Toner-containing radically polymerizable resin composition

Abstract

To provide a toner-containing radical-polymerizable resin composition which has high curability on a surface.SOLUTION: A toner-containing radical-polymerizable resin composition contains the following component (A), and components (D) and (F) composed of the following component (B) and / or component (C), and the component (D) of 0.1-2 pts.mass of the whole, and the component (F) of 1-50 pts.mass of the whole. (A) A resin composition containing either or both of an unsaturated polyester resin (A1) or a vinyl ester resin (A2), and containing component (E) of 1-10 mass% of the component (A), (B) saturated fatty acid, (C) saturated fatty acid ester, (D) component composed of one or two or more kinds of either or both of (B) and (C), and (E) methyl methacrylate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a toner-containing radically polymerizable resin composition. [Background technology]

[0002] Unsaturated polyesters and vinyl esters have high strength and waterproof / corrosion-resistant properties, and are used as coating resin materials. These materials undergo radical polymerization during application to form cured products. However, radical polymerization is inhibited by oxygen, which creates the problem of poor curing of the resin surface when cured in the atmosphere. It has been proposed that adding paraffin wax can improve this problem (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 11-209628 Summary of the Invention [Problem to be solved by the invention]

[0004] In conventional techniques using paraffin wax, including the technique disclosed in Patent Document 1, the paraffin wax precipitates when the resin hardens, forming a wax layer on the resin surface to block oxygen and improve the hardening of the resin surface. However, when toner is used to adjust color tone or block ultraviolet rays, the hardening of the resin surface deteriorates due to the influence of the pigment contained in the toner. Therefore, conventional techniques using paraffin wax have had issues with the hardening of the resin surface when used in combination with toner.

[0005] Therefore, an object of the present invention is to provide a toner-containing radical polymerizable resin composition having high surface curability. [Means for solving the problem]

[0006] The present inventors have conducted extensive research into curable resin compositions from various perspectives, and as a result have come to discover the toner-containing radically polymerizable resin composition of the present invention.

[0007] That is, the toner-containing radical polymerizable resin composition of the present invention contains the following component (A) and components (D) and (F) each consisting of the following component (B) and / or component (C), and the component (D) is For 100 parts by mass of the resin composition of the following component (A): 0.1~2 parts by mass, The aforementioned (F) Radical polymerizable resin composition Overall Per 100 parts by mass It is characterized by containing 1 to 50 parts by mass. (A) Contains either or both of an unsaturated polyester resin (A1) or a vinyl ester resin (A2), and contains 1 to 10% by mass of component (E) based on component (A). and contains styrene resin composition (B) Saturated fatty acids (C) Saturated fatty acid ester (D) A component consisting of one or more of either (B) or (C) or both. (E) Methyl methacrylate (F) Toner [Effects of the Invention]

[0008] The toner-containing radical polymerizable resin composition of the present invention has the advantageous effect of exhibiting excellent surface curing properties when cured at room temperature in the presence of a toner. By providing a resin composition that exhibits excellent surface curing properties at room temperature, it is possible to provide a toner-containing radical polymerizable resin composition and a composite material that can be cured without applying heat when using a toner. DETAILED DESCRIPTION OF THE INVENTION

[0009] The following is an example of a detailed description of the present invention. From the viewpoint of achieving excellent surface curability in the presence of a toner, the radical polymerizable resin composition of the present invention is characterized by containing the following component (A) and components (D) and (F) each consisting of the following component (B) and / or component (C), with component (D) being contained in an amount of 0.1 to 2 parts by mass of the total, and component (F) being contained in an amount of 1 to 50 parts by mass of the total. (A) Either unsaturated polyester resin (A1) or vinyl ester resin (A2) or a resin composition containing both and containing 1 to 10 mass % of component (E). (B) Saturated fatty acids (C) Saturated fatty acid ester (D) A component consisting of one or more of either (B) or (C) or both. (E) Methyl methacrylate (F) Toner

[0010] In the present invention, the composition "contains component (D) consisting of component (A) and component (B) and / or component (C)," but it is preferable to dissolve component (D) consisting of component (B) and / or component (C) in component (A) from the viewpoint of obtaining the mechanical properties of the cured resin. In the present invention, dissolution can refer to the phenomenon in which a gas, liquid, solid, etc. mixes with a liquid to form a uniform liquid phase. Therefore, this differs from the case where the components are simply melted and mixed. This is because, if the components are not dissolved, they may precipitate in the liquid, resulting in an inconsistent uniform phase and potentially adversely affecting the mechanical properties of the cured resin.

[0011] (Component (A)) In the present invention, the component (A) can contain one or both of an unsaturated polyester (A1) and a vinyl ester (A2).

[0012] The unsaturated polyester (A1) is not particularly limited, and can be obtained, for example, by condensing an acid component (A1-1) with an alcohol component (A1-2).

[0013] The acid component (A1-1) is not particularly limited, and various acid components can be used, such as unsaturated dibasic acids and saturated dibasic acids, trifunctional or higher polybasic acids, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, adipic acid, sebacic acid, HET acid, tetrabromophthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic anhydride, halogenated phthalic anhydride, succinic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic dianhydride, and the like, and these may be used alone or in combination of two or more.

[0014] The method for producing the unsaturated polyester (A1) is not particularly limited, and various reactions such as direct esterification, transesterification, reaction between an acid chloride and a hydroxy group, metathesis reaction, ring-opening reaction, and the like may be used. The acid component (A1-1) and the alcohol component (A1-2) may be appropriately set according to the required basic performance depending on the use conditions and application, and the reaction temperature and reaction conditions may also be appropriately set. Specifically, for example, the method described in "Polyester Resin Handbook" (Takiyama Eiichiro, Nikkan Kogyo Shimbun, 1988) has been conventionally known, and the unsaturated polyester (A1) can be produced by these conventional methods.

[0015] The vinyl ester (A2) is not particularly limited, and may be a polymer obtained by addition reaction of an epoxy resin (A2-1) with an unsaturated basic acid (A2-2), which is also called an epoxy acrylate.

[0016] The epoxy resin (A2-1) is not particularly limited, and examples thereof include epi-bis-glycidyl ethers, novolac-type glycidyl ethers, brominated glycidyl ethers, other glycidyl ethers, nitrogen-containing glycidyl esters, peracetic acid-oxidized glycidyl ethers, and glycol-type glycidyl ethers, which may be used alone or in combination of two or more.

[0017] The unsaturated basic acid (A2-2) is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxymethyl methacrylate maleate, hydroxyethyl acrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, and dicyclopentadiene acrylate maleate. These may be used alone or in combination of two or more.

[0018] The method for producing the vinyl ester (A2) is not particularly limited, and various reactions such as phenol modification, acid / acid anhydride modification, acid pendant and phosphate pendant, urethane modification, allyl ether modification, acetoacetylation modification, partial esterification modification, and others may be used. The epoxy resin (A2-1) and the unsaturated basic acid (A2-2) may be appropriately selected according to the required basic performance depending on the use conditions and application, and the reaction temperature and reaction conditions may also be appropriately selected. Specifically, for example, the method described in "Vinyl Ester Resin" (edited by Vinyl Ester Resin Research Group, Kagaku Kogyo Nipposha, 1993) has been publicly known, and the vinyl ester (A2) can be produced by a conventional method.

[0019] Furthermore, the resin compositions (A1) and (A2) may contain a radical polymerizable monomer to improve the operability of the resin composition and the solubility of the reaction system. Examples of the radical polymerizable monomer include vinyl aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene, as monomers having a vinyl group. Among these, styrene is preferred in terms of adjusting the physical properties of the resin composition.

[0020] The acid value of the resin compositions (A1) and (A2) is preferably 30 mgKOH / g or less. If the acid value is too high, the basic physical properties of the resin may be impaired and the surface drying property in the present invention may also be affected. The acid value is more preferably 25 mgKOH / g or less, and preferably 1 to 25 mgKOH / g.

[0021] (acid number) The acid value can be measured in accordance with "JIS K0070:1992 Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products." The acid value indicates the amount of potassium hydroxide required to neutralize the compound. For example, when 1 mL of a 0.1 mol / L KOH ethanol solution is required to neutralize 1 g of a resin composition, the acid value can be calculated as follows: acid value = (amount of KOH solution used × 56.1 × 0.1) / resin composition, resulting in an acid value of 5.61 mgKOH / g.

[0022] (Component (D)) Component (D) of the present invention is used as a wax for imparting surface drying properties to the toner-containing radically polymerizable resin composition, and is a component comprising one or more of either or both of saturated fatty acids (B) and saturated fatty acid esters (C).

[0023] (Saturated fatty acids (B), saturated fatty acid esters (C)) The saturated fatty acid (B) is a compound containing one or more linear carboxylic acids, and the saturated fatty acid ester (C) is a compound containing one or more linear carboxylic acid esters. By dissolving the saturated fatty acid (B) and / or the saturated fatty acid ester (C) in the resin composition (A), surface dryness after curing can be achieved.

[0024] Examples of the saturated fatty acid (B) include palmitic acid, stearic acid, behenic acid, and lauric acid, and examples of the saturated fatty acid ester (C) include ester compounds of the above (B).

[0025] In a preferred embodiment of the toner-containing radically polymerizable resin composition of the present invention, the toner contains 0.1 parts by mass (parts by weight) or more of the component (D). That is, the amount of the component (D) added is preferably 0.01 parts by mass or more, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the resin composition. The upper limit of the amount added is not particularly limited because it does not affect the surface drying property, but if it exceeds about 2 parts by mass, it will not completely dissolve in the resin composition and will precipitate.

[0026] The component (E) is methyl methacrylate, which is an essential component of the toner-containing radically polymerizable resin composition of the present invention as a polymerizable unsaturated monomer. It is blended with component (A) to suppress the odor of styrene during curing, and is preferably contained in an amount of 1 to 15% by mass relative to component (A). It is more preferably 1 to 10% by mass; too much can adversely affect the curability of the surface, while too little cannot suppress the odor of styrene.

[0027] In the present invention, in order to cure the resin composition, a curing agent such as a radical curing agent or a photocuring agent can be added.

[0028] The radical curing agent is not particularly limited, and various radical curing agents such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, and the like can be used, and two or more of them can be used in combination.

[0029] The photocuring agent is not particularly limited, and various photocuring agents such as acetophenone-based, benzoin-based, benzophenone-based, and thioxanthone-based agents can be used, and these can be used alone or in combination of two or more. The radical curing agent and the photocuring agent can also be used in combination.

[0030] The amount of the curing agent added is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the total amount of the resin composition. If an excessive amount is added, the mechanical properties and workability of the cured product may be impaired.

[0031] The present invention can contain various additives depending on the basic performance of the use conditions. The type of additive is not particularly limited, and examples thereof include a curing accelerator, a polymerization inhibitor, an ultraviolet absorber, a colorant, a flame retardant, and a filler. These may be used alone or in combination of two or more.

[0032] The curing accelerator is not particularly limited, and examples thereof include metal soaps such as organic acid cobalt, organic acid copper, organic acid zinc, organic acid manganese, and organic acid potassium; metal chelates such as vanadium acetylacetate, cobalt acetylacetate, and iron acetylacetate; and amines such as N,N-substituted anilines such as aniline, N,N-dimethylaniline, N,N-diethylaniline, p-toluidine, N,N-dimethyl-p-toluidine, and 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, N,N-substituted-p-toluidine, and 4-(N,N-substituted amino)benzaldehyde. These may be used alone or in combination of two or more.

[0033] The amount of the curing accelerator added is preferably 0.001 to 15 parts by mass, more preferably 0.001 to 5 parts by mass, per 100 parts by mass of the resin composition. However, the recommended addition range generally varies depending on the type of accelerator. For example, when adding 6% cobalt naphthenate, the amount is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1.0 part by mass, per 100 parts by mass of the resin composition. If an excessive amount is added, the mechanical properties and workability of the cured product may be impaired.

[0034] The polymerization inhibitor is not particularly limited, and various inhibitors can be used, such as quinones, hydroquinones (polyhydric phenols), phenols, organic and inorganic copper salts, amidines, hydrazine salts, quaternary ammonium salts, amines, nitro compounds, oximes, sulfur, amine hydrochlorides, and the like, and these can be used alone or in combination of two or more.

[0035] The amount of the polymerization inhibitor added is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.5 parts by mass, per 100 parts by mass of the resin composition. If an excessive amount is added, the curability of the resin composition may be significantly reduced.

[0036] The ultraviolet absorber, colorant, and flame retardant are not particularly limited, and any of those usable in radical polymerizable resin compositions can be used. They may be used alone or in combination of two or more kinds.

[0037] The filler is not particularly limited, and examples thereof include inorganic fillers such as aluminum hydroxide, calcium carbonate, alumina, talc, silica, glass powder, mica, and carbon nanotubes, as well as organic fillers. These may be used alone or in combination of two or more.

[0038] The amount of the filler added is preferably 1 to 250 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass of the resin composition. If an excessive amount is added, the flowability may be impaired, workability may be reduced, and mechanical properties may also be reduced.

[0039] (Component (F)) In the present invention, toner (F) is used to adjust the color tone of the product and to block ultraviolet rays. Toner is a toner in which color particles such as pigments, dyes, graphite, and carbon black are kneaded into a polyester vehicle. In the present invention, black toner in which carbon black or graphite is kneaded is preferably used for the purpose of blocking light.

[0040] The amount of the toner added is preferably 1 to 50 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the total radical polymerizable resin composition. If an excessive amount is added, the curability of the toner-containing radical polymerizable resin composition may be significantly reduced, and the mechanical properties may also be reduced.

[0041] The composite material of the present invention can contain the toner-containing radically polymerizable resin composition of the present invention and a reinforcing material. The reinforcing material is not particularly limited, and can be any material that can be used with the toner-containing radically polymerizable resin composition. Examples include inorganic fibers such as glass fiber, carbon fiber, metal fiber, and ceramic fibers; organic fibers such as aramid, polyester, vinylon, phenol, and polytetrafluoroethylene (PTFE); and natural fibers. The form of these fibers is also not particularly limited, and examples include cloth (woven fabric), mats such as chopped strand mat, preformable mat, continuous strand mat, and surfacing mat, chopped mat, roving, and nonwoven fabric. These fibers may be used alone or in combination of two or more. When a reinforcing material is used in the present invention, glass fiber is preferred to obtain the desired mechanical properties of the composite material. When an organic fiber nonwoven fabric is used, glass fiber is also preferably used in combination. [Example]

[0042] Hereinafter, one embodiment of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0043] (Synthesis Example 1) A four-neck flask equipped with a stirrer, thermometer, inert gas inlet, and reflux condenser was charged with 190 parts by mass of ethylene glycol, 100 parts by mass of diethylene glycol, 10 parts by mass of dipropylene glycol, 260 parts by mass of phthalic anhydride, and 250 parts by mass of fumaric acid, and the temperature was raised to 206°C while blowing in nitrogen gas. A dehydration condensation reaction was carried out at the same temperature, yielding an unsaturated polyester with an acid value of 19.2 mgKOH / g. 80 parts by mass of this unsaturated polyester and 20 parts by mass of styrene monomer as a polymerizable unsaturated monomer were mixed to obtain unsaturated polyester resin (A1-1).

[0044] (Synthesis Example 2) A four-neck flask equipped with a stirrer, thermometer, inert gas inlet, and reflux condenser was charged with 186 parts by mass of propylene glycol, 116 parts by mass of diethylene glycol, 15 parts by mass of dipropylene glycol, 265 parts by mass of phthalic anhydride, and 244 parts by mass of maleic anhydride, and the temperature was raised to 206°C while blowing in nitrogen gas, and a dehydration condensation reaction was carried out at the same temperature to obtain an unsaturated polyester with an acid value of 19.6 mgKOH / g. Unsaturated polyester resin (A1-2) was obtained by mixing 70 parts by mass of this unsaturated polyester with 30 parts by mass of styrene monomer as a polymerizable unsaturated monomer.

[0045] (Synthesis Example 3) Equipped with a stirrer, thermometer, inert gas inlet, and reflux condenser, 680 parts by weight of epoxy resin (epoxy equivalent 188), 320 parts by weight of methacrylic acid, and 1 part by weight of 2-methylimidazole were charged and the temperature was slowly raised to 100°C while blowing in air. After the heat generation subsided, the temperature was raised to 130°C and the reaction continued, yielding an epoxy acrylate with polymerizable vinyl groups and an acid value of 9.5 mg KOH / g. Vinyl ester resin (A2-1) was obtained by mixing 70 parts of this epoxy acrylate with 30 parts of styrene as a polymerizable unsaturated monomer.

[0046] (Examples 1 to 25, Comparative Examples 1 to 7) To each of the resins obtained in Synthesis Examples 1 to 3, 0.5 parts by mass of 12% cobalt octylate and 0.4 parts by mass of an 80% aqueous dimethylacetoacetamide solution were added. Methyl methacrylate (MMA) was added as component (E) according to the formulation in Table 1. The inhibitor toluhydroquinone was added and adjusted to give a gel time of 2.5 minutes, resulting in unsaturated polyester resin (A). Subsequently, component (D) was added to 100 parts by mass of the prepared unsaturated polyester resin (A) according to the formulation in Table 1 to obtain a radically polymerizable resin composition. Specifically, the following components were added as component (D): "compound (B) only," "compound (C) only," and "a mixture of compounds (B) and (C)." In Comparative Examples 6 and 7, WAX-125 (manufactured by Nippon Seiro Co., Ltd.) was added as paraffin wax.

[0047] [Compound (B)] Stearic acid (hereinafter referred to as ST) [Compound (C)] Stearyl stearate (hereinafter referred to as STS) [Mixture of compounds (B) and (C)] 1:1 mixture of ST and STS (ST / STS) [Paraffin wax] WAX-125 (manufactured by Nippon Seiro Co., Ltd.)

[0048] (Surface drying evaluation) To 100 parts by mass of the prepared radical polymerization resin composition, 25 parts by mass of toner as component (F) and 1.25 parts by mass of a curing agent (product name: Permec N manufactured by NOF Corporation) were added to prepare a toner-containing radical polymerization resin composition, which was then spread onto a PET film using an applicator to a thickness of 200 μm. Three hours after spreading, the surface was checked by touch and the degree to which a fingerprint remained was used to evaluate the surface dryness. The evaluation results are shown in Table 1 below. <Evaluation method> Surface dryness ◎ No fingerprints left behind 〇 Fingerprints remain, but the resin does not stick to your fingers. △ A small amount of resin sticks to your fingers, but it has hardened enough to be cut with a cutter. × Cannot be cut with a cutter and has not hardened

[0049] (Deposition evaluation) 9 g of the prepared resin composition was placed in a 9 cc vial and allowed to stand in a refrigerator at 5° C. The degree of precipitation of component (B) was visually confirmed. The results are shown in Table 1 below. <Evaluation method> 〇: No precipitation for more than 90 hours △: No precipitation occurs for 70 hours or more, but precipitation occurs within 90 hours ×: Precipitates within 70 hours

[0050] (Odor evaluation) The odor of the cured product was checked 3 hours after spreading, and the results are shown in Table 1.

[0051] [Table 1]

[0052] (evaluation) As can be seen from the above examples, a toner-containing radical polymerization resin composition obtained by containing an appropriate amount of MMA and an appropriate amount of saturated fatty acid and saturated fatty acid ester is a good toner-containing radical polymerization resin composition that has good surface drying properties and odor and is free from precipitation of saturated fatty acid and saturated fatty acid ester during storage.

Claims

[Claim 1] A toner-containing radical polymerizable resin composition comprising the following components (A) and (D) and (F) each consisting of the following components (B) and (C), wherein the component (D) is present in an amount of 0.1 to 2 parts by mass per 100 parts by mass of a resin composition of the following component (A), and the component (F) is present in an amount of 1 to 50 parts by mass per 100 parts by mass of the entire radical polymerizable resin composition. (A) A resin composition containing either or both of an unsaturated polyester resin (A1) or a vinyl ester resin (A2), containing 1 to 10 mass % of component (E) based on component (A), and containing styrene. (B) Saturated fatty acids (C) Saturated fatty acid ester (D) A component consisting of one or more of either (B) or (C) or both. (E) Methyl methacrylate (F) Toner

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