WO2017057617A1

WO2017057617A1 - Organic metal compound-containing composition

Info

Publication number: WO2017057617A1
Application number: PCT/JP2016/078891
Authority: WO
Inventors: 菅野　亮; 山崎　達也; 友斗猿橋; 隆太友寄; 武士斉藤; 池田　哲朗
Original assignee: 日東電工株式会社
Priority date: 2015-10-02
Filing date: 2016-09-29
Publication date: 2017-04-06

Abstract

The purpose of the present invention is to provide an organic metal compound-containing composition that has excellent liquid stability, a long pot life, and excellent productivity. This organic metal compound-containing composition is characterized by containing: at least one organic metal compound (A) selected from the group consisting of metal alkoxides and metal chelates; and a polymerizable compound (B) having a polymerizable functional group and a carboxyl group. The metal of the organic metal compound (A) is preferably titanium, and the polymerizable compound (B) is preferably a radical polymerizable compound.

Description

Organometallic compound-containing composition

The present invention relates to an organometallic compound-containing composition containing an organometallic compound and a polymerizable compound.

Organometallic compounds are used in various applications, for example as catalysts for esterification, polycondensation, polyolefinization, silicone curing, etc. of monomers or polymers, as crosslinking agents for inorganic paints and heat-resistant paints, or as primer materials and titanium oxide film materials. in use.

For example, Patent Document 1 below shows an example in which an alkoxy-containing metal compound is blended in a photosensitive composition used for liquid crystal display elements and organic EL display applications.

JP 2014-56122 A

Among the organometallic compounds, the inventors of the present invention are very particular when at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates is added to the active energy ray-curable component, for example. It has been found that it contributes to improved adhesion and water resistance. However, such organometallic compounds are highly reactive and are stable due to contact with moisture in the air or moisture contained in the composition composition added, causing hydrolysis and self-condensation reactions. It was found to be low. Here, when the present inventors investigated including the said patent document 1, there is no report example which improved the liquid stability of the organometallic compound containing composition at the high level, and when using an organometallic compound, the We found that there is a new issue that should improve stability.

The present invention has been developed in view of the above circumstances, and an object thereof is to provide an organometallic compound-containing composition having excellent liquid stability, a long pot life and excellent productivity.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above object can be achieved by the following organometallic compound-containing composition, and have solved the present invention.

That is, the present invention contains at least one organometallic compound (A) selected from the group consisting of metal alkoxides and metal chelates, and a polymerizable compound (B) having a polymerizable functional group and a carboxyl group. The present invention relates to a composition containing an organometallic compound.

In the above, the metal of the organometallic compound (A) is preferably titanium.

In the above, it is preferable that the metal alkoxide is contained as the organometallic compound (A), and the organic group of the metal alkoxide has 4 or more carbon atoms.

In the above, it is preferable that the organometallic compound (A) contains the metal chelate, and the organic group of the metal chelate has 4 or more carbon atoms.

In the above, the ratio of the organometallic compound (A) in the organometallic compound-containing composition is preferably 5 to 90% by weight.

In the above, the polymerizable compound (B) is preferably a radically polymerizable compound.

In the above, it is preferable that the molecular weight of the polymerizable compound (B) is 100 (g / mol) or more.

In the above, the polymerizable compound (B) is preferably a polymerizable compound having a polymerizable functional group and a carboxyl group via an organic group having 1 to 20 carbon atoms which may contain oxygen.

In the above, when the total amount of the organometallic compound (A) is α (mol) in the organometallic compound-containing composition, the content of the polymerizable compound (B) is 0.25α (mol) or more. It is preferable.

The composition containing the organometallic compound (A) has a tendency that the pot life is shortened and the productivity is deteriorated in any application due to unstable liquid stability. This is because the organometallic compound (A) has a high reactivity and comes into contact with moisture in the atmosphere or moisture contained in a minute amount in the composition, causing a hydrolysis reaction and a self-condensation reaction, resulting in self-aggregation. One of the causes is presumed that the composition liquid becomes cloudy (generation of aggregates, phase separation, precipitation). However, in the present invention, since the metal compound-containing composition contains the polymerizable compound (B) having a polymerizable functional group and a carboxyl group together with the organometallic compound (A), hydrolysis of the organometallic compound (A) is performed. Reaction and self-condensation reaction can be suppressed, and the liquid stability of the organometallic compound (A) in the composition can be dramatically improved. The reason why such an effect is obtained is not clear, but the following reasons (1) to (2) can be estimated.

(1) The carboxyl group of the polymerizable compound (B) is strongly bonded and / or coordinated with the metal of the organometallic compound (A), the metal electron density increases, and other coordination such as water molecules. It is possible to reduce the force that attracts the ligand.
(2) Since the polymerizable compound (B) having a carboxyl group further has a polymerizable functional group and is bulky, the polymerizable compound (B) is bonded / and bonded to the organometallic compound (A) via the carboxyl group. After coordination, it becomes difficult for other ligands to approach the metal.

As described above, in the organometallic compound-containing composition, the carboxyl group of the polymerizable compound (B) is strongly bonded and / or coordinated with the metal of the organometallic compound (A), whereby the organometallic compound ( A) is stabilized. Here, when only the organometallic compound (A) and the polymerizable compound (B) are mixed and reacted, their reaction rate and / or coordination rate greatly increase, and the obtained organometallic compound-containing composition is: It contains a reaction product and / or coordination product of the organometallic compound (A) and the polymerizable compound (B) at a high concentration. Therefore, the organometallic compound-containing composition obtained has a very high stability of the organometallic compound (A), and when the organometallic compound-containing composition is added to and mixed with other components such as active energy ray-curable components. Even so, the stability of the organometallic compound is similarly increased.

As described above, since the organometallic compound-containing composition according to the present invention is remarkably excellent in the stability of the organometallic compound (A) contained therein, the adhesive composition contains many uses, for example, an active energy ray-curable component. As one of the raw materials, or when used in various applications such as a catalyst and a crosslinking agent, the liquid stability is excellent and the pot life can be improved.

The organometallic compound-containing composition according to the present invention comprises at least one organometallic compound (A) selected from the group consisting of metal alkoxides and metal chelates, and a polymerizable compound having a polymerizable functional group and a carboxyl group (B ).

<At least one organometallic compound (A) selected from the group consisting of metal alkoxides and metal chelates>
A metal alkoxide is a compound in which at least one alkoxy group, which is an organic group, is bonded to a metal, and a metal chelate is a compound in which an organic group is bonded or coordinated to the metal via an oxygen atom. Titanium, aluminum, and zirconium are preferable as the metal. Among these, for example, when used as one of the raw materials of an adhesive composition containing an active energy ray-curable component, titanium is used as the metal of the organometallic compound from the viewpoint of improving the adhesive water resistance of the adhesive layer. More preferred.

When the organometallic compound-containing composition according to the present invention contains a metal alkoxide as the organometallic compound, it is preferable to use those having 3 or more carbon atoms in the organic group of the metal alkoxide. More preferably. When the number of carbon atoms is 2 or less, the pot life of the organometallic compound-containing composition is shortened. For example, when used as one of the raw materials of an adhesive composition containing an active energy ray-curable component, The effect of improving the property may be reduced. Examples of the organic group having 4 or more carbon atoms include a butoxy group, which can be preferably used. Examples of suitable metal alkoxides include, for example, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tertiary amyl titanate, tetra tertiary butyl titanate, tetrastearyl titanate, zirconium tetraisopropoxide, zirconium Tetranormal butoxide, zirconium tetraoctoxide, zirconium tetratertiary butoxide, zirconium tetrapropoxide, aluminum sec butyrate, aluminum ethylate, aluminum isopropylate, aluminum butyrate, aluminum diisopropylate monosecondary butyrate, monosec butoxyaluminum And diisopropylate. Of these, tetraoctyl titanate is preferable.

When the organometallic compound-containing composition according to the present invention contains a metal chelate as the organometallic compound, it is preferable that the organic chelate has an organic group having 4 or more carbon atoms. When the number of carbon atoms is 3 or less, the pot life of the organometallic compound-containing composition is shortened and, for example, when used as one of the raw materials of an adhesive composition containing an active energy ray-curable component, The effect of improving the property may be reduced. Examples of the organic group having 4 or more carbon atoms include acetylacetonate group, ethylacetoacetate group, isostearate group, octylene glycolate group and the like. Among these, for example, when used as one of the raw materials of an adhesive composition containing an active energy ray-curable component, acetylacetonate is used as an organic group from the viewpoint of improving the adhesive water resistance of the adhesive layer. Group or ethyl acetoacetate group is preferred. Examples of suitable metal chelates include, for example, titanium acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate, titanium ethylacetoacetate, polyhydroxytitanium stearate, dipropoxy-bis (acetylacetonato) titanium, di Butoxytitanium-bis (octylene glycolate), dipropoxytitanium-bis (ethylacetoacetate), titanium lactate, titanium diethanolamate, titanium triethanolamate, dipropoxytitanium-bis (lactate), dipropoxytitanium-bis ( Triethanolaminate), di-n-butoxytitanium-bis (triethanolaminato), tri-n-butoxytitanium monostearate, diisopropoxy bis (ethylacetoacetate) Titanium, diisopropoxy bis (acetylacetate) titanium, diisopropoxy bis (acetylacetone) titanium, titanium phosphate compound, titanium lactate ammonium salt, titanium-1,3-propanedioxybis (ethylacetoacetate), dodecyl Benzenesulfonic acid titanium compound, titanium aminoethylamino ethanolate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium acetylacetonate bisethylacetoacetate, zirconium acetate, tri-n-butoxyethylacetate Acetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) Tate) zirconium, tetrakis (n-propyl acetoacetate) zirconium, tetrakis (acetyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, aluminum ethyl acetoacetate, aluminum acetylacetonate, aluminum acetylacetonate bisethylacetoacetate, di Isopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum Monoacetylacetonate bis (ethylacetoacetate And aluminum). Of these, titanium acetylacetonate and titanium ethylacetoacetate are preferable.

In addition to the above, the organic metal compounds usable in the present invention include organic carboxylic acid metal salts such as zinc octylate, zinc laurate, zinc stearate, tin octylate, acetylacetone zinc chelate, benzoylacetone zinc chelate, dibenzoylmethane zinc Examples of the chelate include zinc chelate compounds such as ethyl zinc acetoacetate chelate.

In the present invention, the ratio of the organometallic compound (A) in the organometallic compound-containing composition is preferably 5 to 90% by weight, and more preferably 10 to 80% by weight. When the blending amount exceeds 90% by weight, the storage stability of the organometallic compound-containing composition may be deteriorated. Further, when the amount is less than 5% by weight, the effect is not sufficiently exhibited.

<Polymerizable compound having polymerizable functional group and carboxyl group (B)>
The polymerizable compound (B) has a polymerizable functional group and a carboxyl group. The polymerizable functional group and the carboxyl group contained may be either one or two or more.

The polymerizable functional group is not particularly limited, and examples thereof include a carbon-carbon double bond-containing group, an epoxy group, an oxetanyl group, and a vinyl ether group.

As the polymerizable functional group, in particular, the following general formula (I):
H ₂ C═C (R ¹ ) —COO— (I)
(Wherein R ¹ represents hydrogen or an organic group having 1 to 20 carbon atoms), or the following formula (II):
H ₂ C═C (R ² ) —R ³ — (II)
Wherein R ¹ represents hydrogen or an organic group having 1 to 20 carbon atoms, and R ³ represents a direct bond or an organic group having 1 to 20 carbon atoms. ^A radically polymerizable functional group in which ¹ or R ² is hydrogen or a methyl group is particularly preferable.

The bonding position of the carboxyl group in the polymerizable compound (B) is not particularly limited, but from the viewpoint of improving the liquid stability of the organometallic compound (A) in the composition, the radical polymerizable functional group and the carboxyl group are Rather than directly bonded (meth) acrylic acid, a radical polymerizable compound in which a radical polymerizable functional group is bonded to a carboxyl group via an organic group having 1 to 20 carbon atoms which may contain oxygen is preferable.

Further, from the viewpoint of improving the liquid stability of the organometallic compound (A) in the composition, the molecular weight of the polymerizable compound (B) is large, and when bonded and / or coordinated to the organometallic compound (A), the bulk is increased. It is preferable that it is sterically hindered when other ligands are coordinated. When the polymerizable compound (B) is sterically hindered, the reaction rate of the ligand exchange reaction, hydrolysis reaction, and condensation reaction of the organometallic compound (A) is decreased, and the organometallic compound is stabilized. Therefore, the molecular weight of the polymerizable compound (B) is preferably 100 (g / mol) or more, more preferably 125 (g / mol) or more, and further preferably 150 (g / mol) or more. Preferably, it is particularly preferably 200 (g / mol) or more, and most preferably 250 (g / mol) or more. The upper limit of the molecular weight of the polymerizable compound (B) is not particularly limited, but is preferably 400 (g / mol) or less, and more preferably 350 (g / mol) or less.

Further, from the viewpoint of improving the liquid stability of the organometallic compound (A) in the composition, the polymerizable compound (B) can be polymerized via an organic group having 1 to 20 carbon atoms which may contain oxygen. A polymerizable compound having a group and a carboxyl group is preferred. Examples of such organic groups include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, alicyclic groups, unsaturated alicyclic groups, alkyl ester groups, aromatic ester groups, acyl groups, hydroxyalkyl groups, alkylene oxides. Group, and a plurality of the same organic group may be bonded to each other, or a plurality of different organic groups may be bonded to each other. Specific examples of the polymerizable compound (B) include, for example, β-carboxyethyl acrylate, carboxypentyl acrylate, β-carboxyethyl methacrylate, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2- Acryloyloxyethylphthalic acid, ω-carboxy-polycaprolactone monoacrylate, 2-acryloyloxyethyltetrahydrophthalic acid, 2-acryloyloxypropyloxyphthalic acid, 2-acryloyloxypropyltetrahydrophthalic acid, 2-acryloyloxypropylhexahydrophthal Acid, methacryloyloxyethyl succinic acid, methacryloyloxyethyl phthalic acid, methacryloyloxyethyl tetrahydrophthalic acid, methacryloyloxyethyl Hexahydrophthalic acid, 2-methacryloyloxy-propyloxy phthalate, 2-meth Leroy oxy propyl tetrahydrophthalic acid, 2-meth Leroy oxy propyl hexahydrophthalic acid.

From the viewpoint of improving the liquid stability of the organometallic compound (A) in the composition, when the total amount of the organometallic compound (A) is α (mol) in the organometallic compound-containing composition, the polymerizable compound (B ) Content is preferably 0.25α (mol) or more, more preferably 0.35α (mol) or more, still more preferably 0.5α (mol) or more, and 1α (mol). The above is particularly preferable. When there is too little content of a polymeric compound (B), stabilization of an organometallic compound (A) will become inadequate, a hydrolysis reaction and a self-condensation reaction will advance easily, and pot life may become short. The upper limit of the content of the polymerizable compound (B) relative to the total amount α (mol) of the organometallic compound (A) is preferably less than 200 α (mol), more preferably less than 100 α (mol), and less than 20 α (mol). More preferably, it is less than 6α (mol). When the content of the polymerizable compound (B) is too large, the organometallic compound is excessively stabilized. For example, when blended in a curable adhesive composition for a polarizing film, a polarizer and an adhesive layer Reaction may be easily inhibited, and as a result, adhesion and water resistance may be inferior.

The organometallic compound-containing composition according to the present invention is remarkably excellent in the stability of the organometallic compound (A) contained therein, and therefore can be used for various uses such as a catalyst and a crosslinking agent. . As an example of the use, the example used as one of the raw materials of the adhesive composition containing an active energy ray hardening component is shown below. However, the use of the organometallic compound-containing composition according to the present invention is not limited to adhesive use.

When the organometallic compound-containing composition according to the present invention is used for an adhesive composition, particularly a polarizing film curable adhesive composition in which a polarizer and a transparent protective film are laminated via an adhesive layer The curable adhesive composition for a polarizing film contains an active energy ray-curable component (X) and an organometallic compound-containing composition. Such a curable adhesive composition for a polarizing film has good adhesion between the polarizer and the transparent protective film, and forms an adhesive layer having excellent water resistance even under severe conditions such as in a dew condensation environment. In addition, the liquid stability is excellent, the pot life is long, and the productivity is also excellent. The reason why such an effect can be obtained can be estimated as follows.

When a polarizing film in which a transparent protective film is laminated on a polarizer via an adhesive layer is exposed to a dew condensation environment, the mechanism that causes adhesive peeling between the adhesive layer and the polarizer is as follows. Can be estimated. First, moisture that has passed through the protective film diffuses into the adhesive layer, and the moisture diffuses to the polarizer interface side. Here, in the conventional polarizing film, the contribution of hydrogen bonds and / or ionic bonds is large with respect to the adhesive force between the adhesive layer and the polarizer, but at the interface due to moisture diffused to the polarizer interface side. The hydrogen bond and the ionic bond are dissociated, and as a result, the adhesive force between the adhesive layer and the polarizer is reduced. Thereby, adhesive debonding between the adhesive layer and the polarizer may occur in a dew condensation environment.

On the other hand, the curable adhesive composition for polarizing films according to the present invention comprises an organometallic compound-containing composition, in particular, at least one organometallic compound (A) selected from the group consisting of metal alkoxides and metal chelates. contains. Such an organometallic compound (A) becomes an active metal species due to the presence of moisture, and as a result, the organometallic compound (A) is both a polarizer and an active energy ray-curable component (X) constituting an adhesive layer. Interacts strongly with. As a result, even if moisture is present at the interface between the polarizer and the adhesive layer, these are interacting firmly via the organometallic compound (A), so that there is a problem between the polarizer and the adhesive layer. Bonding water resistance is dramatically improved.

As described above, the organometallic compound (A) greatly contributes to the improvement of the adhesiveness and water resistance of the adhesive layer, but the composition containing this has a pot life due to unstable liquid stability. Tends to be shorter and productivity tends to deteriorate. However, in the present invention, in the organometallic compound-containing composition, the carboxyl group of the polymerizable compound (B) is strongly bonded and / or coordinated with the metal of the organometallic compound (A), whereby Since compound (A) is very well stabilized, the hydrolysis reaction and self-condensation reaction of organometallic compound (A) are suppressed, and the liquid stability of organometallic compound (A) in the composition is reduced. It can be improved dramatically.

<Active energy ray-curable component (X)>
The curable adhesive composition for polarizing films, which is one of the applications of the organometallic compound-containing composition according to the present invention, contains an active energy ray-curable component (X) as a curable component.

As the active energy ray curable component (X), an active energy ray curable type such as an electron beam curable type, an ultraviolet ray curable type, and a visible light curable type can be suitably used. Further, the ultraviolet curable and visible light curable adhesive compositions can be classified into radical polymerization curable adhesive compositions and cationic polymerization adhesive compositions. In the present invention, an active energy ray having a wavelength range of 10 nm to less than 380 nm is expressed as ultraviolet light, and an active energy ray having a wavelength range of 380 nm to 800 nm is expressed as visible light.

<1: Radical polymerization curable adhesive composition>
Examples of the curable component include radical polymerizable compounds used in radical polymerization curable adhesive compositions. Examples of the radical polymerizable compound include compounds having a radical polymerizable functional group of a carbon-carbon double bond such as a (meth) acryloyl group and a vinyl group. As these curable components, either a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used. Moreover, these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. As these radically polymerizable compounds, for example, compounds having a (meth) acryloyl group are suitable. In the present invention, (meth) acryloyl means an acryloyl group and / or methacryloyl group, and “(meth)” has the same meaning hereinafter.

≪Monofunctional radical polymerizable compound≫
Examples of the monofunctional radical polymerizable compound include (meth) acrylamide derivatives having a (meth) acrylamide group. A (meth) acrylamide derivative is preferable in terms of securing adhesiveness with a polarizer and various transparent protective films, and having a high polymerization rate and excellent productivity. Specific examples of (meth) acrylamide derivatives include, for example, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N N-alkyl group-containing (meth) acrylamide derivatives such as butyl (meth) acrylamide and N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N— N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as propane (meth) acrylamide; N-aminoalkyl group-containing (meth) acrylamide derivatives such as aminomethyl (meth) acrylamide and aminoethyl (meth) acrylamide; N-methoxy N-alkoxy group-containing (meth) acrylamide derivatives such as methylacrylamide and N-ethoxymethylacrylamide; N-mercaptoalkyl group-containing (meth) acrylamide derivatives such as mercaptomethyl (meth) acrylamide and mercaptoethyl (meth) acrylamide; Can be mentioned. Examples of the heterocyclic-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocyclic ring include, for example, N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine. Etc.

Among the (meth) acrylamide derivatives, N-hydroxyalkyl group-containing (meth) acrylamide derivatives are preferable from the viewpoint of adhesion to polarizers and various transparent protective films, and in particular, N-hydroxyethyl (meth) acrylamide. Is preferred.

In addition, examples of the monofunctional radical polymerizable compound include various (meth) acrylic acid derivatives having a (meth) acryloyloxy group. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-methyl-2-propylpentyl ( (Meth) acrylate, n-o Tadeshiru (meth) (meth) acrylic acid (1-20 carbon atoms) such as acrylates alkyl esters.

Examples of the (meth) acrylic acid derivative include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and cyclopentyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; 2-isobornyl (Meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, dicyclopentenyl (meth) ) Polycyclic (meth) acrylates such as acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxy Ethyl (meth) acrylate Alkoxy groups such as 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, or phenoxy Group-containing (meth) acrylates; and the like.

Examples of the (meth) acrylic acid derivative include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate And [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and other hydroxy acids Containing (meth) acrylate; glycidyl (meth) acrylate, epoxy group-containing (meth) acrylate such as 4-hydroxybutyl (meth) acrylate glycidyl ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2, 2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2- Halogen-containing (meth) acrylates such as hydroxypropyl (meth) acrylate; alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; 3-oxetanylmethyl (meth) acrylate Contains oxetane groups such as acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, 3-butyl-oxetanylmethyl (meth) acrylate, 3-hexyloxoxanylmethyl (meth) acrylate (Meth) acrylate; (meth) acrylate having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and butyrolactone (meth) acrylate, neopentyl glycol (meth) acrylic acid adduct of hydroxypivalate, p-phenylphenol ( And (meth) acrylate.

Also, examples of the monofunctional radically polymerizable compound include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.

Examples of the monofunctional radical polymerizable compound include lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as vinyl pyrrole, vinyl imidazole, vinyl oxazole, and vinyl morpholine.

Also, as the monofunctional radically polymerizable compound, a radically polymerizable compound having an active methylene group can be used. The radical polymerizable compound having an active methylene group is a compound having an active methylene group having an active double bond group such as a (meth) acryl group at the terminal or in the molecule. Examples of the active methylene group include an acetoacetyl group, an alkoxymalonyl group, and a cyanoacetyl group. The active methylene group is preferably an acetoacetyl group. Specific examples of the radical polymerizable compound having an active methylene group include 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetoacetoxy-1-methylethyl (meth) acrylate, and the like. Acetoacetoxyalkyl (meth) acrylate; 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) Examples include acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, and N- (2-acetoacetylaminoethyl) acrylamide. The radical polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.

≪Polyfunctional radical polymerizable compound≫
Examples of the bifunctional or higher polyfunctional radical polymerizable compound include N, N′-methylenebis (meth) acrylamide, tripropylene glycol di (meth) acrylate, and tetraethylene glycol diester which are polyfunctional (meth) acrylamide derivatives. (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) ) Acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate , Neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, dioxane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate (Meth) acrylic such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified diglycerin tetra (meth) acrylate An esterified product of an acid and a polyhydric alcohol, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene. Specific examples include Aronix M-220 (manufactured by Toagosei Co., Ltd.), light acrylate 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), light acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), light acrylate DCP-A (Kyoeisha Chemical Co., Ltd.) SR-531 (Sartomer), CD-536 (Sartomer) and the like are preferable. Moreover, various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, various (meth) acrylate monomers, and the like are included as necessary. The polyfunctional (meth) acrylamide derivative is preferably contained in the curable resin composition because the polymerization rate is high and the productivity is excellent, and the crosslinkability when the resin composition is a cured product is excellent.

The radical polymerizable compound contains the polyfunctional radical polymerizable compound in order to control the water absorption rate of the cured product and to satisfy the optical durability of the polarizing film in a severely humidified environment. preferable. Among the polyfunctional radical polymerizable compounds, those having a high logPow value described later are preferable.

When the organometallic compound-containing composition according to the present invention is blended in a curable adhesive composition for polarizing films, the adhesive composition has a high octanol / water partition coefficient (hereinafter referred to as logPow value). preferable. The logPow value is an index representing the lipophilicity of a substance and means the logarithmic value of the octanol / water partition coefficient. High logPow means that it is lipophilic, that is, low water absorption. The logPow value can be measured (flask immersion method described in JIS-Z-7260), but can also be calculated. In this specification, the logPow value calculated by ChemDraw Ultra manufactured by Cambridge Soft is used. Further, the logPow value of the adhesive composition can be calculated by the following formula.
LogPow of adhesive composition = Σ (logPow × Wi)
logPowi: logPow value of each component of composition Wi: (number of moles of i component) / (total number of moles of adhesive composition)
The logPow value of the curable adhesive composition of the present invention is preferably 1 or more, more preferably 2 or more, and most preferably 3 or more.

Examples of the radical polymerizable compound having a high log Pow value include alicyclic (meth) such as tricyclodecane dimethanol di (meth) acrylate (logPow = 3.05) and isobornyl (meth) acrylate (logPow = 3.27). Acrylate; Long chain aliphatic (meth) acrylate such as 1,9-nonanediol di (meth) acrylate (logPow = 3.68), 1,10-decanediol diacrylate (logPow = 4.10); hydroxypivalic acid Multi-branched (meth) acrylates such as neopentyl glycol (meth) acrylic acid adduct (logPow = 3.35), 2-ethyl-2-butylpropanediol di (meth) acrylate (logPow = 3.92); bisphenol A Di (meth) acrylate (logPow 5.46), bisphenol A ethylene oxide 4 mol adduct di (meth) acrylate (logPow = 5.15), bisphenol A propylene oxide 2 mol adduct di (meth) acrylate (logPow = 6.10), bisphenol A propylene Oxide 4-mol adduct di (meth) acrylate (logPow = 6.43), 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene (logPow = 7.48), p-phenyl (Meth) acrylate containing an aromatic ring such as phenol (meth) acrylate (logPow = 3.98);

Radical polymerizable compounds should be used in combination with monofunctional radical polymerizable compounds and polyfunctional radical polymerizable compounds from the viewpoint of achieving both adhesion to polarizers and various transparent protective films and optical durability in harsh environments. Is preferred. Usually, it is preferable to use a combination of 3 to 80% by weight of the monofunctional radical polymerizable compound and 20 to 97% by weight of the polyfunctional radical polymerizable compound with respect to 100% by weight of the radical polymerizable compound.

<Aspect of radical polymerization curable adhesive composition>
When the organometallic compound-containing composition according to the present invention is blended in a curable adhesive composition for a polarizing film and the curable component is used as an active energy ray curable component, the active energy ray curable adhesive composition is used. Can be used. In the case where the active energy ray-curable adhesive composition uses an electron beam or the like for the active energy ray, the active energy ray-curable adhesive composition need not contain a photopolymerization initiator, When ultraviolet rays or visible rays are used for the active energy rays, it is preferable to contain a photopolymerization initiator.

≪Photopolymerization initiator≫
The photopolymerization initiator in the case of using the radical polymerizable compound is appropriately selected depending on the active energy ray. In the case of curing by ultraviolet light or visible light, a photopolymerization initiator for ultraviolet light or visible light cleavage is used. Examples of the photopolymerization initiator include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2 -Propyl) ketone, aromatic ketone compounds such as α-hydroxy-α, α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy- Acetophenone compounds such as 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin methyl ether; Benzoin ethyl ether, benzoin Benzoin ether compounds such as isopropyl ether, benzoin butyl ether and anisoin methyl ether; aromatic ketal compounds such as benzyldimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; 1-phenone-1 , 1-propanedione-2- (o-ethoxycarbonyl) oxime, photoactive oxime compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichloro Thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone; camphorquinone; halogenated ketone; acylphosphine Inokishido; and acyl phospholipase diisocyanate, and the like. Among photopolymerization initiators, those having a high logPow value are preferred. The logPow value of the photopolymerization initiator is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.

The blending amount of the photopolymerization initiator is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound). The blending amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and further preferably 0.1 to 5 parts by weight.

In addition, when the organometallic compound-containing composition according to the present invention is blended in a curable adhesive composition for a polarizing film and used in a visible light curable type containing a radical polymerizable compound as a curable component, particularly 380 nm or more. It is preferable to use a photopolymerization initiator that is highly sensitive to light. A photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.

As said photoinitiator, the compound represented by following General formula (1);

(Wherein R ¹ and R ² represent —H, —CH ₂ CH ₃ , —iPr or Cl, and R ¹ and R ² may be the same or different), respectively, or a general formula ( It is preferable to use together the compound represented by 1) and a photopolymerization initiator that is highly sensitive to light of 380 nm or more, which will be described later. When the compound represented by the general formula (1) is used, the adhesiveness is excellent as compared with a case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone. Among the compounds represented by the general formula (1), diethyl thioxanthone ^{R 1} and ^{R 2} is _-CH 2 CH ₃ are particularly preferred. The composition ratio of the compound represented by the general formula (1) in the adhesive composition is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component, 0.5 to The amount is more preferably 4 parts by weight, still more preferably 0.9 to 3 parts by weight.

Further, it is preferable to add a polymerization initiation assistant as necessary. Examples of polymerization initiators include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc. Among them, ethyl 4-dimethylaminobenzoate is particularly preferable. When a polymerization initiation assistant is used, its addition amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, most preferably 0 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable component. is there.

Further, a known photopolymerization initiator can be used in combination as necessary. Since the transparent protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator. Specifically, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.

In particular, as a photopolymerization initiator, in addition to the photopolymerization initiator of the general formula (1), a compound represented by the following general formula (2);

Wherein R ³ , R ⁴ and R ⁵ represent —H, —CH ₃ , —CH ₂ CH ₃ , —iPr or Cl, and R ³ , R ⁴ and R ⁵ may be the same or different. It is preferable to use it. As the compound represented by the general formula (2), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907 manufacturer: BASF) which is also a commercial product is suitable. Can be used. In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369 manufacturer: BASF), 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379 manufacturer: BASF) is preferred because of its high sensitivity.

<Radically polymerizable compound (a1) having an active methylene group and radical polymerization initiator (a2) having a hydrogen abstracting action>
In the active energy ray-curable adhesive composition, when the radical polymerizable compound (a1) having an active methylene group is used as the radical polymerizable compound, it is combined with the radical polymerization initiator (a2) having a hydrogen abstraction function. Are preferably used. According to such a configuration, the adhesiveness of the adhesive layer of the polarizing film is remarkably improved even in a high humidity environment or immediately after being taken out from water (non-dried state). The reason for this is not clear, but the following causes are considered. That is, the radically polymerizable compound (a1) having an active methylene group is taken into the main chain and / or the side chain of the base polymer in the adhesive layer while being polymerized together with other radically polymerizable compounds constituting the adhesive layer. Forming an adhesive layer. In this polymerization process, when a radical polymerization initiator (a2) having a hydrogen abstracting action is present, the base polymer constituting the adhesive layer is formed, and hydrogen is generated from the radical polymerizable compound (a2) having an active methylene group. It is extracted and a radical is generated in the methylene group. And the methylene group which the radical generate | occur | produced, and the hydroxyl group of polarizers, such as PVA, react, and a covalent bond is formed between an adhesive bond layer and a polarizer. As a result, it is speculated that the adhesiveness of the adhesive layer of the polarizing film is remarkably improved even in a non-dry state.

In the present invention, examples of the radical polymerization initiator (a2) having a hydrogen abstracting action include thioxanthone radical polymerization initiators and benzophenone radical polymerization initiators. The radical polymerization initiator (a2) is preferably a thioxanthone radical polymerization initiator. Examples of the thioxanthone radical polymerization initiator include compounds represented by the above general formula (1). Specific examples of the compound represented by the general formula (1) include thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone. Among the compounds represented by the general formula (1), diethyl thioxanthone ^{R 1} and ^{R 2} is _-CH 2 CH ₃ are particularly preferred.

In the above active energy ray-curable adhesive composition, when the radical polymerizable compound (a1) having an active methylene group and the radical polymerization initiator (a2) having a hydrogen abstraction function are contained, the total amount of the curable component Is 100% by weight, the radically polymerizable compound (a1) having an active methylene group is 1 to 50% by weight, and the radical polymerization initiator (a2) is 0% by weight based on 100 parts by weight of the total amount of the curable component. It is preferable to contain 1 to 10 parts by weight.

As described above, in the present invention, a radical is generated in the methylene group of the radical polymerizable compound (a1) having an active methylene group in the presence of the radical polymerization initiator (a2) having a hydrogen abstracting action, and the methylene group And a hydroxyl group of a polarizer such as PVA react to form a covalent bond. Therefore, in order to generate radicals in the methylene group of the radically polymerizable compound (a1) having an active methylene group and to sufficiently form such a covalent bond, when the total amount of the curable component is 100% by weight, the active methylene group It is preferable to contain 1 to 50% by weight of the radically polymerizable compound (a1) having a more preferable content of 3 to 30% by weight. In order to sufficiently improve the water resistance and improve the adhesion in a non-dry state, the radical polymerizable compound (a1) having an active methylene group is preferably 1% by weight or more. On the other hand, if it exceeds 50% by weight, the adhesive layer may be poorly cured. The radical polymerization initiator (a2) having a hydrogen abstracting action is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.3 to 9 parts by weight, based on 100 parts by weight of the total amount of the curable component. More preferably. In order for the hydrogen abstraction reaction to proceed sufficiently, it is preferable to use 0.1 parts by weight or more of the radical polymerization initiator (a2). On the other hand, if it exceeds 10 parts by weight, it may not completely dissolve in the composition.

<2: Cationic polymerization curable adhesive composition>
The cationic polymerizable compound used in the cationic polymerization curable resin composition includes a monofunctional cationic polymerizable compound having one cationic polymerizable functional group in the molecule and two or more cationic polymerizable functional groups in the molecule. And having a polyfunctional cationically polymerizable compound. Since the monofunctional cation polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the resin composition can be reduced by containing it in the resin composition. In addition, monofunctional cationically polymerizable compounds often have functional groups that develop various functions, and by incorporating them into the resin composition, various functions are exhibited in the resin composition and / or the cured product of the resin composition. Can be made. The polyfunctional cation polymerizable compound is preferably contained in the resin composition because the cured product of the resin composition can be three-dimensionally crosslinked. The ratio of the monofunctional cation polymerizable compound to the polyfunctional cation polymerizable compound is such that the polyfunctional cation polymerizable compound is mixed in the range of 10 to 1000 parts by weight with respect to 100 parts by weight of the monofunctional cation polymerizable compound. Is preferred. Examples of the cationic polymerizable functional group include an epoxy group, an oxetanyl group, and a vinyl ether group. Examples of the compound having an epoxy group include an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound, and the cationic polymerization curable resin composition of the present invention is excellent in curability and adhesiveness. It is particularly preferable to contain an alicyclic epoxy compound. Examples of the alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate caprolactone-modified products and trimethylcaprolactone-modified products. And valerolactone modified products, and specifically, Celoxide 2021, Celoxide 2021A, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085 (above, Daicel Chemical Industries, Ltd., Cyracure UVR-6105, Cyracure UVR) -6107, Cyracure 30, R-6110 (above, manufactured by Dow Chemical Japan Co., Ltd.), etc. The compound having an oxetanyl group is a cationic polymerization compound of the present invention. The compound having an oxetanyl group is preferably contained because it has the effect of improving the curability of the curable resin composition or lowering the liquid viscosity of the composition, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl -3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, and the like, including Aron Oxetane OXT-101, Aron Oxetane OXT-121, Aron Oxetane OXT-211, Aron Oxetane OXT-221, Aron Oxetane OXT-212 (Above, manufactured by Toagosei Co., Ltd.) The compound having a vinyl ether group is preferably contained because it has the effect of improving the curability of the cationic polymerization curable resin composition of the present invention or lowering the liquid viscosity of the composition. As 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, vinyl ether of diethylene glycol, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxy Examples thereof include ethyl vinyl ether, ethoxyethyl vinyl ether, and pentaerythritol type tetravinyl ether.

<Photocationic polymerization initiator>
The cationic polymerization curable resin composition contains at least one compound selected from a compound having an epoxy group, a compound having an oxetanyl group, and a compound having a vinyl ether group as described above as a curable component. Therefore, a cationic photopolymerization initiator is blended. This cationic photopolymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and starts a polymerization reaction of an epoxy group or an oxetanyl group. As the photocationic polymerization initiator, a photoacid generator described later is preferably used. In addition, when the curable resin composition used in the present invention is used with visible light curability, it is particularly preferable to use a photocationic polymerization initiator that is highly sensitive to light of 380 nm or more. Is generally a compound that exhibits maximum absorption in the vicinity of 300 nm or shorter, and therefore, a photosensitizer that exhibits maximum absorption in light having a wavelength longer than that, specifically, longer than 380 nm should be blended. Thus, it is possible to respond to light having a wavelength in the vicinity and promote generation of cationic species or acid from the photocationic polymerization initiator. Examples of the photosensitizer include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes, and the like. Two or more types may be mixed and used. In particular, anthracene compounds are preferable because of their excellent photosensitization effect, and specific examples include anthracure UVS-1331 and anthracure UVS-1221 (manufactured by Kawasaki Kasei Co., Ltd.). The content of the photosensitizer is preferably 0.1% by weight to 5% by weight, and more preferably 0.5% by weight to 3% by weight.

<Other ingredients>
The curable adhesive composition preferably contains the following components.

<Acrylic oligomer (A)>
The active energy ray-curable adhesive composition according to the present invention may contain an acrylic oligomer (A) formed by polymerizing a (meth) acrylic monomer, in addition to the curable component related to the radical polymerizable compound. it can. By containing the component (A) in the active energy ray-curable adhesive composition, curing shrinkage when the active energy ray is irradiated and cured on the composition is reduced, and the adhesive, polarizer and transparent protection are reduced. Interfacial stress with an adherend such as a film can be reduced. As a result, it is possible to suppress a decrease in adhesiveness between the adhesive layer and the adherend. In order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the content of the acrylic oligomer (A) is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component. Is preferable, and it is more preferably 15 parts by weight or less. If the content of the acrylic oligomer (A) in the adhesive composition is too large, the reaction rate when the active energy ray is irradiated onto the composition is so severe that poor curing may occur. On the other hand, the acrylic oligomer (A) is preferably contained in an amount of 3 parts by weight or more and more preferably 5 parts by weight or more with respect to 100 parts by weight of the total amount of the curable component.

The active energy ray-curable adhesive composition preferably has a low viscosity in consideration of workability and uniformity during coating. Therefore, an acrylic oligomer (A) obtained by polymerizing a (meth) acrylic monomer. It is also preferable that the viscosity is low. The acrylic oligomer having a low viscosity and capable of preventing curing shrinkage of the adhesive layer preferably has a weight average molecular weight (Mw) of 15000 or less, more preferably 10,000 or less, and particularly preferably 5000 or less. preferable. On the other hand, in order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the weight average molecular weight (Mw) of the acrylic oligomer (A) is preferably 500 or more, and more preferably 1000 or more. More preferably, it is particularly preferably 1500 or more. Specific examples of the (meth) acrylic monomer constituting the acrylic oligomer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2 -Methyl-2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, S-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2 -Ethylhexyl (meth) acryl (Meth) acrylic acid (carbon number 1-20) alkyl esters such as 4-methyl-2-propylpentyl (meth) acrylate and N-octadecyl (meth) acrylate, and further, for example, cycloalkyl (meth) Acrylate (eg, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, etc.), aralkyl (meth) acrylate (eg, benzyl (meth) acrylate, etc.), polycyclic (meth) acrylate (eg, 2-isobornyl (meth) Acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, etc.), hydroxyl group-containing (meth) Acrylic esters (e.g., Droxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropylmethyl-butyl (meth) methacrylate, etc.), alkoxy group or phenoxy group-containing (meth) acrylic acid esters (2-methoxyethyl ( (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, etc.), epoxy Group-containing (meth) acrylic acid esters (for example, glycidyl (meth) acrylate), halogen-containing (meth) acrylic acid esters (for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2 , 2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, etc.), alkylaminoalkyl (Meth) acrylate (for example, dimethylaminoethyl (meth) acrylate etc.) etc. are mentioned. These (meth) acrylates can be used alone or in combination of two or more. Specific examples of the acrylic oligomer (A) include “ARUFON” manufactured by Toagosei Co., Ltd., “Act Flow” manufactured by Soken Chemical Co., Ltd., “JONCRYL” manufactured by BASF Japan. Among the acrylic oligomers (A) obtained by polymerizing (meth) acrylic monomers, those having a high logPow value are preferable. The logPow value of the acrylic oligomer (A) obtained by polymerizing the (meth) acrylic monomer is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.

<Photoacid generator (B)>
The said active energy ray hardening-type adhesive composition can contain a photo-acid generator (B). When the active energy ray-curable resin composition contains a photoacid generator, the water resistance and durability of the adhesive layer can be dramatically improved as compared with the case where no photoacid generator is contained. . The photoacid generator (B) can be represented by the following general formula (3).

General formula (3)

(However, L ⁺ represents any onium cation. X ⁻ represents PF6 ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate. Represents a counter anion selected from the group consisting of an anion and SCN-)

Among the above exemplified anions, particularly preferred as the counter anion X ⁻ in the general formula (3) include PF ₆ ⁻ , SbF ₆ ⁻ and AsF ₆ ⁻ , and particularly preferably PF ₆ ⁻ and SbF. ₆ ^- and the like.

Accordingly, specific examples of preferred onium salts constituting the photoacid generator (B) of the present invention include “Syracure UVI-6922” and “Syracure UVI-6974” (above, manufactured by Dow Chemical Japan Co., Ltd.). “Adekaoptomer SP150”, “Adekaoptomer SP152”, “Adekaoptomer SP170”, “Adekaoptomer SP172” (manufactured by ADEKA Corporation), “IRGACURE250” (manufactured by Ciba Specialty Chemicals), “ "CI-5102", "CI-2855" (manufactured by Nippon Soda Co., Ltd.), "Sun-Aid SI-60L", "Sun-Aid SI-80L", "Sun-Aid SI-100L", "Sun-Aid SI-110L", "Sun-Aid SI" -180L "(Sanshin Chemical Co., Ltd.)," CPI-100P " "CPI-100A" (manufactured by San Apro Co., Ltd.), "WPI-069", "WPI-113", "WPI-116", "WPI-041", "WPI-044", "WPI-054" , “WPI-055”, “WPAG-281”, “WPAG-567”, “WPAG-596” (manufactured by Wako Pure Chemical Industries, Ltd.) are preferable specific examples of the photoacid generator (B) of the present invention. It is done.

The content of the photoacid generator (B) is 10 parts by weight or less, preferably 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component. More preferably, the amount is 0.1 to 3 parts by weight.

<Compound (C) containing either an alkoxy group or an epoxy group>
In the active energy ray-curable adhesive composition, the active energy ray-curable adhesive composition can be used in combination with a photoacid generator (B) and a compound (C) containing either an alkoxy group or an epoxy group. .

(Compound having epoxy group and polymer) (C)
When using a compound having one or more epoxy groups in the molecule or a polymer (epoxy resin) having two or more epoxy groups in the molecule, two functional groups having reactivity with the epoxy group are contained in the molecule. Two or more compounds may be used in combination. Here, examples of the functional group having reactivity with an epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, and a primary or secondary aromatic amino group. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.

Examples of the polymer having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, bisphenol F type epoxy derived from bisphenol F and epichlorohydrin. Resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Multifunctional epoxy resin such as naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and tetrafunctional type epoxy resin , Glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, etc. These epoxy resins may be halogenated and hydrogenated It may be. As commercially available epoxy resin products, for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin Co., Ltd., Epicron manufactured by DIC Corporation 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series, manufactured by ADEKA Co., Ltd., Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.) manufactured by Daicel Chemical Co., Ltd., Epolide series, EHPE Series, YD series, YDF series, YDCN series, YDB series, phenoxy resins (polysynthesized from bisphenols and epichlorohydrin) Mud carboxymethyl at both ends with polyether having an epoxy group; and YP series), Nagase ChemteX Corporation of Denacol series manufactured by Kyoeisha although chemical Co. Epo light series are exemplified but not limited thereto. Two or more of these epoxy resins may be used in combination. When calculating the glass transition temperature Tg of the adhesive layer, the compound having an epoxy group and the polymer (C) are not included in the calculation.

(Alkoxyl group-containing compound and polymer) (C) The compound having an alkoxyl group in the molecule is not particularly limited as long as it has one or more alkoxyl groups in the molecule, and known compounds can be used. Representative examples of such compounds include melamine compounds, amino resins, and silane coupling agents. In calculating the glass transition temperature Tg of the adhesive layer, the compound having an alkoxyl group and the polymer (C) are not included in the calculation.

The compounding amount of the compound (C) containing either an alkoxy group or an epoxy group is usually 30 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component, and the content of the compound (C) in the composition When there is too much, adhesiveness falls and the impact resistance with respect to a drop test may deteriorate. The content of the compound (C) in the composition is more preferably 20 parts by weight or less. On the other hand, from the viewpoint of water resistance, the composition preferably contains 2 parts by weight or more of the compound (C), more preferably 5 parts by weight or more.

<Silane coupling agent (D)>
In the case where the curable adhesive composition for polarizing film of the present invention is an active energy ray curable curable composition, the silane coupling agent (D) is preferably an active energy ray curable compound. Even if it is not energy ray curable, the same water resistance can be imparted.

Specific examples of the silane coupling agent (D) include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and the like as active energy ray-curable compounds. -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy Examples thereof include propyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

Preferred are 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.

As a specific example of the silane coupling agent that is not active energy ray-curable, a silane coupling agent (D1) having an amino group is preferable. Specific examples of the silane coupling agent (D1) having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane Γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane , Γ- (6-Aminohexyl) Minopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyl Amino group-containing silanes such as trimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3-dimethylbutyrate) Reden) 3 may be mentioned ketimines type silanes such as (triethoxysilyl) -1-propanamine.

The silane coupling agent (D1) having an amino group may be used alone or in combination of two or more. Among these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane , Γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl)- 1-propanamine is preferred.

The amount of the silane coupling agent (D) is preferably 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the total amount of the curable component. More preferably, it is 1 to 10 parts by weight. This is because if the amount exceeds 20 parts by weight, the storage stability of the adhesive composition deteriorates, and if it is less than 0.1 parts by weight, the effect of adhesion water resistance is not sufficiently exhibited. When calculating the glass transition temperature Tg of the adhesive layer, the silane coupling agent (D) is not included in the calculation.

Specific examples of silane coupling agents that are not active energy ray-curable other than the above include 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxy. Examples include silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and imidazolesilane.

<Compound (E) having a vinyl ether group>
When the curable adhesive composition for a polarizing film contains a compound (E) having a vinyl ether group, it is preferable because the adhesion water resistance between the polarizer and the adhesive layer is improved. The reason why such an effect is obtained is not clear, but one of the reasons is that the adhesive force between the polarizer and the adhesive layer is increased by the interaction of the vinyl ether group of the compound (E) with the polarizer. It is guessed. In order to further increase the water resistance of adhesion between the polarizer and the adhesive layer, the compound (E) is preferably a radical polymerizable compound having a vinyl ether group. The content of the compound (E) is preferably 0.1 to 19 parts by weight with respect to 100 parts by weight of the total amount of the curable component.

<Compound (F) producing keto-enol tautomerism>
The curable adhesive composition for a polarizing film can contain a compound that causes keto-enol tautomerism. For example, in an adhesive composition containing a cross-linking agent or an adhesive composition that can be used by blending a cross-linking agent, an embodiment containing a compound that produces the keto-enol tautomerism can be preferably employed. Thereby, the excessive viscosity rise and gelation of the adhesive composition after the compounding of the organometallic compound and the formation of a microgel product can be suppressed, and the effect of extending the pot life of the composition can be realized.

As the compound (F) that produces the keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane- Β-diketones such as 3,5-dione; acetoacetates such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl acetate propionyl acetates such as tert-butyl; isobutyryl acetates such as ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, tert-butyl isobutylyl acetate; malonic acid esters such as methyl malonate and ethyl malonate Le acids; and the like. Among these, acetylacetone and acetoacetic acid esters are preferable compounds. The compound (F) that produces such keto-enol tautomerism may be used alone or in combination of two or more.

The amount of the compound that generates keto-enol tautomerism is, for example, 0.05 to 10 parts by weight, preferably 0.2 to 3 parts by weight (for example, 0.3 parts by weight) with respect to 1 part by weight of the organometallic compound. Parts by weight to 2 parts by weight). If the amount of the compound used is less than 0.05 parts by weight relative to 1 part by weight of the organometallic compound, it may be difficult to achieve a sufficient use effect. On the other hand, when the amount of the compound used exceeds 10 parts by weight with respect to 1 part by weight of the organometallic compound, it may be difficult to express the desired water resistance due to excessive interaction with the organometallic compound.

<Additives other than the above>
Moreover, various additives can be mix | blended with the curable adhesive composition for polarizing films as another arbitrary component in the range which does not impair the objective of this invention and an effect. Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone oligomers and polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; Plasticizers; UV absorbers; inorganic fillers; pigments; dyes and the like. Among various additives, those having a high logPow value are preferable. The logPow value of various additives is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.

The above additives are usually 0 to 10 parts by weight, preferably 0 to 5 parts by weight, and most preferably 0 to 3 parts by weight with respect to 100 parts by weight of the total amount of the curable component.

<Viscosity of adhesive composition>
Although the curable adhesive composition for polarizing films contains the said sclerosing | hardenable component, it is preferable that the viscosity of the said adhesive composition is 100 cp or less in 25 degreeC from a viewpoint of coating property. On the other hand, when the curable adhesive composition for polarizing film of the present invention exceeds 100 cp at 25 ° C., the temperature of the adhesive composition can be controlled at the time of coating and adjusted to 100 cp or less. A more preferable range of the viscosity is 1 to 80 cp, and most preferably 10 to 50 cp. The viscosity can be measured using an E-type viscometer TVE22LT manufactured by Toki Sangyo Co., Ltd.

In addition, the polarizing film curable adhesive composition preferably uses a material having low skin irritation as the curable component from the viewpoint of safety. Skin irritation is P.I. I. Judgment can be made with the index I. P. I. I is widely used to indicate the degree of skin injury and is measured by the Draise method. The measured value is displayed in the range of 0 to 8, and it is determined that the irritation is lower as the value is smaller. However, since the error of the measured value is large, it should be taken as a reference value. P. I. I is preferably 4 or less, more preferably 3 or less, and most preferably 2 or less.

The curable adhesive composition for a polarizing film is a first mixture in which an active energy ray-curable component (X) and a polymerizable compound (B) having a polymerizable functional group and a carboxyl group are mixed to obtain a mixed curable component. It can be produced by a production method comprising a step and a second mixing step in which at least one organometallic compound (A) selected from the group consisting of metal alkoxides and metal chelates is mixed with the mixed curable component. Components other than (X), (A) and (B) can be mixed at any stage of the first mixing step and the second mixing step.

Furthermore, the curable adhesive composition for polarizing film comprises at least one organometallic compound (A) selected from the group consisting of metal alkoxides and metal chelates, and a polymerizable compound (B) having a polymerizable functional group and a carboxyl group. ) To obtain an organometallic compound-containing composition, and a production method having a second mixing step of mixing an active energy ray-curable component into the organometallic compound-containing composition. . According to such a production method, the stability of the organometallic compound (A) in the organometallic compound-containing composition is dramatically increased, and as a result, the stability of the resulting curable adhesive composition for polarizing film is also enhanced. preferable. In addition, components other than (X), (A) and (B) can be mixed at any stage of the first mixing step and the second mixing step, but the organometallic compound (A) and the polymerizable compound can be mixed. From the viewpoint of increasing the reaction rate and / or coordination rate with (B) and improving the stability of the organometallic compound, the other components are preferably mixed after the first mixing step.

<Bulk water absorption>
The curable adhesive composition for polarizing film has a bulk water absorption of 10 described above, measured when a cured product obtained by curing the curable adhesive composition is immersed in pure water at 23 ° C. for 24 hours. It is preferable that it is below wt%. When a polarizing film is placed in a severe environment of high temperature and high humidity (85 ° C / 85% RH, etc.), moisture that has passed through the transparent protective film and the adhesive layer enters the polarizer and the crosslinked structure is hydrolyzed. As a result, the orientation of the dichroic dye is disturbed, and optical durability such as an increase in transmittance and a decrease in the degree of polarization occurs. By making the bulk water absorption of the adhesive layer 10% by weight or less, the movement of water to the polarizer when the polarizing film is placed in a severe high temperature and high humidity environment is suppressed, and the transmittance of the polarizer is increased. A decrease in the degree of polarization can be suppressed. The bulk water absorption is preferably 5% by weight or less, more preferably 3% by weight or less from the viewpoint of making the optical durability in a harsh environment at a high temperature more favorable for the adhesive layer of the polarizing film. Most preferably, it is 1% by weight or less. On the other hand, when the polarizer and the transparent protective film are bonded together, the polarizer retains a certain amount of moisture, and when the curable adhesive composition and moisture contained in the polarizer come into contact with each other, Such as appearance defects may occur. In order to suppress poor appearance, it is preferable that the curable adhesive composition can absorb a certain amount of moisture. More specifically, the bulk water absorption is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more. Specifically, the bulk water absorption rate is measured by a water absorption rate test method described in JISK 7209.

<Curing shrinkage>
Moreover, since the curable adhesive composition for polarizing films has a curable component, curing shrinkage usually occurs when the curable adhesive composition is cured. The cure shrinkage rate is an index indicating the rate of cure shrinkage when an adhesive layer is formed from the curable adhesive composition for polarizing film. When the cure shrinkage rate of the adhesive layer is increased, it is preferable to suppress the occurrence of poor adhesion due to interface distortion when the polarizing film curable adhesive composition is cured to form the adhesive layer. From the above viewpoint, it is preferable that the curing shrinkage rate of the cured product obtained by curing the curable adhesive composition for polarizing film of the present invention is 10% or less. The curing shrinkage rate is preferably small, and the curing shrinkage rate is preferably 8% or less, more preferably 5% or less. The cure shrinkage rate is measured by the method described in JP2013-104869A, specifically, measured by a method using a cure shrinkage sensor manufactured by Centec.

<Polarizing film>
In the polarizing film, a transparent protective film is bonded to at least one surface of the polarizer via an adhesive layer formed of a cured product layer of the curable adhesive composition for polarizing film. As described above, the adhesive layer that is the cured product layer preferably has a bulk water absorption of 10% by weight or less.

<Adhesive layer>
The thickness of the adhesive layer formed from the curable adhesive composition is preferably controlled to be 0.1 to 3 μm. The thickness of the adhesive layer is more preferably 0.3 to 2 μm, and further preferably 0.5 to 1.5 μm. Setting the thickness of the adhesive layer to 0.1 μm or more is preferable in order to suppress the occurrence of poor adhesion due to the cohesive force of the adhesive layer and the occurrence of poor appearance (bubbles) during lamination. On the other hand, if the adhesive layer is thicker than 3 μm, the polarizing film may not be able to satisfy the durability.

The curable adhesive composition is preferably selected so that the Tg of the adhesive layer formed thereby is 60 ° C. or higher, more preferably 70 ° C. or higher, and further 75 ° C. As described above, it is preferably 100 ° C. or higher, more preferably 120 ° C. or higher. On the other hand, if the Tg of the adhesive layer becomes too high, the flexibility of the polarizing film is lowered. Therefore, the Tg of the adhesive layer is preferably 300 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 180 ° C. or lower. Tg <glass transition temperature> is measured under the following measurement conditions using a TA Instruments dynamic viscoelasticity measuring apparatus RSAIII.
Sample size: width 10mm, length 30mm,
Clamp distance 20mm,
Measurement mode: Tensile, Frequency: 1 Hz, Temperature rising rate: 5 ° C./min Dynamic viscoelasticity was measured and adopted as the temperature Tg of tan δ peak top.

Further, in the curable adhesive composition, the storage elastic modulus of the adhesive layer formed thereby is preferably 1.0 × 10 ⁷ Pa or more at 25 ° C., and 1.0 × 10 ⁸ Pa or more. It is more preferable. The storage elastic modulus of the pressure-sensitive adhesive layer is 1.0 × 10 ³ Pa to 1.0 × 10 ⁶ Pa, which is different from the storage elastic modulus of the adhesive layer. The storage elastic modulus of the adhesive layer affects the polarizer cracks when the polarizing film is subjected to a heat cycle (-40 ° C to 80 ° C, etc.). If the storage elastic modulus is low, defects in the polarizer cracks occur. Cheap. The temperature region having a high storage elastic modulus is more preferably 80 ° C. or less, and most preferably 90 ° C. or less. The storage elastic modulus is measured under the same measurement conditions using a dynamic viscoelasticity measuring device RSAIII manufactured by TA Instruments simultaneously with Tg <glass transition temperature>. The dynamic viscoelasticity was measured and the value of the storage elastic modulus (E ′) was adopted.

In the present invention, the polarizing film has the following production method;
A coating step of applying the curable adhesive composition for polarizing film to at least one surface of the polarizer and the transparent protective film, a bonding step of bonding the polarizer and the transparent protective film, and the polarizer surface side or An adhesion step of adhering the polarizer and the transparent protective film via the adhesive layer obtained by irradiating the active energy ray from the transparent protective film surface side and curing the active energy ray-curable adhesive composition; Can be manufactured by a manufacturing method including: In such a production method, the moisture content of the polarizer in the bonding step is preferably 8 to 19%.

The polarizer and the transparent protective film may be subjected to a surface modification treatment before applying the curable adhesive composition. Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.

The coating method of the curable adhesive composition is appropriately selected depending on the viscosity of the composition and the target thickness. Examples of coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like. In addition, for coating, a method such as a dapping method can be appropriately used.

The polarizer and the transparent protective film are bonded together through the curable adhesive composition applied as described above. Bonding of the polarizer and the transparent protective film can be performed with a roll laminator or the like.

<Curing of the adhesive composition>
The curable adhesive composition for polarizing films is used as an active energy ray-curable adhesive composition. The active energy ray curable adhesive composition can be used in an electron beam curable type, an ultraviolet ray curable type, or a visible ray curable type. The embodiment of the curable adhesive composition is preferably a visible light curable adhesive composition from the viewpoint of productivity.

≪Active energy ray curing type≫
In the active energy ray-curable adhesive composition, after bonding the polarizer and the transparent protective film, the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated to obtain the active energy ray-curable adhesive composition. Cure to form an adhesive layer. The irradiation direction of active energy rays (electron beam, ultraviolet ray, visible light, etc.) can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent protective film side. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron beam, ultraviolet ray, visible light, etc.).

≪Electron beam curing type≫
In the electron beam curable type, any appropriate condition can be adopted as the electron beam irradiation condition as long as the active energy ray curable adhesive composition can be cured. For example, in the electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetration force through the sample is too strong and damages the transparent protective film and the polarizer. There is a risk of giving. The irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the adhesive becomes insufficiently cured, and when it exceeds 100 kGy, the transparent protective film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing, thereby obtaining predetermined optical characteristics. I can't.

The electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition where a little oxygen is introduced. Depending on the material of the transparent protective film, by appropriately introducing oxygen, the transparent protective film surface where the electron beam first hits can be obstructed to prevent oxygen damage and prevent damage to the transparent protective film. An electron beam can be irradiated efficiently.

≪Ultraviolet curing type, visible light curing type≫
In the method for producing a polarizing film, it is preferable to use an active energy ray containing visible light having a wavelength range of 380 nm to 450 nm, particularly an active energy ray having the largest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm. In the case of using a transparent protective film (ultraviolet non-transparent transparent protective film) imparted with ultraviolet absorbing ability in the ultraviolet curable type and visible light curable type, light having a wavelength shorter than about 380 nm is absorbed. Light does not reach the active energy ray-curable adhesive composition and does not contribute to the polymerization reaction. Furthermore, light having a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which causes defects such as curling and wrinkling of the polarizing film. Therefore, when the ultraviolet curable type or the visible light curable type is adopted in the present invention, it is preferable to use a device that does not emit light having a wavelength shorter than 380 nm as the active energy ray generating device, and more specifically, the wavelength range 380. The ratio of the integrated illuminance of ˜440 nm to the integrated illuminance of the wavelength range of 250 to 370 nm is preferably 100: 0 to 100: 50, and more preferably 100: 0 to 100: 40. As the active energy ray according to the present invention, a gallium-encapsulated metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable. Or low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, incandescent bulb, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight A light source including visible light can be used, and ultraviolet light having a wavelength shorter than 380 nm can be blocked using a band pass filter. In order to prevent the polarization film from curling while improving the adhesive performance of the adhesive layer between the polarizer and the transparent protective film, a gallium-encapsulated metal halide lamp can be used and light with a wavelength shorter than 380 nm can be blocked. It is preferable to use an active energy ray obtained through a band pass filter or an active energy ray having a wavelength of 405 nm obtained using an LED light source.

In the ultraviolet curable type or visible light curable type, it is preferable to warm the active energy ray curable adhesive composition (pre-irradiation warming) before irradiating the ultraviolet ray or visible light. It is preferable to heat it to 50 ° C. or higher. It is also preferable to heat the active energy ray-curable adhesive composition after irradiation with ultraviolet rays or visible light (heating after irradiation), in which case it is preferable to heat to 40 ° C. or higher, and to 50 ° C. or higher. It is more preferable to warm.

The active energy ray-curable adhesive composition can be suitably used particularly when an adhesive layer for bonding a polarizer and a transparent protective film having a light transmittance of a wavelength of 365 nm of less than 5% is formed. Here, the active energy ray-curable adhesive composition according to the present invention irradiates ultraviolet rays through the transparent protective film having UV absorption ability by containing the photopolymerization initiator of the general formula (1) described above. Thus, the adhesive layer can be cured and formed. Therefore, an adhesive bond layer can be hardened also in a polarizing film which laminated a transparent protective film which has UV absorption ability on both sides of a polarizer. However, as a matter of course, the adhesive layer can also be cured in a polarizing film in which a transparent protective film having no UV absorbing ability is laminated. In addition, the transparent protective film which has UV absorption ability means the transparent protective film whose transmittance | permeability with respect to light of 380 nm is less than 10%.

Examples of the method for imparting UV absorbing ability to the transparent protective film include a method of containing an ultraviolet absorber in the transparent protective film and a method of laminating a surface treatment layer containing an ultraviolet absorber on the surface of the transparent protective film.

Specific examples of the ultraviolet absorber include conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. .

After laminating the polarizer and the transparent protective film, the active energy ray (electron beam, ultraviolet ray, visible light, etc.) is irradiated to cure the active energy ray-curable adhesive composition to form an adhesive layer. The irradiation direction of active energy rays (electron beam, ultraviolet ray, visible light, etc.) can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent protective film side. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron beam, ultraviolet ray, visible light, etc.).

When the polarizing film is produced in a continuous line, the line speed depends on the curing time of the adhesive composition, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, and further preferably 10 to 100 m / min. is there. When the line speed is too low, the productivity is poor, or the damage to the transparent protective film is too great, and a polarizing film that can withstand the durability test cannot be produced. If the line speed is too high, the adhesive composition may not be sufficiently cured, and the target adhesiveness may not be obtained.

In addition, although a polarizer and a transparent protective film are bonded together through the adhesive bond layer formed by the hardened | cured material layer of the said active energy ray hardening-type adhesive composition, a polarizing film is transparent adhesive film and adhesive agent. An easy-adhesion layer can be provided between the layers. The easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specifically, a stabilizer such as a tackifier, an ultraviolet absorber, an antioxidant, and a heat resistance stabilizer may be used.

The easy-adhesion layer is usually provided in advance on a transparent protective film, and the easy-adhesion layer side of the transparent protective film and the polarizer are bonded together with an adhesive layer. The easy-adhesion layer is formed by coating and drying the material for forming the easy-adhesion layer on the transparent protective film by a known technique. The material for forming the easy-adhesion layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying and the smoothness of coating. The thickness of the easy-adhesion layer after drying is preferably 0.01 to 5 μm, more preferably 0.02 to 2 μm, and still more preferably 0.05 to 1 μm. Note that a plurality of easy-adhesion layers can be provided, but also in this case, the total thickness of the easy-adhesion layers is preferably in the above range.

<Polarizer>
The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye. And polyene-based oriented films such as those obtained by adsorbing a functional material and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.

A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.

In addition, when a thin polarizer having a thickness of 10 μm or less is used as the polarizer, the curable adhesive composition exhibits its effect (satisfying optical durability in harsh environments under high temperature and high humidity). can do. The polarizer having a thickness of 10 μm or less is relatively more affected by moisture than a polarizer having a thickness exceeding 10 μm, and has insufficient optical durability in a high-temperature and high-humidity environment, resulting in increased transmittance and degree of polarization. Decline is likely to occur. Therefore, from the cured product of the curable adhesive composition for a polarizing film according to the present invention, wherein the polarizer of 10 μm or less contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates. When the adhesive layer is further laminated with an adhesive layer having a bulk water absorption of 10% by weight or less, the movement of water to the polarizer is suppressed in a severe environment of high temperature and high humidity. Deterioration of optical durability such as increase in transmittance and decrease in polarization degree can be remarkably suppressed. The thickness of the polarizer is preferably 1 to 7 μm from the viewpoint of thinning. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, and the thickness of the polarizing film can be reduced.

As the thin polarizer, typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, PCT / JP2010 / 001460, or Japanese Patent Application No. 2010- And a thin polarizing film described in Japanese Patent Application No. 269002 and Japanese Patent Application No. 2010-263692. These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.

As the thin polarizing film, among the production methods including the step of stretching in the state of a laminate and the step of dyeing, WO2010 / 100917 pamphlet, PCT / PCT / PCT / JP 2010/001460 specification, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692, the one obtained by a production method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary before extending | stretching in the boric acid aqueous solution as described in Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692 is preferable.

<Transparent protective film>
As a material for forming the transparent protective film provided on one side or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Examples of the polymer that forms the transparent protective film include polymer blends. One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. . When content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.

Examples of the transparent protective film include a polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, B) Resin compositions containing a thermoplastic resin having substituted and / or unsubstituted phenyl and nitrile groups in the side chain. Specific examples include a film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer. As the film, a film made of a mixed extruded product of the resin composition or the like can be used. Since these films have a small phase difference and a small photoelastic coefficient, problems such as unevenness due to the distortion of the polarizing film can be eliminated, and since the moisture permeability is small, the humidification durability is excellent.

In the polarizing film, it is preferable moisture permeability of the transparent protective film is not more than 150g ^/ m 2 ^/ 24h. According to such a configuration, it is difficult for moisture in the air to enter the polarizing film, and a change in the moisture content of the polarizing film itself can be suppressed. As a result, the curling and dimensional change of the polarizing film caused by the storage environment can be suppressed.

As a material for forming a transparent protective film provided on one or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable. / ^m, more preferably not more 2 / 24h or less, particularly preferably those following 140 g ^/ m 2 / 24h, more preferably the following 120 g ^/ m 2 / 24h. The moisture permeability is determined by the method described in the examples.

Examples of the material for forming the transparent protective film satisfying the low moisture permeability include polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; arylate resins; amide resins such as nylon and aromatic polyamide; polyethylene, polypropylene Polyolefin polymers such as ethylene / propylene copolymers, cyclic olefin resins having a cyclo or norbornene structure, (meth) acrylic resins, or a mixture thereof can be used. Among the resins, polycarbonate resins, cyclic polyolefin resins, and (meth) acrylic resins are preferable, and cyclic polyolefin resins and (meth) acrylic resins are particularly preferable.

The thickness of the transparent protective film can be appropriately determined, but is generally about 1 to 100 μm from the viewpoints of workability such as strength and handleability and thin layer properties. 1 to 80 μm is particularly preferable, and 3 to 60 μm is more preferable.

In addition, when providing a transparent protective film on both surfaces of a polarizer, the transparent protective film which consists of the same polymer material may be used by the front and back, and the transparent protective film which consists of a different polymer material etc. may be used.

Functional surfaces such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the transparent protective film to which the polarizer is not adhered. The functional layers such as the hard coat layer, antireflection layer, antisticking layer, diffusion layer and antiglare layer can be provided on the transparent protective film itself, and separately provided separately from the transparent protective film. You can also.

<Optical film>
The polarizing film can be used as an optical film laminated with another optical layer in practical use. The optical layer is not particularly limited. For example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film. One or more optical layers that may be used can be used. In particular, a reflective polarizing film or semi-transmissive polarizing film in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing film of the present invention, an elliptical polarizing film or circularly polarizing film in which a retardation film is further laminated on a polarizing film. A wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on a film or a polarizing film, or a polarizing film obtained by further laminating a brightness enhancement film on the polarizing film is preferred.

An optical film obtained by laminating the above optical layer on a polarizing film can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembly work, and has the advantage of improving the manufacturing process of a liquid crystal display device and the like. Appropriate bonding means such as an adhesive layer can be used for lamination. When adhering the above polarizing film and other optical films, their optical axes can be set at an appropriate arrangement angle in accordance with the target retardation characteristics.

The pressure-sensitive adhesive layer for adhering to other members such as a liquid crystal cell can be provided on the polarizing film described above or an optical film in which at least one polarizing film is laminated. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited. For example, an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is appropriately selected. Can be used. In particular, those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and being excellent in weather resistance, heat resistance and the like can be preferably used.

The adhesive layer can be provided on one side or both sides of a polarizing film or an optical film as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers, such as a different composition, a kind, and thickness, in the front and back of a polarizing film or an optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

The exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination until it is put to practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state. As the separator, except for the above thickness conditions, for example, an appropriate thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet, metal foil, or a laminate thereof, and a silicone-based or long sheet as necessary. Appropriate ones according to the prior art, such as those coated with an appropriate release agent such as a chain alkyl type, fluorine type or molybdenum sulfide, can be used.

<Image display device>
The polarizing film or the optical film can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing film or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses the polarizing film or optical film by invention, and it can apply according to the former. As the liquid crystal cell, any type such as a TN type, an STN type, or a π type can be used.

Appropriate liquid crystal display devices such as a liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed. In that case, the polarizing film or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell. When providing a polarizing film or an optical film on both sides, they may be the same or different. Further, when forming the liquid crystal display device, for example, a single layer or a suitable layer such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.

Examples 1 to 10 and Comparative Examples 1 to 7
(Preparation of organometallic compound-containing composition)
Organometallic compound (A) and radical polymerizable compound (B) according to the recipes shown in Tables 1 and 2 (Comparative Examples 4 to 7, a metal-coordinating compound or primary alcohol having no carboxyl group) The organometallic compound containing composition containing only was prepared. The organic metal compound (A) and the radical polymerizable compound (B) were sufficiently mixed and then allowed to stand for 30 minutes. After standing for 30 minutes, the adhesive composition liquid was transparent, and the liquid stability was evaluated as ◯, and some white turbidity was observed, and white turbidity or precipitation was evaluated as x (this stability evaluation) Is also referred to as “initial evaluation after blending”). Next, 25% by weight of water is mixed with the organometallic compound-containing composition that has been allowed to stand for 30 minutes, and after sufficient mixing, the mixture is allowed to stand for 30 minutes to improve the stability of the organometallic compound-containing composition. Evaluation was performed based on the standard (this stability evaluation is also referred to as “initial evaluation after water blending”). The results are shown in Tables 1 and 2.

According to the recipes shown in Tables 1 and 2, an organic containing only an organometallic compound (A) and a radically polymerizable compound (B) (compounds having no carboxyl group in Comparative Examples 4 to 7). A metal compound-containing composition was prepared. The organometallic compound (A) and the radical polymerizable compound (B) were sufficiently mixed and allowed to stand for 30 minutes. 25 wt% of water was added to the organometallic compound-containing composition and mixed thoroughly. The case where white turbidity or precipitation occurs after 30 minutes is marked as "X", the result is transparent after 30 minutes, but the condition where white turbidity or precipitation occurs after 24 hours is marked as "△", and the result is transparent after 24 hours. The stability of the organometallic compound-containing composition liquid evaluated as ◯ when there was white turbidity or precipitation after 48 hours, and ◎ when the liquid remained transparent after 48 hours. Was evaluated according to the above criteria (this stability evaluation is also referred to as “24 h evaluation after water blending”).
The results are shown in Table 1.

In Table 1 and Table 2,
The organometallic compound (A) is
TA-10: Titanium isopropoxide (organic group carbon number 3), manufactured by Matsumoto Fine Chemical Co., Ltd .;
TA-21: Titanium butoxide (4 carbon atoms of organic group), manufactured by Matsumoto Fine Chemical Co., Ltd .;
TA-30: Titanium octoxide (carbon number of organic group: 8), manufactured by Matsumoto Fine Chemicals;
The radical polymerizable compound (B) is
Acrylic acid: (molecular weight 72.06 g / mol, manufactured by Nippon Shokubai Co., Ltd.);
M-5300: ω-carboxy-polycaprolactone (n≈2) monoacrylate, molecular weight 300.16 g / mol, manufactured by Toagosei Co., Ltd .;
HOA-MS: 2-acryloyloxyethyl-succinic acid, molecular weight 216.19 g / mol, manufactured by Kyoei Chemical Co., Ltd .;
As a compound capable of metal coordination without a carboxyl group,
AAEM: 2-acetoacetoxyethyl methacrylate, molecular weight 214.22 g / mol, manufactured by Nippon Synthetic Chemical Industry;
β-diketone: acetylacetone, molecular weight 100.117 g / mol, manufactured by Daicel Chemical Industries, Ltd .;
Indicates.

Claims

An organometallic compound comprising at least one organometallic compound (A) selected from the group consisting of metal alkoxides and metal chelates, and a polymerizable compound (B) having a polymerizable functional group and a carboxyl group Containing composition.
The organometallic compound-containing composition according to claim 1, wherein the metal of the organometallic compound (A) is titanium.
The organometallic compound-containing composition according to claim 1 or 2, wherein the organometallic compound (A) contains the metal alkoxide, and the organic group of the metal alkoxide has 4 or more carbon atoms.
The organometallic compound-containing composition according to claim 1 or 2, wherein the organometallic compound (A) contains the metal chelate, and an organic group of the metal chelate has 4 or more carbon atoms.
5. The organometallic compound-containing composition according to claim 1, wherein a ratio of the organometallic compound (A) in the organometallic compound-containing composition is 5 to 90% by weight.
6. The organometallic compound-containing composition according to claim 1, wherein the polymerizable compound (B) is a radical polymerizable compound.
The organometallic compound-containing composition according to any one of claims 1 to 6, wherein the molecular weight of the polymerizable compound (B) is 100 (g / mol) or more.
The polymerizable compound (B) is a polymerizable compound having a polymerizable functional group and a carboxyl group via an organic group having 1 to 20 carbon atoms which may contain oxygen. An organometallic compound-containing composition.
2. The content of the polymerizable compound (B) is 0.25α (mol) or more when the total amount of the organometallic compound (A) is α (mol) in the organometallic compound-containing composition. The organometallic compound-containing composition according to any one of 1 to 8.