated as " well "; And if the washing state is good, then be evaluated as " good ".Metering system comprises the steps:
1) metal testing plate be impregnated in after the resin impregnant one minute, take out and placed one minute;
2) be soaked in tap water after 15 seconds, wash up and down for several times with tap water as required;
3) placed one hour after, embrace after the metal testing plate with parchment, with in isobaric ten minutes of book;
4) affirmation sticks to the residue on the parchment.
Oily water separation
Oily water separation is measured by observing the state of embodiment and comparative example and water sepn, if separate stage is bad, then is evaluated as " bad "; If separate stage is general, then be evaluated as " well "; And if separate stage is good, then be evaluated as " good ".
When 1) using beaker: in tap water 85%, add resin impregnant 15% and stir after 30 seconds, place certain hour and also observe separation degree;
When 2) using separating funnel: in tap water 85%, add after resin impregnant 15% and the dandle 10 times, place certain hour and also observe separation degree.
Weight loss on heating
The measurement of loss on heating is after the weight of measuring embodiment and comparative example, remeasures weight after 200 ℃ are placed five hours, if weight loss on heating surpasses 20%, then is evaluated as " bad "; If weight loss on heating surpasses 10%, then be evaluated as " well "; And if weight loss on heating is less than 10%, then be evaluated as " good ".Metering system comprises the steps:
1) resin impregnant of getting about 3g solidifies after the 90 ℃/15min, only gets cured article and measures initial weight;
2) in baking box, after the 200 ℃/5hr of heating, measure its weight;
3) calculate 1) and 2) the difference acquisition weight loss on heating (%) of weight.
Stopping property
Characteristic and dipping processing effect in order to test soaker, then carry out following experiment under the standard test condition:
1) preparation of MIL CUP
MIL CUP is the most representative dipping processing test test piece of MIL-I-6869D defined, be that the thickness that has 200～300 pores that connect from inside to outside by special processing is the cup shape aluminium alloy casting product of 0.25 inch (6.35mm), at this, selective permeability is the MILCUP of 1～25cc/sec.
2) withstand voltage test (initial withstand voltage test) after the dipping processing
Apply 5.6kg/cm to the MIL CUP that utilizes the processing of one embodiment of the invention resin impregnant dipping
2The pressure of G also is deposited in the water of normal temperature, whether to confirm MIL CUP seepage.
3) high temperature durability test
To in initial withstand voltage test, confirm as the cup of sealing (not observing the state of seepage fully) fully, put into temperature be set at 2001 ± 1 ℃ circulating hot air dryer and every took out in 50 hours cool after, implement the withstand voltage test of above-mentioned condition.Till reach 200 hours heat-up time, whether repeat the seepage of air among the test of above-mentioned initial withstand voltage test and high temperature durability and the record MIL CUP, and, the quantity of seepage and the leakage of unit time (cc/sec) etc. among the MIL CUP as required.
As shown in table 9 with the result that recovery liquid carries out leakage test to the new liquid of soaker according to aforesaid method.
Test-results shows that the new liquid of resin impregnation liquid of the present invention or recovery liquid did not all observe any seepage phenomenon in 200 hours.
[table 9]
＜experimental example 4 〉
Comparison with other company's products
Be its company's product (Ultraseal company, the MX-II that sells on comparing embodiment 5 and the market
TM), the rate of recovery, COD etc. after measurement proterties, smell, proportion, year, moisture, gelation time, thermotolerance, washing force, oily water separation, weight loss on heating, cured article state, the oily water separation.Each is measured the character that reclaims preceding (before the oily water separation) and reclaims the character that back (after the oily water separation) is recovered state to individual test portion in experiment.
Proterties, smell, proportion, viscosity, moisture % and gelation time
The result of experiment proterties, smell, proportion, viscosity, moisture % and gelation time is as shown in table 10:
[table 10]
The measurement of gel time is at first to long 10cm, the glass test tube of diameter 0.8cm is poured the resin impregnant about seventy percent into and is that accurate the measurement inserted after the iron wire, the bed that embathes at 90 ℃ solidifies, and to catch Glass tubing together is raised when carrying on the iron wire time as gel time.
Thermotolerance
1. utilize the ultraviolet result of ultraviolet radiation device irradiation 312nm, the colour-change of colourless transparent liquid does not still take place through after three hours in embodiment 5, but other company's products are after through 30 minutes, by fluorescence purple yellowing, and through 10 hours after fixing.
2. the investigation result of placing resin impregnant in the place of direct projection well lighted is: embodiment 5 through three hours after, the colour-change of colourless transparent liquid does not originally still take place, but other company's products are after through 30 minutes, by fluorescence purple yellowing, and after through about five days, solidify.
3. with 75 ℃ of results that embathe be: embodiment 5 is through 150 minutes after fixing, and other company's products are also through 150 minutes after fixing.
Washing force
The result who measures washing force with the method for explanation in the experimental example 3 is: before oily water separation, the washing force of embodiment 5 and other company's products shows peer-level, but after oily water separation, though the washing force of embodiment 5 is kept original level, but because of the oily water separation of other company's products bad, therefore, aspect washing force, there is not direct comparability.
Oily water separation
The result who measures oily water separation with the method for explanation in the experimental example 3 is: the oily water separation of embodiment 5 is obvious, but other company's product oily water separations are bad.
Weight loss on heating
When measuring weight loss on heating with the method for explanation in the experimental example 1, its weight loss on heating is as shown in table 11.Its result shows that all variable color is bigger before and after oily water separation for other company's products, and especially the weight loss on heating after the oily water separation is many, but the heating variable change does not appear in embodiment 5 before and after oily water separation, and its amount is also few.
[table 11]
| Embodiment 5 | Other company's products | |
| Before the oily water separation | 4.89 | 11.0 |
| After the oily water separation | 5.43 | 29.98 |
The cured article state
Embodiment 5 and other company's products solidifyings state afterwards detects by an unaided eye.Observations shows, embodiment 5 before oily water separation, solidify better and color transparent, and after oily water separation, do not have foam and transparent yet, show good hard state.But other company's products do not solidify before oily water separation fully, and after oily water separation, its solid state is very bad.
The rate of recovery
Rate of recovery measuring result is after the oily water separation of embodiment 5 and other company's products: other company's products are bad because of oily water separation, though get all substances on upper strata so be as the criterion with the interface, top, but also show similar to Example 5 about 75% the rate of recovery, therefore, its result shows the rate of recovery height of embodiment 5.
COD
Mixing water 90 weight % in the resin impregnant 10 weight % of embodiment 5 and other company's products, and get except supernatant liquor (resin impregnant part) lower part (waste water) afterwards, as shown in table 12 according to the result of water pollution technological test method (2009) measure CO D.
[table 12]
| Embodiment 5 | Other company's products | |
| COD(ppm) | 18200 | 29400 |
＜experimental example 5 〉
The use of fire retardant
In the embodiment of the invention 7, when changing flame retardant agent content, carry out the weight loss on heating experiment with aforesaid method, and its result is as shown in table 13:
[table 13]
| |
0％ | 0.5％ | 1.0％ | 2.0％ | 3.0％ |
| SJC-9025(Samji Chemteck) | 9.45％ | 6.98％ | 4.98％ | 4.89％ | 4.91％ |
| FR-300(Samji Chemteck) | 9.45％ | 7.26％ | 5.46％ | 5.43％ | 5.41％ |
Its result shows, by adding fire retardant, and the SJC-9025 of every increase by 1 weight %, weight loss on heating reduces 38% approximately, and every increase by 1 weight %FR-300, weight loss on heating reduces 32% approximately.
＜experimental example 6 〉
The use of fluorescent agent
In embodiment 9 and embodiment 9, do not use the resin impregnant irradiation ultraviolet radiation of fluorescent agent to experimentize, judge whether visual inspection is easy.At this moment, fluorescent agent uses 7-diethylin-4-methylcoumarin.Its result shows that if do not add fluorescent agent, then the visual inspection of resin impregnant is difficult, and if add fluorescent agent, then distinguishes obviously (please refer to Fig. 4) when irradiation ultraviolet radiation.
Below, 13 to 20 the present invention will be described in more detail in conjunction with the embodiments.
＜embodiment 13 〉
Mixing is as the isodecyl methacrylate of the 45g of first Acrylic Acid Monomer, as the cyclohexyl methacrylate of the 45g of second Acrylic Acid Monomer and as the trimethylammonium alcohol propane methacrylic ester of the 8g of the 3rd Acrylic Acid Monomer; Then, in the mixed solution of Acrylic Acid Monomer, make the Phosphorus antioxidant songnox of 0.3g
TM1680-PW (Songwon industry) dissolves fully and after the cyanoacrylate photostabilizer that mixes 0.7g fully stirs, adds the first surface promoting agent ISC-100 of 0.5g
TMThe second surface promoting agent oleic acid macrogol ester of (Ilsan chemistry) and 0.5g is with the preparation resin impregnant.
＜embodiment 14 〉
Mixing is as the isodecyl methacrylate of the 50g of first Acrylic Acid Monomer, as the methacrylic acid benzylester of the 38g of second Acrylic Acid Monomer, as the trimethylammonium alcohol propane methacrylic ester of the 8g of the 3rd Acrylic Acid Monomer and as the basic isobutyl acrylate of the 2g of tetrapropylene acid mono; Then, in the mixed solution of Acrylic Acid Monomer, the phenol antioxidant BHT of 0.2g is dissolved fully and after the cyanoacrylate photostabilizer that mixes 0.8g in order to improve thermotolerance fully stirs, add the tensio-active agent ISC-100 of 0.5g
TMThe second surface promoting agent oleic acid macrogol ester of (Ilsan chemistry) and 0.5g is with the preparation resin impregnant.
＜embodiment 15 〉
Mixing is as the isodecyl methacrylate of the 60g of first Acrylic Acid Monomer, as the iso-borneol methacrylic ester of the 32g of second Acrylic Acid Monomer, as the Diethylene Glycol dimethacrylate of the 8g of the 3rd Acrylic Acid Monomer and as the alkyl methacrylate of the 2g of tetrapropylene acid mono; Then, in the mixed solution of Acrylic Acid Monomer, the phenol antioxidant BHT of 0.2g is dissolved fully and after the cyanoacrylate photostabilizer that mixes 0.8g fully stirs, add the tensio-active agent ISC-100 of 0.5g
TMThe second surface promoting agent oleic acid macrogol ester of (Ilsan chemistry) and 0.5g is with the preparation resin impregnant.
＜embodiment 16 〉
Mixing is as the formaldehyde dodecyl acrylate of the 68g of first Acrylic Acid Monomer, as the Rocryl 410 of the 27g of second Acrylic Acid Monomer and as the Diethylene Glycol dimethacrylate of the 3g of the 3rd Acrylic Acid Monomer; Then, in the mixed solution of Acrylic Acid Monomer, make the Phosphorus antioxidant songnox of 0.5g
TM1680-PW (Songwon) dissolves fully and after the cyanoacrylate photostabilizer that mixes 0.5g fully stirs, adds the tensio-active agent ISC-100 of 0.5g
TMThe second surface promoting agent oleic acid macrogol ester of (Ilsan chemistry) and 0.5g is with the preparation resin impregnant.
＜embodiment 17〉to＜embodiment 20 〉
The fluorescent agent 7-diethylin-4-methylcoumarin that respectively adds 0.0015g to embodiment 13 to embodiment 16 prepares the resin impregnant of embodiment 17 to embodiment 20.
Above-described embodiment 13 to 16 and comparative example 1 and 2 arrangements are as shown in table 14 below:
[table 14]
＜experimental example 7 〉
The comparison of embodiment 13 to 16 and comparative example 1 and 2
Utilize above-described embodiment 13 to 16 and comparative example 1 and 2 to measure the thermotolerance of resin impregnant, washing force, stability, oily water separation, weight loss on heating etc., obtain experimental result as shown in Table 15:
[table 15]
| Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Comparative example 1 | Comparative example 2 | |
| 1) thermotolerance | ◆ | ◇ | ◆ | ◆ | x | x |
| 2) washing force | ◇ | ◇ | ◆ | ◇ | ◇ | x |
| 3) oily water separation | ◆ | ◆ | ◇ | ◆ | ◇ | ◇ |
| 4) weight loss on heating | ◆ | ◇ | ◆ | ◇ | x | x |
◆: good; ◇: ◆: good; ◇: good; X: bad
Thermotolerance
At this moment, stable on heating measurement is finished by three kinds of modes, and, if solidify, then be evaluated as " bad "; If variable color takes place, then is evaluated as " well "; And if without any variation, then be evaluated as " good ".Metering system is following three kinds:
1) ultraviolet ray test: utilize ultraviolet radiation device, at the 315nm irradiation ultraviolet radiation; 2) sun exposure test: resin impregnant is placed in the place at the direct projection well lighted; 3) embathe test: in about 60 ℃, embathe.
Washing force
Evaluation to embodiment and comparative example washing force is as follows: if washing out of order, then be evaluated as " bad "; If the washing state is general, then be evaluated as " well "; And if the washing state is good, then be evaluated as " good ".Metering system comprises the steps:
1) metal testing plate be impregnated in after the resin impregnant one minute, take out and placed one minute;
2) be soaked in tap water after 15 seconds, wash up and down for several times with tap water as required;
3) placed one hour after, embrace after the metal testing plate with parchment, with in isobaric ten minutes of book;
4) affirmation sticks to the residue on the parchment.
Oily water separation
Oily water separation is measured by observing the state of embodiment and comparative example and water sepn, if separate stage is bad, then is evaluated as " bad "; If separate stage is general, then be evaluated as " well "; And if separate stage is good, then be evaluated as " good ".
When 1) using beaker: in tap water 85%, add resin impregnant 15% and stir after 30 seconds, place certain hour and also observe separation degree;
When 2) using separating funnel: in tap water 85%, add after resin impregnant 15% and the dandle 10 times, place certain hour and also observe separation degree.
Weight loss on heating
The measurement of loss on heating is after the weight of measuring embodiment and comparative example, remeasures weight after 200 ℃ are placed five hours, if weight loss on heating surpasses 20%, then is evaluated as " bad "; If weight loss on heating surpasses 10%, then be evaluated as " well "; And if weight loss on heating is less than 10%, then be evaluated as " good ".Metering system comprises the steps:
1) resin impregnant of getting about 3g solidifies after the 90 ℃/15min, only gets cured article and measures initial weight;
2) in baking box, after the 200 ℃/5hr of heating, measure its weight;
3) calculate 1) and 2) the difference acquisition weight loss on heating (%) of weight.
Stopping property
Characteristic and dipping processing effect in order to test soaker, then carry out following experiment under the standard test condition:
1) preparation of MIL CUP
MIL CUP is the most representative dipping processing test test piece of MIL-I-6869D defined, be that the thickness that has 200～300 pores that connect from inside to outside by special processing is the cup shape aluminium alloy casting product of 0.25 inch (6.35mm), at this, selective permeability is the MILCUP of 1～25cc/sec.
2) withstand voltage test (initial withstand voltage test) after the dipping processing
Apply 5.6kg/cm to the MIL CUP that utilizes the processing of one embodiment of the invention resin impregnant dipping
2The pressure of G also is deposited in the water of normal temperature, whether to confirm MIL CUP seepage.
3) high temperature durability test
To in initial withstand voltage test, confirm as the cup of sealing (not observing the state of seepage fully) fully, put into temperature be set at 2001 ℃ circulating hot air dryer and every took out in 50 hours cool after, implement the withstand voltage test of above-mentioned condition.Till reach 200 hours heat-up time, whether repeat the seepage of air among the test of above-mentioned initial withstand voltage test and high temperature durability and the record MIL CUP, and, the quantity of seepage and the leakage of unit time (cc/sec) etc. among the MIL CUP as required.
Shown in table 16 with the result that recovery liquid carries out leakage test to the new liquid of soaker according to aforesaid method.
Test-results shows that the new liquid of resin impregnation liquid of the present invention or recovery liquid did not all observe any seepage phenomenon in 200 hours.
[table 16]
＜experimental example 8 〉
Comparison with other company's products
Be its company's product (Ultraseal company, the MX-II that sells on comparing embodiment 13 and the market
TM), the rate of recovery, COD etc. after measurement proterties, smell, proportion, year, moisture, gelation time, thermotolerance, washing force, oily water separation, weight loss on heating, cured article state, the oily water separation.Each is measured the character that reclaims preceding (before the oily water separation) and reclaims the character that back (after the oily water separation) is recovered state to individual test portion in experiment.
Proterties, smell, proportion, viscosity, moisture % and gelation time
The result of experiment proterties, smell, proportion, viscosity, moisture % and gelation time is shown in table 17:
[table 17]
The measurement of gel time is at first to long 10cm, the glass test tube of diameter 0.8cm is poured the resin impregnant about seventy percent into and is that accurate the measurement inserted after the iron wire, the bed that embathes at 90 ℃ solidifies, and to catch Glass tubing together is raised when carrying on the iron wire time as gel time.
Thermotolerance
1. utilize the ultraviolet result of ultraviolet radiation device irradiation 312nm, the colour-change of colourless transparent liquid does not still take place through after three hours in embodiment 13, but other company's products are after through 30 minutes, by fluorescence purple yellowing, and through 10 hours after fixing.
2. the investigation result of placing resin impregnant in the place of direct projection well lighted is: embodiment 13 through three hours after, the colour-change of colourless transparent liquid does not originally still take place, but other company's products are after through 30 minutes, by fluorescence purple yellowing, and after through about five days, solidify.
3. with 75 ℃ of results that embathe be: embodiment 13 is through 150 minutes after fixing, and other company's products are also through 150 minutes after fixing.
Washing force
The result who measures washing force with the method for explanation in the experimental example 7 is: before oily water separation, the washing force of embodiment 13 and other company's products shows peer-level, but after oily water separation, though the washing force of embodiment 13 is kept original level, but because of the oily water separation of other company's products bad, therefore, aspect washing force, there is not direct comparability.
Oily water separation
The result who measures oily water separation with the method for explanation in the experimental example 7 is: the oily water separation of embodiment 13 is obvious, but other company's product oily water separations are bad.
Weight loss on heating
When measuring weight loss on heating with the method for explanation in the experimental example 7, its weight loss on heating is shown in table 18.Its result shows that all variable color is bigger before and after oily water separation for other company's products, and especially the weight loss on heating after the oily water separation is many, but the heating variable change does not appear in embodiment 13 before and after oily water separation, and its amount is also few.
[table 18]
| Embodiment 13 | Other company's products | |
| Before the oily water separation | 5.09 | 11.0 |
| After the oily water separation | 6.09 | 29.98 |
The cured article state
Embodiment 13 and other company's products solidifyings state afterwards detects by an unaided eye.Observations shows, embodiment 13 before oily water separation, solidify better and color transparent, and after oily water separation, do not have foam and transparent yet, show good hard state.But other company's products do not solidify before oily water separation fully, and after oily water separation, its solid state is very bad.
The rate of recovery
Rate of recovery measuring result is after the oily water separation of embodiment 13 and other company's products: other company's products are bad because of oily water separation, though get all substances on upper strata so be as the criterion with the interface, top, but also show similar to Example 13 about 75% the rate of recovery, therefore, its result shows the rate of recovery height of embodiment 13.
COD
Mixing water 90 weight % in the resin impregnant 10 weight % of embodiment 13 and other company's products, and get except supernatant liquor (resin impregnant part) lower part (waste water) afterwards, shown in table 19 according to the result of water pollution technological test method (2009) measure CO D.
[table 19]
| Embodiment 13 | Other company's products | |
| COD(ppm) | 18150 | 29400 |
＜experimental example 9 〉
The use of tensio-active agent
In the embodiment of the invention 13, when changing surfactant content, with aforesaid method test washing force, and its result is shown in chart.
Its result shows, when tensio-active agent comprises 1～3 weight part with respect to first Acrylic Acid Monomer of 100 weight parts, can improve washing force.
＜experimental example 10 〉
The use of fluorescent agent
In embodiment 17 and embodiment 17, do not use the resin impregnant irradiation ultraviolet radiation of fluorescent agent to experimentize, judge whether visual inspection is easy.At this moment, fluorescent agent uses 7-diethylin-4-methylcoumarin.
Its result shows that if do not add fluorescent agent, then the visual inspection of resin impregnant is difficult, and if add fluorescent agent, then distinguishes obviously (please refer to Fig. 6) when irradiation ultraviolet radiation.
Below, 21 to 25 the present invention will be described in more detail in conjunction with the embodiments.
＜embodiment 21 〉
Mixing is as the isodecyl methacrylate of the 45g of first Acrylic Acid Monomer, as the cyclohexyl methacrylate of the 45g of second Acrylic Acid Monomer and as the trimethylammonium alcohol propane methacrylic ester of the 8g of the 3rd Acrylic Acid Monomer; Then, in the mixed solution of Acrylic Acid Monomer, make the Phosphorus antioxidant songnox of 0.3g
TM1680-PW (Songwon industry) dissolves fully and after the cyanoacrylate photostabilizer that mixes 0.7g fully stirs, adds the tensio-active agent ISC-100 of 1g
TMFluorescent agent 7-diethylin-4-methylcoumarin of (Ilsan chemistry) and 0.0015g is with the preparation resin impregnant.
＜embodiment 22 〉
Mixing is as the isodecyl methacrylate of the 50g of first Acrylic Acid Monomer, as the methacrylic acid benzylester of the 38g of second Acrylic Acid Monomer, as the trimethylammonium alcohol propane methacrylic ester of the 8g of the 3rd Acrylic Acid Monomer and as the basic isobutyl acrylate of the 2g of tetrapropylene acid mono; Then, in the mixed solution of Acrylic Acid Monomer, the phenol antioxidant BHT of 0.2g is dissolved fully and after the cyanoacrylate photostabilizer that mixes 0.8g in order to improve thermotolerance fully stirs, add the tensio-active agent ISC-100 of 1g
TMFluorescent agent 7-diethylin-4-methylcoumarin of (Ilsan chemistry) and 0.0015g is with the preparation resin impregnant.
＜embodiment 23 〉
Mixing is as the isodecyl methacrylate of the 60g of first Acrylic Acid Monomer, as the iso-borneol methacrylic ester of the 32g of second Acrylic Acid Monomer, as the Diethylene Glycol dimethacrylate of the 8g of the 3rd Acrylic Acid Monomer and as the alkyl methacrylate of the 2g of tetrapropylene acid mono; Then, in the mixed solution of Acrylic Acid Monomer, the phenol antioxidant BHT of 0.2g is dissolved fully and after the cyanoacrylate photostabilizer that mixes 0.8g fully stirs, add the tensio-active agent ISC-100 of 1g
TMFluorescent agent 7-diethylin-4-methylcoumarin of (Ilsan chemistry) and 0.0015g is with the preparation resin impregnant.
＜embodiment 24 〉
Mixing is as the formaldehyde dodecyl acrylate of the 68g of first Acrylic Acid Monomer, as the Rocryl 410 of the 27g of second Acrylic Acid Monomer and as the Diethylene Glycol dimethacrylate of the 3g of the 3rd Acrylic Acid Monomer; Then, in the mixed solution of Acrylic Acid Monomer, make the Phosphorus antioxidant songnox of 0.5g
TM1680-PW (Songwon) dissolves fully and after the cyanoacrylate photostabilizer that mixes 0.5g fully stirs, adds the tensio-active agent ISC-100 of 1g
TMFluorescent agent 7-diethylin-4-methylcoumarin of (Ilsan chemistry) and 0.0015g is with the preparation resin impregnant.
Above-described embodiment 21 to 24 and comparative example 1 and 2 arrangements are as shown in table 20 below:
[table 20]
＜experimental example 11 〉
The comparison of embodiment 21 to 24 and comparative example 1 and 2
Utilize above-described embodiment 21 to 24 and comparative example 1 and 2 to measure the thermotolerance of resin impregnant, washing force, stability, oily water separation, weight loss on heating etc., obtain experimental result shown in table 21:
[table 21]
| Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 | Comparative example 1 | Comparative example 2 | |
| 1) thermotolerance | ◆ | ◇ | ◆ | ◆ | x | x |
| 2) washing force | ◇ | ◇ | ◆ | ◇ | ◇ | x |
| 3) oily water separation | ◆ | ◆ | ◇ | ◆ | ◇ | ◇ |
| 4) weight loss on heating | ◆ | ◇ | ◆ | ◇ | x | x |
◆: good; ◇: good; X: bad
Thermotolerance
At this moment, stable on heating measurement is finished by three kinds of modes, and, if solidify, then be evaluated as " bad "; If variable color takes place, then is evaluated as " well "; And if without any variation, then be evaluated as " good ".Metering system is following three kinds:
1) ultraviolet ray test: utilize ultraviolet radiation device, at the 315nm irradiation ultraviolet radiation; 2) sun exposure test: resin impregnant is placed in the place at the direct projection well lighted; 3) embathe test: in about 60 ℃, embathe.
Washing force
Evaluation to embodiment and comparative example washing force is as follows: if washing out of order, then be evaluated as " bad "; If the washing state is general, then be evaluated as " well "; And if the washing state is good, then be evaluated as " good ".Metering system comprises the steps:
1) metal testing plate be impregnated in after the resin impregnant one minute, take out and placed one minute;
2) be soaked in tap water after 15 seconds, wash up and down for several times with tap water as required;
3) placed one hour after, embrace after the metal testing plate with parchment, with in isobaric ten minutes of book;
4) affirmation sticks to the residue on the parchment.
Oily water separation
Oily water separation is measured by observing the state of embodiment and comparative example and water sepn, if separate stage is bad, then is evaluated as bad feeding; If separate stage is general, then be evaluated as good feeding; And if separate stage is good, then be evaluated as feeding.
When 1) using beaker: in tap water 85%, add resin impregnant 15% and stir after 30 seconds, place certain hour and also observe separation degree;
When 2) using separating funnel: in tap water 85%, add after resin impregnant 15% and the dandle 10 times, place certain hour and also observe separation degree.
Weight loss on heating
The measurement of loss on heating is after the weight of measuring embodiment and comparative example, remeasures weight after 200 ℃ are placed five hours, if weight loss on heating surpasses 20%, then is evaluated as " bad "; If weight loss on heating surpasses 10%, then be evaluated as " well "; And if weight loss on heating is less than 10%, then be evaluated as " good ".Metering system comprises the steps:
1) resin impregnant of getting about 3g solidifies after the 90 ℃/15min, only gets cured article and measures initial weight;
2) in baking box, after the 200 ℃/5hr of heating, measure its weight;
3) calculate 1) and 2) the difference acquisition weight loss on heating (%) of weight.
Stopping property
Characteristic and dipping processing effect in order to test soaker, then carry out following experiment under the standard test condition:
1) preparation of MIL CUP
MIL CUP is the most representative dipping processing test test piece of MIL-I-6869D defined, be that the thickness that has 200～300 pores that connect from inside to outside by special processing is the cup shape aluminium alloy casting product of 0.25 inch (6.35mm), at this, selective permeability is the MILCUP of 1～25cc/sec.
2) withstand voltage test (initial withstand voltage test) after the dipping processing
Apply 5.6kg/cm to the MIL CUP that utilizes the processing of one embodiment of the invention resin impregnant dipping
2The pressure of G also is deposited in the water of normal temperature, whether to confirm MIL CUP seepage.
3) high temperature durability test
To in initial withstand voltage test, confirm as the cup of sealing (not observing the state of seepage fully) fully, put into temperature be set at 200 ± 1 ℃ circulating hot air dryer and every took out in 50 hours cool after, implement the withstand voltage test of above-mentioned condition.Till reach 200 hours heat-up time, whether repeat the seepage of air among the test of above-mentioned initial withstand voltage test and high temperature durability and the record MIL CUP, and, the quantity of seepage and the leakage of unit time (cc/sec) etc. among the MIL CUP as required.
Shown in table 22 with the result that recovery liquid carries out leakage test to the new liquid of soaker according to aforesaid method.
Test-results shows that the new liquid of resin impregnation liquid of the present invention or recovery liquid did not all observe any seepage phenomenon in 200 hours.
[table 22]
＜experimental example 12 〉
Comparison with other company's products
Be its company's product (Ultraseal company, the MX-II that sells on comparing embodiment 21 and the market
TM), the rate of recovery, COD etc. after measurement proterties, smell, proportion, year, moisture, gelation time, thermotolerance, washing force, oily water separation, weight loss on heating, cured article state, the oily water separation.Each is measured the character that reclaims preceding (before the oily water separation) and reclaims the character that back (after the oily water separation) is recovered state to individual test portion in experiment.
Proterties, smell, proportion, viscosity, moisture % and gelation time
The result of experiment proterties, smell, proportion, viscosity, moisture % and gelation time is shown in table 23:
[table 23]
The measurement of gel time is at first to long 10cm, the glass test tube of diameter 0.8cm is poured the resin impregnant about seventy percent into and is that accurate the measurement inserted after the iron wire, the bed that embathes at 90 ℃ solidifies, and to catch Glass tubing together is raised when carrying on the iron wire time as gel time.
Thermotolerance
1. utilize the ultraviolet result of ultraviolet radiation device irradiation 312nm, the colour-change of colourless transparent liquid does not still take place through after three hours in embodiment 21, but other company's products are after through 30 minutes, by fluorescence purple yellowing, and through 10 hours after fixing.
2. the investigation result of placing resin impregnant in the place of direct projection well lighted is: embodiment 21 through three hours after, the colour-change of colourless transparent liquid does not originally still take place, but other company's products are after through 30 minutes, by fluorescence purple yellowing, and after through about five days, solidify.
3. with 75 ℃ of results that embathe be: embodiment 21 is through 150 minutes after fixing, and other company's products are also through 150 minutes after fixing.
Washing force
The result who measures washing force with the method for explanation in the experimental example 11 is: before oily water separation, the washing force of embodiment 21 and other company's products shows peer-level, but after oily water separation, though the washing force of embodiment 21 is kept original level, but because of the oily water separation of other company's products bad, therefore, aspect washing force, there is not direct comparability.
Oily water separation
The result who measures oily water separation with the method for explanation in the experimental example 11 is: the oily water separation of embodiment 21 is obvious, but other company's product oily water separations are bad.
Weight loss on heating
When measuring weight loss on heating with the method for explanation in the experimental example 11, its weight loss on heating is shown in table 24.Its result shows that all variable color is bigger before and after oily water separation for other company's products, and especially the weight loss on heating after the oily water separation is many, but the heating variable change does not appear in embodiment 21 before and after oily water separation, and its amount is also few.
[table 24]
| Embodiment 21 | Other company's products | |
| Before the oily water separation | 5.10 | 11.0 |
| After the oily water separation | 6.07 | 29.98 |
The cured article state
Embodiment 21 and other company's products solidifyings state afterwards detects by an unaided eye.Observations shows, embodiment 21 before oily water separation, solidify better and color transparent, and after oily water separation, do not have foam and transparent yet, show good hard state.But other company's products do not solidify before oily water separation fully, and after oily water separation, its solid state is very bad.
The rate of recovery
Rate of recovery measuring result is after the oily water separation of embodiment 21 and other company's products: other company's products are bad because of oily water separation, though get all substances on upper strata so be as the criterion with the interface, top, but also show the rate of recovery with embodiment 21 similar about 75%, therefore, its result shows the rate of recovery height of embodiment 21.
COD
Mixing water 90 weight % in the resin impregnant 10 weight % of embodiment 21 and other company's products, and get except supernatant liquor (resin impregnant part) lower part (waste water) afterwards, as shown in Table 25 according to the result of water pollution technological test method (2009) measure CO D.
[table 25]
| Embodiment 21 | Other company's products | |
| COD(ppm) | 18310 | 29400 |
＜experimental example 13 〉
The use of fluorescent agent
In embodiment 21 and embodiment 21, do not use the resin impregnant irradiation ultraviolet radiation of fluorescent agent to experimentize, judge whether visual inspection is easy, and its result as shown in Figure 7.At this moment, fluorescent agent uses 7-diethylin-4-methylcoumarin.
Its result shows that if do not add fluorescent agent, then the visual inspection of resin impregnant is difficult, and if add fluorescent agent, then distinguishes obviously when irradiation ultraviolet radiation.
Above-described embodiment is only unrestricted in order to the present invention to be described, those of ordinary skill in the art is to be understood that, can make amendment, be out of shape the present invention or be equal to replacement, and not break away from the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (19)
1. resin impregnant comprises:
Acrylic Acid Monomer comprises to cured article and gives the first soft Acrylic Acid Monomer, gives the second rigid Acrylic Acid Monomer and to the 3rd Acrylic Acid Monomer of giving bonding force between the monomer to cured article;
Antioxidant;
Cyanoacrylate (cyanoacrylate ester) fluid-like state photostabilizer; And
Tensio-active agent,
Above-mentioned second Acrylic Acid Monomer with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts, comprises 40～100 weight parts; And above-mentioned the 3rd Acrylic Acid Monomer with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts, comprises 4～20 weight parts,
Above-mentioned first Acrylic Acid Monomer comprises at least a material of selecting from the group who is made of isodecyl methacrylate (Isodecyl methacrylate), different 13 esters of methacrylic acid (Isotridecyl methacrylate), methacrylic dodecyl gallate (Dodecyl methacrylate), tridecyl acrylate (Tridecyl acrylate) and composition thereof
Above-mentioned second Acrylic Acid Monomer comprises from by methacrylic acid benzylester (Benzyl methacrylate), isobornyl acrylate (Isobornyl acrylate), iso-borneol methacrylic ester (isobornyl methacrylate), Jia Jibingxisuanyizhi (Ethyl Methacrylate), Propenoic acid, 2-methyl, isobutyl ester (i-butyl Methacrylate), Rocryl 410 (Hydroxypropyl methacrylate), n-BMA (n-butyl methacrylate), methyl methacrylate (Methyl methacrylate), at least a material of selecting among the group that cyclohexyl methacrylate (Cyclohexyl methacrylate) and composition thereof constitutes
Above-mentioned the 3rd Acrylic Acid Monomer comprises from by ethylene glycol dimethacrylate (Ethylene glycol dimethacrylate), Diethylene Glycol dimethacrylate (DiEthylene glycol dimethacrylate), Viscoat 295 (Trimethylol propane triacrylate), trimethylolpropane trimethacrylate (Trimethylol propane trimethacrylate), tri (propylene glycol) diacrylate (Tripropylene glycol diacrylate), at least a material of selecting among the group that TriMethylolPropane(TMP) methacrylic ester (Trimethylol propane methacrylate) and composition thereof constitutes.
2. resin impregnant according to claim 1, it is characterized in that: above-mentioned resin impregnant also comprises the tetrapropylene acid mono, and above-mentioned tetrapropylene acid mono comprises from by Propenoic acid, 2-methyl, isobutyl ester (Isobutyl methacrylate), methacrylic acid 2-ethylhexyl (2-ethylhexyl methacrylate), tridecyl methacrylic ester (Tridecyl methacrylate), methacrylic acid stearyl ester (Stearyl methacrylate), diethyl amido ethyl-methyl acrylate (Diethylaminoethyl methacrylate), ethylene glycol dimethacrylate (Ethylene glycol dimethacrylate), 1,3-butylene glycol dimethacrylate (1,3-butylene glycol dimethacrylate), 1,6-hexanediol dimethacrylate (1,6-hexanediol dimethacrylate), at least a material of selecting among the group that 2-ethoxyethyl group methacrylic ester (2-ethoxyethyl methacrylate) and composition thereof constitutes.
3. resin impregnant according to claim 2, it is characterized in that: above-mentioned tetrapropylene acid mono with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts, comprises 1～4 weight part.
4. resin impregnant according to claim 1, it is characterized in that: above-mentioned tensio-active agent with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts, comprises 1～3 weight part; Above-mentioned antioxidant with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts, comprises 0.2～0.8 weight part; And above-mentioned photostabilizer with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts, comprises 1～2 weight part.
5. resin impregnant according to claim 1, it is characterized in that: above-mentioned antioxidant comprises Phosphorus antioxidant.
6. according to any described resin impregnant of claim 1 to 5, it is characterized in that: also comprise fire retardant.
7. resin impregnant according to claim 6, it is characterized in that: above-mentioned fire retardant with respect to 100 weight part aforesaid propylene acid mono, comprises 1～3.5 weight part.
8. resin impregnant according to claim 7 is characterized in that: above-mentioned fire retardant comprises from by more than one materials of selecting halogen, Phosphorus and the group that hydroxide metal compound constitutes.
9. according to any described resin impregnant of claim 1 to 5, it is characterized in that: above-mentioned tensio-active agent comprises the second surface promoting agent of nonionic higher alcohols first surface promoting agent and nonionic fatty acid ester.
10. resin impregnant according to claim 9 is characterized in that: above-mentioned second surface promoting agent comprises more than one materials of selecting from the group who is made of oleic acid macrogol ester (Polyethylene glycol oleate), sorbitan-fatty acid ester (Sorbitan fatty acid ester), polyoxyethylene sorbitan-fatty acid ester (Polyoxyethylene sorbitan fatty acid ester).
11. resin impregnant according to claim 10 is characterized in that: the weight ratio of above-mentioned first surface promoting agent and above-mentioned second surface promoting agent is 1: 1～1: 3.
12. any described resin impregnant according to claim 1 to 5 is characterized in that: also comprise fluorescent agent.
13. resin impregnant according to claim 12 is characterized in that: luminous material when above-mentioned fluorescent agent is irradiation ultraviolet radiation.
14. resin impregnant according to claim 12, it is characterized in that: above-mentioned fluorescent agent comprises from by 7-diethylin-4-methylcoumarin (4-methyl-7-(diethylamino) coumarin), 2,5-pair-(the 5-tertiary butyl-2-benzoxazolyl) thiophene (2,2 '-(2,5-thiophenediyl) Bis[5-(1,1-dimethylethyl)]-benzoxazole), 2,2 '-(4,4 '-diphenylacetylene) Er benzoxazole (2,2 '-more than one materials of selecting among the group that (4,4 '-diphenylvinyl) di-benzoxazole) constitute.
15. resin impregnant according to claim 12 is characterized in that: above-mentioned fluorescent agent with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts, comprises 0.001～0.003 weight part.
16. a resin impregnant preparation method comprises:
The monomer mixing step mixes to cured article and gives the first soft Acrylic Acid Monomer, gives the second rigid Acrylic Acid Monomer and to the 3rd Acrylic Acid Monomer of giving bonding force between the monomer to cured article;
The additive mixing step is dissolved in the aforesaid propylene acid mono mixed solution antioxidant fully, and after mixing stirring cyanoacrylate photostabilizer, adds tensio-active agent,
Above-mentioned second Acrylic Acid Monomer with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts, comprises 40～100 weight parts; And above-mentioned the 3rd Acrylic Acid Monomer with respect to above-mentioned first Acrylic Acid Monomer of 100 weight parts, comprises 4～20 weight parts,
Above-mentioned first Acrylic Acid Monomer comprises at least a material of selecting from the group who is made of isodecyl methacrylate (Isodecyl methacrylate), different 13 esters of methacrylic acid (Isotridecyl methacrylate), methacrylic dodecyl gallate (Dodecyl methacrylate), tridecyl acrylate (Tridecyl acrylate) and composition thereof
Above-mentioned second Acrylic Acid Monomer comprises from by methacrylic acid benzylester (Benzyl methacrylate), isobornyl acrylate (Isobornyl acrylate), iso-borneol methacrylic ester (isobornyl methacrylate), Jia Jibingxisuanyizhi (Ethyl Methacrylate), Propenoic acid, 2-methyl, isobutyl ester (i-butyl Methacrylate), Rocryl 410 (Hydroxypropyl methacrylate), n-BMA (n-butyl methacrylate), methyl methacrylate (Methyl methacrylate), at least a material of selecting among the group that cyclohexyl methacrylate (Cyclohexyl methacrylate) and composition thereof constitutes
Above-mentioned the 3rd Acrylic Acid Monomer comprises from by ethylene glycol dimethacrylate (Ethylene glycol dimethacrylate), Diethylene Glycol dimethacrylate (DiEthylene glycol dimethacrylate), Viscoat 295 (Trimethylol propane triacrylate), trimethylolpropane trimethacrylate (Trimethylol propane trimethacrylate), tri (propylene glycol) diacrylate (Tripropylene glycol diacrylate), at least a material of selecting among the group that TriMethylolPropane(TMP) methacrylic ester (Trimethylol propane methacrylate) and composition thereof constitutes.
17. resin impregnant preparation method according to claim 16 is characterized in that: when adding above-mentioned tensio-active agent, add fire retardant in the lump.
18. resin impregnant preparation method according to claim 16 is characterized in that: above-mentioned tensio-active agent comprises the second surface promoting agent of nonionic higher alcohols first surface promoting agent and nonionic fatty acid ester.
19. resin impregnant preparation method according to claim 16 is characterized in that: when adding above-mentioned tensio-active agent, add fluorescent agent in the lump.
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| KR1020090131755A KR100980230B1 (en) | 2009-12-28 | 2009-12-28 | Resin impregnant and manufacturing method of the same |
| KR10-2009-0131755 | 2009-12-28 | ||
| KR1020100081567A KR100998867B1 (en) | 2010-08-23 | 2010-08-23 | Resin impregnant and manufacturing method of the same |
| KR10-2010-0081567 | 2010-08-23 | ||
| KR10-2010-0081565 | 2010-08-23 | ||
| KR1020100081566A KR100998866B1 (en) | 2010-08-23 | 2010-08-23 | Resin impregnant and manufacturing method of the same |
| KR1020100081565A KR100994923B1 (en) | 2010-08-23 | 2010-08-23 | Resin impregnant and manufacturing method of the same |
| KR10-2010-0081566 | 2010-08-23 |
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| CN105155338A (en) * | 2015-09-10 | 2015-12-16 | 上海晶华胶粘新材料股份有限公司 | Anti-ultraviolet (UV) water-based paper impregnant and preparation method thereof |
| CN106622400A (en) * | 2016-12-16 | 2017-05-10 | 东至绿洲环保化工有限公司 | Anion exchange resin for decoloring and deacidifying of high-quality juice |
| CN114773537B (en) * | 2022-04-19 | 2024-01-12 | 南京艾布纳新材料股份有限公司 | Efficient-recovery type infiltration sealing material |
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