CN104418988A - Free radical polymerized resin composite and civil construction material - Google Patents
Free radical polymerized resin composite and civil construction material Download PDFInfo
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- CN104418988A CN104418988A CN201410446762.4A CN201410446762A CN104418988A CN 104418988 A CN104418988 A CN 104418988A CN 201410446762 A CN201410446762 A CN 201410446762A CN 104418988 A CN104418988 A CN 104418988A
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Abstract
The aim of the invention is to provide a free radical polymerized resin composite which can provide a coating film being dry in surface and excellent in tensile property. The free radical polymerized resin composite is characterized in that the composite comprises a urethane (meth) acrylate (A), a free radical polymerized monomer (B) and an acrylic polymer (C). In addition, the invention provides a civil construction material, and the civil construction material is characterized by comprising the above free radical polymerized resin composite. By employing the free radical polymerized resin composite, a coating film which is dry in surface and excellent in tensile property can be obtained, and the free radical polymerized resin composite is suitable for the manufacture of civil construction materials such as floor materials, paving materials, waterproof materials, road coatings, priming paint, wall surface coating materials, road marking materials, injecting materials, adhesives, lining materials, wave absorbing plates and the like in factories, warehouses, cleaning rooms and the like.
Description
Technical field
The present invention relates to the free-radical polymerised resin combination of the film obtaining surface drying and stretching physical properties excellent.
Background technology
In civil construction fields such as road pavements, shorten to tackle the duration, and extensively make use of the free-radical polymerised resins such as unsaturated polyester, polyester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate and the free-radical polymerised resin combination containing free radical polymerization monomer (such as with reference to patent documentation 1).
Although above-mentioned free-radical polymerised resin combination has excellent tensile strength and be suitable for spraying, film surface drying in need further to improve.Think that its reason is that the reactivity of the free-radical polymerised resin contained in above-mentioned free-radical polymerised resin combination is low, and then infer that unreacted free-radical polymerised resin is in film coated surface segregation, causes the surface drying reduction of film.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-231231 publication
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is, provides a kind of free-radical polymerised resin combination giving the film of surface drying and stretching physical properties excellent.
For solving the means of problem
The invention provides a kind of free-radical polymerised resin combination, it is characterized in that, said composition contains carbamate (methyl) acrylate (A), free radical polymerization monomer (B) and acrylic polymers (C).
In addition, the invention provides a kind of civil construction material, it is characterized in that, described civil construction material contains above-mentioned free-radical polymerised resin combination.
Invention effect
Free-radical polymerised resin combination of the present invention can obtain film that is surface drying and stretching physical properties excellent, therefore can be suitable for the manufacture of the civil construction materials such as the flooring material of factory, warehouse, clean room etc., pavement material, water-proof material, road coating, priming paint, coating wall compress material, pavement marking material, injecting material, caking agent, lining material, flat plate.
Embodiment
Free-radical polymerised resin combination of the present invention contains carbamate (methyl) acrylate (A), free radical polymerization monomer (B) and acrylic polymers (C) and is used as required composition.
Above-mentioned carbamate (methyl) acrylate (A) obtain excellent stretching physical property (particularly tensile elongation) in be required composition, such as can use polyvalent alcohol (a1), polyisocyanates (a2) and there is (methyl) acrylic compounds (a3) reaction of hydroxyl or isocyanate group and carbamate (methyl) acrylate that obtains.
As above-mentioned polyvalent alcohol (a1), such as polyester polyol (a1-1), polycarbonate polyol (a1-2), polyether glycol, polyacrylic polyols (Port リ ア Network リ Le Port リ オ mono-Le), caprolactone polyol, divinyl polyvalent alcohol etc. can be used.These polyvalent alcohols can be used alone also that two or more kinds may be used.Wherein, from improving stretching physical property and surface drying aspect further, even if containing acrylic polymers described later (C), also preferably use polyester polyol (a1-1) and/or polycarbonate polyol (a1-2).
As the number-average molecular weight of above-mentioned polyvalent alcohol (a1), from the aspect of stretching physical property, be preferably the scope of 800 ~ 5,000, the more preferably scope of 900 ~ 4,000.Be explained, the number-average molecular weight of above-mentioned polyvalent alcohol (a1) represents and utilizes gel permeation chromatography (GPC) method and the value recorded according to following condition.
Determinator: high speed GPC device (TOSOH Co., Ltd's system " HLC-8220GPC ")
Chromatographic column: the following Coupled columns of TOSOH Co., Ltd is connected and uses.
" TSKgel G5000 " (7.8mm I.D. × 30cm) × 1
" TSKgel G4000 " (7.8mm I.D. × 30cm) × 1
" TSKgel G3000 " (7.8mm I.D. × 30cm) × 1
" TSKgel G2000 " (7.8mm I.D. × 30cm) × 1
Detector: RI (differential refractometer)
Column temperature: 40 DEG C
Elutriant: tetrahydrofuran (THF) (THF)
Flow velocity: 1.0mL/ minute
Injection rate: 100 μ L (tetrahydrofuran solution of sample solution concentration 0.4 quality %)
Standard test specimen: use following polystyrene standard to produce typical curve.
(polystyrene standard)
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-500 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-1000 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-2500 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-5000 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-1 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-2 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-4 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-10 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-20 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-40 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-80 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-128 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-288 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-550 "
As above-mentioned polyisocyanates (a2), the formaline condensates of such as phenylene diisocyanate, diphenylmethanediisocyanate, tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, polymethylene polyphenylene(poly)isocyanate, MDI, 4 can be used, the aromatic polyisocyanates such as the carbodiimide modified thing of 4 '-diphenylmethanediisocyanate; The aliphatics such as hexamethylene diisocyanate, lysinediisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, HMDI, xylylene diisocyanate, tetramethylxylylene diisocyanate or ester ring type polyisocyanates etc.These polyisocyanates can be used alone, and also two or more kinds may be used.
As (methyl) acrylic compounds with hydroxyl that can be used as above-mentioned (a3), (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester etc. can be used such as to have (methyl) alkyl acrylate of hydroxyl; Polyethylene glycol monoacrylate, polypropylene glycol mono acrylic ester etc.These compounds can be used alone, and also two or more kinds may be used.
As (methyl) acrylic compounds with isocyanate group that can be used as above-mentioned (a3), can use such as: 2-(methyl) acryloyloxyethyl isocyanate, 2-(2-(methyl) acrylyl oxy-ethyl oxygen base) ethyl isocyanate, 1,1-two ((methyl) acryloyloxymethyl) ethyl isocyanates etc.These compounds can be used alone, and also two or more kinds may be used.
Be explained, in the present invention, " (methyl) acrylate " is one or both in methacrylate and acrylate; " (methyl) acryl " refers to one or both in methacryloyl and acryl; " (methyl) vinylformic acid " is one or both in methacrylic acid and vinylformic acid; " (methyl) acrylic compounds " refers to one or both in acrylic compounds and methacrylic compounds.
As the number-average molecular weight of above-mentioned carbamate (methyl) acrylate (A), from improving the stretching physical property of film, stain resistance and surface drying aspect further, be more preferably 500 ~ 5, the scope of 000, further preferably 1, the scope of 000 ~ 3,000.Be explained, the number-average molecular weight of above-mentioned carbamate (methyl) acrylate represents to be carried out measuring and the value obtained in the same manner as the number-average molecular weight of above-mentioned polyvalent alcohol (a1).
In above-mentioned carbamate (methyl) acrylate (A), can as required and with other free-radical polymerised resin.
As other free-radical polymerised resin above-mentioned, such as unsaturated polyester, polyester (methyl) acrylate, epoxy (methyl) acrylate etc. can be used.
As above-mentioned free radical polymerization monomer (B), (methyl) methyl acrylate can be used such as, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) decyl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) propenoic acid beta-ethoxy ethyl ester, (methyl) 2 cyanoethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, polycaprolactone (methyl) acrylate, diethylene glycol monomethyl ether list (methyl) acrylate, DPGME list (methyl) acrylate, 2-ethylhexyl Trivalin SF (methyl) acrylate, (methyl) acrylic monomers such as isocyanuric acid three (2-acryloyl-oxyethyl) ester (Isocyanuric acid Tris (2-acryloxy ethyl) ester), the boiling points such as dicyclopentenyl oxygen ethyl (methyl) acrylate, dicyclopentenyl (methyl) acrylate, (methyl) acrylate are (methyl) acrylic monomer of more than 100 DEG C, vinylbenzene, alpha-methyl styrene etc. have the monomer etc. of ethylenic unsaturated bond.These monomers can be used alone, and also two or more kinds may be used.Wherein, from improving low fetidity property and surface drying aspect further, boiling point preferably containing more than 50 quality % in free radical polymerization monomer (B) is (methyl) acrylic monomer of more than 100 DEG C, more than a kind (methyl) acrylic monomer be selected from the group be made up of dicyclopentenyl oxygen ethyl (methyl) acrylate, dicyclopentenyl (methyl) acrylate and (methyl) acrylate more preferably containing more than 50 quality % in free radical polymerization monomer (B).
As the mass ratio [(A)/(B)] of above-mentioned carbamate (methyl) acrylate (A) with above-mentioned free radical polymerization monomer (B), from the aspect of the stretching physical property of film, surface drying and stain resistance, be preferably the scope of 10/90 ~ 90/10, be more preferably the scope of 20/70 ~ 80/20.
Aforesaid propylene acids polymers (C) obtain excellent surface drying in be required composition, such as can use the material obtained according to known method polymerization by the polymerizable compound comprising (methyl) acrylic monomer.Be explained, the aforesaid propylene acids polymers (C) used in the present invention does not preferably have the polymkeric substance of free-radical polymerised group, that is, so-called dead polymkeric substance (dead polymer).
As above-mentioned (methyl) acrylic monomer, can use such as: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid peopentyl ester, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid cetyl, (methyl) alkyl acrylates such as (methyl) lauryl acrylate, (methyl) vinylformic acid 2,2,2-trifluoro ethyl ester, (methyl) vinylformic acid 2,2,3,3-tetrafluoro propyl ester, (methyl) vinylformic acid 1H, 1H, 5H-octafluoro pentyl ester, (methyl) vinylformic acid 2-(perfluoro capryl) ethyl ester etc. have (methyl) acrylic monomer of fluorine atom, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid bicyclopentyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester etc. have (methyl) acrylic monomer of alicyclic structure, polyethyleneglycol (methyl) acrylate, (methyl) methoxyethyl acrylate, (methyl) methoxyethyl butyl ester, methoxy triethylene (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate etc. have (methyl) acrylic monomer of ether, (methyl) benzyl acrylate, 2-Ethyl-2-Methyl-[1,3]-dioxolane-4-base-methyl (methyl) acrylate, (methyl) acrylate etc.These (methyl) acrylic monomers can be used alone, and also two or more kinds may be used.
As the polymerizable compound except above-mentioned (methyl) acrylic monomer, such as, vinylbenzene, alpha-methyl styrene etc. can be used.These compounds can be used alone, and also two or more kinds may be used.
When obtaining aforesaid propylene acids polymers (C), can as required with an organic solvent.As above-mentioned organic solvent, such as dimethylbenzene, toluene, ethyl acetate, acetone, methylethylketone, butanols etc. can be used.These organic solvents can be used alone, and also two or more kinds may be used.
As the weight-average molecular weight of aforesaid propylene acids polymers (C), from easy at film coated surface segregation, the surface drying aspect that can improve film further, be preferably 20, more than 000, be more preferably 30,000 ~ 300, the scope of 000.Be explained, the weight-average molecular weight of aforesaid propylene acids polymers (C) represents to be carried out measuring and the value obtained in the same manner as the number-average molecular weight of above-mentioned polyvalent alcohol (a1).
In addition, as the second-order transition temperature (Tmg) of aforesaid propylene acids polymers (C), from improving surface drying aspect further, be preferably the scope of 30 ~ 90 DEG C, the more preferably scope of 40 ~ 80 DEG C.Be explained, the second-order transition temperature (Tmg) of aforesaid propylene acids polymers (C) represents according to JISK7121-1987 and utilizes the value measured by DSC, specifically, represent: in differential scanning type calorimeter device, put into aforesaid propylene acids polymers (C), be warmed up to (Tmg+50 DEG C) with heat-up rate 10 DEG C/min to keep 3 minutes afterwards, then quenching, the intermediate point second-order transition temperature (Tmg) read from obtained differential thermal curve.
As the content of aforesaid propylene acids polymers (C), from improving aspect that is surface drying and stain resistance further, in the total amount of above-mentioned carbamate (methyl) acrylate (A), above-mentioned free radical polymerization monomer (B) and aforesaid propylene acids polymers (C), be preferably the scope of 0.5 ~ 30 quality %, be more preferably the scope of 1 ~ 20 quality %.
Free-radical polymerised resin combination of the present invention contains above-mentioned carbamate (methyl) acrylate (A), above-mentioned free radical polymerization monomer (B) and aforesaid propylene acids polymers (C) and is used as essential component, can also contain other additive as required.
As other additive above-mentioned, such as solidifying agent (D), curing catalyst (E), petroleum wax (F), stopper, pigment, thixotropy conferring agents, antioxidant, solvent, weighting agent, reinforcement material, aggregate, fire retardant etc. can be used.These additives can be used alone, and also two or more kinds may be used.Wherein, free-radical polymerised resin combination of the present invention is when for civil construction material, from the aspect that can improve solidified nature at normal temperatures further, preferably containing more than a kind that is selected from the group that is made up of solidifying agent (D), curing catalyst (E) and petroleum wax (F).
As above-mentioned solidifying agent (D); surface drying aspect under normal temperature; preferred use organo-peroxide, can use such as diacyl peroxide compound, peroxyester compound, hydroperoxide compound, dialkyl peroxide compound, ketone peroxide compound, peroxy ketal compound, alkyl super-acid ester compound, peroxocarbonate compound etc.These solidifying agent can be used alone, and also two or more kinds may be used.As content during use above-mentioned solidifying agent (D), be preferably the scope of 0.01 ~ 10 quality % in free-radical polymerised resin combination.
Above-mentioned curing catalyst (E) has to make the organo-peroxide of above-mentioned solidifying agent (D) be undertaken decomposing by redox reaction and make the generation of living radical become the material of easy this effect, the such as cobalt such as cobalt naphthenate, cobalt octoate organic acid salt can be used, the metallic soaps such as zinc octoate, sad vanadium, copper naphthenate, barium naphthenate, the metallo-chelates such as etheric acid vanadium, etheric acid cobalt, acetopyruvic acid iron, aniline, N, accelerine, N, N-Diethyl Aniline, para-totuidine, N, N-dimethyl-paratoluidine, N, the ethylene oxide adduct of N-dimethyl-paratoluidine, N, N-bis-(2-hydroxyethyl)-para-totuidine, 4-(N, N-dimethylamino) phenyl aldehyde, 4-[N, N-bis-(2 hydroxyethyl) is amino] phenyl aldehyde, 4-(N-methyl-N-hydroxyethylamino) phenyl aldehyde, N, N-bis-(2-hydroxypropyl)-para-totuidine, N-ethyl-meta-aminotoluene, trolamine, meta-aminotoluene, diethylenetriamine, pyridine, phenylmorpholine, piperidines, N, N-bis-(hydroxyethyl) aniline, the N such as diethanolaniline, N-substituted aniline, the amine compound etc. such as N, N-replacement-para-totuidine, 4-(N, N-substituted-amino) phenyl aldehyde.These curing catalysts can be used alone, and also two or more kinds may be used.As content during use above-mentioned curing catalyst (E), be preferably the scope of 0.01 ~ 5 quality % in free-radical polymerised resin combination.
Above-mentioned petroleum wax (F) hinders for preventing the solidification caused by oxygen, and such as preferably use fusing point is the petroleum wax of 30 ~ 80 DEG C, specifically, can use paraffin, Microcrystalline Wax, vaseline (Petrolatum) etc.These petroleum waxes can be used alone, and also two or more kinds may be used.As content during use above-mentioned petroleum wax (F), be preferably the scope of 0.01 ~ 5 quality % in free-radical polymerised resin combination.Be explained, the fusing point of above-mentioned petroleum wax (F) represents according to the value measured by JISK22351991.
The of the present invention free-radical polymerised resin combination obtained by above method can obtain film that is surface drying and stretching physical properties excellent, therefore, the manufacture of the civil construction materials such as the flooring material of factory, warehouse, clean room etc., pavement material, water-proof material, road coating, priming paint, coating wall compress material, pavement marking material, injecting material, caking agent, lining material, flat plate can be suitable for.
Embodiment
Below, the present invention is illustrated in greater detail by embodiment.
The synthesis of [synthesis example 1] urethane methacrylate (A-1)
To in the four-hole boiling flask possessing thermometer, stirrer, inactive gas introducing port, air induction port and reflux cooler, drop into polyester polyol (" Dainippon Ink Chemicals Polylight OD-X-2044 ", number-average molecular weight: 2,000) 1,000 mass parts, tolylene diisocyanate 174 mass parts, in 80 DEG C of reactions 4 hours under stream of nitrogen gas.Confirm that isocyanate group equivalent is 1,100 and substantially reaches theoretical value, be cooled to 50 DEG C.Then, under air draught, add quinhydrones 0.07 mass parts, HEMA 131 mass parts, react 5 hours at 90 DEG C.Reach the time point of less than 0.1% at isocyanic ester %, add tert-butyl catechol 0.07 mass parts, obtain number-average molecular weight: 2, the urethane methacrylate (A-1) of 608.
The synthesis of [synthesis example 2] urethane methacrylate (A2)
To in the four-hole boiling flask possessing thermometer, stirrer, inactive gas introducing port, air induction port and reflux cooler, drop into polycarbonate polyol (Ube Industries, Ltd's system " ETERNACOLL UH-200 ", number-average molecular weight 2,000) 1,000 mass parts, tolylene diisocyanate 174 mass parts, in 80 DEG C of reactions 4 hours under stream of nitrogen gas.Confirm that isocyanate group equivalent is 1,100 and substantially reaches theoretical value, be cooled to 50 DEG C.Then, under air draught, add quinhydrones 0.07 mass parts, HEMA 131 mass parts, react 5 hours at 90 DEG C.Reach the time point of less than 0.1% at isocyanic ester %, add tert-butyl catechol 0.07 mass parts, obtain number-average molecular weight: 2, the urethane methacrylate (A-2) of 608.
The preparation of [embodiment 1] free-radical polymerised resin combination
By obtain in synthesis example 1 urethane methacrylate (A-1) 30 mass parts, dicyclopentenyl oxygen ethylmethyl acrylate 40 mass parts, HEMA 20 mass parts, acrylic polymers (C1) (EVONIK INDUSTRIES Inc. " DEGALAN64/12N ", weight-average molecular weight: 64,000, second-order transition temperature (Tmg): 60 DEG C) 10 mass parts, fusing point be that paraffin 1 mass parts of 54 DEG C mixes and stirs, and obtains free-radical polymerised resin combination.
[embodiment 2 ~ 4, comparative example 1 ~ 3]
The kind of the kind of used free-radical polymerised resin (A), the kind of free radical polymerization monomer (B) and amount and acrylic polymers (C) and amount are changed according to shown in table 1, in addition, operate similarly to Example 1, obtain free-radical polymerised resin combination.
[surface drying evaluation method]
According to the ratio [TF (minute)/GT (minute)] of gelation time (GT) with tack-free time (TF), evaluate surface drying as described below.
< gelation time (GT) >
Relative to free-radical polymerised resin combination 50 mass parts obtained in embodiment and comparative example, add 8 quality % cobalt octoate 0.25 mass parts, toluidine compound aqueous isopropanol (DHMaterialInc. system " RP-191 ") 0.5 mass parts, 40 quality % benzoyl peroxide solution 1 mass parts, and make them mix, make test film.Be impregnated in by test film in the thermostatic bath of 25 DEG C, with this time point for basic point, to generation gelling, the time (minute) become broken string (yarn cuts れ) state is used as gelation time to mensuration.
< tack-free time (TF) >
25 DEG C, the envrionment test of humidity 50% is indoor, use applicator to be coated with above-mentioned test film on a glass, reach 0.25mm to make thickness.With this time point for basic point, confirmed the condition of surface of film by finger touch, the time (minute) be measured to till finger can not adhere to resin is used as tack-free time.
The evaluation > that < is surface drying
" T ": lower than 3
" F ": more than 3
[evaluation method of stretching physical property]
Relative to free-radical polymerised resin combination 100 mass parts obtained in embodiment and comparative example, coordinate 8 quality % cobalt octoate 0.5 mass parts, toluidine compound aqueous isopropanol (" RP-191 ") 1 mass parts, 40 quality % benzoyl peroxide solution 2 mass parts, produce the measurement sample of thick No. 2 dumbbells of 3mm.Use this sample, determine tensile strength (MPa) and the tensile elongation (%) of the breaking point at graticule interval.
[table 1]
Shortenings in his-and-hers watches 1 is described." acrylic polymers (C-2) ": EVONIK INDUSTRIES Inc. " DEGALAN66/02N ", weight-average molecular weight: 60,000, second-order transition temperature (Tmg): 75 DEG C
Known: for the embodiment 1 ~ 4 as free-radical polymerised resin combination of the present invention, film that is surface drying and stretching physical properties excellent can be obtained.
On the other hand, comparative example 1 is the scheme not containing acrylic polymers (C), but surface drying bad, and tensile strength is also insufficient.
Comparative example 2 and comparative example 3 are the schemes not containing carbamate (methyl) acrylate (A), but tensile elongation is obviously bad.
Claims (8)
1. a free-radical polymerised resin combination, is characterized in that, containing carbamate (methyl) acrylate (A), free radical polymerization monomer (B) and acrylic polymers (C).
2. free-radical polymerised resin combination according to claim 1, wherein, described carbamate (methyl) acrylate (A) has the structure being derived from polyester polyol (a1-1) and/or polycarbonate polyol (a1-2).
3. free-radical polymerised resin combination according to claim 2, wherein, (methyl) acrylic compounds (a3) reaction that described carbamate (methyl) acrylate (A) makes to comprise the polyvalent alcohol (a1) of polyester polyol (a1-1) and/or polycarbonate polyol (a1-2), polyisocyanates (a2) and has hydroxyl or an isocyanate group obtains.
4. free-radical polymerised resin combination according to claim 1, wherein, the weight-average molecular weight of described acrylic polymers (C) is 20, more than 000.
5. free-radical polymerised resin combination according to claim 1, wherein, the second-order transition temperature Tmg of described acrylic polymers (C) is the scope of 30 ~ 90 DEG C.
6. free-radical polymerised resin combination according to claim 1, wherein, the content of described acrylic polymers (C) is the scope of 0.5 ~ 30 quality % in the total amount of described carbamate (methyl) acrylate (A), described free radical polymerization monomer (B) and described acrylic polymers (C).
7. free-radical polymerised resin combination according to claim 1, wherein, described free radical polymerization monomer (B) is boiling point is more than 100 DEG C (methyl) acrylic monomers.
8. a civil construction material, is characterized in that, containing the free-radical polymerised resin combination according to any one of claim 1 ~ 7.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI660974B (en) * | 2017-01-23 | 2019-06-01 | 日商昭和電工股份有限公司 | Radical polymerizable resin composition and injection for repairing structure |
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| JP6766321B2 (en) * | 2015-04-22 | 2020-10-14 | Dic株式会社 | Primer for civil engineering and construction and waterproof structure for floor slab |
| JP6766320B2 (en) * | 2015-04-22 | 2020-10-14 | Dic株式会社 | Primer for civil engineering and construction and waterproof structure for floor slab |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1120564A (en) * | 1994-05-19 | 1996-04-17 | 阿托哈斯控股公司 | Process for the preparation of antiscratch and antiabrasion shaped articles based on acrylic polymers |
| CN1129150A (en) * | 1994-11-18 | 1996-08-21 | 赫罗伊斯库尔泽有限公司 | Process for the production of a firmly adhering moisture-proof coating of plastic on a substrate |
| CN1230971A (en) * | 1996-05-30 | 1999-10-06 | 阿科化学技术公司 | Two-component waterborne polyurethane coating |
| CN1413239A (en) * | 1999-12-23 | 2003-04-23 | 阿克佐诺贝尔股份有限公司 | Aqueous coating composition comprising addition polymer and polyurethane |
| CN1656135A (en) * | 2002-04-05 | 2005-08-17 | 诺沃恩Ip控股公司 | Breathable polyurethanes, blends, and articles |
| CN1753919A (en) * | 2003-02-26 | 2006-03-29 | 拜尔材料科学股份公司 | Aqueous coating media based on polyurethane-polyacrylate hybrid dispersions |
| CN101281370A (en) * | 2007-04-06 | 2008-10-08 | 村上精密制版（昆山）有限公司 | Light-sensitive polymer composition with low surface stickiness and application thereof |
| CN101589092A (en) * | 2006-10-17 | 2009-11-25 | 莫门蒂夫性能材料股份有限公司 | Fluorine-free disiloxane surfactant compositions for use in coatings and printing ink compositions |
| CN101970398A (en) * | 2008-03-14 | 2011-02-09 | Dic株式会社 | Process for producing urethane (meth)acrylate |
| CN102388077A (en) * | 2009-04-10 | 2012-03-21 | 太阳控股株式会社 | Photocurable resin and photocurable resin composition |
| CN102549088A (en) * | 2009-09-29 | 2012-07-04 | Dic株式会社 | Primer composition, waterproof floor slab structure using same, and method for waterproofing floor slab |
| CN102549040A (en) * | 2009-09-18 | 2012-07-04 | Dic株式会社 | Acrylic modified urethane urea resin composition and molded article obtained using same |
| CN102844346A (en) * | 2010-03-31 | 2012-12-26 | Dic株式会社 | Active energy ray curable resin composition, cured article and film thereof |
| CN102858824A (en) * | 2010-11-19 | 2013-01-02 | Dic株式会社 | Radical-curable resin composition, coating material and civil engineering building structure each using radical-curable resin composition, and method for constructing civil engineering building structure |
| CN102906137A (en) * | 2010-06-18 | 2013-01-30 | Dic株式会社 | Urethane (meth)acrylate resin composition and coating material using same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07146401A (en) * | 1993-11-25 | 1995-06-06 | Mitsubishi Rayon Co Ltd | Lens sheet |
| JP3605433B2 (en) * | 1995-03-13 | 2004-12-22 | 三菱レイヨン株式会社 | Drainable pavement coating composition and drainable pavement surface forming composition |
| JP2000038546A (en) * | 1998-07-24 | 2000-02-08 | Mitsubishi Rayon Co Ltd | Photocuring adhesive composition and optical member using same |
| JP4299513B2 (en) * | 2002-08-13 | 2009-07-22 | 三菱レイヨン株式会社 | Coating composition and article |
| WO2011013532A1 (en) * | 2009-07-31 | 2011-02-03 | Dic株式会社 | Radical-curable resin composition, pavement materials using same, and paved structures |
-
2013
- 2013-09-04 JP JP2013183013A patent/JP2015048459A/en active Pending
-
2014
- 2014-09-03 CN CN201410446762.4A patent/CN104418988A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1120564A (en) * | 1994-05-19 | 1996-04-17 | 阿托哈斯控股公司 | Process for the preparation of antiscratch and antiabrasion shaped articles based on acrylic polymers |
| CN1129150A (en) * | 1994-11-18 | 1996-08-21 | 赫罗伊斯库尔泽有限公司 | Process for the production of a firmly adhering moisture-proof coating of plastic on a substrate |
| CN1230971A (en) * | 1996-05-30 | 1999-10-06 | 阿科化学技术公司 | Two-component waterborne polyurethane coating |
| CN1413239A (en) * | 1999-12-23 | 2003-04-23 | 阿克佐诺贝尔股份有限公司 | Aqueous coating composition comprising addition polymer and polyurethane |
| CN1656135A (en) * | 2002-04-05 | 2005-08-17 | 诺沃恩Ip控股公司 | Breathable polyurethanes, blends, and articles |
| CN1753919A (en) * | 2003-02-26 | 2006-03-29 | 拜尔材料科学股份公司 | Aqueous coating media based on polyurethane-polyacrylate hybrid dispersions |
| CN101589092A (en) * | 2006-10-17 | 2009-11-25 | 莫门蒂夫性能材料股份有限公司 | Fluorine-free disiloxane surfactant compositions for use in coatings and printing ink compositions |
| CN101281370A (en) * | 2007-04-06 | 2008-10-08 | 村上精密制版（昆山）有限公司 | Light-sensitive polymer composition with low surface stickiness and application thereof |
| CN101970398A (en) * | 2008-03-14 | 2011-02-09 | Dic株式会社 | Process for producing urethane (meth)acrylate |
| CN102388077A (en) * | 2009-04-10 | 2012-03-21 | 太阳控股株式会社 | Photocurable resin and photocurable resin composition |
| CN102549040A (en) * | 2009-09-18 | 2012-07-04 | Dic株式会社 | Acrylic modified urethane urea resin composition and molded article obtained using same |
| CN102549088A (en) * | 2009-09-29 | 2012-07-04 | Dic株式会社 | Primer composition, waterproof floor slab structure using same, and method for waterproofing floor slab |
| CN102844346A (en) * | 2010-03-31 | 2012-12-26 | Dic株式会社 | Active energy ray curable resin composition, cured article and film thereof |
| CN102906137A (en) * | 2010-06-18 | 2013-01-30 | Dic株式会社 | Urethane (meth)acrylate resin composition and coating material using same |
| CN102858824A (en) * | 2010-11-19 | 2013-01-02 | Dic株式会社 | Radical-curable resin composition, coating material and civil engineering building structure each using radical-curable resin composition, and method for constructing civil engineering building structure |
Non-Patent Citations (2)
| Title |
|---|
| 刘益军 主编: "《聚氨酯树脂及其应用》", 31 January 2012, 化学工业出版社 * |
| 郗宏勋 主编: "《汽车涂装技术》", 30 September 2012, 机械工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI660974B (en) * | 2017-01-23 | 2019-06-01 | 日商昭和電工股份有限公司 | Radical polymerizable resin composition and injection for repairing structure |
| CN110114378A (en) * | 2017-01-23 | 2019-08-09 | 昭和电工株式会社 | Free-radical polymerised resin combination and works reparation injectant |
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