JP6859067B2 - Aqueous composition containing a (meth) acrylate having a fluorene skeleton - Google Patents

Description

The present invention relates to an aqueous composition in which a (meth) acrylate having a 9,9-bisarylfluorene skeleton is dissolved in an aqueous solvent.

(Meta) acrylic resins are used in a wide range of industrial applications such as lenses, molding materials, paints, and adhesives. In particular, it is used for optical material applications such as optical lenses because of its excellent transparency and durability. In recent years, with rapid technological innovation, optical materials such as prism sheets for liquid crystal displays and sheets for touch panels have been provided with high-performance characteristics (high refractive index, high heat resistance, low viscosity, scratch resistance, low water absorption, etc.). There is a growing demand for (meth) acrylic resins that have.

As a compound capable of imparting high heat resistance and a high refractive index to a (meth) acrylic resin, a (meth) acrylate compound having a 9,9-bis (aryl) fluorene skeleton is known. For example, in the WO2013 / 022065 pamphlet (Patent Document 1), a 9,9-bis (phenyl) fluorene skeleton and an average number of moles added are described as a (meth) acrylate compound capable of achieving both excellent scratch resistance and a high refractive index. A polyfunctional (meth) acrylate having an alkylene oxide chain of 8.5 to 17 is disclosed.

However, since the (meth) acrylate compound having such a fluorene skeleton has an aromatic ring, it is water or a general-purpose alcohol (highly safe, has moderate volatility, and is excellent in handleability. Poor solubility in ethanol, isopropanol, etc.). In particular, optical materials such as prism sheets for liquid crystal displays and sheets for touch panels are becoming more water-based in recent years due to increasing needs for resource protection, environmental protection, improvement of work stability, and the like. In addition, most of the filler dispersions, especially metal oxides, are aqueous dispersions. Therefore, in order to prevent the agglutination of the filler, the (meth) acrylate compound having a fluorene skeleton is also required to be an aqueous compound.

In order to make the resin water-based, a method of introducing a sulfo group or a carboxyl group to ionize the resin or a method of lengthening the ethylene oxide chain is usually adopted. However, when the resin is ionized, coloring is likely to occur, and when the ethylene oxide chain is lengthened, the refractive index is lowered, so that it cannot be used in applications requiring high optical characteristics.

WO 2013/022065 Pamphlet (Claim 1, paragraph [0041])

Therefore, an object of the present invention is to provide a bifunctional (meth) acrylate having a fluorene skeleton in an aqueous solvent having appropriate volatility and excellent handleability without impairing high functional properties such as high refractive index. To provide an aqueous composition dissolved in.

Another object of the present invention is to provide an aqueous composition containing a bifunctional (meth) acrylate having a fluorene skeleton and capable of forming a uniform film even when coated.

As a result of diligent studies to achieve the above-mentioned problems, the present inventor surprisingly, despite the fact that the bifunctional (meth) acrylate having a fluorene skeleton does not dissolve in water alone and general-purpose alkanol alone. Instead, they found that they were soluble in an aqueous mixed solvent that combined water and general-purpose alkanol, and completed the present invention.

That is, the aqueous composition of the present invention has a bifunctional (meth) acrylate (A) represented by the following formula (1), water (B1), two or more carbon atoms, and a boiling point lower than that of water. It contains a solvent (B) containing an alkanol (B2) having.

(In the formula, ring Z is an arene ring, A is an alkylene group, R ¹ and R ² are substituents, R ³ is a hydrogen atom or a methyl group, the total of n1 and n2 is a number of 6 to 17, and m is 0 to 4. The number of, k is 0 or a number greater than or equal to 1, and s is 0 or 1).

The bifunctional (meth) acrylate represented by the formula (1) may be a bifunctional (meth) acrylate represented by the following formula (1a).

(In the formula, k is a number from 0 to 4, and R ^{1 to} R ³ , n1, n2 and m are the same as described above).

The alkanol (B2) may be C _2-3 alkanol. In the aqueous composition of the present invention, the total ratio of water (B1) and alkanol (B2) is 90% by weight or more with respect to the total solvent (B), and the weight ratio of water (B1) and alkanol (B2). However, the former / the latter = 1/99 to 50/50 (particularly 10/90 to 30/70) may be obtained. Further, the aqueous composition of the present invention further contains an aqueous solvent (B3) in which the solvent (B) has a boiling point higher than that of water, and the ratio of alkanol (B2) is 50 to 100 parts by weight of water (B1). The ratio of the aqueous solvent (B3) may be about 30 to 50 parts by weight with respect to 100 parts by weight of water (B1). The aqueous solvent (B3) may be cellosolves having a boiling point of more than 100 ° C. and 150 ° C. or lower. The weight ratio of the bifunctional (meth) acrylate (A) represented by the formula (1) to the solvent (B) is about 90/10 to 10/90 of the former / the latter.

In the present invention, a bifunctional (meth) acrylate having a fluorene skeleton is placed in an aqueous solvent having appropriate volatility and excellent handleability without impairing high functional properties such as high refractive index and heat resistance. Can be dissolved. Therefore, it can be used as a coating agent having a low environmental load, and for example, even if a filler formed of a metal oxide or the like is blended, aggregation of the filler can be suppressed. Further, by adjusting the ratio and composition of the solvent, it is possible to provide an aqueous composition containing a bifunctional (meth) acrylate having a fluorene skeleton and capable of forming a uniform film even when coated.

The aqueous composition of the present invention contains the bifunctional (meth) acrylate (A) represented by the above formula (1), water (B1), and an alkanol having 2 or more carbon atoms and having a boiling point lower than that of water. Includes solvent (B) containing (B2). In the present invention, the detailed mechanism by which a specific (meth) acrylate dissolves in a mixed solvent of water and a general-purpose alkanol is unknown, but it is due to a hydrogen bond between the hydroxyl group of the alkanol and the carbonyl group of the (meth) acrylate. It can be inferred that factors such as improved fluidity and solubility of alkanol in the fluorene skeleton are involved.

[Bifunctional (meth) acrylate represented by formula (A) (1)]
The bifunctional (meth) acrylate represented by the formula (1) may be a fluorene-containing epoxy (meth) acrylate having an s of 1 in the formula (1), and may be a fluorene-containing epoxy (meth) acrylate having an s of 0. It may be (meth) acrylate. Of these, a fluorene-containing (meth) acrylate having an s of 0 is preferable, and a bifunctional (meth) acrylate represented by the above formula (1a) is particularly preferable because of its high refractive index.

In the above formula (1), examples of the arene ring represented by ring Z include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, and the like, and the polycyclic arene ring is a fused polycyclic type. An arene ring (condensed polycyclic hydrocarbon ring), a ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring), and the like are included.

_{The ring-assembled arene ring includes a bi-C 6-12} arene ring such as a beerene ring, for example, a biphenyl ring, a binaphthyl ring, a phenylnaphthalene ring (1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.), a tellarene ring, for example. Examples thereof include a tel C _6-12 arene ring such as a terphenylene ring. Preferred ring-set arene rings include biC _6-10 arene rings, particularly biphenyl rings and the like.

Examples of the fused polycyclic arene ring include a condensed bicyclic arene (for example, a fused dicyclic C _10-16 arene such as naphthalene) ring and a condensed tricyclic arene (for example, anthracene, phenanthrene, etc.) ring. Examples thereof include fused two- to four-cyclic arene rings. Preferred condensed polycyclic arene rings include naphthalene rings and anthracene rings, and naphthalene rings are particularly preferable.

The two rings Z may be the same ring or different rings, but are usually the same ring. Among these arene rings, a monocyclic arene ring such as a benzene ring, a beerene ring such as a biphenyl ring, a fused bicyclic arene ring such as a naphthalene ring, and the like are widely used, and a benzene ring is preferable.

_{Examples of the alkylene group of the group A constituting the oxyalkylene group include C 2-6} alkylene groups such as an ethylene group, a propylene group, a trimethylene group, a 1,2-butandyl group and a tetramethylene group. The groups A on both sides may be the same alkylene group or different alkylene groups. When n is 2 or more polyoxyalkylene groups, the alkylene groups constituting the polyoxyalkylene group may be different alkylene groups, or may be usually the same alkylene group. As the group A, a C _{2-3 alkylene group is preferable from the viewpoint of optical characteristics, and a C 2-3} alkylene group (particularly an ethylene group) such as an ethylene group or a propylene group is particularly preferable.

The number of repetitions (number of moles added) of the oxyalkylene group AO, n1 and n2 (the number of repetitions of each group AO), may be a total of 6 to 17, preferably 7 to 15, and more preferably 8 to. The number may be about 14 (particularly 10 to 12). Further, the number of added moles may be an average value (additional average value or arithmetic average value). If the total of n1 and n2 is less than 6, a transparent aqueous composition cannot be prepared, and if it exceeds 17, a fluorene-containing (meth) acrylate or a fluorene-containing epoxy (meth) acrylate can be prepared. High-performance characteristics are reduced.

The total of n1 and n2 may be in the above range, and each of n1 and n2 is not particularly limited and may be a number selected from the range of 0 to 17, for example, 1 to 12, preferably 2. The number is 10, more preferably about 3 to 8 (particularly 4 to 7).

In the above formula (1), the substitution position of the (meth) acryloyl group-containing group is not particularly limited, and when the ring Z is a benzene ring, it may be any of the 2nd to 6th positions of the benzene ring substituted at the 9th position of fluorene. There may be, but 4th place is preferable. When the ring Z is a naphthalene ring, it is often at the 5-8 position of the naphthyl group. For example, it is at the 1-, 5-position, 2-, 6-position with respect to the 9-position of fluorene. In many cases, it is a relationship such as (especially a 2- or 6-position relationship).

The substituent R ^1, for example, an alkyl group (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, e.g., a straight chain or branched chain C _1-6 alkyl group such as a t- butyl group) , A hydrocarbon group such as an aryl group (eg, a C _6-10 aryl group such as a phenyl group); a cyano group; a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.) and the like.

These substituents R ¹ may be used singly or in combination. As the substituent R ¹ , an alkyl group [for example, a linear or branched C _1-4 alkyl group (particularly, a C _1-3 alkyl group such as a methyl group)], a cyano group, and a halogen atom are preferable, and particularly Alkyl groups (eg, C _1-2 alkyl groups such as methyl groups) are preferred.

The substitution number m of substituents ^{R 1} are each be selected from the integers from 0 to 4, for example 0-3, preferably 0-2, more preferably may be a 0-1 (especially 0). In the two benzene rings forming the fluorene skeleton, the substitution numbers m may be the same or different from each other ^{, and the types of R 1} may be the same or different from each other. Further, when m is 2 or more, two or more kinds of R ¹ to be substituted with the same benzene ring may be the same or different from each other. The substitution position of R ¹ is not particularly limited, and may be, for example, the 2-position to the 7-position (2-position, 3-position, 7-position, etc.) of the fluorene ring.

Examples of the substituent R ² _{include an alkyl group (for example, a C 1-6} alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group) and a cycloalkyl group (C such as a cyclohexyl group). _5-8 cycloalkyl group, etc.), aryl group (eg, C _{6-10 aryl group such as phenyl group, tolyl group, xsilyl group), aralkyl group (C 6-10} aryl-C such as benzyl group, phenethyl group, etc.) _{Hydrocarbon groups such as 1-4} alkyl groups; alkoxy groups (such as C _1-6 alkoxy groups such as methoxy groups), cycloalkoxy groups (such as C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryl Oxy group (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (C _6-10 aryl-C _1-4 alkyl group such as benzyloxy group); alkylthio group (C _{1 such as methylthio group) -6} Alkylthio group, etc.); Acyl group (C _1-6 acyl group such as acetyl group); Halogen atom (Fluorine atom, Chlorine atom, Bromine atom, Iodine atom, etc.); Nitro group; Cyano group; Dialkylamino group ( _{DiC 1-4} alkylamino group such as dimethylamino group); dialkylcarbonylamino group (diC _1-4 alkyl-carbonylamino group such as diacetylamino group) and the like.

These substituents R 2 may be used singly or in combination. The substituent R 2, C 1-6 alkyl, C 5-8 cycloalkyl group, a C 1-4 alkoxy group, and particularly preferably a C 1-4 alkyl group such as a methyl group.

The substitution number k of the substituents ^{R 2} can be appropriately selected depending on the kind of ring Z, for example, may be about 0-8, preferably 0-4 (e.g. 0-2), more preferably 0 or It may be 1. When k is 1, ring Z may be a benzene ring, a naphthalene ring or a biphenyl ring, and R ² may be a methyl group. In particular, when ring Z is a benzene ring, the substitution number k of the substituents ^{R 2} may be selected from the integer of example 0-4, example 0-3, preferably 0-2, more preferably 0-1 (especially It may be 0). The number of substitutions k in different arene rings may be the same or different from each other. Further, when the substitution number k is 2 or more, two or more kinds of R ² to replace the same arene ring may be the same or different. The substitution position of R ² is not particularly limited, and it may be substituted at a position other than the bond position between the arene ring and the 9-position of the ether bond (-O-) and the fluorene ring.

Among the bifunctional (meth) acrylates represented by the formula (1), typical compounds include 9,9-bis [(meth) acryloyloxy-polyethoxyphenyl] fluorene, 9,9-. 9,9-bis [(meth) acryloyloxy-polyethoxyaryl] fluorene such as bis [(meth) acryloyloxy-polyethoxynaphthyl] fluorene; 9,9-bis [(3- (meth) acryloyloxy-2) -Hydroxypropoxy) polyethoxyphenyl] fluorene, 9,9-bis [(3- (meth) acryloyloxy-2-hydroxypropoxy) polyethoxynaphthyl] fluorene and other 9,9-bis [(3- (meth) acryloyl) Oxy-2-hydroxypropoxy) polyethoxyaryl] Fluolens and the like can be mentioned.

The bifunctional (meth) acrylate represented by the formula (1) can be produced by a conventional method, and for example, the bifunctional (meth) acrylate represented by the formula (1a) is described in Patent Document 1. It may be manufactured by a method.

[(B) Solvent]
The solvent (B) may contain water (B1) and alkanol (B2), but water (B1) and alkanol (B2) are excellent in solubility in bifunctional (meth) acrylate (A). A two-component solvent containing, as a main component, a three-component solvent containing water (B1), an alkanol (B2), and an aqueous solvent (B3) having a boiling point higher than that of water as a main component is preferable.

Alkanol (B2) may have 2 or more carbon atoms and have a boiling point lower than that of water. Specifically, examples of the alkanol (B2) include ethanol, 1-propanol, 2-propanol (isopropanol), 2-butanol (s-butyl alcohol), C _2-4 alkanol such as t-butyl alcohol, and the like. Can be mentioned. These alkanols can be used alone or in combination of two or more. _{Among these alkanols, C 2-3} alkanols such as ethanol and isopropanol are preferable from the viewpoint of excellent solubility in bifunctional (meth) acrylate (A), and isopropanol is preferable from the viewpoint of excellent solubility and handleability. Especially preferable.

The aqueous solvent (B3) may be any aqueous solvent having a boiling point higher than that of water. _{Specifically, examples of the aqueous solvent (B3) include (poly) C 2-4} alkanediols such as aliphatic polyhydric alcohols (ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, and triethylene glycol). Glycerin, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc., C _1-4 alkyl cellosolve, propylene glycol monomethyl ether, etc., propylene glycol mono C _1-4 alkyl ether, etc.), cellosolve acetates (ethyl cellosolve acetate, etc.) C _1-4 alkyl cellosolve acetate, propylene glycol mono C _1-4 alkyl ether acetates such as propylene glycol monomethyl ether acetate), carbitol (methyl carbitol, ethyl carbitol, propyl carbitol, and butyl carbitol C _1-4 alkyl carbitols; diethylene glycol dimethyl ether (diglyme), diethylene glycol methyl ethyl ether, etc.) and the like can be mentioned. These aqueous solvents can be used alone or in combination of two or more.

Among these aqueous solvents, cellosolves such as methyl cellosolve (2-methoxyethanol) and propylene glycol monomethyl ether (1-methoxy-2-propanol) are preferable from the viewpoint of excellent handleability.

The boiling point of the aqueous solvent (B3) may be higher than that of water, but from the viewpoint of handleability, it may be 150 ° C. or lower, for example, 103 to 150 ° C., preferably 105 to 140 ° C., more preferably 110 to 10 ° C. It is about 130 ° C. (particularly 115 to 125 ° C.).

Ratio of main component in solvent (B) [In the case of a two-component system, it is the total ratio of water (B1) and alkanol (B2), and in the case of a three-component system, water (B1), alkanol (B2) and an aqueous solvent ( The total ratio of B3)] may be 90% by weight or more, preferably 95% by weight or more, more preferably 99% by weight or more, and may be only the main component. Examples of the aqueous solvent other than the main component include ketones (diC _1-4 alkyl ketones such as acetone and methyl ethyl ketone) and cyclic ethers (tetrahydrofuran and the like). The ratio of the other aqueous solvent may be, for example, 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, based on the whole solvent (B).

When the solvent (B) is a two-component solvent, the weight ratio of water (B1) and alkanol (B2) can improve the solubility of the bifunctional (meth) acrylate (A). B1) / alkanol (B2) = 1/99 to 50/50, preferably 3/97 to 40/60 (eg 5/95 to 35/65), more preferably 10/90 to 30/70 (particularly 15 /). It is about 85 to 25/75).

When the solvent (B) is a two-component solvent, the weight ratio of water (B1) and alkanol (B2) is that of water (B1) and alkanol (B2) because the uniformity of the coating film can be improved. The weight ratio may be close to the azeotropic mixing ratio. If it is significantly different from the azeotropic mixture ratio, when the aqueous composition is coated and heated, the highly volatile alkanol volatilizes, resulting in an increase in the water content and the solubility of the bifunctional (meth) acrylate (A). Since it is lowered, the coating film tends to become cloudy. When water is further volatilized by continuing heating, the coating film returns to transparent, but there is a risk that the uniformity of the coating film will decrease due to the decrease in solubility during the heating process. For example, when the alkanol (B2) is isopropanol, the weight ratio of water (B1) to isopropanol is water / isopropanol = 5/95 to 40/60, preferably 8/92 to 30/70, more preferably 10. It may be about / 90 to 20/80.

When the solvent (B) is a three-component solvent, the ratio of alkanol (B2) can improve the solubility of the bifunctional (meth) acrylate (A) with respect to 100 parts by weight of water (B1). It is preferably 50 parts by weight or more (for example, 50 to 100 parts by weight), and from the viewpoint of improving the uniformity of the coating film, for example, 50 to 80 parts by weight, preferably 55 to 70 parts by weight, and more preferably 58 to 50 parts by weight. It is about 65 parts by weight. The ratio of the aqueous solvent (B3) is preferably 55 parts by weight or less (for example, 10 to 55 parts by weight) with respect to 100 parts by weight of water (B1), and from the viewpoint of improving the uniformity of the coating film, for example, 25 It is about 50 parts by weight, preferably 30 to 48 parts by weight, and more preferably about 35 to 45 parts by weight.

[Aqueous composition]
In the aqueous composition of the present invention, the weight ratio of the bifunctional (meth) acrylate (A) represented by the formula (1) to the solvent (B) is, for example, the bifunctional (meth) acrylate (A). ) / Solvent (B) = 90/10 to 10/90, preferably about 80/20 to 20/80, and more preferably about 70/30 to 30/70 (particularly 60/40 to 40/60). If the proportion of the bifunctional (meth) acrylate (A) is too large, the handleability may be deteriorated, and if the proportion of the solvent (B) is too large, it may be difficult to form a uniform coating film. ..

In addition to the bifunctional (meth) acrylate (A) and the solvent (B), the aqueous composition of the present invention may further contain other polymerizable components, conventional additives and the like.

Other polymerizable components include, for example, conventional aqueous vinyl compounds other than bifunctional (meth) acrylate (A), such as (meth) acrylic acid, hydroxyalkyl (meth) acrylate (hydroxyethyl acrylate, hydroxypropyl methacrylate). , Etc.), alkoxypolyalkylene glycol (meth) acrylate (methoxypolyethylene glycol acrylate such as methoxytriethylene glycol acrylate), maleic acid, maleic anhydride, polyethylene glycol di (meth) acrylate (tetraethylene glycol diacrylate, etc.), etc. Can be mentioned. The ratio of other polymerizable components is, for example, 50 parts by weight or less, preferably 30 parts by weight or less, and more preferably 10 parts by weight or less (for example, 0. 1 to 5 parts by weight).

Conventional additives include, for example, resin components, polymerization initiators, polymerization inhibitors (hydroquinone, hydroquinone monoethyl ether, etc.), defoamers, coatability improvers, thickeners, lubricants, stabilizers (antioxidants). , Heat stabilizers, light-resistant stabilizers, etc.), plasticizers, surfactants, dissolution accelerators, colorants, fillers, antistatic agents, silane coupling agents, leveling agents, dispersants, dispersion aids, etc. Can be mentioned. These additives can be used alone or in combination of two or more. Among these additives, the aqueous composition of the present invention preferably contains a filler (particularly, an inorganic filler such as a metal oxide), which is difficult to uniformly disperse with the conventional hydrophobic composition.

The proportion of the conventional additive may be 50% by weight or less based on the whole aqueous composition, for example, 0.01 to 50% by weight, preferably 0.1 to 30% by weight, more preferably 0.5% by weight. It is about 10% by weight. When the additive is an inorganic filler (particularly a filler formed of a metal oxide), the proportion of the inorganic filler may be 70% by weight or less based on the entire aqueous composition, for example, 10 to 50% by weight. It is preferably about 15 to 40% by weight, more preferably about 20 to 30% by weight.

Since the aqueous composition of the present invention contains a bifunctional (meth) acrylate (A), it has a high refractive index, and the refractive index at 20 ° C. and a wavelength of 589 nm is 1.5 or more (for example, 1.5). It may be about 1.6 or more), preferably 1.53 or more, and more preferably 1.55 or more (particularly 1.57 or more).

Since the bifunctional (meth) acrylate (A) is dissolved in the solvent (B), the aqueous composition of the present invention has excellent transparency and impairs the transparency of the bifunctional (meth) acrylate. Never. Further, since water (B1) and alkanol (B2) are industrially mass-produced and the like, they can be obtained at low cost, so that the aqueous composition of the present invention can also be provided at low cost.

The aqueous composition of the present invention is mixed by using a conventional stirring means, for example, a mechanical stirring means using a stirring rod or a stirrer (such as a mixer having a rotating blade), an ultrasonic disperser, or the like. Can be prepared.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The abbreviations and details of the raw materials used are shown below. The characteristics of the resin or film were measured and evaluated by the following methods.

[material]
BPEF-A: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] Fluoren, manufactured by Osaka Gas Chemical Co., Ltd. BPEF-3EO: 9,9-bis [4- (2-hydroxyethoxy) phenyl] Addition BPEF-5EO: 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene to which a total of 3 mol of oxyethylene groups (or ethylene oxides) were added to 1 mol of fluorene. On the other hand, for 1 mol of the adduct BPEF-9EO: 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene to which a total of 5 mol of oxyethylene groups were added, the average value was 9 in total. mol adduct BPEF-3EOA oxyethylene groups are added: BPEF-3EO diacrylate [in formula (1a), compound n1 + n2 is 5, ^{R 3} is a hydrogen atom, k and m are 0]
BPEF-5EOA: BPEF-5EO diacrylate BPEF-9EOA: BPEF-9EO diacrylate BPEF-5EO-GA: BPEF-5EO diglycidyl ether with acrylic acid added diacrylate BPEF-9EOA-GA: BPEF-9EO Diacrylate DPHA with acrylic acid added to diglycidyl ether: Dipentaerythritol hexaacrylate, "DPHA" manufactured by Daicel Ornex Co., Ltd.
4EG-A: Tetraethylene glycol diacrylate 9EG-A: Polyethylene glycol diacrylate (average of 9 moles of ethylene oxide adduct)
14EG-A: Polyethylene glycol diacrylate (average 14 mol ethylene oxide adduct)
BisA-10EO: Bisphenol A with a total of 10 mol of oxyethylene groups added on average.

[Refractive index (nD)]
The raw material acrylate uses a multi-wavelength Abbe refractive index meter (manufactured by Atago Co., Ltd., DR-M2 <using a circulating constant temperature water tank 60-C3>) to maintain a temperature of 25 ° C and measure the refractive index at 589 nm. did.

[Solubility]
The aqueous composition obtained by stirring in Examples and Comparative Examples was allowed to stand for 1 minute after the completion of stirring, and then the state of the composition was visually observed and the solubility of the acrylate was evaluated according to the following criteria.

◯: The acrylate was dissolved (mixed) in the solvent and was a transparent one-layer liquid. Δ: The acrylate was not dissolved in the solvent and became cloudy. ×: The acrylate was not dissolved in the solvent and separated into two layers. Was there.

[Coating property]
Using a bar coater, the aqueous composition obtained by stirring in Examples and Comparative Examples was coated on a glass substrate to prepare a coating film of about 100 μm. Then, the state of the film obtained by heating and drying on a hot plate at 80 ° C. for 10 minutes was visually observed and evaluated according to the following criteria.

◯: The obtained coating film was transparent ×: The obtained coating film became cloudy.

Reference Examples 1 to 7 and Examples 1 to 3
Water and isopropanol (2-propanol) were collected in a sample tube at the ratio shown in Table 1 to prepare a mixed solution. 5 parts by weight of this mixed solution and 5 parts by weight of the bifunctional acrylate shown in Table 1 were collected in a sample tube and stirred with a touch-driven stirrer for about 10 seconds to prepare an aqueous composition. Table 1 shows the results of measuring the refractive index of the bifunctional acrylate alone and the results of evaluating the solubility of the obtained aqueous composition.

As is clear from the results in Table 1, in the examples, the bifunctional acrylate having a high refractive index was not dissolved in water alone and isopropanol alone, but was dissolved by mixing both.

Example 4
10 parts by weight of water and 40 parts by weight of isopropanol were collected in a sample tube to prepare a mixed solution. 5 parts by weight of this mixed solution and 5 parts by weight of BPEF-5EOA were collected in a sample tube and stirred with a touch-driven stirrer for about 10 seconds to prepare an aqueous composition. The refractive index of the bifunctional acrylate alone was 1.578, and BPEF-5EOA was dissolved in a solvent to form a transparent one-layer liquid.

Reference Examples 8 to 19 and Examples 5 to 6
Water and the solvent shown in Table 2 (for Reference Examples 16 to 19, other polymerization components also functioning as a solvent) were collected in a sample tube at the ratio shown in Table 2 to prepare a mixed solution. 5 parts by weight of this mixed solution and 5 parts by weight of BPEF-9EOA were collected in a sample tube and stirred with a touch-driven stirrer for about 10 seconds to prepare an aqueous composition. The results of evaluating the solubility of the obtained aqueous composition are shown in Table 2.

As is clear from the results in Table 2, in the examples, the bifunctional acrylate was dissolved by mixing water with a general-purpose alkanol.

Examples 7-10
Water and the solvent shown in Table 3 were collected in a sample tube at the ratio shown in Table 3 to prepare a mixed solution. 5 parts by weight of this mixed solution and 5 parts by weight of BPEF-9EOA were collected in a sample tube and stirred with a touch-driven stirrer for about 10 seconds to prepare an aqueous composition. Table 3 shows the results of evaluating the solubility and coating property of the obtained aqueous composition.

As is clear from the results in Table 3, the solubility of the bifunctional acrylate was high in all the examples, and in particular, the coating properties were also high in Examples 7 and 10.

The aqueous composition of the present invention includes, for example, an ink material, a light emitting material (for example, a light emitting material for an organic EL), an organic semiconductor, a graphite precursor, a gas separation film (for example, a CO ₂ gas separation film), and a coating agent. (For example, an optical overcoat agent or hard coat agent such as a coating agent for an element for an LED (light emitting diode)), a lens [pickup lens (for example, a pickup lens for a DVD (digital versatile disc)), a microlens (For example, microlenses for liquid crystal projectors, etc.), spectacle lenses, etc.], polarizing films (for example, polarizing films for liquid crystal displays, etc.), composite sheets, brightness-enhancing films, prism sheets, antireflection films (or antireflection films, for example, etc.) Antireflection film for display devices, etc.), Touch panel film, Flexible substrate film, Display film [For example, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron emission) Element display), FED (liquid crystal display), NED (nano-emissive display), brown tube, film for display (especially thin display) such as electronic paper (protective film, etc.)], retardation film, diffusion sheet, guide Optical plates, reflective sheets, diffusers, barrier films, protective films, overcoats, flexible film substrates, anisotropic conductive adhesive films (ACF), color filters [for example, lens filters, color filters for displays, etc.], for liquid crystal displays Negative type photoresists [for example, photoresists for TFT array etching, pigment dispersion type photoresists, dye type photoresists, protective films, etc.], interlayer insulating films, solder resists, photospacers for liquid crystal displays, membranes for fuel cells, optical fibers, It can be suitably used for optical waveguides, holograms, various optical adhesives [for example, optical lenses, prisms, optical fibers, optical filters, optical waveguides], keypads, keyboards, touch panels, and the like.

Claims (8)

A solvent (B) containing a bifunctional (meth) acrylate (A) represented by the following formula (1), water (B1), and an alkanol (B2) having 2 or more carbon atoms and having a boiling point lower than that of water. ), The weight ratio of the water (B1) to the alkanol (B2) is the former / the latter = 3/97 to 40/60.

(In the formula, ring Z is an arene ring, A is an alkylene group, R ¹ and R ² are substituents, R ³ is a hydrogen atom or a methyl group, the total of n1 and n2 is a number of 6 to 17, and m is 0 to 4. Number, k is 0 or more than 1, s is 0 or 1) The aqueous composition according to claim 1, wherein the bifunctional (meth) acrylate represented by the formula (1) is a bifunctional (meth) acrylate represented by the following formula (1a).

(In the formula, k is a number from 0 to 4, and R ^{1 to} R ³ , n1, n2 and m are the same as described above). The aqueous composition according to claim 1 or 2, wherein the alkanol (B2) is a C _{2-3 alkanol.} The total ratio of water (B1) and alkanol (B2) is 90% by weight or more with respect to the total solvent (B), and the weight ratio of water (B1) and alkanol (B2) is the former / the latter = 5 /. The aqueous composition according to any one of claims 1 to 3, which is 95 to 35/65. The aqueous composition according to claim 4, wherein the weight ratio of water (B1) and alkanol (B2) is the former / the latter = 10/90 to 30/70. Bifunctional (meth) acrylate (A) represented by the following formula (1), water (B1), alkanol (B2) having 2 or more carbon atoms and a boiling point lower than that of water, and exceeding 100 ° C. An aqueous composition containing a solvent (B) containing an aqueous solvent (B3) having a boiling point of 150 ° C. or lower , wherein the ratio of the alkanol (B2) is 100 parts by weight of the water (B1). An aqueous composition having 50 parts by weight or more and the ratio of the aqueous solvent (B3) to 25 to 50 parts by weight with respect to 100 parts by weight of the water (B1).

(In the formula, ring Z is an arene ring, A is an alkylene group, R ¹ and R ² are substituents, R ³ is a hydrogen atom or a methyl group, the total of n1 and n2 is a number of 6 to 17, and m is 0 to 4. Number, k is 0 or more than 1, s is 0 or 1) The aqueous composition according to claim 6, wherein the aqueous solvent (B3) is a cellosolve having a boiling point of more than 100 ° C. and a boiling point of 150 ° C. or lower. Any one of claims 1 to 7, wherein the weight ratio of the bifunctional (meth) acrylate (A) represented by the formula (1) to the solvent (B) is the former / the latter = 90/10 to 10/90. Aqueous composition according to.