Compositions, cured products, and films for film coatings.

Abstract

The present invention provides a film coating composition, its cured product, and a film that can form a cured product that is flexible yet highly scratch-resistant, possesses high hardness, and also has excellent heat-resistant adhesion, and is low viscosity and easy to handle. [Solution] The film coating composition of the present invention contains at least a polymerizable compound (A) having two to six (meth)acryloyl groups, and a compound (B) other than compound (A) having three to six (meth)acryloyl groups, and an initiator (D), wherein compound (A) has ethylene oxide units in the compound, and the average number of added moles of ethylene oxide units is 1 to 6 moles, and the initiator (D) is contained in an amount of 0.5 to 3.5 parts by mass per 100 parts by mass of the total mass of the polymerizable compound.

Description

Technical Field

[0001] The present invention relates to a composition for film coatings, a cured product, and a film.

Background Art

[0002] Compositions having the property of curing by active energy rays such as ultraviolet rays are widely used, for example, in applications such as protective films used to protect various substrates, adhesive materials, and various coating agents, and are functional materials with high utility value. One application of such a composition is film coating applications. By applying such a composition for film coatings as a paint on the surface of a film such as a substrate and curing it, a film (cured product) can be formed on the film surface to realize the functionalization of the film surface.

[0003] Patent Document 1 discloses preparing an active energy ray-curable coating agent composition by combining two or more specific (meth)acryloyl group-containing compounds, and adjusting the mechanical properties of a film by forming a cured product of such a composition on the film surface.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in applications such as the film coatings described above, further improvements in mechanical properties and suppression of peeling at high temperatures (i.e., improved heat-resistant adhesion) are required for the cured product. In addition, the handling properties of the composition when applying it are also required. While the technology described in Patent Document 1 can be expected to improve mechanical properties to some extent, our investigations have shown that the heat-resistant adhesion is not necessarily sufficient and further improvements are needed. In particular, in recent years there has been a demand for a film coating composition that can form a cured product that is flexible yet has excellent scratch resistance, high hardness, and also excellent heat-resistant adhesion.

[0006] The present invention has been made in view of the above, and aims to provide a film coating composition, its cured product, and a film that can form a cured product that is flexible yet has excellent scratch resistance, high hardness, and also has excellent heat adhesion, and that has low viscosity and excellent handling properties. [Means for solving the problem]

[0007] The inventors of the present invention have diligently conducted research to achieve the above objectives and have found that these objectives can be achieved by including a polyfunctional compound having two or more specific structures and an initiator in a predetermined amount, thereby completing the present invention.

[0008] In other words, the present invention encompasses, for example, the subject matter described in the following sections. Item 1 Compound (A) having two or more and six or fewer (meth)acryloyl groups, and Compound (B) other than the aforementioned compound (A) having 3 to 6 (meth)acryloyl groups The polymerizable compounds contained, Initiator (D) It contains at least the following: The aforementioned compound (A) contains ethylene oxide units, and the average number of moles of ethylene oxide units added is 1 to 6 moles. A film coating composition comprising 0.5 parts by mass or more and 3.5 parts by mass or less of the initiator (D) per 100 parts by mass of the total polymerizable compound. Section 2 The film coating composition according to item 1, wherein the compound (A) is a compound having a dipentaerythritol skeleton. Section 3 The film coating composition according to claim 1 or 2, wherein compound (A) is contained in an amount of 5 parts by mass or more and 90 parts by mass or less, based on a total mass of 100 parts by mass of compound (A) and compound (B). Section 4 A film coating composition according to any one of claims 1 to 3, having active energy ray curability. Section 5 A cured product containing a curing component of a film coating composition described in any one of items 1 to 4. Section 6 A film containing the cured product described in item 5. [Effects of the Invention]

[0009] The film coating composition of the present invention can form a cured product that is flexible yet has excellent scratch resistance, high hardness, and excellent heat adhesion. Furthermore, because the film coating composition of the present invention has low viscosity, it also has excellent handling properties. [Modes for carrying out the invention]

[0010] Embodiments of the present invention will be described in detail below. In this specification, the expressions "containing" and "including" include the concepts of "containing," "including," "substantially consisting of," and "consisting only of."

[0011] In the numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can be arbitrarily combined with the upper or lower limit of a numerical range in another step. In the numerical ranges described in this specification, the upper or lower limit of a numerical range may be replaced with values ​​shown in the examples or values ​​that can be uniquely derived from the examples. Furthermore, in this specification, numbers connected by "~" mean a numerical range that includes the numbers before and after "~" as the lower and upper limits.

[0012] The film coating composition of the present invention contains at least a polymerizable compound (A) having two to six (meth)acryloyl groups, and a compound (B) other than compound (A) having three to six (meth)acryloyl groups, and an initiator (D). Compound (A) has ethylene oxide units in it, and the average number of moles of ethylene oxide units added is 1 to 6 moles. The film coating composition of the present invention contains 0.5 to 3.5 parts by mass of the initiator (D) per 100 parts by mass of the total mass of the polymerizable compound.

[0013] The film coating composition of the present invention contains the above-mentioned compounds (A) and (B), and also contains an initiator (D) in a predetermined proportion, thereby forming a cured product that is flexible yet has excellent scratch resistance, high hardness, and excellent heat-resistant adhesion. Furthermore, since the film coating composition of the present invention has low viscosity, it also has excellent handling properties. "Excellent heat-resistant adhesion" means that the cured product adheres well to the substrate even in high-temperature environments (for example, 120°C), and peeling is unlikely to occur.

[0014] Compound (A) Compound (A) contained in the film coating composition of the present invention has two to six (meth)acryloyl groups, and the compound contains an average number of added moles of 1 to 6 moles (i.e., 1 mole to 6 moles) of ethylene oxide units.

[0015] In this specification, the (meth)acryloyl group is a notation meaning an acryloyl group or a methacryloyl group.

[0016] When the compound (A) is contained in the composition for film coating of the present invention, a cured product excellent in flexibility can be formed, and excellent scratch resistance and heat-resistant adhesion can also be achieved.

[0017] When the number of (meth)acryloyl groups in the compound (A) is less than 2, the cured product formed from the composition for film coating cannot have sufficient hardness. The compound (A) preferably has 3 or more (meth)acryloyl groups in the molecule, and more preferably 4 or more.

[0018] When the compound (A) contains ethylene oxide units, the cured product formed from the composition for film coating can have excellent scratch resistance and high hardness. When the compound (A) does not contain ethylene oxide units, or when it contains other alkylene oxide units instead of ethylene oxide units, the scratch resistance of the cured product may decrease, and the hardness may not be sufficient.

[0019] When the average added mole number of ethylene oxide units contained in the compound (A) is less than 1 mole, the cured product formed from the composition for film coating may have reduced flexibility and heat-resistant adhesion, and the viscosity of the composition for film coating may also tend to increase, possibly impairing the handling property. When the average added mole number of ethylene oxide units contained in the compound (A) exceeds 6 moles, the scratch resistance and heat-resistant adhesion of the cured product may decrease, and the hardness may also decrease.

[0020] The average added mole number of ethylene oxide units contained in the compound (A) is preferably 2 moles or more, more preferably 2.5 moles or more, and preferably 5.5 moles or less, more preferably 5 moles or less.

[0021] The average number of moles of ethylene oxide units added to compound (A) is: 1 It can be estimated from the H-NMR spectrum.

[0022] The structure of compound (A) is not particularly limited, as long as it has two to six (meth)acryloyl groups and the above amount of ethylene oxide units.

[0023] For example, compound (A) is a compound having a structure in which the hydrogen atoms of the hydroxyl group of the polyol compound are substituted with ethylene oxide units or polyethylene oxide units (i.e., -CH2CH2O- or a repeat thereof), and a (meth)acryloyl group is bonded to the terminal oxygen atom of the (poly)ethylene oxide unit and / or the oxygen atom of the hydroxyl group of the polyol compound. The polyol compound is not particularly limited, and dipentaerythritol is an example.

[0024] In other words, compound (A) is preferably a compound having a dipentaerythritol skeleton. When compound (A) is a compound having a dipentaerythritol skeleton, for example, it may have a structure in which at least one hydrogen atom of the hydroxyl group of dipentaerythritol is replaced by an ethylene oxide unit or a (poly)ethylene oxide unit, and in addition, a (meth)acryloyl group is bonded to the oxygen atom at the end of the ethylene oxide unit or polyethylene oxide unit, and / or a structure in which at least one hydrogen atom of the hydroxyl group of dipentaerythritol is replaced by a (meth)acryloyl group.

[0025] Of course, if compound (A) is a compound having the above-mentioned dipentaerythritol skeleton, it also has two to six (meth)acryloyl groups, and the compound contains ethylene oxide units with an average addition number of 1 to 6 moles.

[0026] In this specification, a compound having an average of n moles of ethylene oxide units added to dipentaerythritol and having two to six (meth)acryloyl groups will be referred to as "dipentaerythritol nEO adduct acrylate" (where n is the same as above, i.e., the average number of moles of ethylene oxide units added).

[0027] Compound (A) may retain hydroxyl groups. Furthermore, the terminal end of the ethylene oxide unit in compound (A) may be a hydrogen atom.

[0028] The method for producing compound (A) is not particularly limited, and for example, known production methods can be widely employed. One example is a method in which a polyol compound (e.g., dipentaerythritol) is reacted with ethylene oxide to synthesize an adduct, and this adduct is then reacted with (meth)acrylic acid.

[0029] The reaction between the adduct and (meth)acrylic acid can be carried out in the presence of an acid catalyst as needed. Examples of such catalysts include inorganic acids such as sulfuric acid and hydrochloric acid, organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and camphorsulfonic acid, acid-type ion exchange resins, Lewis acids such as fluorinated boron ether complexes, and water-soluble Lewis acids such as lanthanide triflates.

[0030] The amount of acid used is at least 0.1 molar equivalents, preferably at least 0.5 molar equivalents, relative to the substrate adduct (ethylene oxide-modified dipentaerythritol). On the other hand, there is no upper limit, but it is usually 20 molar equivalents or less, preferably 10 molar equivalents or less.

[0031] The reaction between the adduct and (meth)acrylic acid can be carried out in either a solvent system or a solvent-free system, but a solvent system is preferred due to the generation of by-products and ease of handling during the process. When using a solvent, there are no particular restrictions on the solvent used, but aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, and diethylene glycol dimethyl ether, and halogen solvents such as methylene chloride, chloroform, and carbon tetrachloride are preferably used. These solvents can be used individually or in any combination of several solvents.

[0032] When a solvent is used, the amount of solvent is usually 1% by mass or more, preferably 20% by mass or more, with no particular upper limit, but usually 80% by mass or less, preferably 70% by mass or less, based on the concentration of the raw material, ethylene oxide-modified dipentaerythritol. The reaction is usually carried out at or above the boiling point of the solvent used, while distilling off the water produced. The reaction time is usually 30 minutes or more, preferably 60 minutes or more, with no particular upper limit, but usually 20 hours or less, preferably 10 hours or less.

[0033] Compound (A) can be obtained by manufacturing as described above, or by using commercially available products.

[0034] Compound (A) may be included in one or more of the film coating compositions of the present invention.

[0035] Compound (B) Compound (B) contained in the film coating composition of the present invention is a compound other than compound (A) and has 3 to 6 (meth)acryloyl groups.

[0036] By including compound (B) in the film coating composition of the present invention, it is possible to form a cured product that has excellent scratch resistance and high hardness, as well as excellent flexibility.

[0037] If compound (B) has fewer than three (meth)acryloyl groups, the cured product formed from the film coating composition may not have sufficient hardness. Compound (B) preferably has three or more (meth)acryloyl groups in its molecule, and more preferably four or more.

[0038] The structure of compound (B) is not particularly limited, as long as it has 3 to 6 (meth)acryloyl groups. As mentioned above, compound (B) is a compound other than compound (A), and for example, it is preferable that compound (B) does not have ethylene oxide units. Even if compound (B) has ethylene oxide units, the average number of moles added is less than 1 mole.

[0039] Specific examples of compound (B) include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, urethane(meth)acrylate, and the like.

[0040] In this specification, "(meth)acrylic" means "acrylic" or "methacrylic." For example, "(meth)acrylate" means "acrylate" or "methacrylate," and "(meth)acrylamide" means "acrylamide" or "methacrylamide."

[0041] Compound (B) is preferably a compound having one or more skeletons selected from the group consisting of a pentaerythritol skeleton, a trimethylolpropane skeleton, a ditrimethylolpropane skeleton, and a diethylene glycol skeleton.

[0042] Compound (B) can be obtained by known manufacturing methods, and can also be obtained from commercially available products.

[0043] Compound (B) may be included in one or more of the film coating compositions of the present invention.

[0044] polymerizable compound The polymerizable compound contains at least compound (A) and compound (B), and may optionally contain polymerizable compounds other than compound (A) and compound (B). Hereinafter, such polymerizable compounds will be referred to as "compound (C)".

[0045] Examples of compound (C) include monofunctional polymerizable compounds and difunctional polymerizable compounds. Polymerizable compounds include, for example, compounds having an ethylenically unsaturated group.

[0046] Examples of monofunctional polymerizable compounds include monofunctional (meth)acrylates. Specific examples of monofunctional (meth)acrylates include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; monofunctional (meth)acrylates having alicyclic groups such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; and glycidyl (meth)acrylate. Examples include monofunctional (meth)acrylates having a cyclic ether group, such as t(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)methyl (meth)acrylate, and 3-ethyl-3-oxetanylmethyl (meth)acrylate; aromatic monofunctional (meth)acrylates such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenoxy (meth)acrylate, and p-cumylphenolethylene (meth)acrylate; and hydroxyalkyl (meth)acrylates such as 2-hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate.

[0047] Examples of difunctional polymerizable compounds include difunctional (meth)acrylates having two (meth)acryloyl groups, such as aliphatic diol di(meth)acrylates like ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate and nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; and polyalkylene glycol di(meth)acrylates like diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Examples include polyol di(meth)acrylates such as glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, and dipentaerythritol di(meth)acrylate; and di(meth)acrylates of polyol alkylene oxide adducts such as glycerol alkylene oxide adduct di(meth)acrylate, pentaerythritol alkylene oxide adduct di(meth)acrylate, ditrimethylolpropane alkylene oxide adduct di(meth)acrylate, and dipentaerythritol alkylene oxide adduct di(meth)acrylate.

[0048] When compound (C) is included in the film coating composition of the present invention, compound (C) may be one or two or more types.

[0049] The polymerizable compound may consist only of compound (A) and compound (B), or it may consist only of compound (A), compound (B), and compound (C). The polymerizable compound may contain 50% by mass or more of compound (A) and compound (B), preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0050] Initiator (D) The film coating composition of the present invention contains an initiator (D). Initiator (D) has the effect of promoting the polymerization reaction of compound (A) and compound (B) by active energy rays such as ultraviolet light (i.e., the film coating composition of the present invention can be cured by active energy rays). Therefore, an initiator (D) can be a photoinitiator. Examples of active energy rays include ultraviolet light, electron beams, visible light, X-rays, ion beams, etc., and can be appropriately selected depending on the photopolymerization initiator contained in the adhesive layer. Among these, ultraviolet light or electron beams are preferred from the viewpoint of versatility, and ultraviolet light is particularly preferred. In other words, if the film coating composition of the present invention contains a (photo)initiator, the film coating composition of the present invention can be cured by ultraviolet light.

[0051] Examples of ultraviolet light sources that can be used include chemical lamps, high-pressure mercury lamps, low-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, xenon arc lamps, and electrodeless ultraviolet lamps.

[0052] The type of initiator (D) is not particularly limited, and for example, known photoinitiators that may be included in conventional active energy ray curable compositions can be widely used.

[0053] Examples of initiators (D) include aromatic ketones such as benzophenone, aromatic compounds such as anthracene and α-chloromethylnaphthalene, and sulfur compounds such as diphenyl sulfide and thiocarbamate. Examples of polymerization initiators using active energy rays other than visible light, such as ultraviolet light, include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthones, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and thioxane. Examples include diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone).

[0054] Photoinitiators can be obtained by known manufacturing methods, and can also be obtained from commercially available products. Examples of commercially available photoinitiators include IGM Resins BV "Omnirad TPO N", "Omnirad 819", and "Omnirad 184".

[0055] Compositions for film coatings The film coating composition of the present invention contains a polymerizable compound containing compound (A) and compound (B), and an initiator (D) as essential components.

[0056] Furthermore, as described above, the film coating composition of the present invention contains 0.5 parts by mass or more and 3.5 parts by mass or less of the initiator (D) per 100 parts by mass of the total mass of the polymerizable compound. If the content of the initiator (D) per 100 parts by mass of the polymerizable compound is less than 0.5 parts by mass, the cured product obtained from the film coating composition of the present invention is prone to a significant decrease in heat resistance, scratch resistance, and hardness, and if it exceeds 3.5 parts by mass, the heat resistance and adhesion decrease.

[0057] The content of the initiator (D) per 100 parts by mass of the total mass of the polymerizable compound is preferably 0.6 parts by mass or more, more preferably 0.7 parts by mass or more, even more preferably 0.8 parts by mass or more, particularly preferably 1 part by mass or more, and also preferably 3.3 parts by mass or less, more preferably 2.9 parts by mass or less, even more preferably 2.7 parts by mass or less, and particularly preferably 2.5 parts by mass or less.

[0058] In the film coating composition of the present invention, the content of compound (A) relative to 100 parts by mass of the total mass of compound (A) and compound (B) is not particularly limited, and can be, for example, 5 parts by mass or more and 90 parts by mass or less. As a result, the cured product formed from the film coating composition of the present invention can be made to be flexible, have excellent scratch resistance and high hardness, and also have low viscosity, resulting in a composition with excellent handling properties.

[0059] The content of compound (A) per 100 parts by mass of the total mass of compound (A) and compound (B) is preferably 8 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 13 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 18 parts by mass or more, and also preferably 85 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, and particularly preferably 70 parts by mass or less.

[0060] Other ingredients The film coating composition of the present invention may contain other optional components in addition to compound (A) and compound (B) and initiator (D). Preferably, the total content of compound (A) and compound (B), compound (C) which may be included as needed, and initiator (D) in the film coating composition of the present invention is 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0061] The film coating composition of the present invention may consist only of compound (A) and compound (B), compound (C) which may be included as needed, and an initiator (D), or it may consist only of compound (A) and compound (B) and an initiator (D).

[0062] The film coating composition of the present invention is preferably solvent-free. That is, the film coating composition of the present invention is preferably a solvent-free composition.

[0063] As described above, even though the film coating composition of the present invention is solvent-free, it contains compound (A) and compound (B) and initiator (D) in predetermined proportions, which makes it less likely for viscosity to increase. For this reason, the film coating composition of the present invention has excellent handling properties even though it is solvent-free.

[0064] Even if the film coating composition of the present invention contains a solvent, its content is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and most preferably 1% by mass or less, based on the total mass of the composition.

[0065] The method for preparing the film coating composition of the present invention is not particularly limited, and various known methods can be employed, for example. For example, the film coating composition of the present invention can be prepared by blending and mixing predetermined amounts of compound (A), compound (B), and optionally compound (C) and initiator (D).

[0066] The film coating composition of the present invention can be coated onto various substrates and cured to form a cured product. Such a cured product is formed in the form of a film, thin film, protective film, or other similar material.

[0067] The cured product contains the curing component of the film coating composition of the present invention, and therefore is flexible while possessing excellent scratch resistance and heat adhesion, as well as high hardness. The curing component refers to a polymer of compound (A) and compound (B), or a polymer of compound (A), compound (B), and compound (C).

[0068] The method for forming the cured product is not particularly limited, and for example, conventional methods can be broadly applied in the present invention. For example, a film coating composition is applied to a substrate to a desired thickness to form a coating film, and the coating film is cured by irradiating it with active energy rays. This hardens the coating film and a cured product can be obtained. Such a cured product consists, for example, only of the aforementioned curing components.

[0069] When the cured product is in the form of a film or similar material, its thickness is not particularly limited and can be adjusted to an appropriate thickness depending on the application. For example, the thickness of the cured product can be 1-1000 μm, 1-500 μm, 1-100 μm, 1-50 μm, etc.

[0070] When the cured product is in the form of a film or the like, its surface may be flat or it may have an uneven structure with a predetermined depth, and can be designed appropriately according to the application.

[0071] For example, a film can be formed using the film coating composition of the present invention. Since such a film contains a cured product of the film coating composition of the present invention, it is flexible, has excellent scratch resistance, and possesses high hardness. Therefore, the film coating composition of the present invention is particularly suitable for film coating applications and can be used in various applications such as protective films, coating films such as hard coats, and optical adjustment films, and is particularly suitable for optical applications.

[0072] The cured product of the film coating composition of the present invention may be used as a film, or a laminate may be formed by forming the cured product of the film coating composition of the present invention on a substrate, and such laminate may be used as a film.

[0073] In identifying the inventions contained herein, the components (properties, structures, functions, etc.) described in each embodiment of this disclosure may be combined in any way. That is, this disclosure encompasses all subject matter consisting of any combination of the combinatable components described herein. [Examples]

[0074] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[0075] (raw materials) Film coating compositions for each example and comparative example were prepared by selecting the appropriate raw materials from those listed below.

[0076] <Compound (A)> • Dipentaerythritol 4EO adduct acrylate (obtained in Production Example 1) • Dipentaerythritol 2EO adduct acrylate (obtained in Production Example 2)

[0077] <Compound (a) (for comparison)> • Dipentaerythritol 12EO adduct acrylate (obtained in Production Example 3) • Dipentaerythritol 4PO adduct acrylate (obtained in Production Example 4) • DPHA: Dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd. "Light Acrylate DPE-6A")

[0078] <Compound (B)> • Pentaerythritol tetraacrylate (Shin-Nakamura Chemical Industry Co., Ltd. "NK Ester A-TMMT") • Ditrimethylolpropanetetraacrylate (Shin-Nakamura Chemical Industry Co., Ltd. "NK Ester AD-TMP") • Trimethylolpropane triacrylate (Daiichi Kogyo Seiyaku Co., Ltd. "New Frontier TMPT") • Glycerin triacrylate (Toagosei Co., Ltd. "Aronics M-930")

[0079] <Compound (C)> • Glycerin diacrylate (Toagosei Co., Ltd. "Arronix M-920")

[0080] <Initiator (D)> • TPO-N: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (IGM Resins BV "Omnirad TPO N") ·819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins BV "Omnirad 819") • 184: 1-Hydroxycyclohexylphenyl ketone (IGM Resins BV "Omnirad 184")

[0081] (Manufacturing Example 1) Dipentaerythritol 4EO adduct acrylate was synthesized using the following procedure. First, 254 g (1.0 mol) of dipentaerythritol (Sigma-Aldrich, molecular weight 254), 127 g of toluene, and 0.3 g of KOH were charged into a 1 L autoclave equipped with a stirring device. The mixture was heated to 90°C and stirred to form a slurry. Next, the mixture was heated to 130°C, and 220 g (5 mol) of ethylene oxide was gradually introduced into the autoclave to react. As ethylene oxide was introduced, the temperature inside the autoclave rose. Cooling was applied as needed to maintain the reaction temperature below 140°C. After the reaction, excess ethylene oxide and the by-product ethylene glycol polymer were removed by reducing the pressure to below 10 mmHg of mercury at 140°C. Subsequently, the mixture was neutralized with acetic acid and adjusted to pH 6-7 to obtain ethylene glycol-modified dipentaerythritol with an OH number of 765. 440 g (1 mol) of ethylene glycol-modified dipentaerythritol, 562 g (7.8 mol) of acrylic acid, 50 g of p-toluenesulfonic acid, 900 g of toluene, and 1 g of hydroquinone were placed in a four-necked glass flask and heated while blowing air into it. The water produced in the reaction was removed from the system as it occurred by azeotropic reaction with toluene. The reaction temperature was 100-110°C, and 113 g of reaction water was removed from the system at the end of the reaction. After the reaction, the mixture was washed with alkaline water and then with water to separate the upper toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 665 g (yield 87%) of dipentaerythritol 4EO adduct acrylate. The obtained dipentaerythritol 4EO adduct acrylate had an average of 4 moles of ethylene oxide added and contained 6 acryloyl groups in the compound.

[0082] (Manufacturing example 2) Dipentaerythritol 2EO adduct acrylate was synthesized using the following procedure. First, 254 g (1.0 mol) of dipentaerythritol (Sigma-Aldrich, molecular weight 254), 127 g of toluene, and 0.3 g of KOH were charged into a 1 L autoclave equipped with a stirring device. The mixture was heated to 90°C and stirred to form a slurry. Next, the mixture was heated to 130°C, and 132 g (3 mol) of ethylene oxide was gradually introduced into the autoclave to react. As ethylene oxide was introduced, the temperature inside the autoclave rose. Cooling was applied as needed to maintain the reaction temperature below 140°C. After the reaction, excess ethylene oxide and the by-product ethylene glycol polymer were removed by reducing the pressure to below 10 mmHg of mercury at 140°C. Subsequently, neutralization was carried out with acetic acid, and the pH was adjusted to 6-7 to obtain ethylene glycol-modified dipentaerythritol with an OH number of 982. 343 g (1 mol) of ethylene glycol-modified dipentaerythritol, 562 g (7.8 mol) of acrylic acid, 45 g of p-toluenesulfonic acid, 900 g of toluene, and 0.9 g of hydroquinone were placed in a four-necked glass flask and heated while blowing air into it. The water produced in the reaction was removed from the system as it occurred by azeotropic reaction with toluene. The reaction temperature was 100-110°C, and 112 g of reaction water was removed from the system at the end of the reaction. After the reaction, the mixture was washed with alkaline water and then with water to separate the upper toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 594 g (yield 89%) of dipentaerythritol 2EO adduct acrylate. The obtained dipentaerythritol 2EO adduct acrylate had an average of 2 moles of ethylene oxide added and contained 6 acryloyl groups in the compound.

[0083] (Manufacturing Example 3) Dipentaerythritol 12EO adduct acrylate was synthesized using the following procedure. First, 254 g (1.0 mol) of dipentaerythritol (Sigma-Aldrich, molecular weight 254), 127 g of toluene, and 0.3 g of KOH were charged into a 2 L autoclave equipped with a stirring device. The mixture was heated to 90°C and stirred to form a slurry. Next, the mixture was heated to 130°C, and 572 g (13 mol) of ethylene oxide was gradually introduced into the autoclave to react. As ethylene oxide was introduced, the temperature inside the autoclave rose. Cooling was applied as needed to maintain the reaction temperature below 140°C. After the reaction, excess ethylene oxide and the by-product ethylene glycol polymer were removed by reducing the pressure to below 10 mmHg of mercury at 140°C. Subsequently, the mixture was neutralized with acetic acid and adjusted to pH 6-7 to obtain ethylene glycol-modified dipentaerythritol with an OH value of 434. 776 g (1 mol) of ethylene glycol-modified dipentaerythritol, 562 g (7.8 mol) of acrylic acid, 50 g of p-toluenesulfonic acid, 900 g of toluene, and 1 g of hydroquinone were placed in a four-necked glass flask and heated while blowing air into it. The water produced in the reaction was removed from the system as it occurred by azeotropic reaction with toluene. The reaction temperature was 100-110°C, and 113 g of reaction water was removed from the system at the end of the reaction. After the reaction, the mixture was washed with alkaline water and then with water to separate the upper toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 902 g (82% yield) of dipentaerythritol 12EO adduct acrylate. The obtained dipentaerythritol 12EO adduct acrylate had an average of 12 moles of ethylene oxide added and contained 6 acryloyl groups in the compound.

[0084] (Manufacturing example 4) Dipentaerythritol 4PO adduct acrylate was synthesized using the following procedure. First, 254 g (1.0 mol) of dipentaerythritol (Sigma-Aldrich, molecular weight 254), 127 g of toluene, and 0.5 g of KOH were charged into a 1 L autoclave equipped with a stirring device. The mixture was heated to 90°C and stirred to form a slurry. Next, the mixture was heated to 140°C, and 290 g (5 mol) of propylene oxide was gradually introduced into the autoclave to react. As propylene oxide was introduced, the temperature inside the autoclave rose. Cooling was applied as needed to maintain the reaction temperature below 150°C. After the reaction, excess propylene oxide and the by-product propylene glycol polymer were removed by reducing the pressure to below 10 mmHg of mercury at 150°C. Neutralization with acetic acid was performed to adjust the pH to 6-7, yielding propylene glycol-modified dipentaerythritol with an OH number of 727. 463 g (1 mol) of propylene glycol-modified dipentaerythritol, 562 g (7.8 mol) of acrylic acid, 58 g of p-toluenesulfonic acid, 900 g of toluene, and 1 g of hydroquinone were placed in a four-necked glass flask and heated while blowing air into it. The water produced in the reaction was removed from the system as it occurred by azeotropic reaction with toluene. The reaction temperature was 100-110°C, and 113 g of reaction water was removed from the system at the end of the reaction. After the reaction, the mixture was washed with alkaline water and then with water to separate the upper toluene layer, and the toluene was removed by distillation under reduced pressure to obtain 669 g (85% yield) of dipentaerythritol 4PO adduct acrylate. The obtained dipentaerythritol 4PO adduct acrylate had an average of 4 moles of propylene oxide added and contained 6 acryloyl groups in the compound.

[0085] (Example 1) A film coating composition was prepared by selecting raw materials according to the formulation conditions of Example 1 shown in Table 1. Specifically, the film coating composition was prepared by blending 33.4 parts by mass of dipentaerythritol 4EO adduct acrylate obtained in Production Example 1 as compound (A), 33.3 parts by mass of pentaerythritol tetraacrylate and 33.3 parts by mass of trimethylolpropane triacrylate as compound (B), and 1.5 parts by mass of OmniradTPO N (manufactured by IGM Resins BV) as initiator (D).

[0086] (Examples 2-13) The film coating compositions were prepared in the same manner as in Example 1, except that the raw materials were selected according to the formulations of each example shown in Table 1.

[0087] (Comparative Examples 1-7) The film coating compositions were prepared in the same manner as in Example 1, except that the raw materials were selected according to the formulations of each example shown in Table 2.

[0088] (Evaluation method) [Preparation of cured products of film coating compositions] The film coating compositions obtained in each example and comparative example were used as coating liquids to coat a 100 μm thick PET film (Toyobo Co., Ltd.'s "Cosmoshine A4360") to a dry film thickness of approximately 10 μm. A bar coater was used for coating. A polypropylene film (hereinafter referred to as PP film) was laminated to the coated film (i.e., the coated surface) using a hand roller, and a UV-LED (365 nm) was shone from the PP film side at an illuminance of 3000 mW / cm². 2 , cumulative illuminance 3500 mJ / cm 2 The coating was cured by irradiation. Subsequently, the PP film was peeled off to obtain a laminate containing the cured product of the film coating composition as a test specimen.

[0089] [Steel wool resistance (scratch resistance)] Using #0000 steel wool on the coated surface (cured material) of the test specimen obtained as described above, a load of 500 g / cm² was applied. 2 The material was polished 10 times, and the state of the hardened material after polishing was visually observed. The steel wool resistance (scratch resistance) was evaluated according to the following criteria. ≪Judgment criteria≫ A: The surface of the hardened material has three or fewer scratches and exhibits extremely excellent scratch resistance. B: Only 4 to 10 scratches can be observed on the surface of the hardened material, indicating excellent scratch resistance. C: More than 10 scratches were observed on the surface of the hardened material, indicating poor scratch resistance.

[0090] [Flexibility (Mandrel Test)] According to the mandrel test (JIS K5600-5-1), the diameter of the mandrel at which cracking and delamination of the cured material from the substrate first occurred in the test specimen was recorded, and flexibility was evaluated. Specifically, if the diameter of the mandrel at which delamination first occurred was 8 or less, it was judged to have "excellent flexibility," and if it exceeded 8, it was judged to have "poor flexibility."

[0091] [Pencil hardness] The hardened material on the surface of the test specimen was subjected to testing in accordance with JIS K5400. Specifically, using a pencil scratch tester, the hardened material was scratched sequentially with pencils of different hardnesses under a load of 750g. The hardness of the pencil that did not scratch the hardened material was defined as the pencil hardness of the hardened material.

[0092] [Viscosity (handling properties)] The viscosity of the film coating compositions was measured at 25°C using an E-type viscometer, and their handling properties were evaluated. Specifically, a viscosity of less than 400 mPa·s was judged as "excellent handling properties," a viscosity of 400 mPa·s or more but less than 700 mPa·s was judged as "good handling properties," and a viscosity of 700 mPa·s or more was judged as "poor handling properties."

[0093] [Heat-resistant adhesion] The aforementioned test specimens were heat-treated at 120°C for 24 hours, and then subjected to a 1mm grid test in accordance with JIS K5400-8.5:1990. In this test, the number of peeled-off squares was measured and the following formula was used. Initial adhesion (%) = 100 - (number of squares that peeled off) The expected adhesion was calculated, and if the expected adhesion was 80% or higher, it was determined to have excellent heat-resistant adhesion.

[0094] (Evaluation results) Tables 1 and 2 show the formulation conditions and evaluation results (steel wool resistance (scratch resistance), heat adhesion resistance, flexibility (mandrel test), pencil hardness, viscosity (handling properties)) for the film coating compositions prepared in each example and comparative example. In the formulation conditions of Tables 1 to 3, blank spaces indicate that the raw material was not used.

[0095] Tables 1 and 2 show that the cured products obtained using the film coating compositions prepared in each example, by containing compound (A), compound (B), and initiator (D) in predetermined proportions, were able to form cured products that were flexible yet possessed excellent scratch resistance, heat adhesion resistance, and high hardness. Furthermore, the film coating compositions obtained in the examples had low viscosity, resulting in excellent handling properties.

[0096] [Table 1]

[0097] [Table 2]

Claims

1. Compound (A) having two or more and six or fewer (meth)acryloyl groups, and Compound (B) other than the aforementioned compound (A) having three or more and six or fewer (meth)acryloyl groups The polymerizable compounds contained, Initiator (D) It contains at least the following: The aforementioned compound (A) contains ethylene oxide units, and the average number of moles of ethylene oxide units added is 1 to 6 moles. The aforementioned compound (A) is a compound having a dipentaerythritol skeleton, The compound (B) is a compound having one or more skeletons selected from the group consisting of a pentaerythritol skeleton, a trimethylolpropane skeleton, and a ditrimethylolpropane skeleton. The initiator (D) is contained in an amount of 0.5 parts by mass or more and 3.5 parts by mass or less per 100 parts by mass of the total mass of the polymerizable compound. The total content ratio of compound (A), compound (B), and initiator (D) is 80% by mass or more. A film coating composition having a solvent content of 10% by mass or less.

2. The film coating composition according to claim 1, wherein compound (A) is contained in an amount of 5 parts by mass or more and 90 parts by mass or less, with respect to 100 parts by mass of the total mass of compound (A) and compound (B).

3. The film coating composition according to claim 1, which has active energy ray curability.

4. A cured product containing a curing component of the film coating composition according to any one of claims 1 to 3.

5. A film containing the cured product described in claim 4.

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