Curable compositions and composite materials

Abstract

To provide a curable composition in which a layered compound is dispersed in a liquid phase containing a monomer starting material.SOLUTION: The provided curable composition contains a liquid phase containing a monomer starting material, and a layered compound dispersed in the liquid phase. The layered compound has been subjected to organification using organic ions. The monomer starting material contains a polar monomer (m1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition and a composite material formed from the curable composition. [Background technology]

[0002] Composite materials are known in which layered compounds, such as layered clay minerals, are dispersed in a matrix phase made of a resin material. For example, Patent Document 1 describes how, in order to provide an acrylic adhesive or adhesive sheet that can achieve both transparency and high-temperature adhesive properties, an acrylic monomer is mixed with an organic layered clay mineral and a polymerization initiator together with an organic solvent, and an appropriate external action is applied to this mixture to intercalate the monomer, polymerization initiator and a portion of the organic solvent between the layers of the organic layered clay mineral, then the solvent is removed and a polymerization reaction is carried out to obtain a composite in which the clay mineral is finely dispersed in the resulting polymer (paragraphs 0005-0006). Patent Document 2 is another document relating to an adhesive containing an acrylic polymer and an organic layered clay mineral. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2003-129020 [Patent Document 2] Japanese Patent Publication No. 2003-183457 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Patent Document 1 describes a curable composition in which organic layered clay minerals are finely dispersed, which is obtained by ultrasonic treatment or high-speed shear dispersion in the presence of an organic solvent, and it is shown that dispersibility decreases when an organic solvent is not used (Comparative Example 2). Furthermore, in a specific example described in Patent Document 2, a transparent (well-dispersible) dispersion is prepared by further ultrasonic treatment after mixing with a disperser (paragraph 0047 of Patent Document 2). If a curable composition is provided that can be prepared without requiring organic solvents or ultrasonic treatment, and that can form a cured product in which layered compounds are well dispersed in a matrix phase made of resin material, it would be beneficial from the viewpoint of reducing environmental impact and improving productivity.

[0005] The present invention has been made in view of the above circumstances, and one object is to provide a curable composition in which a layered compound is dispersed in a liquid phase containing monomer raw materials. Another object of the present invention is to provide a composite material which is a cured product of the above curable composition. Another related object is to provide a method for producing the above curable composition. [Means for solving the problem]

[0006] This specification provides a curable composition comprising a liquid phase containing a monomer raw material and a layered compound dispersed in the liquid phase. The layered compound is a layered compound organically modified with organic ions (hereinafter also referred to as layered compound (A)). The monomer raw material contains a polar monomer (m1). The use of the polar monomer (m1) facilitates the dispersion of the layered compound (A) in the liquid phase containing the polar monomer (m1). By curing such a curable composition, a cured product can be formed in which the layered compound (A) is well dispersed in a matrix phase formed from the liquid phase.

[0007] In some embodiments of the technologies disclosed herein (including curable compositions, methods for producing the same, composite materials which are cured products of the curable compositions, adhesive sheets and laminated sheets having the composite material, etc.; the same applies hereinafter), the monomer raw material is a polar monomer containing a nitrogen atom (m1N )(Hereafter, "Nitrogen atom-containing monomer (m1 N )" or "monomer (m1 N It is sometimes written as ")". It is preferable to include ). Nitrogen atom-containing monomer (m1 N ) can preferably contribute to improving the dispersibility of the layered compound (A).

[0008] In some embodiments, the monomer raw material includes a linear alkyl (meth)acrylate (m2) having a linear alkyl group with 4 to 20 carbon atoms at its ester terminus (hereinafter also referred to as "monomer (m2)"). The techniques disclosed herein can preferably be carried out using a monomer raw material containing monomer (m2). The monomer (m2) content in the monomer raw material may be, for example, 55% by weight or more.

[0009] In some embodiments, the monomer raw material is a linear alkyl (meth)acrylate (m2) having a linear alkyl group with 13 to 20 carbon atoms (for example, 15 to 20 carbon atoms) at the ester terminus. L )(Hereafter, "monomer (m2 L ) is also called ). ) includes. The technology disclosed herein is monomer (m2 L This can preferably be carried out using monomer raw materials containing ).

[0010] In some embodiments, the curable composition may further contain a softening agent. By using a combination of monomer raw materials and a softening agent, the properties of the cured product (e.g., flexibility and optical properties) can be appropriately adjusted.

[0011] Some embodiments of curable compositions are configured to form an adhesive by curing with at least one of light and heat. Here, "adhesive" refers to a material that, as described above, exhibits a soft solid (viscoelastic) state in the temperature range near room temperature and has the property of adhering to an adherend by pressure. With such a curable composition, an adhesive can be easily formed in which a layered compound (A) is dispersed in a matrix phase made of a viscoelastic material derived from the liquid phase of the curable composition.

[0012] This specification provides a composite material which is a cured product of any of the curable compositions disclosed herein. In some embodiments, the composite material has the following properties: Moisture permeability (40℃, 92%RH) is 300g / m 2 • Less than 24 hours; and, The haze is 10% or less; It may satisfy both conditions. According to the technology disclosed herein, it is possible to realize a composite material that achieves both low moisture permeability and high transparency.

[0013] Furthermore, this specification provides a method for producing a curable composition. The method comprises mixing a layered compound organically modified with organic ions (i.e., layered compound (A)) with the above-mentioned monomer raw material in the absence of a solvent. The above method is preferred as a method for producing any of the curable compositions disclosed herein.

[0014] Furthermore, combinations of the elements described herein may also be included within the scope of the invention for which patent protection is sought in this patent application. [Brief explanation of the drawing]

[0015] [Figure 1] This is a schematic cross-sectional view showing the structure of a laminated sheet containing a composite material according to one embodiment. [Figure 2] This is a schematic cross-sectional view showing the structure of a laminated sheet containing a composite material according to another embodiment. [Figure 3]This is a schematic cross-sectional view showing the structure of an optical laminate in which a composite material according to one embodiment is laminated on an optical member. [Modes for carrying out the invention]

[0016] Preferred embodiments of the present invention are described below. Matters other than those specifically mentioned herein but necessary for carrying out the present invention can be understood by those skilled in the art based on the teachings on carrying out the invention described herein and the common technical knowledge at the time of filing. The present invention can be carried out based on the contents disclosed herein and the common technical knowledge in the art. Furthermore, in the following drawings, components and parts that perform the same function may be denoted by the same reference numerals and described accordingly, and redundant descriptions may be omitted or simplified. Also, the embodiments shown in the drawings are schematic for the purpose of clearly illustrating the present invention and do not necessarily accurately represent the size or scale of the actual product provided.

[0017] <Layered compound (A)> In the techniques disclosed herein, the layered compound (A) is obtained by organically modifying a layered compound (typically an inorganic layered compound) with organic ions. Examples of the above layered compounds include smectite, vermiculite, illite, kaolinite, halloysite, talc, mica, etc. Layered silicate compounds are preferred, and smectite is particularly preferred. Examples of smectite include montmorillonite, bydelite, nontronite, saponite, hectorite, souconite, stevensite, etc. Layered compounds can be obtained from natural minerals, refined natural minerals, or synthesized compounds. Refined natural mineral layered compounds and synthesized layered compounds (e.g., synthetic smectite) are advantageous from the viewpoint of quality stability.

[0018] The layered compound (A) may have a structure in which organic ions are introduced into the layered compound (preferably a layered silicate compound) as described above. For example, exchangeable inorganic ions (Na) in the layered compound (e.g., a layered silicate compound)+ , Mg 2+ , etc.) may have a structure obtained by ion exchange with an organic cation.

[0019] Examples of the organic cation include organic cations (onium ions) such as organic ammonium, imidazolium, pyridinium, and phosphonium. Examples of the organic ammonium include tetraalkylammonium such as trioctylmethylammonium and dimethyl distearylammonium; ammonium having alkyl and aryl groups such as stearyl dimethyl benzylammonium; ammonium containing a polyoxyalkylene structure such as polyoxypropylene methyl diethylammonium; and the like. Examples of imidazolium include methylstearyl imidazolium, distearyl imidazolium, methylhexyl imidazolium, dihexyl imidazolium, methyloctyl imidazolium, dioctyl imidazolium, methyldodecyl imidazolium, didodecyl imidazolium, and the like. Examples of pyridinium include stearyl pyridinium, hexyl pyridinium, octyl pyridinium, dodecyl pyridinium, and the like. Examples of phosphonium include dodecyltriphenylphosphonium, methyltriphenylphosphonium, lauryltrimethylphosphonium, stearyltrimethylphosphonium, distearyldimethylphosphonium, distearyldibenzylphosphonium, and the like. The counter anion of the organic cation used for ion exchange is, for example, Cl - , B - , Br - , etc.

[0020] In some aspects of the technology disclosed herein, the organic cation is preferably an organic ammonium. As a preferred example of the organic ammonium, an alkyl group having 12 to 20 carbon atoms (hereinafter, "X to Y carbon atoms" is sometimes referred to as C X-Y "). C 4-11 alkyl group (for example, C 6-10 alkyl group), C 1-3Examples of organic ammonium compounds include those having a total of four groups on the nitrogen atom, selected from the group consisting of alkyl groups and polyoxyalkylene groups (e.g., polyoxypropylene groups). From the viewpoint of ion exchangeability, linear alkyl groups are preferred, and more preferably, linear alkyl groups.

[0021] In some embodiments, the organic ammonium comprises 1 to 4 (preferably 1 to 3, for example, 2 or 3) C12. 4-11 An alkyl group and 0 to 3 (preferably 1 to 3, for example 1 or 2) C 1-3 It may be an organic ammonium having alkyl groups such that the sum of the alkyl groups is 4. Here, C 1-3 The number of alkyl groups is 0, which means C 1-3 This means that it does not have an alkyl group. A specific example of the above organic ammonium is trioctylmethylammonium. Such an embodiment may be advantageous in terms of the transparency and barrier properties of the cured product (composite material) formed from the curable composition. The reason for this is that the above organic ammonium is C 4-11 The presence of an alkyl group widens the spacing between the layers constituting the layered compound, weakening interlayer interactions and imparting appropriate hydrophobicity. As a result, the liquid phase containing the polar monomer (m1) can more easily penetrate between the layers of the layered compound (A), improving the ease of dispersibility of the layered compound (A) in the liquid phase. The above organic ammonium is C 12 The absence of the long-chain alkyl group mentioned above can be advantageous in terms of affinity with polar monomers (m1).

[0022] In some other embodiments, the above organic ammonium comprises 1 to 3 (e.g., 2 or 3) C 1-3The organic ammonium may have an alkyl group and 1 to 3 (for example, 1 or 2) polyoxypropylene groups, totaling 4. Such an embodiment may be advantageous from the viewpoint of ease of dispersion of the layered compound (A) in the curable composition, and consequently from the viewpoint of achieving a good dispersion state of the layered compound (A) in the cured product (composite material) formed from the curable composition. The reason for this is that, because the organic ammonium has polyoxypropylene groups, the spacing between the layers constituting the layered compound is widened, the interlayer interactions of the layered compound are weakened, and appropriate hydrophobicity is imparted, as a result the liquid phase containing the polar monomer (m1) can easily penetrate between the layers of the layered compound (A), improving the ease of dispersion of the layered compound (A) in the liquid phase. A preferred example of the organic ammonium is, for example, the following formula (1): [R 1 R 2 R 3 N(CH2CH(CH3)O) n -H] + (1); Examples include polyoxypropylene trialkylammonium represented by the above formula (1). 1 , R 2 , R 3 Each of these is independently a methyl group or an ethyl group, and n is 2 to 50 (preferably 15 to 35). In some embodiments, the lower end of the range of n in formula (1) may be, for example, 5, 10, 15, and 20, and the upper end of the range of n may be, for example, 45, 40, 35, and 30. A suitable example of the compound represented by formula (1) is polyoxypropylene methyldiethylammonium.

[0023] In some embodiments of the curable composition or its cured product (composite material) disclosed herein, the layered compound (A) is preferably dispersed in a liquid phase or matrix phase in the form of plate-like particles with a thickness of about 0.5 nm to 20 nm (preferably about 0.8 nm to 10 nm, more preferably about 0.8 nm to 5 nm, for example about 1 nm) and an average length of about 30 nm to 3000 nm (preferably about 40 nm to 1000 nm, more preferably about 50 nm to 500 nm, for example about 100 nm to 200 nm). The majority of the above plate-like particles (for example, 60% by weight or more, preferably 80% by weight or more, more preferably 95% by weight or more) is preferably a single-layer structure containing only one layer from the layers that the layered compound (A) had before dispersion. The average length of the above plate-like particles means the arithmetic mean of the longer side of the length of the plate-like particle. The average aspect ratio of the plate-like particles may be, for example, 10 to 2000, preferably 20 to 1000, and more preferably 50 to 500 (for example, 100 to 200). The average aspect ratio refers to the arithmetic mean of the ratio (aspect ratio) of the length of the longer side to the thickness of each plate-like particle. The average length and average aspect ratio of the plate-like particles can be determined, for example, by analyzing transmission electron microscope (TEM) images.

[0024] The layered compound, which has been organicized by organic ions, contains exchangeable inorganic ions (Na) in the inorganic layered compound. + Mg 2+ These can be obtained by ion exchange with organic cations. Examples of commercially available organic layered compounds include Smecton (trade names) STN, SAN, SAN-P, SSN, SPN-E, SEN, Kunibis (trade names) 110, 127, and Moistonite (trade name) WO, all manufactured by Kunimine Industries Co., Ltd.

[0025] The curable compositions disclosed herein may contain the layered compound (A) in an amount such that the layered compound (A) content in the cured product of the curable composition is approximately 1% by weight or more. That is, the curable composition may contain the layered compound (A) in an amount such that the weight of the layered compound (A) in the total weight of the cured product is approximately 1% by weight or more. In solvent-free curable compositions, the content of the layered compound (A) in the curable composition and the content of the layered compound (A) in the cured product are generally the same. In some embodiments, the content of the layered compound (A) in the cured product may be, for example, 3% by weight or more, and from the viewpoint of obtaining a higher usage effect, 5.0% by weight or more is appropriate, 7.5% by weight or more is advantageous, 10% by weight or more is preferred, 13.5% by weight or more, 15% by weight or more, 16.5% by weight or more, or 18% by weight or more. The content of the layered compound (A) in the above cured product may be, for example, 50% by weight or less, and from the viewpoint of dispersibility and the properties of the cured product (e.g., adhesive properties, optical properties), it is advantageous to have 45% by weight or less, preferably 42% by weight or less, more preferably 38% by weight or less, it may also be 35% by weight or less, it may be 32% by weight or less, it may be 28% by weight or less, it may be 25% by weight or less, and it may also be 20% by weight or less.

[0026] <Monomer raw materials> The monomer raw material in the technology disclosed herein may contain only one type of monomer, or it may be a mixture containing two or more types of monomers. From the viewpoint of facilitating the formation of a cured product from the curable composition disclosed herein, monomers having polymerizable functional groups that can be polymerized by active energy rays (e.g., light such as ultraviolet rays, visible light, infrared rays, or radiation such as alpha rays, beta rays, gamma rays, electron beams, neutron beams, X-rays) or heat are preferred, and monomers having ethylenically unsaturated groups are preferred. Examples of the above ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, (meth)allyl groups, etc. As monomers constituting the monomer raw material, monomers having one polymerizable functional group in one molecule (monofunclear monomers) are preferably used from the viewpoint of the flexibility of the cured product, etc.

[0027] Herein, "(meth)acryloyl" comprehensively refers to acryloyl and methacryloyl. Similarly, in this specification, "(meth)acrylate" comprehensively refers to acrylate and methacrylate, "(meth)acrylic" comprehensively refers to acrylic and methacrylic, and "meth(allyl)" comprehensively refers to allyl and methallyl. Furthermore, in this specification, a monomer having at least one (meth)acryloyl group in one molecule may be referred to as an "acrylic monomer." The above concept of an acrylic monomer may encompass both monomers having an acryloyl group (acrylic monomers) and monomers having a methacryloyl group (methacrylic monomers). The technology disclosed herein can preferably be implemented in a manner in which the proportion of acrylic monomers in the monomer raw materials is more than 50% by weight (preferably more than 70% by weight, for example more than 90% by weight) from the viewpoint of weather resistance, optical properties, adhesive properties, etc.

[0028] (Polar monomer (m1)) The monomer raw material in the technology disclosed herein includes a polar monomer (m1). The use of the polar monomer (m1) makes it possible to more easily disperse the layered compound (A) in the liquid phase containing the polar monomer (m1). This is because, although not to be interpreted in a particularly restrictive manner, the polar monomer (m1) is thought to easily penetrate between the layers of the layered compound (A), contributing to the promotion of interlayer separation (formation of plate-like particles). As the polar monomer (m1), a monomer having a polar group can be used, and examples of such polar groups include amide groups, imide groups, cyano groups, isocyanate groups, amino groups, nitrogen atom-containing rings, hydroxyl groups, carboxyl groups, sulfonic acid groups, and phosphoric acid groups. The polar monomer (m1) contained in the monomer raw material may be only one type or two or more types.

[0029] Examples of amide group-containing monomers include (meth)acrylamide; N,N-dialkyl(meth)acrylamides such as N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide; N-alkyl(meth)acrylamides such as N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, Nn-butyl(meth)acrylamide; N-vinyl carboxylic acid amides such as N-vinylacetamide; amide group-containing monomers having a hydroxyl group, for example, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxyethyl) Examples include N-hydroxyalkyl(meth)acrylamides such as roxypropyl(meth)acrylamide, N-(1-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, and N-(4-hydroxybutyl)(meth)acrylamide; amide group-containing monomers having an alkoxy group, such as N-alkoxyalkyl(meth)acrylamides such as N-methoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide; and others such as N,N-dimethylaminopropyl(meth)acrylamide, N-(meth)acryloylmorpholine, and N-vinylcyclic amides.

[0030] Examples of imide group-containing monomers include monomers having a succinimide skeleton, such as N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, and N-(meth)acryloyl-8-oxyhexamethylenesuccinimide; monomers having a maleimide skeleton, such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide; monomers having an itaconimide skeleton, such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, and N-laurylitaconimide; and the like. Examples of monomers containing a cyano group include acrylonitrile and methacrylonitrile. Examples of monomers containing an isocyanate group include 2-isocyanate ethyl (meth)acrylate.

[0031] Examples of amino group-containing monomers include N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate, N,N-dimethylaminohexyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dipropylaminoethyl (meth)acrylate, N,N-dibutylaminoethyl (meth)acrylate, and N-methyl-N-ethylaminoethyl (meth)acrylate. Examples include N,N-dialkylaminoalkyl (meth)acrylates such as N-methyl-N-butylaminoethyl (meth)acrylate and N,N-dipropylaminopropyl (meth)acrylate; and N-alkylaminoalkyl (meth)acrylates such as N-methylaminoethyl (meth)acrylate, N-ethylaminoethyl (meth)acrylate, N-isopropylaminoethyl (meth)acrylate, Nt-butylaminoethyl (meth)acrylate and N-butylaminoethyl (meth)acrylate.

[0032] Examples of monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholindione, N-vinylpyrazole, N-vinylisoxazole, N-vinylthiazole, N-vinylisothiazole, and N-vinylpyridazine.

[0033] Examples of monomers containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and hydroxyalkyl (meth)acrylates such as (4-hydroxymethylcyclohexyl)methyl(meth)acrylate.

[0034] Examples of monomers containing a carboxyl group include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Examples of monomers containing a sulfonic acid group or a phosphate group include styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonate, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalenesulfonic acid, and 2-hydroxyethylacryloyl phosphate.

[0035] The content of polar monomer (m1) in the monomer raw material may be, for example, 0.5% by weight or more, and from the viewpoint of making it easier to exert the effects of using polar monomer (m1), it is advantageous to have 1.0% by weight or more, preferably 2.0% by weight or more, more preferably 3.0% by weight or more or 4.0% by weight or more, and may also be 5.0% by weight or more (e.g., more than 5.0% by weight), 6.0% by weight or more, 7.0% by weight or more, 8.0% by weight or more, 9.0% by weight or more, 10% by weight or more, 15% by weight or more or 18% by weight or less. The content of polar monomer (m1) in the monomer raw material may be 100% by weight, and from the viewpoint of the flexibility of the cured product (composite material), it is appropriate to have 70% by weight or less, preferably 50% by weight or less, may also be 35% by weight or less, may also be 25% by weight or less, may also be 20% by weight or less, may also be 15% by weight or less, and may also be 12% by weight or less.

[0036] In some embodiments, a monomer without a cyclic structure, i.e., an acyclic polar monomer, may be preferably used as the polar monomer (m1). Among the polar monomers (m1) exemplified above, those without a cyclic structure can be used as the acyclic polar monomer. For example, it is preferable that 50% or more, 70% or more, or 90% or more by weight of the polar monomer (m1) contained in the monomer raw material are acyclic monomers. Alternatively, 100% by weight of the polar monomer (m1) may be acyclic monomers.

[0037] (Nitrogen atom-containing monomer (m1 N )) In some embodiments of the technology disclosed herein, the monomer raw material is a nitrogen atom-containing monomer (m1) as the polar monomer (m1) N It is preferable that it contains monomer (m1 NExamples of ) include those containing a nitrogen atom among the polar monomers (m1) mentioned above. For example, monomers that fall under at least one of the following categories: amide group-containing monomers, imide group-containing monomers, cyano group-containing monomers, isocyanate group-containing monomers, amino group-containing monomers, and monomers having a nitrogen atom-containing ring are called monomers (m1) N It can be used as a monomer (m1 N ) can be used individually or in combination of two or more types.

[0038] Monomers (m1) in monomer raw materials N The content of the monomer (m1) may be, for example, 0.5% by weight or more. N From the viewpoint of making it easier to exert the effects of using (m1), it is advantageous to have more than 1.0% by weight, preferably more than 2.0% by weight, more preferably more than 3.0% by weight (e.g., more than 4.0% by weight), it may also be more than 5.0% by weight, more than 6.0% by weight, more than 7.0% by weight, more than 8.0% by weight, and more than 9.0% by weight or more. Monomer (m1) in monomer raw materials N The content of ) is appropriate to be 70% by weight or less, preferably 50% by weight or less, and may also be 35% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, or 10% by weight or less, from the viewpoint of the flexibility of the cured product (composite material).

[0039] In polar monomers (m1), monomer (m1 N The content of monomer (m1 N From the viewpoint of making it easier to exert the effects of using ), it is advantageous to have 25% by weight or more, preferably 50% by weight or more, and may also be 75% by weight or more, and may also be 90% by weight or more. Monomer (m1) in polar monomer (m1 N The content of ) may be 100% by weight. That is, one or more monomers (m1) may be used as polar monomers (m1) N) may be used only. Also, in some embodiments, monomer (m1) in polar monomer (m1 N The content of ) may be 60% by weight or less, 30% by weight or less, 15% by weight or less, or 5% by weight or less.

[0040] The monomer raw material is a nitrogen atom-containing monomer (m1 N ) if it contains monomer (m1 N The content of polar monomers other than (m1) may be, for example, less than 10% by weight, and monomer (m1 N From the viewpoint of better demonstrating the effectiveness of the monomer (m1 N It is not necessary to use polar monomers other than (m1) in the monomer raw material. N The content of polar monomers other than (m1) may be 0% by weight.

[0041] In some aspects, monomer (m1 N As such, amide group-containing monomers can preferably be used. Preferred examples of amide group-containing monomers include, but are not limited to, acyclic amides such as the various N,N-dialkyl(meth)acrylamides and N-alkyl(meth)acrylamides mentioned above; cyclic amides such as N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam; and others. Amide group-containing monomers can be used individually or in combination of two or more.

[0042] The content of amide group-containing monomers in the monomer raw material may be, for example, 0.5% by weight or more, and from the viewpoint of making it easier to exert the effects of using amide group-containing monomers, it is advantageous to be more than 1.0% by weight, preferably more than 2.0% by weight, more preferably more than 3.0% by weight (for example more than 4.0% by weight), may be more than 5.0% by weight, may be more than 6.0% by weight, may be more than 7.0% by weight, may be more than 8.0% by weight, and may be more than 9.0% by weight or more. From the viewpoint of the flexibility of the cured product (composite material), the content of amide group-containing monomers in the monomer raw material is appropriate to be 70% by weight or less, preferably 50% by weight or less, may be 35% by weight or less, may be 25% by weight or less, may be 20% by weight or less, may be 15% by weight or less, and may be 10% by weight or less.

[0043] The content of the amide group-containing monomer in the polar monomer (m1) may be, for example, 10% by weight or more, preferably 25% by weight or more, more preferably 50% by weight or more, may be 75% by weight or more, may be 90% by weight or more, or may be 100% by weight. In some embodiments, the content of the amide group-containing monomer in the polar monomer (m1) may be 60% by weight or less, 30% by weight or less, 15% by weight or less, or 5% by weight or less.

[0044] Monomer (m1 N The content of the amide group-containing monomer in ) may be, for example, 10% by weight or more, preferably 25% by weight or more, more preferably 50% by weight or more, may be 75% by weight or more, may be 90% by weight or more, or may be 100% by weight. In some embodiments, the monomer (m1 N The content of the amide group-containing monomer in the product may be 60% by weight or less, 30% by weight or less, 15% by weight or less, or 5% by weight or less.

[0045] In some aspects, monomer (m1 N ) preferably uses monomers that do not have a cyclic structure, i.e., acyclic monomers. N) is a monomer (m1) that has a cyclic structure due to its molecular structure. N Compared to ), it tends to penetrate more easily into the interlayers of layered compounds (A), and this can effectively contribute to facilitating the dispersion of layered compounds. Acyclic monomer (m1 N Preferred examples of monomers include acyclic amides (chain amides) such as N,N-dialkyl(meth)acrylamide and N-alkyl(meth)acrylamide. In such acyclic amides, the number of carbon atoms in each alkyl group bonded to the nitrogen atom is advantageous to be 1 to 4, preferably 1 to 3, and more preferably 1 or 2 (for example, 1). When the number of carbon atoms in the alkyl group is 3 or more (for example, 3 or 4), it is preferable that it be a linear alkyl group. Monomer (m1 N The content of acyclic monomers in ) may be, for example, 10% by weight or more, preferably 25% by weight or more, more preferably 50% by weight or more, may be 75% by weight or more, may be 90% by weight or more, or may be 100% by weight.

[0046] (Monomer (m2)) The above monomer raw material may further contain, in addition to the polar monomer (m1), a linear alkyl (meth)acrylate (m2) having a linear alkyl group with 4 to 20 carbon atoms at the ester terminal (i.e., monomer (m2)). The linear alkyl group at the ester terminal may be linear or branched. Monomer (m2) can be useful for adjusting the coating properties of the curable composition, adjusting the viscoelasticity of the cured product (composite material) formed from the curable composition, suppressing discoloration of the cured product, etc. Monomer (m2) can be used alone or in combination of two or more types.

[0047] The monomer (m2) is given by the following formula (2): CH2=CR 1 (C=O)-OR 2 (2); An alkyl (meth)acrylate represented by the above formula (2) can preferably be used. Here, R 1 R is a hydrogen atom or a methyl group,2 C 4-20 It is a chain-like alkyl group. Specific examples of monomers (m2) represented by the above formula (2) include n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate. Examples include acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc. In some embodiments, R 2 C 6-20 (For example C 8-20 A monomer (m2) which is a chain alkyl group of ) can preferably be used.

[0048] The monomer (m2) content in the monomer raw material can be set within a range where the total content with polar monomer (m1) does not exceed 100% by weight. The monomer (m2) content in the monomer raw material may be, for example, 5.0% by weight or more, and from the viewpoint of making it easier to exert the effect of monomer (m2), it is appropriate to be 10% by weight or more, advantageous to be 30% by weight or more, and may be 45% by weight or more or 50% by weight or more. In some embodiments, the monomer (m2) content in the monomer raw material is preferably 55% by weight or more, more preferably 60% by weight or more, may be 70% by weight or more, may be 80% by weight or more, and may be 90% by weight or more. Furthermore, the monomer (m2) content in the monomer raw material may be, for example, 99.5% by weight or less. From the viewpoint of making it easier to exert the effect of using the polar monomer (m1), it is advantageous to be 99.0% by weight or less, preferably 98.0% by weight or less, preferably 97.0% by weight or less or 96.0% by weight or less, and may also be 95% by weight or less (for example, less than 95% by weight), 94% by weight or less, 93% by weight or less, 92% by weight or less, or 91% by weight or less. In some embodiments, the monomer (m2) content in the monomer raw material may be 90% by weight or less, 85% by weight or less, 80% by weight or less, or 75% by weight or less.

[0049] (monomer (m2 L )) In some embodiments of the technology disclosed herein, the monomer raw material is a linear alkyl (meth)acrylate (m2) having a linear alkyl group with 13 to 20 carbon atoms (more preferably 15 to 20, for example 16 to 20) at the ester terminus. L )(that is, monomer (m2 L It is preferable that it contains monomer (m2 L ) is R in equation (2) above. 2 C 13-20 (FutureC 15-20 For example, C 16-20A chain-like alkyl group of monomer (m2) is preferably an alkyl (meth)acrylate. L The long-chain alkyl group, having 13 or more carbon atoms (preferably 15 or more, for example 16 or more), contributes to reducing the moisture permeability of the cured product due to its hydrophobicity. Furthermore, the presence of the long-chain alkyl group can improve compatibility with low-polarity softeners (for example, low-polarity liquid rubbers such as liquid polybutadiene), and consequently, improve transparency. Monomer (m2 L ) can be used individually or in combination of two or more types.

[0050] Monomers (m2) in monomer raw materials L The content of ) can be set within a range in which the total content with other monomers does not exceed 100% by weight, for example, it may be 5.0% by weight or more, and monomer (m2 L From the viewpoint of making it easier to exert the effects of using (m2), it is advantageous to have 10% by weight or more, preferably 30% by weight or more, more preferably 45% by weight or more, may be 50% by weight or more, may be 55% by weight or more, may be 70% by weight or more, may be 80% by weight or more, and may be 90% by weight or more. In addition, monomer (m2) in monomer raw materials L The content of ) may be, for example, 99.5% by weight or less, and from the viewpoint of making it easier to exert the effect of using polar monomer (m1), it is advantageous to be 99.0% by weight or less, preferably 98.0% by weight or less, more preferably 97.0% by weight or less or 96.0% by weight or less, and may also be 95% by weight or less (for example, less than 95% by weight), and may also be 94% by weight or less, 93% by weight or less, 92% by weight or less, 91% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less or 75% by weight or less.

[0051] monomer(m2) in monomer(m2) L The content of monomer (m2) may be, for example, 1.0% by weight or more. LFrom the viewpoint of making it easier to exert the effects of the use of ), it is appropriate to have 5.0% by weight or more, preferably 15% by weight or more, more preferably 30% by weight or more, it may also be 50% by weight or more, it may also be 70% by weight or more, it may also be 90% by weight or more, and it may also be 100% by weight. In addition, in some embodiments, the monomer (m2) in monomer (m2) L The content of ) may be 80% by weight or less, 60% by weight or less, 40% by weight or less, 20% by weight or less, or 10% by weight or less.

[0052] (Other monomers) The monomer raw materials in the technologies disclosed herein are copolymers of a polar monomer (m1) and may optionally include monomers that do not fall under either the polar monomer (m1) or monomer (m2) (hereinafter also referred to as "other monomers"). The above other monomers can be used individually or in combination of two or more.

[0053] Specific examples of the above other monomers include: Chain alkyl (meth)acrylates having a chain alkyl group with 1 to 3 carbon atoms at the ester terminus, specifically methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate; A chain-like alkyl group with 21 or more carbon atoms at the ester end (for example, C 21-30 Chain-like alkyl (meth)acrylate having a chain-like alkyl group: (Meth)acrylates having alicyclic hydrocarbon groups, such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and adamantyl (meth)acrylate: (Meth)acrylates having an aromatic ring, such as phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate; Vinyl esters such as vinyl acetate and vinyl propionate; Aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; 2-Methoxyethyl (meth)acrylate, 3-Methoxypropyl (meth)acrylate, 2-Ethoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and other alkoxy group-containing monomers; Monomers containing alkoxysilyl groups, such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, and 3-(meth)acryloxypropylmethyldiethoxysilane; Epoxy group-containing monomers such as glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and allyl glycidyl ether; Olefins such as ethylene, propylene, butadiene, isoprene, and isobutylene; Chlorine atom-containing monomers such as vinyl chloride and vinylidene chloride; These are some examples, but are not limited to these.

[0054] The content of the above-mentioned other monomers in the monomer raw material can be set within a range in which the total content with other monomers does not exceed 100% by weight. From the viewpoint of making it easier to balance the properties in the cured product, in some embodiments, the content of the above-mentioned other monomers in the monomer raw material is suitable to be 40% by weight or less, preferably 25% by weight or less, more preferably 20% by weight or less, may also be 15% by weight or less, may be 10% by weight or less, may be 5.0% by weight or less, may be 3.0% by weight or less, may be 1.0% by weight or less, or may be 0.5% by weight or less. Other monomers do not need to be used.

[0055] (calculated Tg) In the technologies disclosed herein, the glass transition temperature (hereinafter also referred to as "calculated Tg") calculated based on the composition of the monomer raw material for a polymer corresponding to the composition of the monomer raw material is not particularly limited and may be in the range of approximately -80°C or higher and approximately 60°C or lower. The above calculated Tg may be, for example, 40°C or lower, 20°C or lower, or 10°C or lower. In some embodiments, from the viewpoint of the flexibility and tackiness of the cured product, the above calculated Tg is appropriate to be 0°C or lower or less, and may be -3°C or lower, -5°C or lower, -10°C or lower, -20°C or lower, -30°C or lower, -40°C or lower, -50°C or lower, or -60°C or lower. Furthermore, from the viewpoint of gas barrier properties and shape retention of the cured product, in some embodiments, the calculated Tg is advantageous to be -70°C or higher, but may also be -65°C or higher, -45°C or higher, -35°C or higher, -25°C or higher, -20°C or higher, or -15°C or higher.

[0056] Here, the calculated Tg of the monomer raw materials refers to the Tg obtained by Fox's formula based on the composition of the above monomer raw materials. Fox's formula is a relationship between the Tg of a copolymer and the glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below. 1 / Tg = Σ(Wi / Tgi) In Fox's equation above, Tg represents the glass transition temperature of the copolymer (unit: K), Wi represents the weight fraction of monomer i in the copolymer (weight-based copolymerization ratio), and Tgi represents the glass transition temperature of the monomer i homopolymer (unit: K).

[0057] The glass transition temperature of the homopolymer used in calculating Tg shall be the value specified in publicly available documents. For example, for the monomers listed below, the following values ​​shall be used as the glass transition temperature of the homopolymer of the monomer. n-butyl acrylate -55℃ 2-Ethylhexyl acrylate -70℃ Isostearyl acrylate -18℃ N,N-dimethylacrylamide 119℃ N-vinylpyrrolidone 54℃ Acrylic acid 106℃

[0058] For homopolymers of monomers other than those exemplified above, the values ​​listed in the "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) shall be used. For monomers for which multiple values ​​are listed in this document, the highest value shall be adopted. For monomers for which homopolymer glass transition temperatures are not listed in the Polymer Handbook, the values ​​obtained by the measurement method described in Japanese Patent Publication No. 2007-51271 shall be used. For monomers for which nominal values ​​for homopolymer glass transition temperatures are provided by the manufacturer, etc., those nominal values ​​may be adopted.

[0059] <Softener> The curable compositions disclosed herein may contain a softener. The softener contained in the curable composition is typically a component of the liquid phase and can be used to adjust the fluidity of the curable composition and the properties (e.g., flexibility and optical properties) of the cured product formed from the curable composition. In some embodiments, from the viewpoint of ease of preparation of the curable composition, a softener that is liquid at least 30°C may be preferred. A softener that is liquid at 25°C is more preferred. Here, being liquid at a given temperature means that the viscosity at that temperature is 2000 Pa·s or less, preferably 1000 Pa·s or less, and more preferably 500 Pa·s or less. The lower limit of the viscosity of the softener at the above temperature is not particularly limited and may be, for example, 0.005 Pa·s or more or 0.01 Pa·s or more.

[0060] Materials that may be options for pliants in the technologies disclosed herein include, for example, liquid rubber pliants such as liquid polybutadiene, liquid polyisoprene, liquid polyisobutylene, and liquid polybutene; olefin pliants such as ethylene-butene copolymer, ethylene-propylene-butene copolymer, propylene-butene copolymer, ethylene-butene-non-conjugated diene copolymer, and ethylene-propylene-butene-non-conjugated diene copolymer; oil pliants such as paraffinic process oil, naphthenic process oil, and aromatic process oil; polyoxyalkylene glycol pliants such as polyoxypropylene glycol and polyoxytetramethylene glycol; oligomer pliants such as urethane oligomers and acrylic oligomers; and liquid tackifying resins such as liquid rosin ester (e.g., hydrogenated rosin methyl ester), liquid terpene phenol resin, and liquid xylene resin. Examples of plasticizers include, but are not limited to, aromatic carboxylic acid ester plasticizers, aliphatic carboxylic acid ester plasticizers, polyester plasticizers, etc.

[0061] The molecular weight of the softener may be, for example, 50,000 or less, preferably 30,000 or less, advantageously 15,000 or less, preferably 10,000 or less or less than 10,000, may be 7,000 or less, may be 5,000 or less, may be 3,500 or less, may be 3,000 or less, may be 2,500 or less, may be 2,000 or less, or may be 1,800 or less. Having a molecular weight of the softener that is not too large can be advantageous from the viewpoint of ease of preparation of the curable composition containing the softener and improvement of compatibility (and thus transparency) in the cured product. The lower limit of the molecular weight of the softener is not particularly limited and may be, for example, 250 or more, 300 or more, or 350 or more. From the viewpoint of the property stability of the cured product, in some embodiments, the molecular weight of the softener is preferably 500 or more, more preferably 800 or more, may be 1,000 or more, or may be 1,200 or more.

[0062] For pliable agents that are non-polymers or polymers with a low degree of polymerization (e.g., around 2-5 mers), the molecular weight can be calculated based on the chemical structure or measured using matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS). For pliable agents that are polymers with a higher degree of polymerization, the number-average molecular weight (Mn) based on GPC performed under appropriate conditions can be used. If the manufacturer provides a nominal molecular weight, that nominal value can be adopted.

[0063] The amount of softener used per 100 parts by weight of monomer raw material may be, for example, 1 part by weight or more, or 5 parts by weight or more. From the viewpoint of obtaining a higher softening effect (plasticizing effect), in some embodiments, the amount of softener used per 100 parts by weight of monomer raw material is appropriately 10 parts by weight or more, advantageously 15 parts by weight or more, preferably 30 parts by weight or more (for example 32 parts by weight or more), may be 40 parts by weight or more, may be 50 parts by weight or more, may be 60 parts by weight or more, may be 70 parts by weight or more, or may be 80 parts by weight or more. Furthermore, the amount of softener used per 100 parts by weight of monomer raw material may be, for example, 300 parts by weight or less. From the viewpoint of easily obtaining appropriate cohesiveness in the cured product and the stability of the properties of the cured product, it is advantageous to be 250 parts by weight or less, preferably 200 parts by weight or less, and may also be 150 parts by weight or less, 120 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 55 parts by weight or less, 35 parts by weight or less, 25 parts by weight or less, or 20 parts by weight or less.

[0064] <Curable composition> The curable compositions disclosed herein preferably contain substantially no organic solvents, and more preferably substantially no organic solvents or aqueous solvents. That is, the curable compositions are preferably organic solvent-free, and more preferably solvent-free. Organic solvent-free curable compositions are also preferable from the viewpoint of environmental hygiene of the curable composition and its cured product. Solvent-free curable compositions are advantageous from the viewpoint of productivity and energy efficiency because they do not require drying (removal of solvent) in the process of forming the cured product from the curable composition. For similar reasons, the liquid phase of the curable compositions disclosed herein preferably contains substantially no organic solvents, and more preferably substantially no organic solvents or aqueous solvents. That is, the liquid phase is preferably organic solvent-free, and more preferably solvent-free. Here, "substantially free" means that the content in the subject (curable composition or liquid phase) is 3% by weight or less (preferably 1% by weight or less, more preferably 0.5% by weight or less, and even more preferably 0.1% by weight or less), and includes the case where the content is 0% by weight. Therefore, for example, a curable composition being solvent-free means that the total weight of the solvent contained in the curable composition (total amount of organic solvent and aqueous solvent) is 0% by weight or more and 3% by weight or less (preferably 1% by weight or less, more preferably 0.5% by weight or less, and even more preferably 0.1% by weight or less) of the total weight (100% by weight) of the curable composition. The solvent refers to volatile components that are to be removed in the process of forming a cured product from the curable composition, that is, volatile components that are not intended to become components of the final cured product.

[0065] (Content of layered compound (A)) In the curable compositions disclosed herein, the content of the layered compound (A) per 100 parts by weight of monomer raw material may be, for example, 1 part by weight or more, preferably 5 parts by weight or more, and from the viewpoint of obtaining a higher usage effect, it is advantageous to be 8 parts by weight or more, preferably 10 parts by weight or more, more preferably 12 parts by weight or more, may be 15 parts by weight or more, may be 18 parts by weight or more, or may be 20 parts by weight or more. In some embodiments, the content of the layered compound (A) per 100 parts by weight of monomer raw material may be 25 parts by weight or more, may be 30 parts by weight or more, may be more than 30 parts by weight (for example 32 parts by weight or more), or may be 35 parts by weight or more. Furthermore, the content of the layered compound (A) per 100 parts by weight of monomer raw material may be, for example, 100 parts by weight or less, and from the viewpoint of ease of dispersion and properties of the cured product (e.g., adhesive properties, optical properties), it is appropriate to be 70 parts by weight or less, preferably 60 parts by weight or less, more preferably 50 parts by weight or less, may be 45 parts by weight or less, may be 40 parts by weight or less, may be 35 parts by weight or less, may be 30 parts by weight or less, or may be 25 parts by weight or less.

[0066] In embodiments in which the curable composition contains a softener, the content of the layered compound (A) per 100 parts by weight of the total amount of monomer raw materials and softener may be, for example, 1 part by weight or more, preferably 5 parts by weight or more, and from the viewpoint of obtaining a higher usage effect, it is advantageous to have 8 parts by weight or more, preferably 10 parts by weight or more, more preferably 12 parts by weight or more, and may also be 15 parts by weight or more, 18 parts by weight or more, or 20 parts by weight or more. Furthermore, the content of the layered compound (A) per 100 parts by weight of the total amount of monomer raw materials and softener may be, for example, 70 parts by weight or less, and from the viewpoint of ease of dispersion and properties of the cured product (e.g., adhesive properties, optical properties), it is appropriate to have 50 parts by weight or less, preferably 40 parts by weight or less, may also be 35 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less.

[0067] (Polymerization initiator) The curable compositions disclosed herein are preferably configured to cure by light (preferably ultraviolet light) or heat to form a cured product. That is, the curable compositions are preferably photocurable and / or thermocurable. In some preferred embodiments, the curing involves a polymerization reaction of monomer raw materials. Curable compositions of such embodiments may optionally contain known or conventional photopolymerization initiators or thermopolymerization initiators. The polymerization initiators may be used alone or in appropriate combinations of two or more.

[0068] While not particularly limited, the following can be used as photopolymerization initiators: ketal-based photopolymerization initiators, acetophenone-based photopolymerization initiators, benzoin ether-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, photoactive oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like.

[0069] Specific examples of ketal-based photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, "Omnirad 651" from IGM Resins). Specific examples of acetophenone-based photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone (e.g., "Omnirad 184" from IGM Resins), 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (e.g., "Omnirad 2959" from IGM Resins), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., "Omnirad 1173" from IGM Resins), and methoxyacetophenone. Specific examples of benzoin ether-based photopolymerization initiators include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether, as well as substituted benzoin ethers such as anisole methyl ether. Specific examples of acylphosphine oxide-based photopolymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (e.g., "Omnirad 819" from IGM Resins), bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (e.g., "Omnirad TPO" from IGM Resins), and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Specific examples of α-ketol-based photopolymerization initiators include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one. Specific examples of aromatic sulfonyl chloride-based photopolymerization initiators include 2-naphthalenesulfonyl chloride. Specific examples of photoactive oxime-based photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime. Specific examples of benzoin-based photopolymerization initiators include benzoin. Specific examples of benzyl-based photopolymerization initiators include benzyl. Specific examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenyl ketone. Specific examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

[0070] While not particularly limited, thermal polymerization initiators such as azo polymerization initiators, persulfates, peroxide initiators, and substituted ethane initiators can be used. More specifically, examples include, but are not limited to, azo-based initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutylamidine), and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate; persulfates such as potassium persulfate and ammonium persulfate; peroxide-based initiators such as benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide; and substituted ethane-based initiators such as phenyl-substituted ethane.

[0071] The amount of such thermal polymerization initiator or photopolymerization initiator used can be the usual amount depending on the polymerization method and polymerization mode, and is not particularly limited. For example, approximately 0.001 to 5 parts by weight of polymerization initiator (typically approximately 0.01 to 2 parts by weight, for example, approximately 0.01 to 1 part by weight, or approximately 0.05 to 0.5 parts by weight) can be used per 100 parts by weight of monomer raw material.

[0072] (Crosslinking agent) The curable compositions disclosed herein may contain crosslinking agents as needed for purposes such as adjusting the cohesive force of the cured product. Examples of crosslinking agents include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, and metal chelate-based crosslinking agents, which are known in the field of adhesives. Other examples of crosslinking agents include monomers having two or more polymerizable functional groups (preferably ethylenically unsaturated groups) in one molecule, i.e., polyfunctional monomers. Crosslinking agents can be used alone or in combination of two or more. Examples of preferred crosslinking agents include, but are not limited to, polyfunctional monomers in photocurable compositions and isocyanate-based crosslinking agents in thermosetting compositions.

[0073] Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate, and 1,6-hexa Examples include sandiol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, butyldiol di(meth)acrylate, hexyldiol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, bisphenoxyethanol full orange(meth)acrylate, bisphenol A di(meth)acrylate, and the like. In some embodiments, polyfunctional monomers with three or more functions (i.e., monomers having three or more polymerizable functional groups in one molecule) can be preferably used. Polyfunctional monomers can be used individually or in combination of two or more.

[0074] The amount of polyfunctional monomer used is not particularly limited and can be appropriately set so as to achieve the purpose of using the polyfunctional monomer. The amount of polyfunctional monomer used may be, for example, 10 parts by weight or less, or 5.0 parts by weight or less, per 100 parts by weight of monomer. In some embodiments, from the viewpoint of the flexibility of the cured product, the amount of polyfunctional monomer used per 100 parts by weight of monomer is preferably 3.0 parts by weight or less, more preferably 1.5 parts by weight or less, and may be 1.0 part by weight or less, 0.5 parts by weight or less, or 0.3 parts by weight or less. There is no particular lower limit to the amount of polyfunctional monomer used. In some embodiments, from the viewpoint of appropriately exhibiting its effects, the amount of polyfunctional monomer used may be, for example, 0.001 parts by weight or more, 0.005 parts by weight or more, 0.01 parts by weight or more, or 0.05 parts by weight or more, per 100 parts by weight of monomer.

[0075] As isocyanate crosslinking agents, isocyanate compounds with two or more functions can be used, for example: aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), and 1,3-bis(isocyanatomethyl)cyclohexane; aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate (XDI); and polyisocyanate modified products obtained by modifying the above isocyanate compounds with allophanate bonds, biuret bonds, isocyanurate bonds, uretdione bonds, urea bonds, carbodiimide bonds, uretonimine bonds, oxadiazinetrione bonds, etc. Examples of commercially available products include the product names Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takenate D178N (all manufactured by Takeda Pharmaceutical Company Limited), Sumijoule T80, Sumijoule L, Desmodule N3400 (all manufactured by Sumika Bayer Urethane Co., Ltd.), Myrionate MR, Myrionate MT, Coronate L, Coronate HL, Coronate HX (all manufactured by Tosoh Corporation). Isocyanate compounds can be used individually or in combination of two or more. A bifunctional isocyanate compound may be used in combination with a trifunctional or higher isocyanate compound.

[0076] Examples of epoxy crosslinking agents include bisphenol A, epichlorohydrin-type epoxy resins, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane. These can be used individually or in combination of two or more.

[0077] As an oxazoline crosslinking agent, any agent having one or more oxazoline groups in one molecule can be used without particular limitation. Examples of aziridine crosslinking agents include trimethylolpropantris[3-(1-aziridinyl)propionate] and trimethylolpropantris[3-(1-(2-methyl)aziridinylpropionate)]. As the carbodiimide crosslinking agent, low-molecular-weight or high-molecular-weight compounds having two or more carbodiimide groups can be used.

[0078] The amount of crosslinking agent other than polyfunctional monomers used is not particularly limited and can be appropriately set so as to achieve the purpose of using the crosslinking agent. The amount of the crosslinking agent used may be, for example, 10 parts by weight or less per 100 parts by weight of monomer, and in some embodiments, from the viewpoint of the flexibility of the cured product, it may be 5.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.5 parts by weight or less, 1.0 part by weight or less, 0.5 parts by weight or less, 0.2 parts by weight or less, or 0.1 parts by weight or less. There is no particular lower limit on the amount of crosslinking agent other than polyfunctional monomers used. In some embodiments, from the viewpoint of appropriately exhibiting its effect, the amount of the crosslinking agent used may be, for example, 0.0001 parts by weight or more, 0.005 parts by weight or more, 0.01 parts by weight or more, or 0.05 parts by weight or more per 100 parts by weight of monomer.

[0079] (Other ingredients) In addition, the curable compositions disclosed herein may contain various additives (additives known in the field of adhesives) as needed, depending on the purpose and application. Examples of the above-mentioned additives include tackifying resins with a softening point of 60°C or higher, colorants such as dyes and pigments, antistatic agents, surfactants, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, metal foils, etc. Additives can be used individually or in combination of two or more.

[0080] Examples of the tackifying resins with a softening point of 60°C or higher (hereinafter also referred to as "solid tackifying resins") include rosin-based tackifying resins, terpene-based tackifying resins, phenol-based tackifying resins, hydrocarbon-based tackifying resins, ketone-based tackifying resins, polyamide-based tackifying resins, epoxy-based tackifying resins, etc. The solid tackifying resin is preferably soluble in the monomer raw material and is typically included in the curable composition in a form dissolved in the liquid phase as a component of the liquid phase. The amount of solid tackifying resin used per 100 parts by weight of monomer raw material is appropriately 30 parts by weight or less, preferably 20 parts by weight or less from the viewpoint of transparency of the cured product, and may also be 10 parts by weight or less, or 5 parts by weight or less. The use of solid tackifying resin is optional.

[0081] The curable compositions disclosed herein may optionally contain acrylic oligomers as other components, from the viewpoint of improving adhesive strength and other factors. As the acrylic oligomer, for example, one may be used in which the calculated Tg based on the composition of the monomer raw material corresponding to the acrylic oligomer (i.e., the monomer raw material used as the synthesis raw material for the acrylic oligomer) is approximately 20°C or higher. Acrylic oligomers with a calculated Tg of X°C or higher are usually solid (non-liquid) at least X°C.

[0082] In some embodiments, the calculated Tg of the acrylic oligomer is preferably 25°C or higher, more preferably 30°C or higher, and may also be 40°C or higher, 50°C or higher, or 60°C or higher. Having the calculated Tg of the acrylic oligomer above any of the lower limits mentioned above can be advantageous from the viewpoint of improving adhesion and cohesiveness. On the other hand, there is no particular upper limit to the calculated Tg of the acrylic oligomer, but from the viewpoint of ease of preparation and compatibility of the curable composition, it is appropriate in some embodiments to be about 300°C or lower. By having the calculated Tg within the above range, the adhesion can be suitably improved while balancing the properties.

[0083] The weight-average molecular weight (Mw) of acrylic oligomers is typically between approximately 1,000 and less than approximately 30,000, preferably between approximately 1,500 and less than approximately 20,000, and more preferably between approximately 2,000 and less than approximately 10,000. Having Mw within this range is preferable because it allows for good adhesion and retention properties. The Mw of acrylic oligomers can be measured by gel permeation chromatography (GPC) and determined as a value equivalent to standard polystyrene. Specifically, it is measured using an HPLC8020 manufactured by Tosoh Corporation, with two TSKgelGMH-H(20) columns, at a flow rate of approximately 0.5 ml / min in tetrahydrofuran solvent.

[0084] Examples of monomers that make up acrylic oligomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, and nonyl (meth)acrylate. Examples include linear alkyl(meth)acrylates such as isononyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, undecyl(meth)acrylate, and dodecyl(meth)acrylate; esters of (meth)acrylic acid with alicyclic alcohols such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and dicyclopentanyl(meth)acrylate; aryl(meth)acrylates such as phenyl(meth)acrylate and benzyl(meth)acrylate; and (meth)acrylates obtained from terpene compound derivative alcohols. Such (meth)acrylates can be used individually or in combination of two or more.

[0085] As acrylic oligomers, it is preferable from the viewpoint of further improving the adhesion of the adhesive layer that the oligomer contains relatively bulky acrylic monomers as monomer units, such as alkyl(meth)acrylates having a branched alkyl group structure, like isobutyl(meth)acrylate and t-butyl(meth)acrylate; esters of (meth)acrylic acid and alicyclic alcohols, like cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and dicyclopentanyl(meth)acrylate; and aryl(meth)acrylates having a cyclic structure, such as phenyl(meth)acrylate and benzyl(meth)acrylate (for example, containing 10% or more, 30% or more, or 50% or more by weight of the above-mentioned relatively bulky acrylic monomers of the total monomer units). Furthermore, when ultraviolet light is used during the synthesis of acrylic oligomers or the preparation of adhesive layers, materials having saturated bonds are preferred because they are less likely to inhibit polymerization. Alkyl (meth)acrylates with branched alkyl groups, or esters with alicyclic alcohols, can be suitably used as monomers constituting acrylic oligomers.

[0086] From this perspective, suitable acrylic oligomers include, for example, homopolymers of dicyclopentanyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), dicyclopentanyl acrylate (DCPA), 1-adamantyl methacrylate (ADMA), and 1-adamantyl acrylate (ADA), as well as copolymers of CHMA and isobutyl methacrylate (IBMA), CHMA and IBXMA, CHMA and acryloylmorpholine (ACMO), CHMA and diethylacrylamide (DEAA), ADA and methyl methacrylate (MMA), DCPMA and IBXMA, DCPMA and MMA, and the like.

[0087] When the curable composition disclosed herein contains an acrylic oligomer, the content is not particularly limited and can be set appropriately within a range that does not significantly impair the effects of the present invention. In some embodiments, the content of the acrylic oligomer is appropriately about 20 parts by weight or less, preferably about 15 parts by weight or less, and more preferably about 10 parts by weight or less (for example, about 5 parts by weight or less) per 100 parts by weight of monomer raw materials contained in the curable composition. The technology disclosed herein can also be preferably carried out in embodiments that do not use an acrylic oligomer.

[0088] The curable compositions disclosed herein can be produced by mixing the constituent materials of the curable composition such that a layered compound (A) is dispersed in a liquid phase. The curable composition can be produced, for example, by a method comprising mixing a liquid containing at least a portion of the components constituting the liquid phase of the curable composition with the layered compound (A). The liquid preferably contains monomer raw materials. The monomer raw materials contained in the liquid may be a portion or all of the monomer raw materials used in the production of the target product (curable composition). In the embodiment in which the liquid contains a portion of the monomer raw materials, the curable composition can be obtained by mixing the liquid with the layered compound (A) and then adding and mixing the remainder of the monomer raw materials all at once or in stages.

[0089] From the viewpoint of ease of dispersibility of the layered compound (A), the above liquid more preferably contains at least a polar monomer (m1) among the monomer raw materials. The polar monomer (m1) contained in the above liquid may be all or part of the polar monomer (m1) used in the production of the target product. In embodiments in which the monomer raw materials contain monomers other than polar monomer (m1), the monomers other than polar monomer (m1) may be included in the above liquid together with the polar monomer (m1) beforehand, may be mixed with the layered compound (A) at the same time as the liquid containing the polar monomer (m1), or may be added and mixed after the liquid containing the polar monomer (m1) and the layered compound (A) have been mixed.

[0090] In some preferred embodiments, a curable composition (preferably a solvent-free curable composition) is produced by a method comprising mixing a layered compound (A) and a monomer raw material in the absence of a solvent. For example, it is preferable to mix a liquid containing a monomer raw material and substantially free of solvent with a layered compound (A) that is substantially free of solvent (in a dry state). The monomer raw material contained in the liquid may be a part of or all of the monomer raw material used in the production of the target product (curable composition). In some embodiments, the monomer raw material mixed with the layered compound (A) preferably contains a part or all of the polar monomer (m1) used in the production of the target product, from the viewpoint of the ease of dispersibility of the layered compound (A).

[0091] In a curable composition comprising one or more constituent materials (e.g., a softener, a crosslinking agent, a polymerization initiator, etc.) in addition to a monomer raw material and a layered compound (A), each of the constituent materials may be included in the liquid beforehand, mixed with the layered compound (A) together with the liquid, or added and mixed after mixing the liquid and the layered compound (A). From the viewpoint of ease of dispersibility of the layered compound (A), in some embodiments, a method may be preferably employed in which the layered compound (A) is mixed and dispersed in the monomer raw material, and then the other constituent materials are added and mixed simultaneously or sequentially.

[0092] The curable composition disclosed herein has good dispersibility of the layered compound (A) in a liquid phase containing the monomer raw material, due to the inclusion of a polar monomer (m1) in the monomer raw material. Therefore, a good dispersion state of the layered compound (A) can be easily achieved even by mixing in the absence of a solvent. Taking advantage of this, in some embodiments, the operation of mixing the layered compound (A) and the monomer raw material (preferably in the absence of a solvent) to disperse the layered compound (A) can be carried out using a shear-type disperser such as a disper, homomixer, or three-one motor, and without applying ultrasound. The above dispersion can be carried out under conditions of, for example, 200 rpm or more, 700 rpm or more, 1200 rpm or more, 1700 rpm or more, or 2000 rpm or more, and also under conditions of, for example, 12000 rpm or less, 7000 rpm or less, 4000 rpm or less, 3000 rpm or less, or 2500 rpm or less. Furthermore, the time for the above dispersion can be, for example, 3 minutes or more, 6 minutes or more, 9 minutes or more, or 12 minutes or more, or for example, 60 minutes or less, 45 minutes or less, 30 minutes or less, or 20 minutes or less. Not requiring ultrasonic application to disperse the layered compound (A) is advantageous from the viewpoint of simplifying and saving space in the equipment for manufacturing the curable composition, and reducing energy costs. On the other hand, in some embodiments, there is no prejudice to auxiliaryly apply ultrasonic application for purposes such as promoting dispersion.

[0093] <Composite materials> This specification provides a composite material which is a cured product of any of the curable compositions disclosed herein. Such a composite material typically has a structure in which a layered compound (A) is dispersed in a matrix phase derived from the liquid phase of the curable composition. Curable compositions in which the layered compound (A) is highly dispersed in the liquid phase tend to form a composite material in which the layered compound (A) is better dispersed in the matrix phase. Improving the dispersibility of the layered compound (A) in the composite material may be advantageous from the viewpoint of improving the performance of the composite material.

[0094] The composite material described above can be formed by curing the curable composition disclosed herein by an appropriate method (ultraviolet irradiation, heating, etc.). When curing is performed by ultraviolet irradiation, known high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, etc., can be used for the ultraviolet irradiation.

[0095] (Film-like composite material) The composite materials disclosed herein may be formed in the form of a film. A film-like composite material (hereinafter also referred to as a "cured film") can be formed, for example, by curing a liquid film formed from the curable composition disclosed herein in an appropriate manner (preferably by light or heat). The liquid film can be formed, for example, by coating. Various conventionally known methods can be used as methods for coating the curable composition. Specifically, examples include roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, and extrusion coating methods using a die coater.

[0096] The above-mentioned film-like cured material may be adhesive or non-adhesive. Here, an adhesive film-like cured material refers to a film-like cured material in accordance with JIS Z0237 (2009), in which a SUS304 stainless steel plate is used as the substrate, and after pressing the substrate with a 2 kg roller for one back-and-forth motion in a measurement environment of 23°C, the peel strength when peeled in the 180° direction at a tensile speed of 300 mm / min after 30 minutes is 0.1 N / 25 mm or more. Such an adhesive film-like cured material can also be understood as an adhesive layer or an adhesive sheet (substrate-less adhesive sheet) consisting of the adhesive layer.

[0097] The thickness of the above-mentioned film-like cured material (e.g., adhesive layer) is not particularly limited and may be, for example, about 1 μm to 1000 μm. In some embodiments, the thickness of the above-mentioned film-like cured material may be, for example, 5 μm or more, preferably 15 μm or more, more preferably 25 μm or more, may be 30 μm or more, may be 40 μm or more, may be 50 μm or more, may be 60 μm or more, may be 70 μm or more, may be 80 μm or more, or may be 90 μm or more. Having a film-like cured material with a thickness greater than a predetermined amount may be advantageous from the viewpoint of barrier properties (e.g., gas barrier properties), shock absorption properties, adhesive properties, etc. On the other hand, from the viewpoint of the optical properties of the film-like cured product (e.g., light transmittance, haze), in some embodiments, the thickness of the film-like cured product may be, for example, 700 μm or less, 500 μm or less, 400 μm or less, 300 μm or less, 200 μm or less, or 150 μm or less.

[0098] The haze value of the film-like cured product (e.g., adhesive layer) disclosed herein is not particularly limited. The haze value may be 100%, or for example, 70% or less, 50% or less, 30% or less, or 20% or less. In some embodiments, considering suitability for optical applications, the haze value of the film-like cured product (e.g., adhesive layer) is suitable to be 10% or less (e.g., 9.0% or less), advantageous to be 8.0% or less, preferred to be 5.0% or less (e.g., 4.0% or less), more preferred to be 3.5% or less, even more preferred to be 2.5% or less, may be 2.0% or less, may be 1.5% or less, may be 1.0% or less, or may be less than 1.0%. Higher dispersion of the layered compound (A) within the film-like cured product may be advantageous in reducing the haze of the film-like cured product. There is no particular lower limit to the haze value of the film-like cured product, and a smaller haze value is preferable from the viewpoint of improving transparency. On the other hand, in some embodiments, taking into consideration the balance with other characteristics (such as barrier properties), the above haze value may be, for example, 0.05% or more, 0.1% or more, 0.2% or more, 0.3% or more, or 0.4% or more.

[0099] Here, "haze value" refers to the ratio of diffusely transmitted light to total transmitted light when visible light is shone on the object being measured. It is also called the cloudiness value. The haze value can be expressed by the following formula. Th(%) = Td / Tt × 100 In the above formula, Th is the haze value (%), Td is the scattered light transmittance, and Tt is the total light transmittance. The haze value can be measured according to the method described in the examples below.

[0100] The total light transmittance of the film-like cured product (e.g., adhesive layer) disclosed herein is not particularly limited. The total light transmittance may be 0%, or for example, 5% or more, 10% or more, 20% or more, 30% or more, or 40% or more. In some embodiments, considering suitability for optical applications, the total light transmittance is suitable to be greater than 50%, advantageous to be 70% or more, preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. The upper limit of the total light transmittance is theoretically 100% minus the light loss due to reflection at the air interface (Fresnel loss), and in practice may be approximately 98% or less, and considering the balance with other properties (e.g., barrier properties), it may be approximately 95% or less, approximately 94% or less, or approximately 92% or less. The total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136:2000. As the light transmittance meter, the "HAZEMETER HM-150" manufactured by Murakami Color Technology Laboratory, or an equivalent product, is used. More specifically, the total light transmittance can be measured according to the example described below.

[0101] The film-like cured product (e.g., an adhesive layer) disclosed herein may exhibit good gas barrier properties by having a configuration in which layered cured material (A) is dispersed in the matrix phase of the cured product, typically in the form of plate-like particles formed by interlayer separation of the layered cured material (A). In some embodiments, the film-like cured product has a moisture permeability (unit: g / m³) measured by the method described in the examples below. 2 24 hours. The same applies below. However, it may be, for example, 350 or less, it is advantageous to be 300 or less, it is preferable to be 200 or less, it is more preferable to be 100 or less (for example, less than 100), it may be 70 or less, it may be 60 or less, and it may be 50 or less.

[0102] In some embodiments of the film-like cured product disclosed herein, it is preferable that the film-like cured product satisfies any of the above-mentioned moisture permeability requirements and has a haze of 10% or less. Generally, increasing the content of the layered cured product (A) in the film-like cured product tends to decrease its moisture permeability. On the other hand, increasing the content of the layered cured product (A) in the film-like cured product tends to decrease its transparency (e.g., haze). In other words, moisture permeability and transparency are essentially in a trade-off relationship. According to the technology disclosed herein, by improving the dispersibility of the layered compound (A) in the cured product, the decrease in transparency associated with an increase in the content of the layered cured product (A) can be made more gradual compared to cured products with lower dispersibility of the layered compound (A). This makes it possible to realize a cured product that balances low moisture permeability and high transparency well.

[0103] <Adhesive sheet> This specification provides an adhesive layer which is a film-like cured product of any of the curable compositions disclosed herein, and an adhesive sheet containing the adhesive layer. The adhesive sheet may be an adhesive sheet with a substrate having an adhesive layer on one or both sides of a non-peelable substrate (support substrate), or it may be a substrate-less adhesive sheet (i.e., an adhesive sheet without a non-peelable substrate; typically an adhesive sheet consisting of an adhesive layer) in which the adhesive layer is held by a release liner. The concept of an adhesive sheet as used herein may include adhesive tapes, adhesive labels, adhesive films, etc. The adhesive sheet disclosed herein may be in roll form, sheet form, or adhesive sheet in a form processed into various shapes.

[0104] Figure 1 shows an example of the configuration of the adhesive sheet disclosed herein. This adhesive sheet 1 is configured as a single-sided adhesive sheet (single-sided adhesive sheet) including an adhesive layer (composite material) 10 whose first surface 10A is the surface that adheres to the adherend (adhesive surface), and a support base material 20 laminated on the second surface 10B of the adhesive layer 10. The second surface 10B of the adhesive layer 10 is bonded to the first surface (non-peelable surface) 20A of the support base material 20. As the support base material 20, for example, a plastic film such as a polyester film may be used. The support base material 20 may also be an optical film such as a polarizing plate. Before use (before being attached to the adherend), the adhesive sheet 1 may be in the form of an adhesive sheet 50 with a release liner, where the adhesive surface 10A is protected by a release liner 30, at least on the adhesive layer side, which is a peelable surface (peel surface), as shown in Figure 1. Alternatively, the second surface 20B of the support substrate 20 (the surface opposite to the first surface 20A, also called the back surface) may be a release surface, and the adhesive surface 10A may be protected by being wound or laminated so that it comes into contact with this second surface 20B. The adhesive layer 10 may be a single-layer structure, or it may be a laminated structure in which two or more sub-adhesive layers of different compositions are laminated in direct contact (i.e., without being separated by a layer made of non-adhesive material).

[0105] The release liner is not particularly limited, and for example, a release liner whose surface has been peeled off, such as a resin film or paper, or a release liner made of a low-adhesion material such as a fluoropolymer (polytetrafluoroethylene, etc.) or a polyolefin resin (polyethylene, polypropylene, etc.) can be used. For the above-mentioned peeling treatment, for example, a silicone-based or long-chain alkyl-based release agent can be used. In some embodiments, a peeled resin film can be preferably used as the release liner.

[0106] The adhesive sheet disclosed herein may be a substrate-less double-sided adhesive sheet consisting of an adhesive layer. As shown in Figure 2, the substrate-less double-sided adhesive sheet 2 may, before use, be in a form in which the first surface (first adhesive surface) 10A and the second surface (second adhesive surface) 10B of the adhesive layer 10 are protected by release liners 31, 32, at least on the side facing the adhesive layer, which are release surfaces. Alternatively, the back surface (the surface opposite to the adhesive side) of the release liner 31 may be the release surface, and the adhesive surfaces 10A and 10B may be protected by winding or laminating so that the adhesive surface 10B abuts against the back surface of the release liner 31. Such a substrate-less double-sided adhesive sheet can be used, for example, by joining a substrate (which may be an optical component such as an optical film) to at least one of the adhesive surfaces of the first and second adhesive surfaces. The adhesive layer constituting the substrate-less double-sided adhesive sheet may be a single-layer structure, similar to the adhesive layer 10 in the adhesive sheet 1 shown in Figure 1, or it may be a laminated structure in which two or more sub-adhesive layers with different compositions are directly in contact and laminated.

[0107] The adhesive sheet disclosed herein may be a component of an optical member with an adhesive sheet, in which an optical member is bonded to one surface of an adhesive layer. For example, the adhesive sheet 1 shown in Figure 1 may be a component of an optical member with an adhesive sheet 100, in which an optical member 70 is bonded to one surface 10A of an adhesive layer 10, as shown in Figure 3. The optical member may be, for example, a glass plate, a resin film, a metal plate, etc. Furthermore, in the adhesive sheet 1 shown in Figure 1, if the support base material 20 is an optical member such as an optical film, the adhesive sheet 1 may be understood as an optical member with an adhesive sheet, in which an optical member is bonded to a second surface 10B of the adhesive layer 10.

[0108] Furthermore, the adhesive sheet disclosed herein may also be in the form of a double-sided adhesive sheet with a substrate (double-sided adhesive sheet with a substrate), comprising a support substrate having a non-peelable first surface and a second surface, with a first adhesive layer fixedly laminated on the first surface and a second adhesive layer fixedly laminated on the second surface. An example of such a double-sided adhesive sheet with a substrate is the single-sided adhesive sheet 1 shown in Figure 1, in which the second surface 20B of the support substrate 20 is a non-peelable surface and a second adhesive layer is provided on the second surface 20B, the second surface of the second adhesive layer is bonded to the second surface 20B of the support substrate 20, and the first surface of the second adhesive layer (the surface opposite to the second surface) is the second adhesive surface of the double-sided adhesive sheet with a substrate. The composition of the adhesive constituting the second adhesive layer may be the same as or different from the composition of the adhesive constituting the first adhesive layer. A double-sided adhesive sheet with a substrate attached before use may be in a form in which the first adhesive surface and the second adhesive surface are protected by a release liner, similar to the double-sided adhesive sheet without a substrate described above.

[0109] (Supporting base material) In an adhesive sheet having a supporting substrate, the material of the supporting substrate (hereinafter sometimes abbreviated as "substrate") is not particularly limited and can be appropriately selected according to the purpose and manner of use of the adhesive sheet. Non-limiting examples of substrates that can be used include: plastic films such as polyolefin films mainly composed of polyolefins such as polypropylene (PP) and ethylene-propylene copolymer; polyester films mainly composed of polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); and polyvinyl chloride films mainly composed of polyvinyl chloride; foam sheets made of foams such as polyurethane foam, polyethylene (PE) foam, and polychloroprene foam; woven and nonwoven fabrics made by single-originating or blending various fibrous materials (which may be natural fibers such as hemp and cotton, synthetic fibers such as polyester and vinylon, semi-synthetic fibers such as acetate, etc.); papers such as Japanese paper, fine paper, kraft paper, and crepe paper; and metal foils such as aluminum foil and copper foil. Substrates with a composite composition of these may also be used. Examples of such composite substrates include, for instance, a substrate with a structure in which metal foil and the above-mentioned plastic film are laminated, and a plastic substrate reinforced with inorganic fibers such as glass cloth.

[0110] In some embodiments, various film substrates can be preferably used. The film substrate may be a porous substrate such as a foamed film or a nonwoven fabric sheet, a non-porous substrate, or a substrate with a structure in which a porous layer and a non-porous layer are laminated. In some embodiments, the film substrate may preferably include a resin film that is independently shape-retaining (self-supporting or independent) as a base film. Here, "resin film" means a resin film with a non-porous structure, which is typically substantially free of air bubbles (voidless). Therefore, the resin film is a concept distinct from foamed films and nonwoven fabrics. The resin film may preferably be one that is independently shape-retaining (self-supporting or independent). The resin film may have a single-layer structure or a multilayer structure of two or more layers (for example, a three-layer structure).

[0111] Materials that make up resin films include, for example, polyester resins mainly composed of polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); polyolefin resins mainly composed of polyolefins such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, and ethylene-butene copolymer; cellulose resins such as triacetylcellulose; acetate resins; polysulfone resins; polyethersulfone resins; polycarbonate resins; polyamide (PA) resins such as nylon 6, nylon 66, and partially aromatic polyamides; and polyimide (PI) resins. Examples include resins, transparent polyimide resins, polyamide-imide (PAI), polyetheretherketone (PEEK), polyethersulfone (PES), norbornene-based resins and other cyclic polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, ethylene-vinyl acetate copolymer resins, ethylene-vinyl alcohol copolymer resins, polyarylate resins, polyphenylene sulfide (PPS) resins, polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), polytetrafluoroethylene (PTFE), and fluorinated polyimide resins, among others.

[0112] The above-mentioned resin film may be formed using a resin material containing one of these resins alone, or it may be formed using a resin material blended with two or more of these resins. The above-mentioned resin film may be unoriented or oriented (e.g., uniaxially oriented or biaxially oriented). For example, PET film, PBT film, PEN film, unoriented polypropylene (CPP) film, biaxially oriented polypropylene (OPP) film, low-density polyethylene (LDPE) film, linear low-density polyethylene (LLDPE) film, PP / PE blend film, etc., can be preferably used. Examples of resin films preferred from the viewpoint of strength and dimensional stability include PET film, PEN film, PPS film, and PEEK film. PET film and PPS film are particularly preferred from the viewpoint of availability, and PET film is preferred among them.

[0113] The resin film may contain known additives such as light stabilizers, antioxidants, antistatic agents, colorants (dyes, pigments, etc.), fillers, slip agents, and antiblocking agents, as needed, within a range that does not significantly impair the effects of the present invention. The amount of additives to be added is not particularly limited and can be appropriately set depending on the application of the adhesive sheet, etc.

[0114] The method for manufacturing the resin film is not particularly limited. For example, conventionally known general resin film molding methods such as extrusion molding, inflation molding, T-die casting, and calender roll molding can be used as appropriate.

[0115] The above-mentioned substrate may be substantially composed of such a base film. Alternatively, the substrate may include auxiliary layers in addition to the base film. Examples of such auxiliary layers include optical property adjustment layers (e.g., coloring layers, anti-reflective layers), printing layers or lamination layers for imparting a desired appearance to the substrate, antistatic layers, undercoating layers, release layers, and other surface treatment layers.

[0116] In some embodiments, a light-transmitting substrate (hereinafter also referred to as a light-transmitting substrate) may be preferably used as the support substrate. This makes it possible to construct an adhesive sheet with a light-transmitting substrate. The total light transmittance of the light-transmitting substrate may be, for example, more than 50%, and may be 70% or more. In some preferred embodiments, the total light transmittance of the support substrate may be 80% or more, more preferably 90% or more, and may be 95% or more (for example, 95-100%). The above total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136:2000. As the transmittance meter, the product name "HAZEMETER HM-150" manufactured by Murakami Color Technology Laboratory or an equivalent product may be used. A preferred example of the above light-transmitting substrate is a light-transmitting resin film. The above light-transmitting substrate may also be an optical film.

[0117] The thickness of the base material is not particularly limited and can be selected according to the purpose and manner of use of the adhesive sheet. The thickness of the base material may be, for example, 500 μm or less, preferably 300 μm or less from the viewpoint of handling and processability of the adhesive sheet, and may also be 150 μm or less, 100 μm or less, 50 μm or less, 25 μm or less, or 10 μm or less. As the thickness of the base material decreases, the ability to conform to the surface shape of the adherend tends to improve. Also, from the viewpoint of handling and processability, the thickness of the base material may be, for example, 2 μm or more, 10 μm or more, or 25 μm or more.

[0118] The surface of the substrate on which the adhesive layer is laminated may be subjected to conventionally known surface treatments as needed, such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, or formation of an undercoat layer by applying an undercoat agent (primer). Such surface treatments may be performed to improve the anchoring ability of the adhesive layer to the substrate. The composition of the primer used to form the undercoat layer is not particularly limited and can be appropriately selected from known ones. The thickness of the undercoat layer is not particularly limited, but is usually appropriate at about 0.01 μm to 1 μm, and preferably at about 0.1 μm to 1 μm. Other treatments that may be applied to the substrate as needed include antistatic layer formation treatment, coloring layer formation treatment, and printing treatment. These treatments can be applied individually or in combination.

[0119] (Peel strength) The adhesive sheet disclosed herein may exhibit a peel strength of 0.1 N / 25 mm or more against a glass plate. The above peel strength (peel strength against glass plate) may be, for example, 0.2 N / 25 mm or more or greater than 0.2 N / 25 mm, preferably 0.5 N / 25 mm or more, more preferably 1.0 N / 25 mm or more, may be 1.5 N / 25 mm or more, may be 2.0 N / 25 mm or more, may be 3.0 N / 25 mm or more, may be 4.0 N / 25 mm or more, may be 5.0 N / 25 mm or more, or may be 6.0 N / 25 mm or more. A higher degree of dispersion of the layered compound (A) within the adhesive layer may be advantageous from the viewpoint of increasing the peel strength against glass plate. There is no particular upper limit to the peel strength against glass plate. In some embodiments, the peel strength against glass plate may be, for example, 30 N / 25 mm or less, or 20 N / 25 mm or less.

[0120] The peel strength against the glass plate is determined by pressing the adhesive surface of the adhesive sheet to be measured against the glass plate by moving a 2kg rubber roller back and forth once, and measuring the peel strength when peeling the adhesive sheet from the glass plate using a tensile testing machine in an environment of 23°C and 50%RH, in accordance with JIS Z 0237:2000, under conditions of a peel angle of 180 degrees and a tensile speed of 300 mm / min. Specifically, it is measured by the method described in the examples below. Depending on the configuration of the adhesive sheet (for example, if the adhesive sheet has a support base material with sufficient strength), backing (reinforcement) with PET film or the like may not be necessary.

[0121] <Application> In the curable composition disclosed herein, the layered compound (A) is typically dispersed in a liquid phase containing monomer raw materials in the form of plate-like particles formed by delamination of the layered compound (A). As a result, these plate-like particles can function as a thickener that increases the viscosity of the curable composition. Moderately increasing the viscosity of the curable composition can improve its coatability. For example, when applying a relatively thick coating of the curable composition (e.g., 50 μm or more, 70 μm or more), a moderately high viscosity of the curable composition is preferable from the viewpoint of improving the uniformity of the coating thickness (suppressing unevenness due to flow and sagging). The composite material, which is a cured product of the curable composition disclosed herein, can exhibit good barrier properties against gases such as water vapor and ammonia gas due to the contribution of the layered compound (A) dispersed in the cured product (typically dispersed as plate-like particles). Utilizing these barrier properties, the composite material can be used, for example, in the form of a film-like cured product, as a barrier material to protect an object from water vapor and other gases. Furthermore, in the above-mentioned composite material, good dispersion of the layered compound (A), i.e., uniform dispersion (typically in the form of plate-like particles), is advantageous for improving heat transfer and electrical conductivity. Furthermore, the composite material described above can be used for adsorption, retention, stabilization, etc., of target substances (e.g., various functional substances) by utilizing the increase in surface area due to the dispersion of the layered compound (A) (typically in the form of plate-like particles).

[0122] As can be understood from the above description and the following examples, the matters disclosed in this specification include the following: [1] A liquid phase containing monomer raw materials, The layered compound dispersed in the above liquid phase, Includes, The above layered compound is a layered compound that has been organically modified with organic ions. The above monomer raw material is a curable composition containing a polar monomer (m1). [2] The above monomer raw material is a polar monomer containing nitrogen atoms (m1 N The curable composition described in [1] above, comprising ) [3] The above monomer raw material contains a linear alkyl (meth)acrylate (m2) having a linear alkyl group with 4 to 20 carbon atoms at the ester terminus. The curable composition according to [1] or [2] above, wherein the content of the chain-like alkyl (meth)acrylate (m2) in the monomer raw material is 55% by weight or more. [4] The above monomer raw material is a linear alkyl (meth)acrylate (m2) having a linear alkyl group with 13 to 20 carbon atoms at the ester terminus. L The curable composition described in [3] above, which includes ) [5] A curable composition according to any one of [1] to [4] above, further comprising a softening agent. [6] A curable composition according to any one of [1] to [5] above, which hardens by light and / or heat to form an adhesive. [7] A composite material which is a cured product of any of the curable compositions described in [1] to [6] above. [8] The above composite material is formed in the form of a film, and has a moisture permeability (40°C, 92%RH) of 300 g / m². 2 The composite material described in [7] above, wherein the time is 24 hours or less and the haze is 10% or less. [9] A method for producing a curable composition as described in any of [1] to [6] above, A method for producing the above-mentioned layered compound and the above-mentioned monomer raw material, comprising mixing them in the absence of a solvent. [Examples]

[0123] The following describes several embodiments of the present invention, but the present invention is not intended to be limited to those examples shown. In the following description, "parts" and "%" refer to weight unless otherwise specified.

[0124] <Preparation of curable composition> (Example 1) Fifty parts of isostearyl acrylate (ISTA) and twenty parts of an organic layered compound (manufactured by Kunimine Industries Co., Ltd., trade name "Smecton STN") were mixed with a stirrer (manufactured by Thinky Co., Ltd., product name "ARV-310") at 2000 rpm for 15 minutes to obtain a dispersion. To this dispersion, 50 parts of liquid polybutadiene (hydrogenated polybutadiene with hydroxyl groups at both ends, manufactured by Nippon Soda Co., Ltd., trade name "GI-1000", number average molecular weight 1500) as a softening agent, 0.07 parts of a crosslinking agent (trimethylolpropane triacrylate; hereinafter sometimes referred to as "TMPTA"), and 0.1 parts of a photoinitiator (trade names "Omnirad 184" and "Omnirad 651" manufactured by IGM Resins, used in a weight ratio of 1:1) were added. The mixture was then stirred at 2000 rpm for 15 minutes using the above stirrer, and then centrifuged and degassed at 2200 rpm for 15 minutes to prepare the curable composition according to this example.

[0125] (Example 2) 47.5 parts of ISTA, 5 parts of N,N-dimethylacrylamide (DMAA) as a polar monomer, and 20 parts of the same organic layered compound as in Example 1 were mixed with the above stirrer at 2000 rpm for 15 minutes to obtain a dispersion. To this dispersion, 47.5 parts of the same softener as in Example 1, 0.07 parts of the same crosslinking agent as in Example 1, and 0.1 parts of the same photoinitiator as in Example 1 were added, mixed at 2000 rpm for 15 minutes, and then centrifuged and degassed at 2200 rpm for 15 minutes to prepare the curable composition according to this example.

[0126] (Examples 3-5) The curable compositions for each example were prepared in the same manner as in Example 2, except that the amounts of ISTA and DMAA used, and the type and amount of softener used were as shown in Table 1. In Table 1, GI-2000 and GI-3000 refer to hydroxylated polybutadiene with hydroxyl groups at both ends, manufactured by Nippon Soda Co., Ltd., trade name "GI-2000" (number average molecular weight 2000) and trade name "GI-3000" (number average molecular weight 3100), respectively.

[0127] (Example 6) 47.5 parts of ISTA, 47.5 parts of 2-ethylhexyl acrylate (2EHA), 5 parts of DMAA, and 20 parts of the same organic layered compound as in Example 1 were mixed with the above stirrer at 2000 rpm for 15 minutes to obtain a dispersion. To this dispersion, 0.07 parts of the same crosslinking agent as in Example 1 and 0.1 parts of the same photoinitiator as in Example 1 were added, and the mixture was mixed with the above stirrer at 2000 rpm for 15 minutes, followed by centrifugal degassing at 2200 rpm for 15 minutes to prepare the curable composition according to this example.

[0128] (Example 7) 95 parts of 2EHA, 5 parts of DMAA, and 23 parts of the same organic layered compound as in Example 1 were mixed with the above stirrer at 2000 rpm for 15 minutes to obtain a dispersion. To this dispersion, 0.07 parts of the same crosslinking agent as in Example 1 and 0.1 parts of the same photoinitiator as in Example 1 were added, and the mixture was mixed with the above stirrer at 2000 rpm for 15 minutes, followed by centrifugal degassing at 2200 rpm for 15 minutes to prepare the curable composition according to this example.

[0129] (Example 8) The curable composition for this example was prepared in the same manner as in Example 7, except that the amounts of 2EHA and DMAA used were as shown in Table 1.

[0130] (Example 9) A curable composition according to this example was prepared in the same manner as in Example 7, except that N-vinyl-2-pyrrolidone (NVP) was used instead of DMAA.

[0131] <Fabrication of laminated sheets> The curable composition of each example was applied to the release-treated surface of a release film in which one surface of a 38 µm-thick polyethylene terephthalate (PET) film is a release-treated surface treated with a silicone release agent, such that the final thickness became 100 µm, to form a coating layer. A release film in which one surface of a 38 µm-thick PET film is a release-treated surface treated with a silicone release agent was placed over the coating layer, with the release-treated surface of the film facing the coating layer side, to shield the coating layer from oxygen. Then, using a chemical light lamp (manufactured by Toshiba Corporation), the illuminance was 2.4 mW / cm 2 ultraviolet ray was irradiated for 960 seconds to cure the coating layer. In this way, a laminated sheet having a three-layer structure was obtained, in which the PET film is laminated on the first surface and the second surface of a composite material layer (pressure-sensitive adhesive layer) formed of a UV-cured product of the coating layer. The above illuminance value is a value measured with an industrial UV checker (manufactured by Topcon Corporation, trade name "UVR-T1", light-receiving unit model UD-T36) having a peak sensitivity wavelength of about 350 nm.

[0132] <Measurement and Evaluation> (Total Light Transmittance and Haze Value) A test piece was prepared by laminating the pressure-sensitive adhesive layer of each example to an alkali-free glass (thickness: 0.8 to 1.0 mm, total light transmittance: 92%, haze: 0.4%), and in a measurement environment at 23°C, in accordance with JIS K 7136:2000, the total light transmittance and haze of the test piece were measured using a haze meter (manufactured by Murakami Color Research Laboratory, trade name "HAZEMETER HM-150"). The values obtained by subtracting the total light transmittance and haze of the alkali-free glass from the measured values were taken as the total light transmittance (light transmittance) [%] and haze [%] of the pressure-sensitive adhesive layer. The results are shown in Table 1.

[0133] (Peel Strength) Under a measurement environment of 23°C and 50% RH, one release film was peeled off from the laminated sheet for each example, and a 50 μm thick PET film was bonded to the exposed adhesive layer as a backing. The resulting piece was then cut to a size of 25 mm wide and 100 mm long to serve as a test specimen. The other release film was peeled off from this test specimen to expose the adhesive layer, and a 2 kg roller was applied to the surface of an alkali glass plate (Matsunami Glass Industry Co., Ltd., 1.35 mm thick, blue plate with polished edges) as the adherend, with one back-and-forth motion. After leaving this in the same environment for 30 minutes, the peel strength [N / 25 mm] was measured using a universal tensile and compression tester in accordance with JIS Z 0237:2000, under conditions of a peel angle of 180 degrees and a tensile speed of 300 mm / min. The universal tensile and compression tester used was the "Tensile and Compression Tester, TG-1kN" manufactured by Minebea Co., Ltd. The results are shown in Table 1.

[0134] [Table 1]

[0135] As shown in Table 1, among the curable compositions of Examples 1 to 9, which were prepared without the use of organic solvents and without sonication, the curable composition of Example 1, which used monomer raw materials that did not contain polar monomers, had high haze in the cured product formed from the composition and insufficient dispersion of the layered compound. On the other hand, the curable compositions of Examples 2 to 9, which used monomer raw materials containing DMAA or NVP as the polar monomer (m1), had a layered compound content equal to or greater than that of Example 1, yet showed significantly lower haze compared to Example 1 and formed cured products with good dispersion of the layered compound.

[0136] (moisture permeability) The moisture permeability in the thickness direction of the adhesive layer in Example 2 was evaluated using the moisture permeability test method (cup method) for moisture-proof packaging materials in accordance with JIS Z0208. The measurement conditions were a temperature of 40°C and a humidity of 92%RH, and the measurement was taken with the adhesive layer laminated to a 40 μm thick triacetylcellulose (TAC) film with the release film removed. The results are shown in Table 2.

[0137] (Ammonia permeability) The ammonia permeability in the thickness direction of the pressure-sensitive adhesive layer according to Example 2 was measured by the following method. Specifically, a sample cut into a disk shape with a diameter of 20 mm was sandwiched between septa whose center had been punched into a circular shape with a diameter of 10 mm, and the assembly was set on a lid. 1 mL of a 1% aqueous ammonia solution was added to a 20 mL capacity SHS (static head space) vial, which was then sealed with the above lid, and this vial and 20 mL of a collection liquid (ultra-pure water) were added into a polypropylene container, which was then capped. After allowing to stand still at room temperature (25°C) for 6 hours, the collection liquid was analyzed by ion chromatography (IC), thereby measuring the ammonia permeability. The results are shown in Table 2.

[0138] Further, as a reference example, moisture permeability and ammonia permeability were measured by the same method for a commercially available acrylic pressure-sensitive adhesive layer (a substrate-free pressure-sensitive adhesive sheet for optical use; thickness: 100 µm; the pressure-sensitive adhesive layer does not contain a layered compound or any other inorganic powder). The results are shown in Table 2.

[0139] [Table 2]

[0140] As shown in Table 2, it was confirmed that compared with the pressure-sensitive adhesive layer according to the reference example that does not contain a layered compound, the pressure-sensitive adhesive layer according to Example 2, in which the layered compound is well dispersed, has both significantly lower moisture permeability and significantly lower ammonia permeability, and is excellent in gas barrier properties.

[0141] The moisture permeability of the pressure-sensitive adhesive layers of Examples 3 to 7 and 9 was measured in the same manner as in Example 2. As a result, the moisture permeability of Example 3 was 31 g / m 2 ·24h, the moisture permeability of Example 4 was 31 g / m 2 ·24h, the moisture permeability of Example 5 was 29 g / m 2 ·24h, and all were within the range of 20 to 50 g / m 2 ·24h (more specifically, 25 g / m 2 ·24h or higher and 35 g / m 2 ·24h or lower). Further, the moisture permeability of Example 6 was 96 g / m 2 ·24h, and the moisture permeability of Example 7 was 148 g / m• 24 hours, the moisture permeability of Example 9 is 146 g / m² 2 • 24h, all 95-300g / m² 2 • 24h (For more details, see 95g / m²) 2 ·150g / m for 24 hours or more 2 It was within the range of 24 hours or less.

[0142] Although specific examples of the present invention have been described in detail above, these are merely illustrative and do not limit the scope of the claims. The technologies described in the claims include various modifications and changes to the specific examples illustrated above. [Explanation of Symbols]

[0143] 1,2 Adhesive sheets 10 Adhesive layer 10A First surface (adhesive side) 10B Second surface 20 Supporting base material 20A, Page 1 20B 2nd side (back) 30, 31, 32 Release Liner 50 Adhesive sheets with release liner 70 Optical components 100 Adhesive sheet-attached components

Claims

1. A curable composition that hardens to form an adhesive by light and heat, A liquid phase containing monomer raw materials, The layered compound dispersed in the liquid phase, Includes, The aforementioned layered compound is a layered compound that has been organically modified with organic ions. The monomer raw material includes a polar monomer (m1), The monomer raw material further comprises a linear alkyl (meth)acrylate (m2) having a linear alkyl group with 4 to 20 carbon atoms at the ester terminus. The linear alkyl (meth)acrylate (m2) includes a linear alkyl (meth)acrylate (m2 L) having a linear alkyl group with 13 to 20 carbon atoms at the ester terminus. A curable composition wherein the content of the chain-like alkyl (meth)acrylate (m² L) in the monomer raw material is 30% by weight or more.

2. The monomer raw material is a polar monomer containing nitrogen atoms (m1 Ｎ A curable composition according to claim 1, comprising )

3. The curable composition according to claim 1 or 2, wherein the content of the chain-like alkyl (meth)acrylate (m2) in the monomer raw material is 55% by weight or more.

4. The chain alkyl (meth)acrylate (m2) in the monomer raw material. Ｌ The curable composition according to claim 1 or 2, wherein the content of ) is 55% by weight or more.

5. The curable composition according to claim 1 or 2, further comprising a softening agent.

6. A composite material which is a cured product of the curable composition according to claim 1 or 2.

7. The composite material is formed in the form of a film, and has a moisture permeability (40°C, 92% RH) of 300 g / m². ２ - The composite material according to claim 6, wherein the time is 24 hours or less and the haze is 10% or less.

8. A method for producing a curable composition according to claim 1 or 2, A method for producing a compound, comprising mixing the layered compound and the monomer raw material in the absence of a solvent.

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