CN107531856A - Free-radical polymerised resin combination and civil construction priming paint - Google Patents
Free-radical polymerised resin combination and civil construction priming paint Download PDFInfo
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- CN107531856A CN107531856A CN201680022903.7A CN201680022903A CN107531856A CN 107531856 A CN107531856 A CN 107531856A CN 201680022903 A CN201680022903 A CN 201680022903A CN 107531856 A CN107531856 A CN 107531856A
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- free
- radical polymerised
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- cyclodextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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Abstract
The present invention provides a kind of free-radical polymerised resin combination, it is characterised in that contains being air-dried property unsaturated-resin (A), free radical polymerization monomer (B) and cyclodextrin and/or its derivative (C).The free-radical polymerised resin combination of the present invention can be suitably employed in the earth material of manufacturing works, warehouse, ultra-clean chamber etc.；The civil construction materials such as pavement material, waterproof material, coating, priming paint, metope coating material, road marking material, injection material, encapsulant, moulding by casting product, stacking product, bonding agent, lining material, flat plate, are used as civil construction priming paint with being particularly suitable for.
Description
Technical field
The present invention relates to free-radical polymerised resin combination excellent in adhesion surface drying and for wet side.
Background technology
Instantly, due to increased traffic load-carrying, the distribution of antifreezing agent and cause the road and bridge floor headed by highway
Early stage deterioration gradually becomes notable.Mechanism as the early stage deterioration, it is believed that rainwater, antifreezing agent etc. by asphalt pavement and
The crack that is generated in reinforced concrete floor and invade into works so that reinforcement corrosion, causes the durability of works to drop
It is low.
As the method for the durability for improving these floor, to being sequentially laminated with floor layer, waterproof layer and drip road and bridge
The floor water-proof structure of blue or green pave-load layer has carried out various researchs.
As foregoing floor water-proof structure, disclose and be for example sequentially laminated with floor layer, carbamate waterproof material
The floor water-proof structure of layer, carbamate bond layer and asphalt mixture surfacing (referring for example to patent document 1).Foregoing bonding
The carbamate resins used in oxidant layer are high in Japanese popularization degree because cost is cheap, but surface drying slow, the phase
Hope and shorten the duration.In addition, construction when waterproof layer soaked by rain when, under how wet environment in use, also exist no
To this problem of desired cementability.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-117368 publications
The content of the invention
The invention problem to be solved
The problem to be solved by the present invention is that, there is provided free radical excellent in adhesion surface drying and for wet side
Polymer resin composition.
Means for solving the problems
The present invention provides a kind of free-radical polymerised resin combination, it is characterised in that unsaturated containing being air-dried property
Resin (A), free radical polymerization monomer (B) and cyclodextrin and/or its derivative (C).
In addition, the present invention provides a kind of civil construction priming paint for including foregoing free-radical polymerised resin combination.
The effect of invention
Surface drying and for wet side cementability (the following letter of the free-radical polymerised resin combination of the present invention
Referred to as " wet side cementability ") it is excellent.Therefore, free-radical polymerised resin combination of the invention can be suitably employed in manufacture
The earth material of factory, warehouse, ultra-clean chamber etc.；Pavement material, waterproof material, coating, priming paint, metope coating material, road sign material
The civil construction materials such as material, injection material, encapsulant, moulding by casting product, stacking product, bonding agent, lining material, flat plate,
It is used as civil construction priming paint with being particularly suitable for.
Embodiment
The free-radical polymerised resin combination of the present invention contains being air-dried property unsaturated-resin (A), radical polymerization
Property monomer (B) and cyclodextrin and/or its derivative (C) are used as essential component.
Free-radical polymerised resin combination as the present invention takes into account excellent surface drying and wet side cementability
Mechanism, it is believed that：In being air-dried property components utilising air possessed by aforementioned air drying property unsaturated-resin (A)
Oxygen and oxidation polymerization occurs, therefore in the case where not hindering radical polymerization suppress film solidification it is bad also, foregoing
Cyclodextrin and/or its derivative (C) are easily settled down to film bottom, the molecular separating force based on strength and with the sticky surface phase of moistening
Interaction.
Aforementioned air drying property unsaturated-resin (A) to assign the compound of group with being air-dried property as raw material and
Obtain, such as being air-dried property unsaturated polyester (UP), being air-dried property polyester (methyl) acrylate, being air-dried property can be used
Epoxy (methyl) acrylate, being air-dried property carbamate (methyl) acrylate etc..These resins can be used alone,
Two or more can also be applied in combination.
As the foregoing compound that group is assigned with being air-dried property, can use for example comprising ring-type unsaturated fat
The compound of race's polyacid and its derivative, the compound comprising the allyl ether with α positions hydrogen, pass through polyalcohol and drying oil
Ester exchange reaction obtained from alcoholysis compounds, there is the compound comprising dicyclopentadienyl etc. of hydroxyl.These chemical combination
Thing may be used singly or in combination of two or more.By making these compounds in manufacture aforementioned air drying property insatiable hunger
With generation esterification when resin (A) and/or urethane reaction, the tax of being air-dried property can be imported into resin matrix
Give composition.
As the foregoing compound comprising ring-type unsaturated aliphatic polyacid and its derivative, such as tetrahydrochysene can be used
Phthalic anhydride, Nadic anhydride, methyl tetrahydrophthalic anhydride, α-terpinene/maleic anhydride
Addition product, trans-m-pentadiene/maleic anhydride adduct etc..These compounds may be used alone, can also be used in combination 2 kinds
More than.
As it is foregoing include with α positions hydrogen allyl ether compound, can use such as ethylene glycol monoallyl ether,
Diethylene glycol mono allyl ether, triethylene glycol mono allyl ether, polyethylene glycol mono allyl ether, propane diols mono allyl ether, two
Propane diols mono allyl ether, tripropylene glycol mono allyl ether, polypropylene glycol mono allyl ether, 1,2- butanediols mono allyl ether,
1,3 butylene glycol mono allyl ether, trimethyolol propane monoallyl ether, trimethylolpropane allyl ether, glycerine monoene
Propyl ether, glycerol diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, the allyl of pentaerythrite three
The allyl ether compound of the polyalcohols such as base ether；Allyl glycidyl ether etc. has the allyl etherization of oxirane ring
Compound etc..These compounds may be used singly or in combination of two or more.
As the foregoing polyols used when manufacturing foregoing alcoholysis compounds, such as glycerine, trihydroxy methyl can be used
The trihydroxylic alcohols such as ethane, trimethylolpropane, trishydroxymethylaminomethane；Tetrahydroxylic alcohols such as pentaerythrite etc..These alcohol can be single
Solely use, two or more can also be applied in combination.
In addition, as the foregoing drying oil that uses when manufacturing foregoing alcoholysis compounds, such as linseed oil, big can be used
Soya-bean oil, cottonseed oil, peanut oil, coconut oil etc..These drying oil may be used singly or in combination of two or more.
As the foregoing compound for including dicyclopentadienyl with hydroxyl, such as dicyclopentenyl epoxide first can be used
Alcohol, dicyclopentenyl ethoxy-ethanol, dicyclopentenyl epoxide propyl alcohol etc..These compounds may be used alone, can also be used in combination 2
More than kind.
It is compatible with aftermentioned (C) composition excellent compatible from showing as aforementioned air drying property unsaturated-resin (A)
Property, from the viewpoint of making free-radical polymerised resin combination lowering viscousity, further can improving coating operations, preferably make
With being air-dried property unsaturated polyester (UP), the unsaturated polyester (UP) with dicyclopentadienyl is more preferably used.
, can be foregoing with being air-dried property imparting group using for example making as aforementioned air drying property unsaturated polyester (UP)
Compound, comprising α, the binary acid and polyalcohol of β-unsaturated dibasic acid carry out material obtained from esterification.
As foregoing α, β-unsaturated dibasic acid, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, clothing can be used
Health acid anhydrides etc..These binary acid may be used singly or in combination of two or more.
As the binary acid that can be used in addition except foregoing α, β-unsaturated dibasic acid, monounsaturated dicarboxylic acid can be used,
Such as phthalic acid, phthalic anhydride, halophthalic acid acid anhydride, M-phthalic acid, terephthalic acid (TPA), four can be used
Hydrogen phthalic acid, tetrabydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydro terephthalic acid,
Hexahydro M-phthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, decanedioic acid, 1,12 dodecanedioic acid, 2,6- naphthalene diformazans
Acid, 2,7- naphthalenedicarboxylic acids, 2,3- naphthalenedicarboxylic acids, 2,3- naphthalic anhydrides, 4,4'- biphenyl dicarboxylic acids or their dialkyl group
Ester etc..These binary acid can be used alone, two or more can also be applied in combination.
As foregoing polyols, can use for example ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propane diols,
DPG, polypropylene glycol, 2- methyl-1,3-propanediols, 1,3 butylene glycol, neopentyl glycol, hydrogenated bisphenol A, 1,4- butanediols,
Alkylene oxide adducts, 1,2,3,4- erythritols, glycerine, trimethylolpropane, 1,3- propane diols, the 1,2- of bisphenol-A
Cyclohexanediol, 1,3- cyclohexanediols, 1,4- cyclohexanediols, 1,4 cyclohexane dimethanol, paraxylene glycol, connection hexamethylene -4,
4'- glycol, 2,6- decahydronaphthalenes glycol, 2,7- decahydronaphthalene glycol etc..These polyalcohols may be used alone, can also be used in combination
Two or more.
As the number-average molecular weight of aforementioned air drying property unsaturated-resin (A), from good mechanical strength can be obtained
From the viewpoint of surface drying, more preferably 500~5,000 scope.It should illustrate, aforementioned air drying property is unsaturated
The number-average molecular weight of resin (A) represents the value determined under the following conditions by gel permeation chromatography (GPC) method.
Determine device：High speed GPC devices (" HLC-8220GPC " of TOSOH Co., Ltd's manufacture)
Post：Following posts that TOSOH Co., Ltd manufactures are connected in series use.
" TSKgel G5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector：RI (differential refraction rate meter)
Column temperature：40℃
Eluent：Tetrahydrofuran (THF)
Flow velocity：1.0mL/ minute
Injection rate：100 μ L (sample solution concentration is 0.4 mass % tetrahydrofuran solution)
Standard specimen：Standard curve is made using following polystyrene standards.
(polystyrene standard)
" the TSKgel polystyrene standards A-500 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards A-1000 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards A-2500 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards A-5000 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards F-1 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards F-2 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards F-4 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards F-10 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards F-20 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards F-40 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards F-80 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards F-128 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards F-288 " of TOSOH Co., Ltd's manufacture
" the TSKgel polystyrene standards F-550 " of TOSOH Co., Ltd's manufacture
As the content of aforementioned air drying property unsaturated-resin (A), from can be maintained with high level it is surface drying and
It is preferably 10~60 mass % scope, more in free-radical polymerised resin combination from the viewpoint of wet side cementability
Preferably 15~50 mass % scope.
As foregoing free radical polymerization monomer (B), such as (methyl) methyl acrylate, (methyl) acrylic acid can be used
Ethyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid oneself
Ester, (methyl) 2-EHA, (methyl) n-octyl, (methyl) decyl acrylate, (methyl) acrylic acid 2-
Hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) propenoic acid beta-ethoxy ethyl ester, (methyl) acrylic acid 2- cyano group second
Ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid diethylamino ethyl ester, (methyl) lauryl acrylate, (methyl) third
Olefin(e) acid stearyl ester, polycaprolactone (methyl) acrylate, diethylene glycol monomethyl ether list (methyl) acrylate, DPG list
Methyl ether list (methyl) acrylate, 2- ethylhexyls carbitol (methyl) acrylate, three (2- hydroxyethyls) isocyanuric acids
(methyl) acrylate etc. (methyl) acrylic monomer；(methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, (methyl) acrylic acid
The boiling points such as dicyclopentenyl base ester, (methyl) acrylate are more than 100 DEG C (methyl) acrylic monomer etc..This
A little monomers may be used singly or in combination of two or more.
As free radical polymerization monomer (B) content, in terms of it can obtain the good mechanical strength of film, certainly
By being preferably 10~80 mass % scope in base polymer resin composition, being more preferably 30~70 mass % scope.
As foregoing cyclodextrin and/or its derivative (C), such as cyclodextrin can be used；Alkylated cyclodextrin, acetyl group
Change cyclodextrin, hydroxy alkylated cyclodextrin etc. to substitute the hydroxyl hydrogen atom in the glucose unit of cyclodextrin with other functional groups
Obtained from material etc..In addition, as the cyclodextrin skeleton in cyclodextrin and cyclodextrine derivatives, can use by 6 grapes
The alpha-cyclodextrin of sugar unit composition, the beta-schardinger dextrin being made up of 7 glucose units, the γ-ring being made up of 8 glucose units
Any one of dextrin.These compounds may be used singly or in combination of two or more.Among these, from can enter
From the viewpoint of one step improves the compatibility compatible with foregoing (A) and (B) composition, preferably using cyclodextrine derivatives, more preferably
Use alkylated cyclodextrin.
As the substitution value of other functional groups in foregoing cyclodextrine derivatives, from compatible with foregoing (A) and (B) composition
From the viewpoint of compatibility, preferably the scope of 0.3~14/glucose, more preferably 0.5~8/glucose scope.
As aforesaid alkyl cyclodextrin, can use such as methyl-alphacyclodextrin, methyl-B-cyclodextrin, methyl-γ-
Cyclodextrin etc..These compounds may be used singly or in combination of two or more.
As foregoing acetylating cyclodextrin, such as monoacylphosphine-alpha-cyclodextrin, monoacylphosphine-β-ring can be used to paste
Essence, monoacylphosphine-gamma-cyclodextrin etc..These compounds may be used singly or in combination of two or more.
As foregoing hydroxy alkylated cyclodextrin, such as hydroxypropyl-alpha-cyclodextrin, hydroxypropyl-β-ring can be used
Dextrin, hydroxypropyl-gamma-cyclodextrin etc..These compounds may be used singly or in combination of two or more.
As the content of foregoing cyclodextrin and/or its derivative (C), from the sight that can obtain good wet side cementability
Point sets out, and is preferably 0.1~20 mass % scope, more preferably 0.3~10 matter in free-radical polymerised resin combination
Measure % scope.
The present invention free-radical polymerised resin combination contain aforementioned air drying property unsaturated-resin (A), it is foregoing from
Essential component is used as by base polymerizable monomer (B) and foregoing cyclodextrin and/or its derivative (C), but can also be as needed
Contain other additives.
As foregoing other additives, for example free-radical polymerised resin, curing agent, curing accelerator, resistance can be used
Poly- agent, pigment, thixotropy conferring agents, antioxidant, solvent, filler, supporting material, framework material, fire retardant, pertroleum wax etc.
In more than a kind.
Foregoing free-radical polymerised resin can use to adjust the mechanical strength of film, can use such as insatiable hunger
With polyester, polyester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate etc..As
It is preferably 0.1~30 matter in free-radical polymerised resin combination using usage amount during foregoing free-radical polymerised resin
Measure % scope.
As aforementioned curing agent, from normal temperatures surface drying from the viewpoint of, preferably using organic peroxide,
Such as diacyl peroxides compound, peroxy ester compounds, hydroperoxide compound, dialkyl can be used
Compound, ketone peroxide compound, ketal peroxide compound, alkyl over-churning compound, peroxocarbonate compound etc..These are solid
Agent may be used singly or in combination of two or more.Usage amount during as use aforementioned curing agent, in free radical
It is preferably 0.01~10 mass % scope in polymer resin composition.
Said curing accelerator is that have the organic peroxide that aforementioned curing agent is decomposed by redox reaction, and
The easily material of this effect of generation living radical, can use cobalt acylate, octanoic acid such as cobalt naphthenate, cobalt octoate
The metals such as the metallic soaps such as zinc, sad vanadium, copper naphthenate, barium naphthanate, acetoacetate vanadium, acetoacetate cobalt, acetyl acetone iron
Chelate；Aniline, N, accelerine, N, N- diethylanilines, para-totuidine, N, N- dimethyl-p-toluidines, N, N- bis-
Ethylene oxide adduct, the N of methyl para-totuidine, N- double (2- hydroxyethyls) para-totuidine, 4- (N, N- dimethylamino) benzene
Formaldehyde, 4- [double (2- hydroxyethyls) amino of N, N-] benzaldehyde, 4- (N- methyl-N-hydroxies ethylamino) benzaldehyde, N, N- are double
(2- hydroxypropyls) para-totuidine, N-ethyl-m-toluidine, triethanolamine, meta-aminotoluene, diethylenetriamines, pyridine, phenyl
The N such as morpholine, piperidines, N, N- double (hydroxyethyl) aniline, diethanolanilines, N- substituted anilines；N, N- substitution para-totuidine, 4-
Amines such as (N, N- substituted-amino) benzaldehyde etc..These curing accelerators may be used alone, can also be used in combination 2 kinds
More than.Usage amount during as the said curing accelerator of use, it is preferably 0.01~5 in free-radical polymerised resin combination
Quality % scope.
It is the material for preventing from solidifying caused by oxygen obstruction as aforementioned petroleum wax, is 30 preferably using such as fusing point
~80 DEG C of pertroleum wax, specifically, paraffin wax, microwax, vaseline etc. can be used.These pertroleum waxes can individually make
With two or more can also be applied in combination.Usage amount during as use aforementioned petroleum wax, in free-radical polymerised resin combination
It is preferably 0.01~5 mass % scope in thing.
Model as the viscosity, preferably such as 10~100mPas of the free-radical polymerised resin combination of the present invention
Enclose., can during using unsaturated polyester (UP) with dicyclopentadienyl in addition, as aforementioned air drying property unsaturated-resin (A)
To realize further lowering viscousity, for example, 1~50mPas scope.It should illustrate, foregoing free-radical polymerised resin
The viscosity of composition is represented according to JISK6901:2008 " 5.5.1 uses the situation of Brookfield type viscometer methods " measure
Value.
More than, the surface drying and wet side of free-radical polymerised resin combination of the invention is excellent in adhesion.Cause
This, free-radical polymerised resin combination of the invention can be suitably employed in the ground plane materiel of manufacturing works, warehouse, ultra-clean chamber etc.
Material；Pavement material, waterproof material, coating, priming paint, metope coating material, road marking material, injection material, encapsulant, pour into
The civil construction materials such as type product, stacking product, bonding agent, lining material, flat plate, it is used as civil construction with being particularly suitable for and uses
Priming paint.
Embodiment
Embodiment used below, is described in more detail the present invention.
[synthesis example 1] has the synthesis of the unsaturated polyester (UP) (A-1) of dicyclopentadienyl
To the four-hole boiling flask for possessing thermometer, mixer, non-active gas introducing port, air induction port and reflux condenser
Middle input water 270 mass parts, the mass parts of bicyclopentadiene 1,980, the mass parts of quinhydrones 0.5, the mass parts of ethylene glycol 450, in nitrogen
Reacted 4 hours with 80 DEG C under air-flow.At the time of acid number reaches 210mgKOH/g, the mass parts of maleic anhydride 1,370 are put into, with
200 DEG C react 6 hours, obtain acid number be 8mgKOH/g the unsaturated polyester (UP) (A-1) with dicyclopentadienyl (hereinafter referred to as
For " DCPD-UPE (A-1) ").
The synthesis of [synthesis example 2] epoxy methacrylates (1)
To the four-hole boiling flask for possessing thermometer, mixer, non-active gas introducing port, air induction port and reflux condenser
1,850 mass parts of middle input epoxide (DIC companies manufacture " Epiclon 850 "), the mass parts of methacrylic acid 860,
The mass parts of quinhydrones 1.36, the mass parts of triethylamine 10.8, are warming up to 120 DEG C, at the same time between react 10 hours, as radical polymerization
Conjunction property resin (1), obtain the epoxy methacrylates (1) that acid number is 3.5mgKOH/g.
The synthesis of [synthesis example 3] urethane methacrylate (2)
To the four-hole boiling flask for possessing thermometer, mixer, non-active gas introducing port, air induction port and reflux condenser
The mass parts of polybutadiene diol 500, the mass parts of toluene di-isocyanate(TDI) 114 that middle input number-average molecular weight is 1,200, in nitrogen
Reacted 2 hours with 80 DEG C under air-flow.Confirm NCO equivalent and reach 500 this approximation theory value, be cooled to 50 DEG C.Connect
, the mass parts of quinhydrones 0.07, the mass parts of 2-hydroxyethyl methacrylate 89 are added under air draught, it is small with 90 DEG C of reactions 10
When.At the time of isocyanates % reaches below 0.1%, the mass parts of tert-butyl catechol 0.07 are added, as radical polymerization
Conjunction property resin (2), obtain the urethane methacrylate (2) that number-average molecular weight is 2,067.
The synthesis of [synthesis example 4] urethane methacrylate (3)
To the four-hole boiling flask for possessing thermometer, mixer, non-active gas introducing port, air induction port and reflux condenser
The mass parts of PCDL 500, the mass parts of toluene di-isocyanate(TDI) 172 that middle input number-average molecular weight is 1,000, in nitrogen
Reacted 2 hours with 80 DEG C under air-flow.Confirm NCO equivalent and reach 600 this approximation theory value, be cooled to 50 DEG C.Connect
, the mass parts of quinhydrones 0.07, the mass parts of 2-hydroxyethyl methacrylate 135 are added under air draught, react 4 at 90 DEG C
Hour.At the time of isocyanates % reaches below 0.1%, the mass parts of tert-butyl catechol 0.07 are added, as free radical
Polymerizing resin (3), obtain the urethane methacrylate (3) that number-average molecular weight is 1,582.
The preparation of [embodiment 1] free-radical polymerised resin combination
The epoxy methacrylic acid that will be obtained in the mass parts of DCPD-UPE (A-1) 30 obtained in synthesis example 1, synthesis example 2
The mass parts of ester (1) 5, the mass parts of methyl methacrylate 29, the mass parts of methacrylic acid dicyclopentenyl epoxide ethyl ester 36, pureization
" methyl-B-cyclodextrin " 4 mass parts for learning Co., Ltd.'s manufacture are mixed, stirred, so as to obtain free-radical polymerised resin
Composition.
[embodiment 2~5, comparative example 1~4]
Except amount, the freedom according to being air-dried property unsaturated-resin (A) used in changing like that shown in table 1~2
Outside the amount of the species and/or amount of base polymerizing resin, the amount of free radical polymerization monomer and cyclodextrin (C), with implementation
The identical mode of example 1 obtains free-radical polymerised resin combination.
[surface drying evaluation method]
8 mass % are added into the mass parts of free-radical polymerised resin combination 50 obtained by embodiment and comparative example
The mass parts of cobalt octoate 0.25, the aqueous isopropanol " RP-191 " of manufacture (DIC Material companies) of toluidine compound
0.5 mass parts, the 40 mass % mass parts of benzoyl peroxide solution 1 simultaneously mix, and test film is made.By the test film in slabstone
With 1kg/m on (slate plate)2Amount hairbrush it is spreadable.In this, as basic point, measure with finger touch to inadhesion when
Between (minute).
[evaluation method of wet side cementability]
The test film obtained in evaluation using foregoing [surface drying evaluation method].Soaking 1 day and taking thereafter
Go out and wipe the mating formation on plate of water droplet away, by afore-mentioned test piece with 0.2kg/m2Amount hairbrush it is spreadable.The film is cured 1 day
Afterwards, using build grind formula cupping machine (SANKO TECHNO companies manufacture " TechnoStar RT-3000LD ") carry out it is vertical
Stretching, determine peel strength.
[assay method of viscosity]
By the free-radical polymerised resin combination obtained by embodiment and comparative example according to JIS K6901：2008
" 5.5.1 uses the situation of Brookfield type viscometer methods ", viscosity is determined by the i types of table 7, BM viscosimeters.
[table 1]
| Table 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Being air-dried property unsaturated-resin (A) | |||||
| DCPD-UPE (A-1) (mass parts) | 30 | 30 | 30 | 25 | 35 |
| Other free-radical polymerised resins | |||||
| Epoxy methacrylates (1) (mass parts) | 5 | 5 | 5 | ||
| Urethane methacrylate (3) (mass parts) | 5 | ||||
| Free radical polymerization monomer (B) | |||||
| Methyl methacrylate (mass parts) | 29 | 29 | 29 | 29 | |
| Acrylic acid dicyclopentenyl epoxide ethyl ester (mass parts) | 36 | 36 | 65 | 36 | 36 |
| Cyclodextrin and/or its derivative (C) | |||||
| Methyl-B-cyclodextrin (mass parts) | 4 | 1 | 3 | 3 | 1 |
| Surface drying (minute) | 40 | 30 | 30 | 50 | 30 |
| Wet side cementability (N/mm2) | 4 | 3.3 | 3.6 | 3.2 | 3.1 |
| Viscosity (mPas) | 8 | 7 | 49 | 19 | 6 |
[table 2]
| Table 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Being air-dried property unsaturated-resin (A) | ||||
| DCPD-UPE (A-1) (mass parts) | 30 | 25 | ||
| Other free-radical polymerised resins | ||||
| Epoxy methacrylates (1) (mass parts) | 5 | 10 | 5 | |
| Urethane methacrylate (2) (mass parts) | 34 | 26 | ||
| Free radical polymerization monomer (B) | ||||
| Methyl methacrylate (mass parts) | 29 | 60 | 29 | |
| Acrylic acid dicyclopentenyl epoxide ethyl ester (mass parts) | 66 | 36 | 36 | |
| Cyclodextrin and/or its derivative (C) | ||||
| Methyl-B-cyclodextrin (mass parts) | 3 | |||
| Surface drying (minute) | >60 | >60 | 30 | >60 |
| Wet side cementability (N/mm2) | 3.4 | 3.1 | 2 | 2.6 |
| Viscosity (mPas) | 340 | 220 | 8 | 18 |
Understand：Surface drying and moistening as the embodiment 1~5 of the free-radical polymerised resin combination of the present invention
Face is excellent in adhesion, and is low viscosity.
On the other hand, comparative example 1~2 is free from being air-dried property unsaturated-resin (A) mode, it is surface drying not
It is good.In addition, viscosity also shows that high level.
Comparative example 3~4 is free from the mode of cyclodextrin and/or its derivative (C), and wet side cementability is insufficient.
Claims (5)
1. a kind of free-radical polymerised resin combination, it is characterised in that containing being air-dried property unsaturated-resin (A), freely
Base polymerizable monomer (B) and cyclodextrin and/or its derivative (C).
2. free-radical polymerised resin combination according to claim 1, wherein, the cyclodextrin and/or its derivative
(C) content is 0.1~20 mass % scope in free-radical polymerised resin combination.
3. free-radical polymerised resin combination according to claim 1, wherein, the cyclodextrin and/or its derivative
(C) it is alkylated cyclodextrin.
4. free-radical polymerised resin combination according to claim 1, wherein, the being air-dried property unsaturated-resin
(A) it is the unsaturated polyester (UP) with dicyclopentadienyl.
5. a kind of civil construction priming paint, it includes free-radical polymerised resin combination according to any one of claims 1 to 4
Thing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015087559 | 2015-04-22 | ||
| JP2015-087559 | 2015-04-22 | ||
| PCT/JP2016/061792 WO2016171034A1 (en) | 2015-04-22 | 2016-04-12 | Radical polymerizable resin composition and primer for civil engineering and construction |
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| CN107531856A true CN107531856A (en) | 2018-01-02 |
| CN107531856B CN107531856B (en) | 2021-03-23 |
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| Country | Link |
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| JP (1) | JP6066027B1 (en) |
| CN (1) | CN107531856B (en) |
| WO (1) | WO2016171034A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736498A (en) * | 2022-05-26 | 2022-07-12 | 泉州永悦新材料有限公司 | Synthesis method of thixotropic unsaturated resin |
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| JP2005154627A (en) * | 2003-11-27 | 2005-06-16 | Dainippon Ink & Chem Inc | Putty composition |
| WO2006115211A1 (en) * | 2005-04-25 | 2006-11-02 | Kaneka Corporation | Cyclodextrin-containing polyester polymer and process for producing the same |
| CN103865004A (en) * | 2012-12-14 | 2014-06-18 | Dic株式会社 | Radical-polymerizable resin composition, primer and waterproof floor slab structure |
| CN104419300A (en) * | 2013-09-09 | 2015-03-18 | Dic株式会社 | Free radical polymerized resin composition and civil engineering material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS50124941A (en) * | 1974-03-22 | 1975-10-01 | ||
| JPS6268869A (en) * | 1985-09-20 | 1987-03-28 | Nichiban Co Ltd | Pressure-sensitive adhesive composition usable in water |
| US20120108700A1 (en) * | 2009-06-18 | 2012-05-03 | Mitsuyuki Kanzaki | Air-drying polyester (meth)acrylate resin composition, structure, and method for applying the resin composition |
| CN105658602B (en) * | 2013-10-30 | 2019-04-05 | Dic株式会社 | Concrete repairing material |
| WO2015186433A1 (en) * | 2014-06-04 | 2015-12-10 | Dic株式会社 | Radically polymerizable composition, concrete repair material, and primer for roads |
| WO2015194239A1 (en) * | 2014-06-17 | 2015-12-23 | Dic株式会社 | Civil engineering material |
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2016
- 2016-04-12 JP JP2016559370A patent/JP6066027B1/en active Active
- 2016-04-12 WO PCT/JP2016/061792 patent/WO2016171034A1/en active Application Filing
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Patent Citations (4)
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|---|---|---|---|---|
| JP2005154627A (en) * | 2003-11-27 | 2005-06-16 | Dainippon Ink & Chem Inc | Putty composition |
| WO2006115211A1 (en) * | 2005-04-25 | 2006-11-02 | Kaneka Corporation | Cyclodextrin-containing polyester polymer and process for producing the same |
| CN103865004A (en) * | 2012-12-14 | 2014-06-18 | Dic株式会社 | Radical-polymerizable resin composition, primer and waterproof floor slab structure |
| CN104419300A (en) * | 2013-09-09 | 2015-03-18 | Dic株式会社 | Free radical polymerized resin composition and civil engineering material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736498A (en) * | 2022-05-26 | 2022-07-12 | 泉州永悦新材料有限公司 | Synthesis method of thixotropic unsaturated resin |
| CN114736498B (en) * | 2022-05-26 | 2023-07-25 | 泉州永悦新材料有限公司 | Synthesis method of thixotropic unsaturated resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107531856B (en) | 2021-03-23 |
| JPWO2016171034A1 (en) | 2017-05-18 |
| JP6066027B1 (en) | 2017-01-25 |
| WO2016171034A1 (en) | 2016-10-27 |
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