Classifications

• • 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
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G

Definitions

• the present invention relates to a radically polymerizable composition.
• a radically polymerizable resin composition that contains an air-drying unsaturated resin, a radically polymerizable monomer, and a cyclodextrin derivative (see, for example, Patent Document 1).
• this radically polymerizable resin composition has the problem of insufficient curing in thin films.
• the problem that the present invention aims to solve is to provide a radically polymerizable composition that has low viscosity, excellent thin film curing properties, and can produce a coating film that has excellent wet surface adhesive strength.
• a radically polymerizable composition containing a specific radically polymerizable resin, a (meth)acrylic monomer, a cyclodextrin derivative, and a wax can produce a coating film that has low viscosity, excellent thin film curing properties, and excellent wet surface adhesive strength, thus completing the present invention.
• the present invention provides a radical polymerizable composition containing a radical polymerizable resin (A) containing a polyester (meth)acrylate (A1), a (meth)acrylic monomer (B), a cyclodextrin derivative (C), and a wax (D), wherein the polyester (meth)acrylate (A1) has a cyclic unsaturated aliphatic polybasic acid as an essential raw material, and the amount of the (meth)acrylic monomer (B) is 120 to 1,000 parts by mass per 100 parts by mass of the radical polymerizable resin (A).
• the radically polymerizable composition of the present invention has low viscosity, excellent thin film curing properties, and produces a coating film with excellent wet surface adhesive strength, making it suitable for use as a primer for concrete and other civil engineering and construction applications.
• the radical polymerizable composition of the present invention is a radical polymerizable composition containing a radical polymerizable resin (A) containing a polyester (meth)acrylate (A1), a (meth)acrylic monomer (B), a cyclodextrin derivative (C), and a wax (D), in which the polyester (meth)acrylate (A1) has a cyclic unsaturated aliphatic polybasic acid as an essential raw material, and the (meth)acrylic monomer (B) is 120 to 1,000 parts by mass per 100 parts by mass of the radical polymerizable resin (A).
• (meth)acrylate refers to either or both of methacrylate and acrylate
• (meth)acrylic monomer refers to either or both of acrylic monomer and methacrylic monomer
• the polyester (meth)acrylate (A1) can be obtained, for example, by reacting an unsaturated polyester (a1) having carboxyl groups at both ends with glycidyl (meth)acrylate.
• the unsaturated polyester (a1) is obtained by an esterification reaction between a polybasic acid raw material containing a cyclic unsaturated aliphatic polybasic acid and a polyhydric alcohol, but other polybasic acids such as aromatic dibasic acids and saturated dibasic acids can also be used as the polybasic acid raw material.
• Examples of the cyclic unsaturated aliphatic polybasic acid that can be used include tetrahydrophthalic acid, tetrahydrophthalic anhydride, tetrahydromethylphthalic acid, tetrahydromethylphthalic anhydride, endomethylenetetrahydrophthalic acid, endomethylenetetrahydrophthalic anhydride, ⁇ -terpinene-maleic anhydride adduct, trans-piperylene-maleic anhydride adduct, etc.
• polybasic acids examples include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, furandicarboxylic acid, 1,12-dodecane diacid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4'-biphenyldicarboxylic acid, and dialkyl esters thereof.
• the amount of cyclic unsaturated aliphatic polybasic acid in the polybasic acid raw material is preferably 30 to 80 mass%, more preferably 40 to 70 mass%, since this further improves thin film curing properties.
• the polyhydric alcohols include, 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, and alkylene oxide adducts of bisphenol A.
• 1,2,3,4-tetrahydroxybutane glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, 2,7-decalin glycol, etc. can be used.
• These polyhydric alcohols may be used alone or in combination of two or more.
• the radical polymerizable resin (A) contains polyester (meth)acrylate (A1) as an essential component, but other resins such as epoxy (meth)acrylate (A2), urethane (meth)acrylate (A3), and unsaturated polyester (A4) can also be used. These radical polymerizable resins can be used alone or in combination of two or more kinds.
• the epoxy (meth)acrylate (A1) may be, for example, one obtained by reacting a bisphenol-type epoxy compound or a mixture of a bisphenol-type epoxy compound and a novolac-type epoxy compound with an unsaturated monobasic acid by a conventionally known method.
• the bisphenol type epoxy compound may be, for example, a glycidyl ether type epoxy compound having two or more epoxy groups in one molecule obtained by reacting epichlorohydrin with bisphenol A or bisphenol F, a dimethylglycidyl ether type epoxy compound obtained by reacting methylepichlorohydrin with bisphenol A or bisphenol F, or an epoxy compound obtained by reacting an alkylene oxide adduct of bisphenol A with epichlorohydrin or methylepichlorohydrin.
• These epoxy compounds may be used alone or in combination of two or more.
• novolac type epoxy compound for example, an epoxy compound obtained by reacting phenol novolac or cresol novolac with epichlorohydrin or methyl epichlorohydrin can be used. These epoxy compounds may be used alone or in combination of two or more kinds.
• unsaturated monobasic acid for example, (meth)acrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, monobutene maleate, sorbic acid, mono(2-ethylhexyl) maleate, etc. can be used. These unsaturated monobasic acids can be used alone or in combination of two or more kinds.
• the urethane (meth)acrylate (A2) may be, for example, one obtained by reacting a polyol, a polyisocyanate, and a (meth)acrylic compound having a hydroxyl group or an isocyanate group by a conventionally known method.
• polyester polyol for example, polyester polyol, polycarbonate polyol, polyether polyol, acrylic polyol, caprolactone polyol, butadiene polyol, etc. can be used. These polyols can be used alone or in combination of two or more kinds.
• polyisocyanate examples include aromatic diisocyanates such as phenylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; and aromatic polyisocyanates such as xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polyphenylene polymethylene polyisocyanate, formalin condensates of methylene diphenyl diiso
• Examples of the (meth)acrylic compound having a hydroxyl group include (meth)acrylic acid alkyl esters having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; polyethylene glycol monoacrylate, and polypropylene glycol monoacrylate. These compounds may be used alone or in combination of two or more.
• Examples of the (meth)acrylic compound having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate. These compounds may be used alone or in combination of two or more.
• the unsaturated polyester resin (A3) is a product of reacting a polybasic acid, including an ⁇ , ⁇ -unsaturated dibasic acid, with a polyhydric alcohol, but it is preferable to use a dicyclopentadiene compound, as this improves curing properties.
• the polybasic acid and the polyhydric alcohol can be, for example, those mentioned above as raw materials for the unsaturated polyester (a1).
• dicyclopentadiene compounds examples include dicyclopentadiene, hydroxydicyclopentadiene, and dicyclopentadiene maleate (monoester of dicyclopentadiene and maleic acid).
• the number average molecular weight of the radical polymerizable resin (A) is preferably 500 to 10,000, more preferably 500 to 8,000, and even more preferably 500 to 6,000, because this provides a better balance between low viscosity, thin film curing properties, and wet surface adhesive strength.
• the average molecular weight in this invention is a value measured by gel permeation chromatography (GPC).
• the (meth)acrylic monomer (B) is not particularly limited as long as it can dilute the resin viscosity, but examples thereof include 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, and the like.
• aliphatic (meth)acrylic monomers such as acrylate, 3-methylbutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, neopentyl (meth)acrylate, hexadecyl (meth)acrylate, and isoamyl (meth)acrylate;
• (meth)acrylic monomers having an alicyclic structure such as isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; acrylic monomers; (meth)acrylic monomers having an ether group such as 3-methoxybutyl (me
• the amount of the (meth)acrylic monomer (B) used is 120 to 1,000 parts by mass per 100 parts by mass of the radical polymerizable resin (A), but 150 to 800 parts by mass is more preferable, and 200 to 600 parts by mass is even more preferable, as this provides a better balance between low viscosity, thin film curing properties, and wet surface adhesive strength.
• cyclodextrin derivative (C) for example, cyclodextrin; alkylated cyclodextrin, acetylated cyclodextrin, hydroxyalkylated cyclodextrin, and other cyclodextrins in which the hydrogen atoms of the hydroxyl groups of the glucose units of the cyclodextrin are replaced with other functional groups can be used.
• any of ⁇ -cyclodextrin consisting of six glucose units, ⁇ -cyclodextrin consisting of seven glucose units, and ⁇ -cyclodextrin consisting of eight glucose units can be used.
• These cyclodextrin derivatives (C) may be used alone or in combination of two or more kinds. Among these, hydroxypropylated ⁇ -cyclodextrin and methylated ⁇ -cyclodextrin are preferred because of their excellent solubility in resins.
• the content of the cyclodextrin derivative (C) is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the radical polymerizable resin (A) because this further improves the wet surface adhesive strength.
• the wax (D) prevents inhibition of curing by oxygen, and examples thereof include paraffin wax, microcrystalline wax, and petrolactam. From the viewpoint of compatibility with the radical polymerizable resin (A) and the (meth)acrylic monomer (B) and thin film curing properties, it is preferable to use paraffin wax.
• the melting point of the wax (D) is preferably 40 to 75°C, more preferably 45 to 60°C, from the viewpoint of compatibility with the radical polymerizable resin (A) and the (meth)acrylic monomer (B) and thin film curing properties.
• the melting point of the wax (D) is the melting point measured based on JIS K2235.
• the content of the wax (D) is preferably 0.01 to 3 parts by mass, and more preferably 0.02 to 0.5 parts by mass, per 100 parts by mass of the total of the radical polymerizable resin (A) and the (meth)acrylic monomer (B), from the viewpoint of thin film thermosetting property and recoatability.
• the radically polymerizable composition of the present invention contains polyester (A), (meth)acrylic monomer (B), polymerization inhibitor (C), and wax (D), and may contain other additives, etc., as necessary.
• the other additives that can be used include, for example, organic peroxides, curing accelerators, polymerization inhibitors, pigments, thixotropic agents, antioxidants, solvents, fillers, reinforcing materials, aggregates, and flame retardants.
• organic peroxides and curing accelerators because they have better curing properties.
• These additives may be used alone or in combination of two or more kinds.
• organic peroxide for example, diacyl peroxide compounds, peroxyester compounds, hydroperoxide compounds, dialkyl peroxide compounds, ketone peroxide compounds, peroxyketal compounds, alkyl perester compounds, percarbonate compounds, etc. can be used, but among these, from the viewpoint of superiority in coating film curing properties, it is preferable to use diacyl peroxide compounds, hydroperoxide compounds, and ketone peroxide compounds, and it is more preferable to use diacyl peroxide compounds and hydroperoxide compounds. These compounds may be used alone or in combination of two or more kinds.
• diacyl peroxide compound for example, benzoyl peroxide, toluyl peroxide, acetyl peroxide, lauroyl peroxide, etc. can be used, and among these, it is preferable to use benzoyl peroxide. These compounds may be used alone or in combination of two or more kinds.
• hydroperoxide compound for example, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, etc. can be used, but among these, cumene hydroperoxide and diisopropylbenzene hydroperoxide are preferably used, and cumene hydroperoxide is more preferably used, in view of the superiority of the coating film curing properties. These compounds may be used alone or in combination of two or more kinds.
• the amount of the organic peroxide used is preferably 0.5 to 10 parts by mass, and more preferably 1 to 6 parts by mass, per 100 parts by mass of the polyester (A) and the (meth)acrylic monomer (B) in total, from the viewpoint of low-temperature curing properties.
• the curing accelerator is preferably a substance that decomposes the organic peroxide through a redox reaction and facilitates the generation of active radicals
• examples of such substances include cobalt salts of organic acids such as cobalt naphthenate and cobalt octoate; organic acid salts such as zinc octoate, vanadium octoate, copper naphthenate, and barium naphthenate; metal chelate compounds such as vanadium acetylacetate, cobalt acetylacetate, and iron acetylacetonate; aniline, N,N-dimethylaniline, N,N-diethylaniline, 4-(N,N-dimethylamino)benzaldehyde, 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, 4-(N-methyl-N-hydroxyethyl)benzaldehyde, and the like.
• N,N-substituted anilines such as N,N-substituted p-toluidine, 4-(N,N-substituted amino)benzaldehyde, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylimorpholine, piperidine, N,N-bis(hydroxyethyl)aniline, and diethanolaniline, amine compounds such as N,N-substituted p-toluidine, 4-(N,N-substituted amino)benzaldehyde, p-toluidine, N,N-dimethyl-p-toluidine, ethylene oxide adduct of N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxypropyl)-p-toluidine, and N-ethy
• cobalt salts of an organic acid or an amine compound may be used alone or in combination of two or more.
• cobalt salt of an organic acid cobalt naphthenate and cobalt octylate are preferred, and as the amine compound, a toluidine compound is preferred.
• the amount of the curing accelerator used is preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 2 parts by mass, per 100 parts by mass of the polyester (A) and the (meth)acrylic monomer (B) in total, from the viewpoint of low-temperature curing properties.
• polymerization inhibitor examples include dibutylhydroxytoluene, hydroquinone, trimethylhydroquinone, 4-t-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, and copper chloride, with dibutylhydroxytoluene being preferred as it provides a better balance between pot life and curability.
• These polymerization inhibitors can be used alone or in combination of two or more.
• the radically polymerizable composition of the present invention has low viscosity, excellent thin film curing properties, and produces a coating film with excellent wet surface adhesive strength, making it suitable for use as a primer for concrete and other civil engineering and construction applications.
• the concrete primer of the present invention can be used as a primer for concrete such as cement concrete, asphalt concrete, mortar concrete, resin concrete, water-permeable concrete, and ALC (Autoclaved Lightweight Aerated Concrete) boards.
• concrete such as cement concrete, asphalt concrete, mortar concrete, resin concrete, water-permeable concrete, and ALC (Autoclaved Lightweight Aerated Concrete) boards.
• the concrete primer of the present invention has low viscosity, excellent thin-film curing properties, and produces a coating film with excellent wet surface adhesive strength, making it suitable for use as a primer for various types of concrete.
• Measurement device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used, connected in series. "TSKgel G5000” (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mm I.D.
• polyester (meth)acrylate (A1-1) having a number average molecular weight of 5,400.
• HEMA 2-hydroxyethyl methacrylate
• Example 1 Preparation and evaluation of radically polymerizable composition (1)
• a light-shielding container equipped with a stirrer, a reflux condenser, and a thermometer was charged with 5 parts by mass of polyester (meth)acrylate (A1-1), 5 parts by mass of epoxy methacrylate (A2-1), 10 parts by mass of unsaturated polyester resin (A4-1), 25 parts by mass of methyl methacrylate, 5 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, 25 parts by mass of dicyclopentenyloxyethyl methacrylate, 5 parts by mass of phenoxyethyl methacrylate, 5 parts by mass of diethylene glycol dimethacrylate, 5 parts by mass of EO-modified bisphenol A dimethacrylate, 0.5 parts by mass of methylated ⁇ -cyclodextrin, and 0.1 parts by mass of 130° F.
• this radical polymerizable composition (1) 0.5 parts by mass of 6% cobalt octylate, 0.2 parts by mass of N,N-bis(2-hydroxyethyl)-p-toluidine, and 0.2 parts by mass of N,N-dimethyl-p-toluidine were added as a curing accelerator and mixed to obtain a composition for evaluation (1).
• Examples 2 to 4 Preparation and evaluation of radically polymerizable compositions (2) to (4)
• Radical polymerizable compositions (2) to (4) were prepared in the same manner as in Example 1, except that the formulation in Example 1 was changed as shown in Table 1, and the physical properties were evaluated.
• Radical polymerizable compositions (R1) to (R3) were prepared in the same manner as in Example 1, except that the formulation in Example 1 was changed as shown in Table 1, and the physical properties were evaluated.
• compositions of the radically polymerizable compositions (1) to (4) obtained above are shown in Table 1.
• compositions of the radically polymerizable compositions (R1) to (R3) obtained above are shown in Table 2.
• MMA methyl methacrylate
• 2-EHA 2-ethylhexyl acrylate
• HEMA 2-hydroxyethyl methacrylate
• ACMO acryloylmorpholine
• DCPDOEMA dicyclopentenyloxyethyl methacrylate
• PheOEMA phenoxyethyl methacrylate
• DEGDMA diethylene glycol dimethacrylate
• NPGDMA neopentyl glycol dimethacrylate
• Comparative Example 1 is an example in which a cyclic unsaturated aliphatic polybasic acid is not used as a raw material for polyester (meth)acrylate (A1), and it was confirmed that the thin film curing property was insufficient.
• Comparative Example 2 is an example in which the amount of (meth)acrylic monomer (B) used relative to the radical polymerizable resin (A) is below the lower limit of the present invention, but it was confirmed that the viscosity was too high.
• Comparative Example 3 is an example in which the cyclodextrin derivative (C) and wax (D) are not used, and it was confirmed that the wet surface adhesion and thin film curing properties were insufficient.

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• 2023
  • 2023-11-30 JP JP2024565719A patent/JPWO2024135270A1/ja active Pending
  • 2023-11-30 WO PCT/JP2023/042850 patent/WO2024135270A1/ja active Application Filing

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