CN117327435A - Radical polymerizable composition - Google Patents

Radical polymerizable composition Download PDF

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Publication number
CN117327435A
CN117327435A CN202310600181.0A CN202310600181A CN117327435A CN 117327435 A CN117327435 A CN 117327435A CN 202310600181 A CN202310600181 A CN 202310600181A CN 117327435 A CN117327435 A CN 117327435A
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meth
mass
acrylate
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polyester
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入江博美
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DIC Corp
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DIC Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Abstract

The present invention provides a radical polymerizable composition which has low viscosity, long usable time, excellent low-temperature curability and can obtain a coating film excellent in low-temperature flexibility. A radically polymerizable composition is used which is characterized by comprising a polyester (meth) acrylate (A) having a (meth) acryloyl group at both ends, a (meth) acrylic monomer (B), a polymerization inhibitor (C) and a wax (D), wherein the concentration of polymerizable double bonds in the polyester (meth) acrylate (A) is 0.1 to 1mol/kg and the concentration of aromatic rings is 3mol/kg or less.

Description

Radical polymerizable composition
Technical Field
The present invention relates to a radical polymerizable composition.
Background
Recently, early deterioration of road and bridge cement boards, including highways, has become remarkable with increasing traffic load and spraying of antifreeze. The early deterioration is considered to be due to the fact that rainwater, an antifreezing agent, or the like penetrates into the structure through cracks generated in the asphalt pavement and the reinforced concrete slab, and the corrosion of the reinforcing bars is caused, thereby reducing the durability of the structure.
Therefore, for the purpose of extending the life of these road structures, there has been studied a structure having 4 layers, i.e., a surface layer, a base layer, a roadbed, and a bed, which has high durability.
For resin materials, quick curability is required to allow completion of the work in a short period of time even under low temperature conditions, and for example, resin compositions containing polyether acrylic urethane resins, air-drying property-imparting polymers, and ethylenically unsaturated monomers have been proposed (for example, see patent document 1). However, this resin composition has a problem that the flexibility of the coating film is insufficient.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. Hei 8-259643
Disclosure of Invention
Problems to be solved by the invention
The present invention aims to provide a radical polymerizable composition which has low viscosity, long pot life, excellent low-temperature curability, and can obtain a coating film excellent in low-temperature flexibility.
Means for solving the problems
As a result of intensive studies to solve the above problems, the present inventors have found that a radically polymerizable composition containing a specific polyester (meth) acrylate, (meth) acrylic monomer, a polymerization inhibitor and a wax has a low viscosity, a long pot life and excellent low-temperature curability, and a coating film having excellent low-temperature flexibility can be obtained, and have completed the present invention.
Specifically, the present invention provides a radically polymerizable composition comprising a polyester (meth) acrylate (A) having a (meth) acryloyl group at both ends, a (meth) acrylic monomer (B), a polymerization inhibitor (C) and a wax (D), wherein the polyester (meth) acrylate (A) has a polymerizable double bond concentration of 0.1 to 1mol/kg and an aromatic ring concentration of 3mol/kg or less.
Effects of the invention
The radically polymerizable composition of the present invention has low viscosity, long pot life, excellent low-temperature curability, and can provide a coating film excellent in low-temperature flexibility, and thus can be suitably used for various civil engineering and construction material applications such as concrete protective materials, mortar binders, crack repair materials, and the like.
Detailed Description
The radically polymerizable composition of the present invention comprises a polyester (meth) acrylate (A) having a (meth) acryloyl group at both ends, a (meth) acrylic monomer (B), a polymerization inhibitor (C) and a wax (D), wherein the polymerizable double bond concentration of the polyester (meth) acrylate (A) is 0.1 to 1mol/kg or less and the aromatic ring concentration is 3mol/kg or less.
In the present invention, the term "(meth) acryl" means one or both of acryl and methacryl, the term "(meth) acrylate" means one or both of methacrylate and acrylate, the term "(meth) acrylic monomer" means one or both of acrylic monomer and methacrylic monomer, and the term "(meth) acrylic compound" means one or both of acrylic compound and methacrylic compound.
The polyester (meth) acrylate (a) can be obtained by, for example, a reaction between a saturated polyester or an unsaturated polyester and glycidyl (meth) acrylate, but a saturated polyester is preferably used in view of further improving the flexibility of the coating film.
The polyester may be obtained by an esterification reaction of a dibasic acid with a polyhydric alcohol, and the saturated polyester is a polyester obtained by using only a saturated dibasic acid as a dibasic acid, and the unsaturated polyester is a polyester obtained by using an α, β -unsaturated dibasic acid as a part or all of the dibasic acid.
For example, phthalic acid, phthalic anhydride, halophthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, furandicarboxylic acid, 1, 12-dodecanedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic anhydride, 4' -biphthalic acid, and dialkyl esters of these acids can be used as the saturated dibasic acid. These dibasic acids may be used alone or in combination of 2 or more.
For example, maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, etc. can be used as the above-mentioned α, β -unsaturated dibasic acid. These dibasic acids may be used alone or in combination of 2 or more.
The dibasic acid is preferably an aliphatic dibasic acid in terms of reducing the aromatic ring concentration of the polyester (meth) acrylate (a) and obtaining more excellent coating flexibility.
For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1, 3-propanediol, 1, 3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1, 4-butanediol, alkylene oxide adducts of bisphenol A, 1,2,3, 4-tetrahydroxybutane, glycerol, trimethylolpropane, 1, 3-propanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanedimethanol, p-xylene glycol, dicyclohexyl-4, 4' -diol, 2, 6-decalin diol, 2, 7-decalin diol, and the like can be used as the polyhydric alcohol. These polyols may be used alone or in combination of 2 or more.
The concentration of the polymerizable double bond in the polyester (meth) acrylate (A) is 0.1 to 1mol/kg, but is more preferably 0.2 to 0.8mol/kg in terms of further improving the balance between low-temperature curability and flexibility of the coating film. Here, the polymerizable double bond concentration is a value obtained by the following formula.
Concentration of polymerizable double bond= ("mole number of polymerizable double bond derived from unsaturated dibasic acid" + "(mole number of polymerizable double bond derived from glycidyl (meth) acrylate")/mass of polyester (meth) acrylate)
The aromatic ring concentration of the polyester (meth) acrylate (A) is 3mol/kg or less, but is more preferably 2.5mol/kg or less in view of further improving the flexibility of the coating film. Here, the aromatic ring concentration is a value obtained by the following formula.
Aromatic ring concentration= "mole number of aromatic ring derived from aromatic compound"/"mass of polyester methacrylate"
The (meth) acryl equivalent of the polyester (meth) acrylate (a) is preferably 200 to 8000g/eq, more preferably 250 to 4000g/eq, from the viewpoint of further improving the balance of low viscosity, usable time, low-temperature curability, and coating flexibility. Here, the (meth) acryl equivalent is a value calculated from the number average molecular weight.
The number average molecular weight of the polyester (meth) acrylate (a) is preferably 400 to 16000, more preferably 500 to 8000, from the viewpoint of further improving the balance of low viscosity, usable time, low-temperature curability, and coating flexibility.
The average molecular weight of the present invention means a value measured by a Gel Permeation Chromatography (GPC) method.
The radically polymerizable composition of the present invention can provide a coating film excellent in low-temperature flexibility by using the polyester (meth) acrylate (a) as an essential component, but epoxy (meth) acrylate, urethane (meth) acrylate, and the like may be used in combination in a range not impairing low-temperature flexibility.
The (meth) acrylic monomer (B) is not particularly limited as long as the resin viscosity can be diluted, and for example, an alicyclic (meth) acrylic monomer such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate can be used; aliphatic (meth) acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, 3-methylbutyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, neopentyl (meth) acrylate, cetyl (meth) acrylate, and isopentyl (meth) acrylate; (meth) acrylic monomers having an ether group, such as 3-methoxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, and methoxypolyethylene glycol acrylate having an addition mole number of ethylene oxide in the range of 1 to 15, ethoxy-diethylene glycol (meth) acrylate, and ethylcarbitol (meth) acrylate; a (meth) acrylic monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; aromatic (meth) acrylic monomers such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol acrylate, phenyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate; (meth) acrylic monomers having a nitrogen atom such as (meth) acrylamide, dimethyl (meth) acrylamide, acryloylmorpholine, dimethylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, diethyl (meth) acrylamide, diacetone (meth) acrylamide, and hydroxyethyl acrylamide. Among them, from the viewpoint of excellent curability, (meth) acrylate compounds having a molecular weight of 300 or less are preferred, and methyl (meth) acrylate is more preferred. These (meth) acrylic monomers may be used alone or in combination of 2 or more.
The amount of the (meth) acrylic monomer (B) used is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, per 100 parts by mass of the polyester (meth) acrylate (a), from the viewpoint of low viscosity, excellent curability, and excellent flexibility.
Examples of the polymerization inhibitor (C) include dibutylhydroxytoluene, hydroquinone, trimethylhydroquinone, 4-t-butylcatechol, t-butylhydroquinone, methylhydroquinone (tolluoquinone), p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, and copper chloride, and dibutylhydroxytoluene is preferable from the viewpoint of further improving the balance between pot life and curability. These polymerization inhibitors may be used alone or in combination of 2 or more.
The content of the polymerization inhibitor (C) is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total of the polyester (meth) acrylate (a) and the (meth) acrylic monomer (B), in terms of further improving the balance between the pot life and the low-temperature curability.
The wax (D) is a substance that prevents the inhibition of curing by oxygen, and examples thereof include paraffin wax, microcrystalline wax, petrolatum (Petrolatum), and the like, and paraffin wax is preferably used from the viewpoints of compatibility with the polyester (meth) acrylate (a) and the (meth) acrylic monomer (B) and low-temperature drying property.
The melting point of the wax (D) is preferably 40 to 75 ℃, more preferably 45 to 60 ℃ from the viewpoints of compatibility with the polyester (meth) acrylate (a) and the (meth) acrylic monomer (B) and low-temperature drying property. The melting point of the wax (D) is a melting point measured in accordance with JIS K2235.
The amount of the wax (D) used is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the total of the polyester (meth) acrylate (a) and the (meth) acrylic monomer (B), from the viewpoints of low-temperature drying property and recoatability.
The radically polymerizable composition of the present invention contains the polyester (meth) acrylate (a), (meth) acrylic monomer (B), polymerization inhibitor (C), and wax (D), but may contain other additives and the like as required.
For example, organic peroxides, curing accelerators, petroleum waxes, pigments, thixotropic agents, antioxidants, solvents, fillers, reinforcing materials, aggregates, flame retardants and the like can be used as the other additives, but from the viewpoint of further excellent curability, organic peroxides and curing accelerators are preferably used. These additives may be used alone or in combination of 2 or more.
For example, diacyl peroxide compounds, peroxy ester compounds, peroxy compounds, dialkyl peroxide compounds, peroxy ketone compounds, peroxy ketal compounds, alkyl perester compounds, peroxy carbonate compounds and the like can be used as the organic peroxides, and among them, diacyl peroxide compounds, peroxy compounds and peroxy ketone compounds are preferable from the viewpoint of the superiority of the coating film curability, and diacyl peroxide compounds and hydrogen peroxide compounds are more preferable. These compounds may be used alone or in combination of 2 or more.
For example, benzoyl peroxide, methylbenzoyl peroxide, acetyl peroxide, lauroyl peroxide and the like can be used as the diacyl peroxide compound, and among them, benzoyl peroxide is preferably used. These compounds may be used alone or in combination of 2 or more.
For example, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide and the like can be used as the hydrogen peroxide compound, and among them, cumene hydroperoxide and diisopropylbenzene hydroperoxide are preferably used, and cumene hydroperoxide is more preferably used, from the viewpoint of the superiority of the coating film curability. These compounds may be used alone or in combination of 2 or more.
The amount of the organic peroxide used is preferably 0.5 to 10 parts by mass, more preferably 1 to 6 parts by mass, based on 100 parts by mass of the total of the polyester (meth) acrylate resin (a) and the (meth) acrylic monomer (B), in terms of low-temperature curability.
The curing accelerator is preferably a substance having an effect of decomposing the organic peroxide by oxidation-reduction reaction to facilitate the generation of active radicals, and for example, cobalt salts of organic acids such as cobalt naphthenate and cobalt octoate can be used; organic acid salts such as zinc octoate, vanadium octoate, copper naphthenate, barium naphthenate, and the like; metal chelate compounds such as vanadium acetoacetate, cobalt acetoacetate, iron acetylacetonate, and the like; aniline, N-dimethylaniline, N-diethylaniline, 4- (N, N-dimethylamino) benzaldehyde, 4- [ N, N-bis (2-hydroxyethyl) amino ] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N-bis (hydroxyethyl) aniline, diethanolamin and the like, amine compounds such as N-substituted aniline, N-substituted-p-toluidine, 4- (N, N-substituted amino) benzaldehyde, p-toluidine, N-dimethyl-p-toluidine, ethylene oxide adducts of N, N-dimethyl-p-toluidine, N-bis (2-hydroxyethyl) -p-toluidine, N-bis (2-hydroxypropyl) -p-toluidine, and N-ethyl-m-toluidine. These compounds may be used alone or in combination of 2 or more. In view of excellent curability of the coating film, a cobalt salt of an organic acid and an amine compound are preferably used, and a combination of these compounds is more preferable. Cobalt naphthenate and cobalt octoate are preferable as the cobalt salt of the organic acid, and toluidine compound is preferable as the amine compound.
The amount of the curing accelerator used is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the total of the (meth) acrylate resin (a) and the (meth) acrylic monomer (B), in terms of low-temperature curability.
The radically polymerizable composition of the present invention has a low viscosity, a long pot life, and excellent low-temperature curability, and can provide a coating film having excellent low-temperature flexibility, and thus can be suitably used for various civil engineering and construction materials such as concrete protective materials, mortar binders, and crack repairing materials.
Examples
The present invention will be described in further detail with reference to the following examples. The average molecular weight is a value measured under the following GPC measurement conditions.
[ GPC measurement conditions ]
Measurement device: high speed GPC apparatus (HLC-8220 GPC, manufactured by TOSOH Co., ltd.);
chromatographic column: the following chromatographic columns manufactured by TOSOH Co., ltd were used in series.
"TSKgel G5000" (7.8 mmI.D..times.30 cm). Times.1 root;
"TSKgel G4000" (7.8 mmI.D..times.30 cm). Times.1 root;
"TSKgel G3000" (7.8 mmI.D..times.30 cm). Times.1 root;
"TSKgel G2000" (7.8 mmI.D..times.30 cm). Times.1 root;
a detector: RI (differential refractometer);
column temperature: 40 ℃;
eluent: tetrahydrofuran (THF);
flow rate: 1.0 mL/min;
injection amount: 100. Mu.L (tetrahydrofuran solution with sample concentration of 4 mg/mL);
standard sample: standard curves were made using monodisperse polystyrene as described below.
(monodisperse polystyrene)
"TSKgel Standard polystyrene A-500" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene A-1000" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene A-2500" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene A-5000" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene F-1" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene F-2" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene F-4" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene F-10" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene F-20" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene F-40" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene F-80" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene F-128" manufactured by TOSOH Co., ltd;
"TSKgel Standard polystyrene F-288" manufactured by TOSOH Co., ltd;
TOSOH Co., ltd. "TSKgel Standard polystyrene F-550".
( Synthesis example 1: synthesis of polyester (meth) acrylate (A-1) )
47 parts by mass of ethylene glycol, 150 parts by mass of triethylene glycol, 59 parts by mass of 1, 6-hexanediol, 59 parts by mass of succinic acid, 405 parts by mass of sebacic acid were charged into a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and the reaction was carried out at 220℃for 4 hours. After cooling to 100℃and adding 71 parts by mass of glycidyl methacrylate, the mixture was reacted at 130℃for 4 hours to obtain a polyester methacrylate (A-1) having a number average molecular weight of 3000, an acid value of 0.1, a polymerizable double bond concentration of 0.71mol/kg and an aromatic ring concentration of 0.00 mol/kg.
( Synthesis example 2: synthesis of polyester (meth) acrylate (A-2) )
To a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 318 parts by mass of diethylene glycol, 156 parts by mass of 1, 5-pentanediol, 26 parts by mass of neopentyl glycol, 472 parts by mass of succinic acid, 146 parts by mass of adipic acid, 0.3 part by mass of dibutyltin oxide, and 0.2 part by mass of methyl hydroquinone were added, and the mixture was reacted at 220℃for 4 hours. After cooling to 100℃and adding 71 parts by mass of glycidyl methacrylate, the mixture was reacted at 130℃for 4 hours to obtain polyester methacrylate (A-2) having a number average molecular weight of 4419, an acid value of 0.1, a polymerizable double bond concentration of 0.45mol/kg and an aromatic ring concentration of 0.00 mol/kg.
( Synthesis example 3: synthesis of polyester (meth) acrylate (A-3) )
To a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 225 parts by mass of 1, 4-butanediol, 234 parts by mass of neopentyl glycol, 295 parts by mass of 1, 6-hexanediol, 295 parts by mass of succinic acid, 265 parts by mass of adipic acid, 505 parts by mass of sebacic acid, 0.3 part by mass of dibutyltin oxide, and 0.2 part by mass of methyl hydroquinone were charged, and the reaction was carried out at 220℃for 4 hours. After cooling to 100℃and adding 71 parts by mass of glycidyl methacrylate, the mixture was reacted at 130℃for 4 hours to obtain a polyester methacrylate (A-3) having a number average molecular weight 7447, an acid value of 0.1, a polymerizable double bond concentration of 0.27mol/kg and an aromatic ring concentration of 0.00 mol/kg.
( Synthesis example 4: synthesis of polyester (meth) acrylate (A-4) )
To a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 414 parts by mass of triethylene glycol, 190 parts by mass of propylene glycol, 260 parts by mass of neopentyl glycol, 354 parts by mass of 1, 6-hexanediol, 74 parts by mass of phthalic anhydride, 76 parts by mass of tetrahydrophthalic anhydride, 65 parts by mass of itaconic acid, 1388 parts by mass of adipic acid, 0.3 part by mass of dibutyltin oxide, and 0.1 part by mass of methyl hydroquinone were charged, and the mixture was reacted at 220℃for 4 hours. After cooling to 130℃and adding 71 parts by mass of glycidyl methacrylate, the mixture was reacted at 130℃for 4 hours to obtain polyester methacrylate (A-4) having a number average molecular weight 10797, an acid value of 0.1, a polymerizable double bond concentration of 0.56mol/kg and an aromatic ring concentration of 0.74 mol/kg.
( Synthesis example 5: synthesis of polyester (meth) acrylate (A-5) )
225 parts by mass of 1, 4-butanediol, 234 parts by mass of 1, 5-pentanediol, 29 parts by mass of fumaric acid, 177 parts by mass of succinic acid, 438 parts by mass of adipic acid, 51 parts by mass of sebacic acid, 0.3 part by mass of dibutyltin oxide, and 0.2 part by mass of methyl hydroquinone were charged into a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, and reacted at 220℃for 4 hours. 124 parts by mass of glycidyl methacrylate was added thereto after cooling to 100℃and reacted at 130℃for 4 hours to obtain a polyester methacrylate (A-5) having a number average molecular weight of 4561, an acid value of 0.1, a polymerizable double bond concentration of 0.44mol/kg and an aromatic ring concentration of 0.00 mol/kg.
( Synthesis example 6: synthesis of polyester (meth) acrylate (A-6) )
To a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 159 parts by mass of diethylene glycol, 150 parts by mass of triethylene glycol, 45 parts by mass of 1, 4-butanediol, 207 parts by mass of 1, 6-hexanediol, 222 parts by mass of phthalic anhydride, 146 parts by mass of adipic acid, 506 parts by mass of sebacic acid, 0.3 part by mass of dibutyltin oxide, and 0.1 part by mass of methyl hydroquinone were added, and the mixture was reacted at 220℃for 4 hours. After cooling to 130℃and adding 50 parts by mass of glycidyl methacrylate, the mixture was reacted at 130℃for 4 hours to obtain a polyester methacrylate (A-6) having a number average molecular weight of 5683, an acid value of 0.1, a polymerizable double bond concentration of 0.40mol/kg and an aromatic ring concentration of 2.11 mol/kg.
( Synthesis example 7: synthesis of polyester (meth) acrylate (A-7) )
To a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 62 parts by mass of ethylene glycol, 375 parts by mass of triethylene glycol, 113 parts by mass of 1, 4-butanediol, 76 parts by mass of tetrahydrophthalic anhydride, 295 parts by mass of succinic acid, 292 parts by mass of adipic acid, 0.3 part by mass of dibutyltin oxide, and 0.1 part by mass of methyl hydroquinone were charged, and the reaction was carried out at 220℃for 4 hours. After cooling to 130℃and adding 190 parts by mass of glycidyl methacrylate, the mixture was reacted at 130℃for 4 hours to obtain polyester methacrylate (A-7) having a number average molecular weight of 4797, an acid value of 0.1, a polymerizable double bond concentration of 0.15mol/kg and an aromatic ring concentration of 0.00 mol/kg.
( Synthesis example 8: synthesis of polyester (meth) acrylate (A-8) )
47 parts by mass of ethylene glycol, 57 parts by mass of propylene glycol, 260 parts by mass of 1, 5-pentanediol, 120 parts by mass of 1, 9-nonanediol, 74 parts by mass of phthalic anhydride, 177 parts by mass of succinic acid, 607 parts by mass of sebacic acid, 0.3 part by mass of dibutyltin oxide, and 0.1 part by mass of methyl hydroquinone were charged into a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, and reacted at 220℃for 4 hours. After cooling to 130℃and adding 190 parts by mass of glycidyl methacrylate, the mixture was reacted at 130℃for 4 hours to obtain polyester methacrylate (A-8) having a number average molecular weight of 5311, an acid value of 0.1, a polymerizable double bond concentration of 0.39mol/kg and an aromatic ring concentration of 0.75 mol/kg.
( Synthesis example 9: synthesis of polyester (meth) acrylate (RA-1) )
To a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 400 parts by mass of propylene glycol, 573 parts by mass of neopentyl glycol, 245 parts by mass of maleic anhydride, 1242 parts by mass of adipic acid, 0.3 part by mass of dibutyltin oxide, and 0.1 part by mass of methyl hydroquinone were added, and the mixture was reacted at 220℃for 4 hours. 190 parts by mass of glycidyl methacrylate was added thereto and reacted at 130℃for 4 hours to obtain a polyester methacrylate (RA-1) having a number average molecular weight of 9349, an acid value of 0.1, a polymerizable double bond concentration of 2.35mol/kg and an aromatic ring concentration of 0.00 mol/kg.
( Synthesis example 10: synthesis of polyester (meth) acrylate (RA-2) )
To a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 106 parts by mass of diethylene glycol, 148 parts by mass of succinic acid, 0.3 part by mass of dibutyltin oxide, and 0.1 part by mass of methyl hydroquinone were added, and the mixture was reacted at 220℃for 4 hours. 190 parts by mass of glycidyl methacrylate was added thereto and reacted at 130℃for 4 hours to obtain a polyester methacrylate (RA-2) having a number average molecular weight 1227, an acid value of 0.1, a polymerizable double bond concentration of 1.63mol/kg and an aromatic ring concentration of 0.00 mol/kg.
( Synthesis example 11: synthesis of polyester (meth) acrylate (RA-3) )
To a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 175 parts by mass of diethylene glycol, 466 parts by mass of triethylene glycol, 741 parts by mass of phthalic anhydride, 0.3 parts by mass of dibutyltin oxide, and 0.1 parts by mass of methyl hydroquinone were added, and the mixture was reacted at 220℃for 4 hours. 190 parts by mass of glycidyl methacrylate was added thereto and reacted at 130℃for 4 hours to obtain a polyester methacrylate (RA-3) having a number average molecular weight of 5467, an acid value of 0.1, a polymerizable double bond concentration of 0.73mol/kg and an aromatic ring concentration of 7.31 mol/kg.
( Synthesis example 12: synthesis of urethane methacrylate (1) )
500 parts by mass of polypropylene glycol having a number average molecular weight of 1000 and 172 parts by mass of toluene diisocyanate were charged into a reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser, and reacted at 80℃for 2 hours under a nitrogen flow. After the NCO equivalent had reached 600, which is almost the theoretical equivalent value, it was cooled to 50 ℃. Under an air flow, 0.07 parts by mass of hydroquinone was added, 67 parts by mass of 2-hydroxyethyl methacrylate and 135 parts by mass of pentaerythritol triallyl ether were added, and the mixture was reacted at 90℃for 4 hours. 0.07 parts by mass of t-butylcatechol was added at a time when the NCO% was 0.1% or less, to obtain urethane methacrylate (1) having a number average molecular weight of 1775.
Synthesis example 13 Synthesis of epoxy acrylate (1)
To a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 1850 parts by mass of an epoxy resin (EPICLON 850, manufactured by DIC Co., ltd.), 860 parts by mass of acrylic acid, 1.36 parts by mass of hydroquinone, and 10.8 parts by mass of triethylamine were charged, and the temperature was raised to 120℃and the mixture was reacted for 10 hours at the same time to obtain an epoxy acrylate (1) having a number average molecular weight of 512 and an acid value of 3.5.
( Example 1: preparation and evaluation of radically polymerizable composition (1) )
To a light shielding container equipped with a stirrer, a reflux condenser and a thermometer, 75 parts by mass of the above polyester methacrylate (A-1), 20 parts by mass of methyl methacrylate (B-1), 5 parts by mass of 2-ethylhexyl methacrylate, 0.2 part by mass of paraffin wax 130℃F. And 0.4 part by mass of ethylene oxide 2 molar adduct of p-toluidine (PTD-2 EO), 0.5 part by mass of cobalt octoate (DIC "DINATE 208V" manufactured by DIC Co., ltd.), 0.3 part by mass of dibutylhydroxytoluene (BHT) and 2 parts by mass of organic peroxide (NYPER NS "manufactured by Niday oil Co., ltd.) were added to obtain a radical polymerizable composition (1).
[ evaluation of operability (viscosity) ]
75 parts by mass of the polyester (meth) acrylate (A-1) obtained in Synthesis example 1, 20 parts by mass of methyl methacrylate, and 5 parts by mass of 2-ethylhexyl methacrylate were mixed and dissolved, and the obtained resin composition was subjected to JISK6901:2008 "case of using a Brookfield viscometer with 5.5.1", the viscosity at 25℃was measured by using a type i or BM viscometer of Table 7, and the evaluation was performed by using the following criteria.
O: less than 250 mPas;
x: 250 mPas or more.
[ evaluation of operability (usable time) ]
The time required for the radically polymerizable composition (1) obtained above to lose fluidity at 5℃was measured and evaluated by the following criteria.
O: for more than 15 minutes;
x: less than 15 minutes.
[ evaluation of Low-temperature curability ]
The radical polymerizable tree obtained aboveFat composition (1) at 0.2kg/m 2 The amount of (2) was spread on a slate board by brush coating. The time (minutes) for which the finger touch measurement became non-tacky was evaluated at 5℃using the following criteria.
O: less than 60 minutes;
x: and 60 minutes or longer.
[ evaluation of softness ]
Using the radically polymerizable resin composition (1) obtained above, a test article was prepared in accordance with JIS K6251, and tensile properties were measured under the following measurement conditions using the test article.
The tensile strength was set at 5N/mm 2 The above cases were defined as O, and the ratio was less than 5N/mm 2 The case of (2) is set to x.
The tensile elongation was defined as "o" when 100% or more, and as "x" when less than 100%.
The using device comprises: "Universal tester AG-I" manufactured by Shimadzu corporation;
test speed (H, S): 500mm/min;
reticle pitch: 20mm;
measuring temperature: 23℃or-10 ℃.
( Examples 2 to 8: preparation and evaluation of radically polymerizable compositions (2) to (8) )
The radical polymerizable compositions (2) to (8) were prepared in the same manner as in example 1 except that the polyester methacrylate and the (meth) acrylic monomer used in example 1 were changed as shown in table 1 or table 2, and the respective physical properties were evaluated.
( Comparative examples 1 to 5: preparation and evaluation of radically polymerizable compositions (R1) to (R5) )
A radical polymerizable composition (R1) to (R5) was prepared in the same manner as in example 1 except that the polyester methacrylate and the (meth) acrylic monomer used in example 1 were changed as shown in table 3, and each physical property was evaluated.
The compositions and evaluation results of the radically polymerizable compositions (1) to (8) and (R1) to (R4) obtained in the above are shown in tables 1 to 2.
TABLE 1
TABLE 2
The shorthand notation in the table is as follows.
MMA: methyl methacrylate
2-EHA: 2-ethylhexyl acrylate
IBXA: isobornyl acrylate
DCPD EMA: dicyclopentenyloxyethyl methacrylate
1,9NDDA:1, 9-nonanediol diacrylate
n-BA: acrylic acid n-butyl ester
ACMO: acryl morpholines.
Confirmation: the radically polymerizable compositions of examples 1 to 8 have low viscosity, can be used for a long period of time, are excellent in low-temperature curability, and can give coating films excellent in low-temperature flexibility.
Comparative examples 1 and 2 are examples in which the concentration of the polymerizable double bond of the polyester (meth) acrylate (A) is more than 1mol/kg as the upper limit, and it was confirmed that the coating film flexibility at low temperature was insufficient.
Comparative example 3 shows that the aromatic ring concentration of the polyester (meth) acrylate (A) is more than 3mol/kg as the upper limit, and that the coating film flexibility at low temperature is insufficient.
Comparative example 4 is an example in which urethane acrylate was used instead of the polyester (meth) acrylate (a), and it was confirmed that the flexibility of the coating film at low temperature was insufficient.

Claims (3)

1. A radically polymerizable composition characterized by comprising,
comprises a polyester (meth) acrylate A having (meth) acryloyl groups at both ends, a (meth) acrylic monomer B, a polymerization inhibitor C, and a wax D,
the concentration of the polymerizable double bond of the polyester (meth) acrylate A is 0.1mol/kg to 1mol/kg, and the concentration of the aromatic ring is 3mol/kg or less.
2. The radically polymerizable composition according to claim 1, wherein,
the polymerization inhibitor C is 0.01 to 5 parts by mass relative to 100 parts by mass of the total of the polyester (meth) acrylate A and the (meth) acrylic monomer B.
3. The radically polymerizable composition according to claim 1, wherein,
the wax D is 0.01 to 3 parts by mass relative to 100 parts by mass of the total of the polyester (meth) acrylate a and the (meth) acrylic monomer B.
CN202310600181.0A 2022-06-30 2023-05-25 Radical polymerizable composition Pending CN117327435A (en)

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