Radical curable resin composition

Abstract

To provide a radical curable resin composition which is excellent in surface dryness and storage stability after curing while suppressing an emission amount of formaldehyde at the time of curing.SOLUTION: A radical curable resin composition contains a radical-polymerizable resin, and an allyl group-containing primary amine and / or an allyl group-containing secondary amine.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a radically curable resin composition. [Background technology]

[0002] BACKGROUND ART Radical-curable resin compositions containing radical-polymerizable resins such as unsaturated polyester resins have been used in the construction industry to finish building materials.

[0003] On the other hand, these radically curable resin compositions may generate formaldehyde during curing, which may pose a serious health hazard.

[0004] Therefore, as a radical curable resin composition, for example, a radical curable resin composition containing an unsaturated polyester resin and piperidine has been proposed (see, for example, Example 4 of Patent Document 1 below). In this radical curable resin composition, the amount of formaldehyde emitted is suppressed by the use of piperidine. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-282912 Summary of the Invention [Problem to be solved by the invention]

[0006] However, following a partial revision of the JIS to combat sick house syndrome in building materials, there is a demand for further reductions in formaldehyde emissions.

[0007] Furthermore, from the viewpoint of improving workability, the radical curable resin composition may be required to have a surface dryability after curing, and the radical curable resin composition may be required to have storage stability depending on the application and purpose.

[0008] The present invention provides a radically curable resin composition that suppresses the amount of formaldehyde emitted during curing, while exhibiting excellent surface drying properties and storage stability after curing. [Means for solving the problem]

[0009] The present invention [1] is a radically curable resin composition containing a radically polymerizable resin and an allyl group-containing primary amine and / or an allyl group-containing secondary amine.

[0010] The present invention [2] includes the radical-curable resin composition according to the above [1], which further contains a metal soap and an agent for imparting air-drying properties. [Effects of the Invention]

[0011] The radical-curable resin composition contains an allyl group-containing primary amine and / or an allyl group-containing secondary amine, which can reduce the amount of formaldehyde emitted during curing and improve the surface drying properties and storage stability after curing. DETAILED DESCRIPTION OF THE INVENTION

[0012] The radically curable resin composition of the present invention contains a radically polymerizable resin and an allyl group-containing primary amine and / or an allyl group-containing secondary amine.

[0013] <Radical polymerizable resin> Examples of radically polymerizable resins include unsaturated polyester resins, vinyl ester resins, and urethane (meth)acrylates. From the viewpoint of excellent physical properties (toughness, strength, durability, weather resistance, hot water resistance, and transparency), unsaturated polyester resins are preferred.

[0014] The unsaturated polyester resin contains an unsaturated polyester and a polymerizable monomer, that is, the unsaturated polyester resin is an unsaturated polyester resin composition containing an unsaturated polyester and a polymerizable monomer.

[0015] Unsaturated polyesters are condensation products of polybasic acids and polyhydric alcohols.

[0016] The polybasic acid includes a polybasic acid having an ethylenically unsaturated double bond as an essential component (hereinafter referred to as an ethylenically unsaturated bond-containing polybasic acid) and a polybasic acid not having an ethylenically unsaturated double bond as an optional component (hereinafter referred to as an ethylenically unsaturated bond-free polybasic acid).

[0017] Examples of ethylenically unsaturated bond-containing polybasic acids include ethylenically unsaturated aliphatic dibasic acids and anhydrides thereof, halides of ethylenically unsaturated aliphatic dibasic acids, and alkyl esters of ethylenically unsaturated aliphatic dibasic acids.

[0018] Examples of ethylenically unsaturated aliphatic dibasic acids include maleic acid, fumaric acid, itaconic acid, and dihydromuconic acid. Furthermore, examples of ethylenically unsaturated bond-containing polybasic acids include acid anhydrides derived from the above-mentioned ethylenically unsaturated aliphatic dibasic acids. Examples of acid anhydrides derived from ethylenically unsaturated aliphatic dibasic acids include maleic anhydride. Examples of ethylenically unsaturated bond-containing polybasic acids include maleic anhydride.

[0019] Examples of polybasic acids not containing ethylenically unsaturated bonds include saturated aliphatic polybasic acids, saturated alicyclic polybasic acids, aromatic polybasic acids, anhydrides of these acids, halides of these acids, and alkyl esters of these acids.

[0020] Examples of saturated aliphatic polybasic acids include saturated aliphatic dibasic acids.

[0021] Examples of saturated aliphatic dibasic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylsuccinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Saturated aliphatic polybasic acids include acid anhydrides derived from the above saturated aliphatic dibasic acids. Examples of acid anhydrides derived from saturated aliphatic dibasic acids include oxalic anhydride and succinic anhydride.

[0022] Examples of saturated alicyclic polybasic acids include saturated alicyclic dibasic acids.

[0023] Examples of saturated alicyclic dibasic acids include HET acid, 1,2-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid (cis- or trans-1,4-cyclohexanedicarboxylic acid or a mixture thereof). Examples of saturated alicyclic polybasic acids include acid anhydrides derived from the above saturated alicyclic dibasic acids. Examples of acid anhydrides derived from saturated alicyclic dibasic acids include HET acid anhydride.

[0024] Examples of aromatic polybasic acids include aromatic dibasic acids.

[0025] Examples of aromatic dibasic acids include phthalic acid (orthophthalic acid, isophthalic acid, terephthalic acid), trimellitic acid, and pyromellitic acid. Examples of aromatic polybasic acids include acid anhydrides derived from the above aromatic dibasic acids. Examples of acid anhydrides derived from aromatic dibasic acids include phthalic anhydride.

[0026] The polybasic acids can be used alone or in combination of two or more kinds.

[0027] When the polybasic acid includes an ethylenically unsaturated bond-containing polybasic acid and an ethylenically unsaturated bond-free polybasic acid, the blending ratio of the ethylenically unsaturated bond-containing polybasic acid to the polybasic acid is, for example, 10 mol% or more, preferably 20 mol% or more, and for example, 99 mol% or less, preferably 80 mol% or less.

[0028] Polyhydric alcohols include, for example, dihydric alcohols and trihydric alcohols.

[0029] Examples of dihydric alcohols include aliphatic diols, alicyclic diols, and aromatic diols. Examples of aliphatic diols include alkanediols and ether diols. Examples of alkanediols include ethylene glycol, propylene glycol (1,2- or 1,3-propanediol or a mixture thereof), butylene glycol (1,2-, 1,3-, or 1,4-butylene glycol or a mixture thereof), 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, and 3,3-dimethylolheptane. Examples of ether diols include diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of alicyclic diols include cyclohexanediol (1,2-, 1,3-, or 1,4-cyclohexanediol or a mixture thereof), cyclohexanedimethanol (1,2-, 1,3-, or 1,4-cyclohexanedimethanol or a mixture thereof), cyclohexanediethanol (1,2-, 1,3-, or 1,4-cyclohexanediethanol or a mixture thereof), and hydrogenated bisphenol A. Examples of aromatic diols include bisphenol A, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A.

[0030] Examples of trihydric alcohols include glycerin, trimethylolpropane, and triisopropanolamine.

[0031] The polyhydric alcohol is preferably a dihydric alcohol, more preferably an ether diol, and even more preferably diethylene glycol.

[0032] The polyhydric alcohols can be used alone or in combination of two or more kinds.

[0033] The unsaturated polyester can be obtained by polycondensation of a polybasic acid and a polyhydric alcohol.

[0034] To polycondense a polybasic acid and a polyhydric alcohol, the polybasic acid and the polyhydric alcohol are first mixed in the following equivalent ratio.

[0035] The equivalent ratio of polyhydric alcohol to polybasic acid (hydroxyl groups of polyhydric alcohol / carboxyl groups of polybasic acid) is, for example, 0.9 or more, preferably 0.95 or more, and for example, 1.2 or less, preferably 1.1 or less.

[0036] After mixing the polybasic acid and the polyhydric alcohol, the polybasic acid and the polyhydric alcohol are reacted with each other under normal pressure and under a nitrogen atmosphere while stirring. The reaction temperature is, for example, 150°C or higher, preferably 190°C or higher, and, for example, 250°C or lower, preferably 230°C or lower.

[0037] In the above reaction, a known solvent and a known reaction catalyst may be added as needed.

[0038] This gives an unsaturated polyester.

[0039] The acid value of the unsaturated polyester (measurement method: in accordance with JIS K6901 (2008)) is, for example, 5 mgKOH / g or more, preferably 10 mgKOH / g or more, and for example, less than 40 mgKOH / g, preferably 30 mgKOH / g or less.

[0040] The weight average molecular weight of the unsaturated polyester is, for example, 2,000 or more, preferably 4,000 or more, and for example, 25,000 or less, preferably 20,000 or less.

[0041] The weight average molecular weight is a weight average molecular weight calculated in terms of polystyrene by GPC (gel permeation chromatography), and can be determined by measuring the unsaturated polyester by GPC.

[0042] Examples of the polymerizable monomer include styrene-based monomers and (meth)acrylic acid ester-based monomers.

[0043] Examples of styrene-based monomers include styrene, vinyltoluene, t-butylstyrene, and chlorostyrene.

[0044] Examples of (meth)acrylic acid ester monomers include (meth)acrylic acid alkyl esters, (meth)acrylic acid allyl esters, ring-containing (meth)acrylic acid esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid alkoxyalkyl esters, (meth)acrylic acid aminoalkyl esters, (meth)acrylic acid fluoroalkyl esters, and polyfunctional (meth)acrylic acid esters. Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate. Examples of (meth)acrylic acid allyl esters include allyl (meth)acrylate. Examples of ring-containing (meth)acrylic acid esters include cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate. Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Examples of alkoxyalkyl (meth)acrylates include 2-methoxyethyl (meth)acrylate and 2-ethoxyethyl (meth)acrylate. Examples of aminoalkyl (meth)acrylates include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and chloride salts thereof. Examples of the fluoroalkyl (meth)acrylate include trifluoroethyl (meth)acrylate and heptadecafluorodecyl (meth)acrylate.Examples of polyfunctional (meth)acrylic acid esters include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0045] The polymerizable monomer is preferably a styrene-based monomer, more preferably styrene.

[0046] The polymerizable monomers can be used alone or in combination of two or more kinds.

[0047] The unsaturated polyester resin is prepared by dissolving the unsaturated polyester in the polymerizable monomer. In preparing the unsaturated polyester resin, the blending ratio of the polymerizable monomer is, for example, 50 parts by mass or more, preferably 60 parts by mass or more, and for example, 100 parts by mass or less, per 100 parts by mass of the unsaturated polyester.

[0048] <Allyl Group-Containing Primary Amines and Allyl Group-Containing Secondary Amines>

[0049] Examples of allyl group-containing primary amines include monoallylamine and 2-methylallylamine.

[0050] Examples of allyl group-containing secondary amines include diallylamine, N-allylbenzylamine, N-allyl-N-tert-butylamine, and N-allyldodecan-1-amine, with diallylamine being preferred.

[0051] Of the allyl group-containing primary amine and the allyl group-containing secondary amine, the allyl group-containing secondary amine is preferably selected. That is, the radical-curable resin composition preferably does not contain an allyl group-containing primary amine but contains an allyl group-containing secondary amine.

[0052] <Preparation of radically curable resin composition> The radically curable resin composition is prepared by mixing a radically polymerizable resin with an allyl group-containing primary amine and / or an allyl group-containing secondary amine.

[0053] The blending ratio of the allyl group-containing primary amine or the blending ratio of the allyl group-containing secondary amine is, relative to 100 parts by mass of the radical polymerizable resin, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 0.8 parts by mass or more, from the viewpoint of suppressing the amount of formaldehyde emitted during curing, and for example, 3 parts by mass or less, preferably 2 parts by mass or less, from the viewpoint of improving the surface dryness after curing.

[0054] [Metal soap] In the preparation, a metal soap may be added to improve the surface dryness after curing. In such a case, the radical curable resin composition contains the metal soap.

[0055] Examples of metal soaps include metal naphthenates and metal octylates. Examples of metal naphthenates include cobalt naphthenate, potassium naphthenate, calcium naphthenate, manganese naphthenate, and copper naphthenate. Examples of metal octylates include cobalt octylate, potassium octylate, calcium octylate, manganese octylate, and copper octylate, with metal octylates being preferred, and cobalt octylate being more preferred.

[0056] The mixing ratio of the metal soap relative to 100 parts by mass of the radical polymerizable resin is, for example, 0.1 parts by mass or more, preferably 0.4 parts by mass or more, and for example, 1 part by mass or less, preferably 0.6 parts by mass or less.

[0057] The metal soaps can be used alone or in combination of two or more types.

[0058] [Air-drying agent] In the preparation, an agent for imparting air-drying property may be blended in. In such a case, the radical-curable resin composition contains the agent for imparting air-drying property.

[0059] When the radical polymerizable resin cures to form a cured product, the air-drying property imparting agent precipitates on the surface of the cured product, forming a barrier layer against air. This prevents oxygen in the air from inhibiting the radical polymerization of the radical polymerizable resin. As a result, the surface dryness after curing can be improved. Furthermore, by blending the air-drying property imparting agent together with the metal soap described above, the surface dryness after curing can be further improved.

[0060] Air-drying agents include, for example, waxes and allyl compounds.

[0061] Waxes include, for example, natural waxes and synthetic waxes.

[0062] Examples of natural waxes include vegetable waxes, animal waxes, mineral waxes, and petroleum waxes. Examples of vegetable waxes include candelilla wax, carnauba wax, rice wax, Japan wax, and jojoba oil. Examples of animal waxes include beeswax and lanolin. Examples of mineral waxes include montan wax, ozokerite, and ceresin. Examples of petroleum waxes include paraffin wax, microcrystalline wax, and petrolatum.

[0063] The synthetic wax may be, for example, a synthetic hydrocarbon wax.

[0064] The wax is preferably a natural wax, more preferably paraffin wax.

[0065] Examples of allyl compounds include the allyl group-containing primary amines and allyl group-containing secondary amines described above. Use of such allyl compounds can suppress the amount of formaldehyde emitted during curing and improve the surface dryness after curing.

[0066] In addition to the allyl compounds mentioned above, examples of the allyl compound include triallylamine, N,N-dimethylallylamine, allyl acetate, allyl ether, allyl glycidyl ether, ethylene glycol monoallyl ether, allyl methacrylate, allyl alcohol, diallyldimethylammonium hydrochloride, 2-allylphenol, allylbenzene, diallyl isophthalate, diallyl phthalate, diallyl maleate, and diallyl adipate, with triallylamine and diallyl phthalate being preferred. Use of such allyl compounds can improve the surface dryness after curing.

[0067] The mixing ratio of the air-drying property imparting agent relative to 100 parts by mass of the radical polymerizable resin is, for example, 0.01 parts by mass or more, preferably 0.3 parts by mass or more, and for example, 1 part by mass or less, preferably 0.6 parts by mass or less.

[0068] The air-drying property imparting agents can be used alone or in combination of two or more.

[0069] [β-diketone] In the preparation, a β-diketone is preferably blended in. That is, the radical curable resin composition preferably contains a β-diketone.

[0070] The β-diketone is a co-accelerator for accelerating the curing of the radical polymerizable resin.

[0071] Examples of β-diketones include compounds represented by the following general formulas (1) to (6). [ka] In the above formula (1), R1 represents an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms. R2 represents an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a substituted alkoxy group.

[0072] Examples of the compound represented by the general formula (1) include acetylacetone (in the general formula (1), R1 represents a methyl group and R2 represents a methyl group), methyl acetoacetate (in the general formula (1), R1 represents a methyl group and R2 represents a methoxy group), and ethyl acetoacetate (in the general formula (1), R1 represents a methyl group and R2 represents an ethoxy group), and preferably acetylacetone and ethyl acetoacetate. [ka] In the above formula (2), R1 has the same meaning as in the above formula (1), and n represents an integer of 1 or more and 5 or less.

[0073] An example of the compound represented by the general formula (2) above is α-acetyl-γ-butyrolactone (in the general formula (2) above, R1 represents a methyl group, and n represents 2). [ka] In the formula (3), R1 has the same meaning as in the formula (1), and n has the same meaning as in the formula (2). [ka] In the above formula (4), R1 has the same meaning as in the above formula (1). R3 and R4 have the same meaning as R1. R1, R3, and R4 may be the same or different.

[0074] An example of the compound represented by the general formula (4) above is N,N-dimethylacetoacetamide (in the general formula (4) above, R1, R3 and R4 represent methyl groups). [ka] In the formula (5), R1 has the same meaning as in the formula (1), and m represents an integer of 2 or more and 7 or less. [ka] In the above formula (6), R1 has the same meaning as in the above formula (1).

[0075] Preferred examples of the β-diketone include the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (4).

[0076] The blending ratio of the β-diketone is, relative to 100 parts by mass of the radical polymerizable resin, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, from the viewpoint of suppressing the amount of formaldehyde emitted during curing and sufficiently shortening the cure start time, and for example, 1 part by mass or less, from the viewpoint of improving storage stability and suppressing an excessively fast curing rate.

[0077] The β-diketones can be used alone or in combination of two or more kinds.

[0078] [Polymerization inhibitor] In the preparation, a polymerization inhibitor may be blended in. In such a case, the radical curable resin composition contains the polymerization inhibitor.

[0079] The polymerization inhibitor is added to adjust the pot life and the curing reaction.

[0080] Examples of polymerization inhibitors include hydroquinone compounds, benzoquinone compounds, catechol compounds, phenol compounds, and N-oxyl compounds. Examples of hydroquinone compounds include hydroquinone, methylhydroquinone, and mono-t-butylhydroquinone. Examples of benzoquinone compounds include p-benzoquinone and methyl-p-benzoquinone. Examples of catechol compounds include t-butylcatechol. Examples of phenol compounds include 2,6-di-t-butyl-4-methylphenol and 4-methoxyphenol.Examples of N-oxyl compounds include 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 4-hydroxy-2,2,6,6-tetrapiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate, and 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoate. 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-4-t-butylbenzoate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-oxyl-2,2 ,6,6-tetramethylpiperidin-4-yl) n-butyl malonate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N,N'-bis(1-oxyl-2 ,2,6,6-tetramethylpiperidin-4-yl)adipamide, N-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)caprolactam, N-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)dodecylsuccinimide, 2,4,6-tris-[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-s-triazine, and 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one.

[0081] As the polymerization inhibitor, preferably, a hydroquinone compound is used, and more preferably, mono-t-butylhydroquinone is used.

[0082] The mixing ratio of the polymerization inhibitor relative to 100 parts by mass of the radical polymerizable resin is, for example, 0.001 parts by mass or more and, for example, 0.5 parts by mass or less.

[0083] The polymerization inhibitors can be used alone or in combination of two or more.

[0084] [Hardening agent] In the preparation, a curing agent may be blended in. In such a case, the radical curable resin composition contains the curing agent.

[0085] The curing agent may, for example, be an organic peroxide. Examples of organic peroxides include acetylacetone peroxide, methyl ethyl ketone peroxide, diethyl ketone peroxide, methyl propyl ketone peroxide, methyl isobutyl ketone peroxide, methyl acetoacetate peroxide, ethyl acetoacetate peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, cumene peroxide, benzoyl peroxide, t-butyl isopropyl peroxycarbonate, 1,1-dibutylperoxy-3,3,5-trimethylcyclohexanone, t-butylperoxy-2-ethylhexanoate, amylperoxy-p-2-ethylhexanoate, 2-ethylhexylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, and t-hexylperoxybenzoate, and preferably methyl ethyl ketone peroxide.

[0086] The mixing ratio of the curing agent relative to 100 parts by mass of the radical polymerizable resin is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 5 parts by mass or less, preferably 2 parts by mass or less.

[0087] The curing agents can be used alone or in combination of two or more.

[0088] [Additives] In the preparation, additives may be added in appropriate proportions as needed, such as low-profile agents, wetting and dispersing agents, release agents, colorants, flame retardants, fillers, thickeners, patterning agents, antibacterial agents, hydrophilic agents, photocatalysts, ultraviolet absorbers, ultraviolet stabilizers, anti-separation agents, silane coupling agents, antistatic agents, thixotropic agents, thixotropic stabilizers, and polymerization accelerators.

[0089] In this way, a radical curable resin composition is prepared.

[0090] <Action and effect> The radically curable resin composition contains an allyl group-containing primary amine and / or an allyl group-containing secondary amine, which can reduce the amount of formaldehyde emitted during curing.

[0091] Specifically, the radical curable resin composition may generate formaldehyde when cured.

[0092] On the other hand, the radical-curable resin composition contains an allyl group-containing primary amine and / or an allyl group-containing secondary amine, and therefore the amount of formaldehyde emitted can be suppressed.

[0093] Furthermore, the radical-curable resin composition contains an allyl group-containing primary amine and / or an allyl group-containing secondary amine, which can improve the surface drying property and storage stability after curing. Furthermore, primary amines that do not contain an allyl group (allyl group-free primary amines) and / or secondary amines that do not contain an allyl group (allyl group-free secondary amines) can also suppress the amount of formaldehyde emitted, but they are inferior in curability to allyl group-containing primary amines and / or allyl group-containing secondary amines, and also have reduced drying property and storage stability.

[0094] Such radical-curable resin compositions can suppress the amount of formaldehyde emitted during curing while improving the surface drying properties and storage stability after curing, and therefore can be suitably used for, for example, plastic molded products including films and sheets, solar cells, polymer batteries, home appliances, steel products, large structures, automobiles, ships, building materials, woodworking, guard fences, signs, machinery, tools, industrial equipment, glass products, primers, intermediate coats, and top coats for various industrial products, artificial marble, and decorative laminates, and can particularly be suitably used for finishing building materials in the construction field.Furthermore, fiber-reinforced plastics can be produced by blending reinforcing fibers (e.g., glass fibers) with the radical-curable resin compositions. [Example]

[0095] Specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values ​​(numeric values ​​defined as "not more than" or "less than") or lower limit values ​​(numeric values ​​defined as "not less than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Description of the Invention." Furthermore, unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0096] <Preparation of Unsaturated Polyester Resin> Synthesis Example 1 (Preparation of Unsaturated Polyester Resin) A four-neck flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser was charged with 1,120 parts by weight of diethylene glycol and 747 parts by weight of terephthalic acid. While blowing in nitrogen gas, the mixture was subjected to a condensation reaction at 210°C until the acid value reached 3. The mixture was cooled to 150°C, and 518 parts by weight of phthalic anhydride and 196 parts by weight of maleic anhydride were added. The mixture was then heated to 210°C and subjected to a condensation reaction for 15 hours, yielding an unsaturated polyester with a weight-average molecular weight of 4,500. To 60 parts by weight of this unsaturated polyester, 40 parts by weight of styrene and 0.005 parts of mono-t-butylhydroquinone were added to obtain an unsaturated polyester resin with an acid value of 10 mgKOH / g and a viscosity of 0.6 Pa s.

[0097] <Preparation of radically curable resin composition> Example 1 The following components were added in order and mixed to prepare a radically curable resin composition. Unsaturated polyester resin: 100 parts by mass of the unsaturated polyester resin of Synthesis Example 1 Allyl group-containing secondary amine: diallylamine 0.1 parts by mass β-diketone: N,N-dimethylacetoacetamide 0.5 parts by mass Metal soap: 0.5 parts by mass of cobalt octylate (mineral spirit solution with 8% cobalt content) Polymerization inhibitor: mono-t-butylhydroquinone 0.15 parts by mass Air-drying agent: 0.5 parts by mass of paraffin wax (mineral oil solution containing 10% by mass of paraffin wax, product name "BYK-S 750 N", manufactured by BYK-Chemie) Hardener: 1 part by mass of methyl ethyl ketone peroxide (dimethyl phthalate solution containing 55% by mass of methyl ethyl ketone peroxide, product name "Kayamec M", manufactured by Kayaku Nouryon Co., Ltd.)

[0098] Example 2 ~4, Example 6 ~ Example 17 and Comparative Example 1 ~ Comparative Example 1 4 A radically curable resin composition was prepared according to the same procedure as in Example 1. However, the compounding recipe was changed according to the descriptions in Tables 1 and 2.

[0099] <Evaluation> [Gelation time at room temperature] The room temperature gel time of each radically curable resin composition of each Example and Comparative Example was measured in accordance with the room temperature gel time (Method A) described in JIS K6901 (1999). The results are shown in Tables 1 and 2.

[0100] [Formaldehyde emission amount] A silicone guide was placed on one side of a 170 mm long x 170 mm wide glass plate, and 50.0 g of the radical curable resin composition of each Example and Comparative Example was spread evenly over the entire inside of the guide using a brush or the like to prepare a cured product measuring 150 mm long x 150 mm wide x approximately 2.0 mm thick, which was then aged for 7 days at 23°C.

[0101] Using this cured product, a formaldehyde emission test was conducted in accordance with JIS K 5601-4-1 (revised in 2012). The results are shown in Tables 1 and 2. The formaldehyde emission was also evaluated based on the following criteria. The results are shown in Tables 1 and 2. (standard) ◎: The amount of formaldehyde emitted was less than 0.06 mg / L. ○: The amount of formaldehyde emitted was 0.06 mg / L or more and less than 0.12 mg / L. ×: The amount of formaldehyde emitted was 0.12 mg / L or more.

[0102] [Drying property (surface drying property)] A silicone guide was placed on one side of a glass plate measuring 170 mm in length and 170 mm in width, and 50.0 g of the radical curable resin composition of each Example and Comparative Example was spread evenly over the entire inside of the guide using a brush or the like to prepare a cured product measuring 150 mm in length, 150 mm in width, and approximately 2.0 mm thick. This was then aged for 7 days at 23°C.

[0103] Then, 2 hours, 4 hours, and 8 hours after the addition of the curing agent, the surface of the cured product was checked with a finger, and its drying property (surface drying property) was evaluated based on the following criteria. (standard) ⊚: No stickiness was observed after 2 hours. ◯: Stickiness was observed after 2 hours, but no stickiness was observed after 4 hours. △: Stickiness was observed after 2 hours and 4 hours, but no stickiness was observed after 8 hours. ×: Stickiness was observed after 2 hours, 4 hours, and 8 hours.

[0104] [Storage stability] For each example and comparative example, a radically curable resin composition containing no curing agent was prepared. Then, this radically curable resin composition was filled to 95% capacity in a 500 ml oil can with a sealable lid, and the can was stored in a 50°C environment with the lid closed.

[0105] The time (unit: days) until the radical curable resin composition gelled was recorded, and the storage stability was evaluated based on the following criteria. The results are shown in Tables 1 and 2. ⊚: No gelation occurred after 14 days or more. ◯: Gelation occurred within 7 days or more and less than 14 days. △: Gelation occurred in 3 days or more but less than 7 days. ×: Gelation occurred within 3 days.

[0106] [Table 1]

[0107] [Table 2]

Claims

1. A composition comprising a radical polymerizable resin and an allyl group-containing secondary amine, Does not contain allyl group-containing primary amines, the radical polymerizable resin comprises an unsaturated polyester resin, The radical-curable resin composition of claim 1, wherein the allyl group-containing secondary amine is present in an amount of 3 parts by mass or less relative to 100 parts by mass of the radical-polymerizable resin.

2. Further, the composition contains a metal soap and an air-drying agent, The radical curable resin composition according to claim 1, wherein the air-drying agent is a wax.

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