JP6927233B2 - Active energy ray-curable composition - Google Patents

Description

The present invention relates to an active energy ray-curable composition, preferably a solvent-free active energy ray-curable composition, and particularly preferably an active energy ray-curable composition for a shaped material and an active energy ray-curable composition for a hard coat. Regarding goods, they belong to these technical fields.
In the present specification, "acryloyl group and / or methacryloyl group" is referred to as "(meth) acryloyl group", "acrylate and / or methacrylate" is referred to as "(meth) acrylate", and "acrylic acid and / or methacrylic acid". "Acid" is expressed as "(meth) acrylic acid".

Lens sheets such as prism sheets, antireflection films (so-called moth-eye films) having a microconcavo-convex structure with a period equal to or less than the wavelength of visible light on the surface, antiglare films, light extraction films for organic EL / LEDs, light for solar cells Molded films such as confinement films and heat ray retroreflective films are usually produced by the following methods.
That is, an active energy ray-curable composition is filled between a stamper having an inverted structure having a fine concavo-convex structure on its surface and a transparent base material, cured by irradiation with active energy rays, and then the stamper is released. A method of transferring a fine concavo-convex structure to a cured product, or an active energy ray-curable composition is filled between the stamper and a transparent substrate, and then the stamper is released to obtain an active energy ray-curable composition. A method is used in which the fine concavo-convex structure is transferred and then the active energy ray-curable composition is cured by irradiation with active energy rays.

As such a curable composition for a shaped material, an active energy ray-curable composition containing trimethylolpropane triacrylate (hereinafter referred to as "TMPTA") is conventionally known (Patent Document 1).
However, since the composition has a low viscosity, it has a problem that the cured product has poor scratch resistance, although it has excellent transferability of a fine concavo-convex structure.

Therefore, in order to improve scratch resistance, a solvent-based active energy ray-curable composition containing inorganic fine particles is known (Patent Document 2).
However, although the composition has a low viscosity because it contains a solvent and has excellent transferability of a fine concavo-convex structure, there is a problem that productivity is lowered because the solvent needs to be dried after application to the substrate.

As described above, there is an eager desire for a solvent-free active energy ray-curable composition that has low viscosity, high hardness, excellent substrate adhesion, and does not require solvent drying. In addition, the solvent-free UV-curable composition does not require ancillary equipment such as a drying oven and solvent recovery equipment, so that the equipment can be simplified, and it is preferable as a plastic hard coat material in addition to the excipient material. (Patent Document 3). However, in the conventional active energy ray-curable composition for solvent-free hard coat, low viscosity and high hardness tend to be in a trade-off relationship, and further improvement is required.

Japanese Unexamined Patent Publication No. 2000-071290 Japanese Unexamined Patent Publication No. 2014-126761 Japanese Unexamined Patent Publication No. 2008-049623

The present inventors have developed a solvent-free active energy ray-curable composition which has low viscosity without using a solvent in the composition and is excellent in hardness, scratch resistance and substrate adhesion of the cured product of the composition. A diligent study was carried out to find an active energy ray-curable composition for a shaped material and an active energy ray-curable composition for a hard coat.

As a solvent-free, low-viscosity, high-hardness composition, a compound having two or more (meth) acryloyl groups having a high (meth) acryloyl group concentration and a small molecular weight (hereinafter, "polyfunctional (hereinafter," polyfunctional ""Meta)acrylate") is considered to be effective, and glycerin tri (meth) acrylate (hereinafter referred to as "GLY-TA") is considered to be effective as one of the candidates.
In order to obtain GLY-TA industrially, a production method by dehydration esterification of glycerin and (meth) acrylic acid can be considered. However, in the esterification reaction, since the reactivity of the secondary hydroxyl group is particularly low, a large amount of high molecular weight compounds are produced, which is difficult to obtain industrially. Therefore, conventionally, the curable composition containing GLY-TA is not known.

In order to solve the above problems, the present inventors have prepared an active energy ray-curable composition containing a specific GLY-TA and inorganic fine particles, which is solvent-free and have a low viscosity, and have hardness and scratch resistance of the cured product. The present invention has been completed by finding that it has excellent substrate adhesion.
Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, it is solvent-free and has a low viscosity, and the cured product can be excellent in hardness, scratch resistance, and substrate adhesion.

The present invention is a composition containing the following components (A), (B) and (C).
In the total of 100% by weight of the components (A), (B) and (C), 40 to 95% by weight of the component (A), 5 to 60% by weight of the component (B) and 0 to 55% by weight of the component (C). The present invention relates to an active energy ray-curable composition containing% by weight.
Component (A): A (meth) acrylate mixture containing GLY-TA [glycerintri (meth) acrylate] as a main component, and the high molecular weight compound in the component (A) is gel permeation based on the formula (1). The area% of the mixture by chromatography (hereinafter referred to as “GPC”) is less than 30%. Area% of the high molecular weight compound = [(RIL) / R] × 100 ... (1)
The symbols and terms in formula (1) mean the following.
-R: Total area of detected peaks in component (A) -I: Area of detected peaks containing GLY-TA-L: Total area of detected peaks having a smaller weight average molecular weight than the detected peaks containing GLY-TA (B) ) Component: Filler (C) Component: Compound having an ethylenically unsaturated group other than the (A) component The following describes the component (A), the component (B), the component (C), other components, and the method of use.

1. 1. Component (A) The component (A), which is an essential component of the present invention, is a (meth) acrylate mixture containing GLY-TA as a main component.
In the present invention, since the main component of the component (A) is GLY-TA, the area% of the high molecular weight body defined by the following formula (1) is less than 30%, preferably 25%. Less than, more preferably less than 20%.

Area% of high molecular weight body = [(RIL) / R] × 100 ... (1)
The symbols and terms in formula (1) mean the following.
-R: Total area of detected peaks in component (A) -I: Area of detected peaks containing GLY-TA-L: Weight average molecular weight (hereinafter referred to as "Mw") larger than that of detected peaks containing GLY-TA Total area of small detection peaks In the present invention, Mw means a value obtained by converting the molecular weight measured by GPC with reference to the molecular weight of polystyrene using tetrahydrofuran (hereinafter referred to as “THF”) as a solvent. ..

By setting the area% of the high molecular weight substance in the component (A) to less than 30%, the composition can have a low viscosity and excellent cured physical properties. When the area% of the high molecular weight body is 30% or more, the viscosity of the composition increases, so that the shape reproducibility deteriorates when used as a shaping material, and the coatability when used as a hard coat agent. Get worse.
The molecular weight measured by GPC in the present invention means a value measured under the following conditions.
・ Detector: Differential refractometer (RI detector)
-Column type: Cross-linked polystyrene column-Column temperature: In the range of 25 to 50 ° C.-Eluent: THF

The component (A) contains GLY-TA as a main component, and preferably has a low hydroxyl value. Specifically, the hydroxyl value is preferably 60 mgKOH / g or less, and more preferably 45 mgKOH / g or less.
By setting the hydroxyl value of the component (A) in this range, the composition can have a low viscosity, and a composition having excellent hardness of the cured product can be obtained.
In the present invention, the hydroxyl value means the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of the sample.

As the component (A), a compound obtained by transesterifying glycerin with a compound having one (meth) acryloyl group [hereinafter, referred to as monofunctional (meth) acrylate]] is preferable.
As described above, in the production method in which glycerin and (meth) acrylic acid are subjected to a dehydration esterification reaction, a large amount of high molecular weight compound is produced due to the low reactivity of the secondary hydroxyl group, and GLY-TA is industrially produced. Is difficult. On the other hand, a transesterification reaction between glycerin and a monofunctional (meth) acrylate makes it possible to produce a (meth) acrylate mixture containing GLY-TA as a main component.

In the case of transesterification reaction of glycerin and monofunctional (meth) acrylate, a mixture of (meth) acrylate is obtained. Specifically, in addition to GLY-TA, glycerin di (meth) acrylate and a high molecular weight substance can be obtained, and a small amount of glycerin mono (meth) acrylate can be obtained depending on the production conditions.
Examples of the high molecular weight material include a polyfunctional (meth) acrylate having a Michael-added structure such as a compound in which a hydroxyl group of glycerindi (meth) acrylate is Michael-added to the (meth) acryloyl group of GLY-TA. Can be mentioned.

Hereinafter, a method for producing a polyhydric alcohol, a monofunctional (meth) acrylate, a catalyst, and a method for producing the component (A) will be described with respect to the method for producing the component (A) by a transesterification reaction, which is a preferable method for producing the component (A).

1-1. The polyhydric alcohol used as a raw material for the polyhydric alcohol (A) component is glycerin.
The raw material glycerin may contain a small amount of water or a glycerin condensate such as diglycerin. The purity of glycerin is not particularly limited, but is preferably 90% by weight or more, and more preferably 95% by weight or more. If the purity of glycerin is less than 90% by weight, the viscosity of the component (A) increases, which may make handling difficult.
In addition, glycerin may contain a trace amount of peroxide derived from the manufacturing process. The concentration of the peroxide contained in the glycerin used as the raw material of the component (A) is preferably 5 wtppm or less, more preferably 2 wtppm or less. If the concentration of the peroxide exceeds 5 wtppm, the (meth) acryloyl group may be polymerized during production, or the color tone of the reaction solution may be deteriorated.
In the present invention, glycerin and one or more kinds of polyhydric alcohols other than glycerin (hereinafter referred to as "other polyhydric alcohols") may be arbitrarily combined and used as long as the effects of the present invention are not impaired. ..
The ratio when other polyhydric alcohols are used in combination is preferably 50 parts by weight or less with respect to 100 parts by weight of glycerin.

Other polyvalent alcohols include aliphatic alcohols having at least two or more alcoholic hydroxyl groups in the molecule, alicyclic alcohols, aromatic alcohols, polyhydric alcohol ethers and the like, and other functional groups and bonds in the molecule. For example, phenolic hydroxyl group, ketone group, acyl group, aldehyde group, thiol group, amino group, imino group, cyano group, nitro group, vinyl group, ether bond, ester bond, carbonate group, amide bond, imide bond, peptide bond. , Urethane bond, acetal bond, hemiacetal bond, hemicetal bond and the like.

Specific examples of the dihydric alcohol having two alcoholic hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, trimethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and butanediol. Examples thereof include pentandiol, hexanediol, heptanediol, nonanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, and dioxane glycol.

Specific examples of the trihydric alcohol having three alcoholic hydroxyl groups include trihydric alcohols such as trimethylolethane, trimethylolpropane, tris (2-herodoxyethyl) isocyanurate, hexanetriol, octanetriol, and decantriol, and Examples thereof include alkylene oxide adducts of trihydric alcohols.

Specific examples of the tetrahydric alcohol having four alcoholic hydroxyl groups include tetrahydric alcohols such as ditrimethylolethane, ditrimethylolpropane, diglycerin, and pentaerythritol, and alkylene oxide adducts of the tetrahydric alcohols. ..

Specific examples of the pentahydric alcohol having five alcoholic hydroxyl groups include pentahydric alcohols such as trimethylolethane, trimethylolpropane, and triglycerin, and alkylene oxide adducts of the pentahydric alcohols.

Specific examples of polyhydric alcohols having 6 or more alcoholic hydroxyl groups include hexahydric or higher alcohols such as polytrimethylolethane, polytrimethylolpropane, polyglycerin, dipentaerythritol, tripentaerythritol, and polypentaerythritol. , And alkylene oxide adducts of alcohols having a valence of 6 or more.

Specific examples of other polyhydric alcohols include compounds listed in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732, in addition to the above.

1-2. The monofunctional (meth) acrylate used as a raw material for the monofunctional (meth) acrylate (A) component is a compound having one (meth) acryloyl group in the molecule, and is represented by, for example, the following general formula (1). Examples include compounds that are used.

In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents an organic group having 1 to 50 carbon atoms.

^{Preferred specific examples of R 2} in the above general formula (1) include 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a 2-ethylhexyl group. Alkyl alkyl groups of ~ 8 such as alkyl groups, 2-methoxyethyl groups, 2-ethoxyethyl groups and 2-methoxybutyl groups, and N, N-dimethylaminoethyl groups, N, N-diethylaminoethyl groups, N, N. Examples thereof include dialkylamino groups such as −dimethylaminopropyl group and N, N-diethylaminopropyl group.
^{Specific examples of R 2} in the general formula (1) include the functional groups mentioned in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732. ..

In the present invention, these monofunctional (meth) acrylates can be used alone or in any combination of two or more.
Among these monofunctional (meth) acrylates, carbons such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate Alkyl (meth) acrylates having an alkyl group of several 1 to 8, alkoxyalkyl (meth) acrylates such as 2-methoxyethyl acrylate, and N, N-dimethylaminoethyl (meth) acrylates are preferable, and most polyhydric alcohols are particularly preferable. A (meth) acrylate having an alkyl group having 1 to 4 carbon atoms and an alkoxyalkyl (meth) acrylate having an alkyl group having 1 to 2 carbon atoms, which show good reactivity with respect to the above and are easily available, are preferable.
Further, an alkoxyalkyl (meth) acrylate having an alkyl group having 1 to 2 carbon atoms, which promotes the dissolution of the polyhydric alcohol and exhibits extremely good reactivity, is more preferable, and 2-methoxyethyl (meth) acrylate is particularly preferable.
Furthermore, as the monofunctional (meth) acrylate, acrylate is particularly preferable because it has excellent reactivity.

The ratio of the polyhydric alcohol and the monofunctional (meth) acrylate used in the method for producing the component (A) is not particularly limited, but the monofunctional (meth) acrylate is 0.4 for a total of 1 mol of hydroxyl groups in the polyhydric alcohol. It is preferably ~ 10.0 mol, more preferably 0.6-5.0 mol. Adverse reactions can be suppressed by increasing the amount of monofunctional (meth) acrylate to 0.4 mol or more. Further, by setting the amount to 10.0 mol or less, the amount of GLY-TA produced can be increased and the productivity can be improved.

1-3. As the transesterification reaction catalyst in the method for producing the catalyst (A) component, conventionally known catalysts such as tin-based catalysts, titanium-based catalysts, and sulfuric acid can be used.
In the present invention, it is preferable to use the following catalysts X and Y together as a catalyst in that GLY-TA can be efficiently produced in a high yield.
Catalyst X: Cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof (hereinafter referred to as "azabicyclo compound"), amidine or a salt or complex thereof (hereinafter referred to as "amidine compound"), a compound having a pyridine ring or One or more compound catalyst Y: a compound containing zinc selected from the group consisting of the salt or complex (hereinafter referred to as "pyridine compound") and phosphine or a salt or complex thereof (hereinafter referred to as "phosphine compound").
Hereinafter, the catalyst X and the catalyst Y will be described.

1-3-1. Catalyst X
The catalyst X is one or more compounds selected from the group consisting of azabicyclo-based compounds, amidine-based compounds, pyridine-based compounds, and phosphine-based compounds.
As the catalyst X, one or more compounds selected from the group consisting of azabicyclo-based compounds, amidine-based compounds and pyridine-based compounds are preferable among the above-mentioned compound groups. These compounds have excellent catalytic activity and can preferably produce the component (A). In addition, since they form a complex with the catalyst Y described later after the reaction is completed, they can be easily obtained from the reaction solution after the reaction by a simple method such as filtration and adsorption. Can be removed. In particular, the azacyclo compound can be more easily removed by filtration, adsorption or the like because the complex with the catalyst Y becomes sparingly soluble in the reaction solution.
On the other hand, although the phosphine compound has excellent catalytic activity, it is difficult to form a complex with the catalyst Y, and most of the phosphine compound remains dissolved in the reaction solution after the reaction is completed. Difficult to remove from liquid. For this reason, the phosphine-based catalyst remains in the final product, which causes turbidity and catalyst precipitation during storage of the product, and thickening or gelation over time, resulting in storage stability. It may cause problems, and it may have similar problems when used as a component of a composition.

Specific examples of the azabicyclo-based compound include a cyclic tertiary amine having an azabicyclo structure, a salt of the amine, and various compounds as long as they satisfy the complex of the amine, and preferred compounds include quinuclidine and 3. -Hydroxyquinuclidine, 3-quinucridinone, 1-azabicyclo [2.2.2] octane-3-carboxylic acid, and triethylenediamine (also known as 1,4-diazabicyclo [2.2.2] octane. DABCO ") and the like.
Specific examples of the azabicyclo-based compound include the functional groups mentioned in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732.

Specific examples of the amidine-based compound include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinyl imidazole, 1-allyl imidazole, 1 , 8-diazabicyclo [5.4.0] undec-7-ene (hereinafter referred to as "DBU"), 1,5-diazabicyclo [4.3.0] nona-5-ene (hereinafter referred to as "DBN") , N-Methylimidazole hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazole acetate, DBU acetate, DBN acetate, N-methylimidazole acrylate, DBU acrylate, DBN acrylate, and Examples include phthalimide DBU and the like.

Major specific examples of pyridine compounds include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, and N, N-dimethyl-. Examples thereof include 4-aminopyridine (hereinafter referred to as "DMAP").
Specific examples of the pyridine compound include the functional groups mentioned in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732.

Examples of the phosphine or a salt or complex thereof include a compound containing a structure represented by the following general formula (2).

[In the formula (2), R ³ , R ⁴ and R ⁵ are a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, and 6 carbon atoms. It means an aryl group of ~ 24 or a cycloalkyl group having 5 to 20 carbon atoms. R ³ , R ⁴ and R ⁵ may be the same or different]
show. )

Specific examples of the phosphine compound include triphenylphosphine, tris (4-methoxyphenyl) phosphine, tri (p-tolyl) phosphine, tri (m-tolyl) phosphine, and the like.
Examples thereof include tris (4-methoxy-3,5-dimethylphenyl) phosphine and tricyclohexylphosphine.
Specific examples of the phosphine-based compound include functional groups mentioned in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732 in addition to the above.

In the present invention, these catalysts X can be used alone or in any combination of two or more. Among these catalysts X, quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN and DMAP are preferable, and particularly good reactivity with most polyhydric alcohols is obtained. More preferred are 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP, which are shown and readily available.

The ratio of the catalyst X used in the method for producing the component (A) is not particularly limited, but it is preferable to use 0.0001 to 0.5 mol of the catalyst X with respect to 1 mol of the total hydroxyl groups in the polyhydric alcohol. More preferably, it is 0.0005 to 0.2 mol. By using 0.0001 mol or more of the catalyst X, the amount of the target GLY-TA produced can be increased, and by using 0.5 mol or less, the formation of by-products and the coloring of the reaction solution are suppressed. Therefore, the purification step after the reaction is completed can be simplified.

1-3-2. Catalyst Y
The catalyst Y is a compound containing zinc.
As the catalyst Y, various compounds can be used as long as they are compounds containing zinc, but zinc organic acid and zinc diketone enolate are preferable because of their excellent reactivity.
Examples of the zinc organic acid include zinc dibasate such as zinc oxalate and a compound represented by the following general formula (3).

[In the formula (3), R ⁶ and R ⁷ are linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkenyl groups having 1 to 20 carbon atoms, and 6 to 24 carbon atoms. It means an aryl group or a cycloalkyl group having 5 to 20 carbon atoms. R ⁶ and R ⁷ may be the same or different]
As the compound of the formula (3), a compound in which R ⁶ and R ⁷ are linear or branched alkyl groups having 1 to 20 carbon atoms is preferable. In R ⁶ and R ⁷ , the linear or branched alkyl group having 1 to 20 carbon atoms is a functional group having no halogen atom such as fluorine and chlorine, and the catalyst Y having the functional group has a high yield. It is preferable because GLY-TA can be produced in the above.

Examples of the zinc diketone enolate include compounds represented by the following general formula (4).

[In formula (4), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are hydrogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. It means a linear or branched alkenyl group, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different]

Specific examples of the zinc-containing compound represented by the above general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octylate, zinc neodecanoate, zinc laurate, zinc myristate, and the like. Examples thereof include zinc stearate, zinc cyclohexane butyrate, zinc 2-ethylhexanate, zinc benzoate, zinc t-butyl benzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.
If a complex with the hydrate, solvate, or catalyst X of these zinc-containing compounds is present, the complex with the hydrate, solvate, and catalyst X is also a component (A). Can be used as the catalyst Y in the production method of.

Specific examples of the zinc-containing compound represented by the above general formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, bis (2,6-dimethyl-3,5-heptandionat) zinc, and bis. Examples thereof include (2,2,6,6-tetramethyl-3,5-heptandionat) zinc and bis (5,5-dimethyl-2,4-hexanezonato) zinc. If a complex with the hydrate, solvate, or catalyst X of these zinc-containing compounds is present, the complex with the hydrate, solvate, and catalyst X is also a component (A). Can be used as the catalyst Y in the production method of.

As the zinc organic acid and the zinc diketone enolate in the catalyst Y, the above-mentioned compounds can be directly used, but these compounds can also be generated and used in the reaction system. For example, zinc compounds such as metallic zinc, zinc oxide, zinc hydroxide, zinc chloride and zinc nitrate (hereinafter referred to as "raw zinc compound") are used as raw materials, and in the case of organic acid zinc, the raw material zinc compound and organic acid In the case of zinc diketone enolate, a method of reacting the raw material zinc compound with 1,3-diketone and the like can be mentioned.

In the present invention, these catalysts Y can be used alone or in any combination of two or more. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferable, and in particular, they show good reactivity with most polyhydric alcohols and are easily available. Zinc acetate, zinc acrylate and zinc acetylacetonate are preferred.

The ratio of the catalyst Y used in the method for producing the component (A) is not particularly limited, but it is preferable to use 0.0001 to 0.5 mol of the catalyst Y with respect to 1 mol of the total hydroxyl groups in the polyhydric alcohol. More preferably, it is 0.0005 to 0.2 mol. By using 0.0001 mol or more of the catalyst Y, the amount of the target GLY-TA produced can be increased, and by using 0.5 mol or less, the formation of by-products and the coloring of the reaction solution are suppressed. Therefore, the purification step after the reaction is completed can be simplified.

1-4. Method for Producing Component (A) Component (A) is produced by transesterifying glycerin with a monofunctional (meth) acrylate in the presence of a transesterification catalyst.
As described above, as a method for producing the component (A), a production method in which the catalysts X and Y are used in combination as a catalyst is preferable, and the production method will be described below.

The ratio of the catalyst X and the catalyst Y used in the method for producing the component (A) is not particularly limited, but it is preferable to use 0.005 to 10.0 mol of the catalyst X with respect to 1 mol of the catalyst Y. It is preferably 0.05 to 5.0 mol. By using 0.005 mol or more, the amount of the target GLY-TA produced can be increased, and by using 10.0 mol or less, the formation of by-products and the coloring of the reaction solution can be suppressed, and the reaction can be carried out. The purification process after completion can be simplified.

As the combination of the catalyst X and the catalyst Y used in combination in the present invention, it is preferable that the catalyst X is an azabicyclo-based compound, the catalyst Y is a compound represented by the general formula (3), and the azabicyclo-based compound is DABCO. Most preferably, the compound represented by the general formula (3) is zinc acetate and / or zinc acrylate.
This combination can be suitably used for various industrial applications in which color tone is important because GLY-TA can be obtained in good yield and the color tone after completion of the reaction is excellent. Furthermore, since it is a catalyst that can be obtained at a relatively low cost, it is an economically advantageous production method.

The catalyst X and the catalyst Y used in the present invention may be added from the beginning of the above reaction or may be added from the middle. Further, the desired amount to be used may be added all at once, or may be added in divided portions.

The reaction temperature in the method for producing the component (A) is preferably 40 to 180 ° C, more preferably 60 to 160 ° C. By setting the reaction temperature to 40 ° C. or higher, the reaction rate can be increased, and by setting the reaction temperature to 180 ° C. or lower, thermal polymerization of the (meth) acryloyl group in the raw material or product is suppressed, and the reaction solution is colored. Can be suppressed, and the purification step after the reaction is completed can be simplified.

The reaction pressure in the method for producing the component (A) is not particularly limited as long as a predetermined reaction temperature can be maintained, and may be carried out in a reduced pressure state or in a pressurized state. The reaction pressure is preferably 0.000001 to 10 MPa (absolute pressure).

In the method for producing the component (A), a monohydric alcohol derived from a monofunctional (meth) acrylate is produced as a by-product as the transesterification reaction progresses. The monohydric alcohol may remain coexisting in the reaction system, but the progress of the transesterification reaction can be further promoted by discharging the monohydric alcohol out of the reaction system.

In the method for producing the component (A), the reaction can be carried out without using a solvent, but a solvent may be used if necessary.
Specific examples of the solvent include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, and diamyl. Hydrocarbons such as benzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin and tetralin; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl acetal , T-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether, dimethyl cellosolve, diglyme, triglyme, tetraglyme and other ethers; 18-crown-6 and other crown ethers; benzo Ethers such as methyl acid and γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and benzophenone; carbonates such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate and the like. Compounds; Sulfons such as sulfolanes; Sulfoxides such as dimethyl sulfoxide; Ureas or derivatives thereof; Phosphine oxides such as tributylphosphine oxide, ionic liquids such as imidazolium salt, piperidinium salt and pyridinium salt; Silicon oil and; Examples include water.
Among these solvents, hydrocarbons, ethers, carbonate compounds and ionic liquids are preferred.
These solvents may be used alone, or two or more kinds may be arbitrarily combined and used as a mixed solvent.

In the method for producing the component (A), an inert gas such as argon, helium, nitrogen or carbon dioxide may be introduced into the system for the purpose of maintaining a good color tone of the reaction solution, but the (meth) acryloyl group is used. An oxygen-containing gas may be introduced into the system for the purpose of preventing the polymerization of the above. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like. As a method for introducing the oxygen-containing gas, there is a method of dissolving it in the reaction solution or blowing it into the reaction solution (so-called bubbling).

In the method for producing the component (A), it is preferable to add a polymerization inhibitor to the reaction solution for the purpose of preventing the polymerization of the (meth) acryloyl group.
Specific examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-tert. -Butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamineammonium, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine Organic polymerization inhibitors such as -1-oxyl, inorganic polymerization inhibitors such as copper chloride, copper sulfate and iron sulfate, and organic salts such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt. Polymerization inhibitors can be mentioned.
The polymerization inhibitor may be added alone or in combination of two or more, may be added from the beginning of the present invention, or may be added in the middle. Further, the desired amount to be used may be added all at once, or may be added in divided portions. Moreover, you may add continuously via a rectification tower.
The addition ratio of the polymerization inhibitor is preferably 5 to 30,000 wtppm, more preferably 25 to 10,000 wtppm in the reaction solution. By setting this ratio to 5 wtppm or more, the polymerization inhibitory effect can be exhibited, and by setting it to 30,000 wtppm or less, coloring of the reaction solution can be suppressed, and the purification step after the reaction is completed can be simplified. In addition, it is possible to prevent a decrease in the curing rate of the obtained component (A).

The reaction time in the method for producing the component (A) varies depending on the type and amount of the catalyst used, the reaction temperature, the reaction pressure, and the like, but is preferably 0.1 to 150 hours, more preferably 0.5 to 80 hours.

The method for producing the component (A) can be carried out by any of a batch method, a semi-batch method and a continuous method. As an example of the batch type, a polyhydric alcohol, a monofunctional (meth) acrylate, a catalyst and a polymerization inhibitor are charged in a reactor, and oxygen-containing gas is bubbling in the reaction solution and stirred at a predetermined temperature. After that, the monohydric alcohol produced as a by-product with the progress of the transesterification reaction can be extracted from the reactor at a predetermined pressure to produce the desired component (A).

For the reaction product obtained by the method for producing the component (A), it is preferable to carry out a separation / purification operation because GLY-TA can be obtained with high purity.
Examples of the separation / purification operation include a crystallization operation, a filtration operation, a distillation operation, an extraction operation, and the like, and it is preferable to combine these operations. Examples of the crystallization operation include cold crystallization and concentrated crystallization, examples of the filtration operation include pressure filtration, suction filtration and centrifugal filtration, and examples of the distillation operation include simple distillation, fractional distillation and molecular distillation. And steam distillation and the like, and examples of the extraction operation include solid-liquid extraction and liquid-liquid extraction.
A solvent may be used in the separation and purification operation.
Further, a neutralizing agent for neutralizing the catalyst and / or the polymerization inhibitor used in the present invention, an adsorbent for adsorbing and removing, an acid and / or alkali for decomposing or removing by-products, and a color tone. Activated carbon for improving the above, silica soil for improving the filtration efficiency and the filtration rate, and the like may be used.

The content ratio of the component (A) is 40 to 95% by weight, preferably 30 to 90% by weight, in the total 100% by weight of the components (A), (B) and (C).
If the content ratio of the component (A) is less than 40% by weight, the surface hardness will be low, while if it exceeds 95% by weight, the adhesion will be lowered.

2. (B) component The composition of the present invention contains a filler as the component (B) as an essential component in order to increase the hardness.
Examples of the component (B) include an inorganic filler and an organic filler.
Specific examples of the inorganic filler include silica, hollow silica, alumina, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimon oxide, and antimonthine oxide (ATO). , Cerium oxide, potassium oxide, and composite oxides in which two or more of these compounds are compounded.
Specific examples of the organic filler include polyurethane, poly (meth) acrylate, polyamide, polyurea, nylon, polystyrene, polymers such as polyethylene and polypropylene, carbon nanotubes, and cellulose nanofibers.

In order to have excellent optical properties and improve the hardness of the cured product, it is preferable that the component (B) is in a state where no agglomerates are present as much as possible.
Therefore, as the component (B), it is preferable to use an organic solvent-dispersed sol dispersed in an organic solvent, an organic solvent-dispersed sol of an inorganic filler is preferable, and an organic solvent-dispersed sol of inorganic oxide fine particles is more preferable.
However, since the composition of the present invention is preferably used as a solvent-free composition, after blending the component (A) or the components (A) and (C) with the component (B), a solvent removal treatment is performed. It is preferable to do so.

The organic solvent used as the dispersion medium is not particularly limited, but for example, alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate and γ -Esters such as butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; and dimethylformamide, dimethylacetamide. , N-Methylpyrrolidone and the like.
Among these, methanol, isopropanol, methyl ethyl ketone and ethyl acetate are preferable because the dispersion stability of the inorganic oxide fine particles is good, the boiling point is low and the solvent can be easily replaced.

Further, the average primary particle size of the component (B) is preferably 1 nm or more and 200 nm or less, and particularly preferably 5 nm or more and 100 nm or less, from the viewpoint of handling and transparency. When the average primary particle size is 1 nm or more, the particle surface is low in activity, so that it is easy to maintain the dispersed state, and aggregation and gelation are unlikely to occur. On the other hand, if the average primary particle size is 200 nm or less, haze due to Rayleigh scattering is difficult to observe. Since Rayleigh scattering is proportional to the square of the particle volume, that is, the sixth power of the particle size, the scattering is small for particles having an average primary particle size of 1/4 or less of the wavelength of visible light, which is suitable for transparent materials. Can be used for.
The average primary particle size is determined by, for example, observing inorganic oxide fine particles with a high-resolution transmission electron microscope, arbitrarily selecting 100 inorganic oxide particle images from the observed fine particle images, and using a known image data statistical processing method. It can be obtained as a number average particle size.

Commercially available products as organic solvent dispersion sol of silica fine particles include, for example, colloidal silica such as OSCAL-1132, OSCAL-1432M, OSCAL-1432, OSCAL-1632 manufactured by JGC Catalysts and Chemicals Co., Ltd., and Nissan Chemical Industry Co., Ltd. Methanol Silica Sol, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, PGM-ST, MEK-ST, MEK-ST-L, MEK- Examples thereof include ST-ZL, MIBK-ST, PMA-ST, EAC-ST, PL-1-IPA manufactured by Fuso Chemical Co., Ltd., PL-2L-PGME, PL-2L-MEMK and the like.

In the present invention, it is preferable to use fine particles having a modified surface because the hardness of the cured product is high and the dispersibility of the fine particles is excellent. Examples of the type of surface modification include organosilane treatment, silazane treatment, silicone treatment and the like, but the organosilane treatment is preferable in that the hardness of the cured product is high.
Commercially available products as organic solvent dispersion sol of surface-modified fine particles include MEK-EC-2130Y, MEK-AC-2140Z, MEK-AC-4130Y MEK-AC-5140Z, PGM-manufactured by Nissan Chemical Industries, Ltd. AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z and the like can be mentioned.

Examples of commercially available products as organic solvent-dispersed sol of zirconia fine particles include Nanouse OZ-30M and Nanouse OZS30K manufactured by Nissan Chemical Industries, Ltd. Further, examples of commercially available products as organic solvent-dispersed sol of titania fine particles include OPTOLAKE 1130Z and OPTPLAKE 6320Z manufactured by JGC Catalysts and Chemicals Co., Ltd.

The shape of the component (B) includes spherical, hollow spherical, beaded, flat plate, fibrous, etc., but spherical, hollow, and beaded are preferable in terms of good handleability and dispersibility, and the spherical shape is preferable. Especially preferable.
Examples of beaded silica include IPA-ST-UP (trade name) manufactured by Nissan Chemical Industry Co., Ltd., and examples of hollow silica include Sururia (trade name) manufactured by JGC Catalysts and Chemicals Co., Ltd. And so on.
Further, as the fine particles, inorganic oxide fine particles having an average particle size equal to or less than the wavelength of visible light are preferable because they have excellent optical characteristics and the hardness of the cured product is high.

Further, as the component (B), a dispersed sol previously dispersed in the component (A) is used, and when the component (C) is used, it is used as a dispersed sol dispersed in the component (A) and / or the component (C). Is preferable.
The component (A) and / and the component (C) serving as a dispersion medium preferably have a low viscosity, and the component (C) is one component (C) in a molecule having a homopolymer glass transition temperature of 70 ° C. or higher. A compound having an ethylenically unsaturated group [(C-1) component] is preferable.

As a method for producing a sol in which the component (B) is dispersed in the component (A) or / and the component (C), an organic solvent-dispersed sol in which the component (B) is dispersed in an organic solvent is prepared in advance, and then the organic solvent-dispersed sol is prepared. A method of substituting the organic solvent with the component (A) or / and the component (C) is preferable.
Specifically, an organic solvent-dispersed sol in which the component (B) is dispersed in an organic solvent is added and mixed with the component (A) and / and the component (C) under an inert gas atmosphere, and the pressure is further reduced under heating. Then, a method of completely removing the organic solvent and the like can be mentioned.
By doing so, it is possible to prevent the agglomeration of the component (B) while making the composition of the present invention solvent-free.

The content ratio of the component (B) is 5 to 60% by weight, preferably 10 to 40% by weight, based on 100% by weight of the total amount of the components (A), (B) and (C).
If the content of the component (B) is less than 5% by weight, the hardness of the cured product will decrease, and if it exceeds 60% by weight, the viscosity of the composition will become too high and the solvent-free coatability will be improved. It will drop.

3. 3. Component (C) Component (C) is a compound having an ethylenically unsaturated group other than the component (A).
Examples of the ethylenically unsaturated group in the component (C) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group and a (meth) allyl group, and a (meth) acryloyl group is preferable.
In the following, "monofunctional" means a compound having one ethylenically unsaturated group, and "○ functional" means a compound having ○ ethylenically unsaturated groups, and is "polyfunctional". Means a compound having two or more ethylenically unsaturated groups.

The content ratio of the component (C) needs to be 0 to 55% by weight, preferably 5 to 40% by weight, in 100% by weight of the total amount of the components (A), (B) and (C).
If the content of the component (C) exceeds 55% by weight, the cured product becomes brittle.

As an example of the component (C), a compound having one ethylenically unsaturated group (hereinafter referred to as "monofunctional unsaturated compound") and a compound having two or more ethylenically unsaturated groups (hereinafter referred to as "polyfunctional"). "Unsaturated compounds").

3-1. Monofunctional Unsaturated Compounds Specific examples of the monofunctional unsaturated compound include the same compounds as the monofunctional (meth) acrylate described above, and methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and the like. 2-Ethylhexyl (meth) acrylates, tert-butylcyclohexyl (meth) acrylates, and 2-methoxyethyl (meth) acrylates are preferred.
Examples of compounds other than the above-mentioned monofunctional (meth) acrylates include (meth) acrylic acid, Michael-added dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, and monohydroxyethyl phthalate (meth) acrylate. , Ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate with alkylene oxide adduct of phenol. , Alkylphenol alkylene oxide adduct (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, paracumylphenol alkylene oxide adduct (Meta) acrylate, orthophenylphenol (meth) acrylate, (meth) acrylate of alkylene oxide adduct of orthophenylphenol, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (meth) acryloxyethyl) hexahydrophthalimide, N -(2- (Meta) acryloxyethyl) tetrahydrophthalimide, N, N-dimethylacrylamide, acryloylmorpholin, N-vinylpyrrolidone, N-vinylcaprolactam and the like can be mentioned.

Among the monofunctional unsaturated compounds, the homopolymer has a glass transition temperature (hereinafter referred to as “Tg”) of 70 ° C. or higher and has one ethylenically unsaturated group in the molecule [hereinafter, “(C-”). 1) component "] is preferable in terms of achieving both low viscosity and high hardness. As the component (C-1), in terms of substrate adhesion, a compound containing nitrogen in the molecule, having a homopolymer Tg of 70 ° C. or higher, and having one ethylenically unsaturated group in the molecule. [Hereinafter referred to as "(C-1-N)) component"] is particularly preferable.
In the present invention, Tg means a value measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC), and is at the glass transition temperature midpoint (Tmg) in the ΔT-temperature curve. Means a value.

The components (C-1) include acrylic acid (Tg = 103 ° C.), methacrylic acid (Tg = 130 ° C.), isobornyl acrylate (Tg = 94 ° C.), isobornyl methacrylate (Tg = 180 ° C.), and di. Cyclopentenyl acrylate (Tg = 120 ° C), dicyclopentanyl acrylate (Tg = 120 ° C), dicyclopentanyl methacrylate (Tg = 175 ° C), N-hydroxyethylacrylamide (Tg = 98 ° C), N, N- Examples thereof include dimethylacrylamide (Tg = 119 ° C.), acryloylmorpholin (Tg = 145 ° C.), N-vinylpyrrolidone (Tg = 80 ° C.), N-vinylcaprolactam (Tg = 90 ° C.) and the like.
Examples of the (C-1-N) component include N-hydroxyethylacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam and the like.

3-2. Polyfunctional unsaturated compound As the polyfunctional unsaturated compound, polyfunctional (meth) acrylate is preferable.
Specific examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di. (Meta) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, di (meth) acrylate of alkylene oxide adduct of bisphenol A, and alkylene of bisphenol F. Examples thereof include di (meth) acrylate as an oxide adduct.

Examples of the trifunctional or higher (meth) acrylate include various compounds as long as they are compounds having three or more (meth) acryloyl groups. For example, trimethylolpropantri (meth) acrylate, pentaerythritol tri or tetra ( Polycarbonate poly (meth) acrylates such as tri or tetra (meth) acrylates of meta) acrylates, ditrimethylol propane, tri or tetra (meth) acrylates of diglycerin and tri, tetra, penta or hexa (meth) acrylates of dipentaerythritol. And tri (meth) acrylate of glycerin alkylene oxide adduct, tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, tri or tetra (meth) acrylate of ditrimethylolpropanealkylene oxide adduct, diglycerin alkylene oxide addition. Poly (meth) acrylates of polyol alkylene oxide adducts such as tri or tetra (meth) acrylates, dipentaerythritol alkylene oxide adducts, tetra, penta or hexa (meth) acrylates; and isocyanuric acid alkylene oxide adducts. Tori (meth) acrylate and the like can be mentioned.
Examples of the above-mentioned alkylene oxide adduct include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.

As the polyfunctional (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate and the like can also be used in addition to the above-mentioned compounds.
Among these compounds, urethane (meth) acrylate [hereinafter referred to as "(C-2) component"] is preferable because the cured product of the obtained composition has high hardness and excellent substrate adhesion, and will be described in detail below. ..

The component (C-2) includes a reaction product of a polyhydric alcohol, a polyhydric isocyanate and a hydroxyl group-containing (meth) acrylate, and a reaction product of an organic polyhydric isocyanate and a hydroxyl group-containing (meth) acrylate compound (hereinafter, “urethane adduct”). ").

As the component (C-2), urethane adduct is preferable in that the curability of the composition, the hardness of the cured product, and the scratch resistance are excellent.

Examples of the polyhydric alcohol include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by reacting the polyhydric alcohol with the polybasic acid, the polyhydric alcohol, the polybasic acid and ε-caprolactone. Examples thereof include a caprolactone polyol obtained by the reaction with and a polycarbonate polyol (for example, a polycarbonate polyol obtained by the reaction of 1,6-hexanediol and diphenyl carbonate).

Examples of the organic polyvalent isocyanate include diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate and dicyclopentanyl diisocyanate;
Examples thereof include organic polyisocyanates having three or more isocyanate groups such as hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate and hydroxyoctyl. Hydroxyl-containing mono (meth) acrylates such as (meth) acrylates, trimethylol propane mono (meth) acrylates and pentaerythritol mono (meth) acrylates;
And hydroxyl groups such as trimethylolpropane di (meth) acrylate, pentaerythritol di or tri (meth) acrylate, ditrimethylolpropane di or tri (meth) acrylate and dipentaerythritol di, tri, tetra or penta (meth) acrylate. Examples thereof include polyfunctional (meth) acrylate contained.

Examples of the organic multivalent isocyanate and the hydroxyl group-containing (meth) acrylate compound in the urethane adduct include the above compounds.
In the urethane adduct, those using a hydroxyl group-containing polyfunctional (meth) acrylate as the hydroxyl group-containing (meth) acrylate are preferable.
Among these, a compound having three or more (meth) acryloyl groups and one hydroxyl group is preferable because the cured product is superior in hardness and scratch resistance, and specifically, pentaerythritol tri (meth). Examples thereof include acrylate, ditrimethylolpropane tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.

Another preferred compound of urethane adduct includes a reaction product of an organic polyisocyanate having three or more isocyanate groups and a hydroxyl group-containing mono (meth) acrylate.
Examples of the hydroxyl group-containing mono (meth) acrylate include compounds similar to those described above.
Examples of the organic polyisocyanate having three or more isocyanate groups include the hexamethylene diisocyanate trimer and the isophorone diisocyanate trimer described above.

As the component (C-2), those produced by a conventional method can be used.
For example, in the presence of an addition catalyst such as dibutyltin dilaurate, an organic polyvalent isocyanate and a polyvalent oar are heated and stirred to carry out an addition reaction to produce an isocyanate group-containing compound, and a hydroxyl group-containing (meth) acrylate is further added to the compound and heated. -A method of stirring and adding reaction can be mentioned.
In the case of urethane adduct, a method of heating and stirring an organic polyvalent isocyanate and a hydroxyl group-containing (meth) acrylate in the presence of an addition catalyst to cause an addition reaction can be mentioned.

Examples of urethane poly (meth) acrylates other than these include compounds as described on pages 70 to 74 of the document "UV / EB Curing Material" [CMC Co., Ltd., published in 1992]. ..

The content ratio of the component (C-2) is preferably 0 to 40% by weight, more preferably 0 to 20% by weight, in 100% by weight of the total amount of the components (A), (B) and (C). be.
By setting the content ratio of the component (C-2) to 40% by weight or less, toughness can be imparted to the cured product of the composition, the viscosity of the composition becomes too high, and the coating property without solvent is used. Can be prevented from decreasing.

4. Active energy ray-curable composition The present invention is a composition containing the above-mentioned components (A), (B) and (C), and is contained in a total of 100% by weight of the components (A), (B) and (C). It is an active energy ray-curable composition containing 40 to 95% by weight of the component (A), 5 to 60% by weight of the component (B), and 0 to 55% by weight of the component (C).
As a method for producing the composition of the present invention, the components (A) to (C), a method of stirring and mixing the components (A) to (C) and other components described later as necessary (hereinafter referred to as "manufacturing method 1"), the component (A) or A method of mixing / and (C) with other components described later as necessary, adding the component (B) to the mixture, and then stirring and mixing (hereinafter referred to as "manufacturing method 2") can be mentioned. , Production method 2 is preferable because the component (B) can be dispersed throughout the composition.
Further, in the production method 2, when the organic solvent-dispersed sol of the component (B) is used and the composition of the present invention is a solvent-free composition, the components (A) and / and (C) and ( B) A production method in which the organic solvent-dispersed sol of the component is stirred and mixed, and then heated under reduced pressure to evaporate the organic solvent is more preferable.
In this case, the depressurization degree and the heating temperature may be appropriately set according to the organic solvent used in the organic solvent dispersion sol of the component (B), but the decompression degree is preferably 500 mmHg or less, and the heating temperature is preferably 500 mmHg or less. 30 to 60 ° C. is preferable.

Further, as a method for producing the composition, a (meth) acrylate mixture containing GLY-TA as a main component, which is obtained by transesterifying glycerin and a monofunctional (meth) acrylate in the presence of the catalysts X and Y, is used. A method for producing a composition including a step of producing (A) is preferable.
According to the production method, the component (A) can be produced in a high yield, and since the amount of the high molecular weight substance in the obtained component (A) is small, the viscosity is low and the impurities are small. It is preferable in that it can have excellent physical properties.
As the step, the method for producing the component (A) described above may be followed.
The method for producing the composition when the other components described later are blended may be according to a conventional method, and the component (A) and, if necessary, the other components described later can be mixed and produced by stirring and mixing.

The viscosity of the composition may be appropriately set according to the intended purpose, preferably 20 to 3,000 mPa · s, and more preferably 20 to 1,500 mPa · s. By setting the viscosity within this range, it is possible to have excellent shape reproducibility when used as a shaping material and excellent coatability when used as a hard coat material.
The viscosity in the present invention means a value measured at 25 ° C. using an E-type viscometer (cone plate type viscometer).

The composition of the present invention contains the above-mentioned components (A) to (C) as essential components, but various components can be blended depending on the purpose.
Specific examples of the other components include a photopolymerization initiator and / or a sensitizer [hereinafter referred to as “component (D)”], a thermal polymerization initiator, an organic solvent, an antioxidant, an ultraviolet absorber, and a leveling agent. Examples thereof include silane coupling agents, surface modifiers and polymerization inhibitors.
Hereinafter, these components will be described.
As the other components described later, only one of the illustrated compounds may be used, or two or more of them may be used in combination.

4-1. Component (D) When the composition of the present invention is used as an active energy ray-curable composition and further used as an electron beam-curable composition, it may be cured by an electron beam without containing the component (D). It is possible.
When the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays and visible rays are used as the active energy rays, the component (D) is further added from the viewpoint of easiness of curing and cost. It is preferable to contain it.
When an electron beam is used as the active energy ray, it is not always necessary to blend it, but it can be blended in a small amount if necessary in order to improve the curability.

Specific examples of the component (C) include benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl. ] -2-Hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methylvinyl) phenyl] propanone, 2-hydroxy-1-[ 4- [4- (2-Hydroxy-2-methyl-propionyl) benzyl] phenyl] -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpho) Acetphenone compounds such as phosphorus-4-yl-phenyl) butane-1-one and 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole;
Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1- [4- (4-benzoylphenyl sulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and 4-methoxy-4' -Benzophenone compounds such as dimethylaminobenzophenone;
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. Acylphosphine oxide compounds; as well as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2 -Il-oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride, fluorothioxanthone and other thioxanthone compounds can be mentioned.
Examples of compounds other than the above include benzyl, methyl phenylglioxyate, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, ethyl anthraquinone and phenanthrenequinone, camphorquinone and the like.

Among these compounds, α-hydroxyphenylketones are preferable because they have good surface curability even when coated with a thin film in the atmosphere, and specifically, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2. -Methyl-1-phenyl-propane-1-one is more preferable.
Further, when it is necessary to increase the film thickness of the cured product, for example, when it is necessary to make it 50 μm or more, for the purpose of improving the curability inside the cured product, or when using an ultraviolet absorber or a pigment together, a screw is used. (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6-dimethoxy) Acylphosphine oxide compounds such as benzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropan-1-one, 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane It is preferable to use -1-one or the like together.

The content ratio of the component (D) is preferably 0.1 to 25 parts by weight, more preferably 0.1 to 25 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (C) [hereinafter, these are collectively referred to as "curable component"]. Is 0.1 to 20 parts by weight. By setting the ratio of the component (D) to 0.1 parts by weight or more, the photocurability of the composition can be improved and the adhesion can be improved. By setting the ratio to 25 parts by weight or less, the cured product can be obtained. The internal curability of the material can be improved, and the adhesion to the substrate can be improved.

4-2. Thermal polymerization initiator When the composition of the present patent is used as a thermosetting composition, a thermal polymerization initiator can be blended.
As the thermal polymerization initiator, various compounds can be used, and organic peroxides and azo-based initiators are preferable.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, and 1 , 1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoleperoxy) hexane, t-butylper Oxyisopropyl monocarbonate, t-butylperoxy2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2, 2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α '-Bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-menthan hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, diisopropylbenzenehydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 , 3-Tetramethylbutylhydroperoxide, cumenehydroperoxide, t-hexylhydroperoxide, t-butylhydroperoxide and the like.
Specific examples of azo compounds include 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. , Azobis-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. In addition, the organic peroxide can be combined with a reducing agent to cause a redox reaction.

The amount of these thermal polymerization initiators used is preferably 10 parts by weight or less with respect to 100 parts by weight of the total amount of curable components.
When the thermal polymerization initiator is used alone, it may be carried out according to the usual means of radical thermal polymerization, and in some cases, it may be used in combination with the component (D), and after being photocured, it is heated for the purpose of further improving the reaction rate. It can also be cured.

4-3. Solvent The composition of the present invention does not substantially require a solvent, but may contain an organic solvent if necessary for the purpose of adjusting the viscosity or the like.
Examples of the organic solvent include the same compounds as the organic solvent used as the dispersion medium for the component (B) described above.
As the organic solvent, the dispersion medium of the component (B) described above can be used as it is, or can be further blended separately.
The content ratio of the organic solvent is preferably 0.1 to 1000 parts by weight, more preferably 5 to 500 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (C). Within the above range, the composition can have a viscosity suitable for coating, and the composition can be easily applied by a known coating method described later.

4-4. Antioxidants Antioxidants are added for the purpose of improving durability such as heat resistance and weather resistance of cured products.
Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like.
Examples of the phenolic antioxidant include hindered phenols such as dit-butylhydroxytoluene. Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA CORPORATION.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphite and triaryl phosphite. Commercially available products of these derivatives include, for example, ADEKA CORPORATION PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. And so on.
Examples of the sulfur-based antioxidant include thioether-based compounds, and examples of commercially available products include AO-23, AO-212S, and AO-503A manufactured by ADEKA CORPORATION.
These may use one kind or two or more kinds. Preferred combinations of these antioxidants include a combination of a phenol-based antioxidant and a phosphorus-based antioxidant, and a combination of a phenol-based antioxidant and a sulfur-based antioxidant.
The content ratio of the antioxidant may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of curable components. Is.
When the content ratio is 0.1 parts by weight or more, the durability of the composition can be improved, while when the content ratio is 5 parts by weight or less, the curability and adhesion can be improved.

4-5. Ultraviolet absorber An ultraviolet absorber is added for the purpose of improving the light resistance of a cured product.
Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole-based ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
The content ratio of the ultraviolet absorber may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of the curable component. Is. When the content ratio is 0.01% by weight or more, the light resistance of the cured product can be improved, while when it is 5% by weight or less, the curability of the composition is excellent. be able to.

4-6. Silane Coupling Agent The silane coupling agent is blended for the purpose of improving the interfacial adhesive strength between the cured product and the substrate.
The silane coupling agent is not particularly limited as long as it can contribute to improving the adhesiveness with the substrate.

Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-. Glycydoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned.

The blending ratio of the silane coupling agent may be appropriately set according to the intended purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component. ..
By setting the blending ratio to 0.1 parts by weight or more, the adhesive strength of the composition can be improved, while by setting the blending ratio to 10 parts by weight or less, it is possible to prevent the adhesive strength from changing with time.

4-7. Surface modifier In the composition of the present invention, a surface modifier may be added for the purpose of enhancing the leveling property at the time of application, increasing the slipperiness of the cured product and enhancing the scratch resistance, and the like.
Examples of the surface modifier include a surface conditioner, a surfactant, a leveling agent, a defoaming agent, a slipperiness-imparting agent, an antifouling agent, and the like, and these known surface modifiers can be used. ..
Among them, a silicone-based surface modifier and a fluorine-based surface modifier are preferably mentioned. Specific examples include a silicone polymer and oligomer having a silicone chain and a polyalkylene oxide chain, a silicone polymer and an oligomer having a silicone chain and a polyester chain, and a fluoropolymer having a perfluoroalkyl group and a polyalkylene oxide chain. And oligomers, as well as fluoropolymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
Further, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group in the molecule may be used for the purpose of enhancing the sustainability of slipperiness.

The content ratio of the surface modifier is preferably 0.01 to 1.0 parts by weight with respect to 100 parts by weight of the total amount of the curable components. Within the above range, the surface smoothness of the cured product is excellent.

5. Applications The present invention relates to an active energy ray-curable composition, preferably a solvent-free active energy ray-curable composition, and particularly preferably an active energy ray-curable composition for a shaped material and an active energy ray-curable composition for a hard coat. Regarding the composition. As the shaping material, a shaping film having a fine concavo-convex structure such as a lens sheet, a moth-eye film, an antiglare film, a light extraction film for organic EL / LED, a light confining film for a solar cell, and a heat ray retroreflective film. It can be used for manufacturing, and for hard coats, it can be used to improve the surface hardness and scratch resistance of various plastics.

6. Method of use As a method of using the composition of the present invention as a shaping material or a hard coat, a conventional method may be followed.
Specifically, if it is a shaping material, the composition is applied or injected into a mold (stamper) having a desired shape, and laminated with a film or sheet base material (hereinafter collectively referred to as "film base material"). do.
After that, in the case of the active energy ray-curable composition, a method of using a transparent film base material and irradiating the active energy ray from the film base material side to cure the composition can be mentioned. Further, in the case of a thermosetting composition, a method of heating and curing may be mentioned.
In the case of a hard coat, the composition is applied to a film substrate, and in the case of an active energy ray-curable composition, a method of irradiating and curing the active energy ray can be mentioned. Further, in the case of a thermosetting composition, a method of heating and curing may be mentioned.

Examples of the film base material include plastic and glass, and plastic is preferable.
Plastics include polymethylmethacrylate, polymethylmethacrylate-styrene copolymer film, polyethylene terephthalate, polyethylene naphthalate, polyarylate, polyacrylic nitrile, polycarbonate, polysulfone, polyethersulfone, polyetherimide, polyetherketone, polyimide, Cycloolefin polymers, vinyl chloride, diallyl carbonate, allyldiglycol carbonate, polymethylpentene and the like can be mentioned.

The film substrate is preferably transparent or translucent (for example, milky white). The thickness of the film base material is preferably 20 to 10 mm.

Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, electron beams and the like, but ultraviolet rays are preferable.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).
The irradiation energy may be appropriately set according to the type and compounding composition of the active energy rays. For example, when a high-pressure mercury lamp is used, the irradiation energy ^{is preferably 50 to 5,000 mJ / cm 2} , preferably 200 to 200. More preferably, 1,000 mJ / cm ^2.

An example of producing a lens sheet using the composition of the present invention will be described.
When producing a lens sheet having a relatively thin film thickness, the composition of the present invention is applied to a transparent substrate, and then a mold having a desired lens shape is brought into close contact with the transparent substrate.
Next, the composition is cured by irradiating it with active energy rays from the transparent substrate side, and then peeled off from the mold.

On the other hand, in the case of producing a lens sheet having a relatively thick film thickness, the composition of the present invention is poured between a mold having a target lens shape and a transparent substrate.
Next, the composition is cured by irradiating the active energy ray from the transparent substrate side, and then the mold is removed.

The material of the mold is not particularly limited, and examples thereof include metals such as brass and nickel, and plastics such as epoxy resin and polymethylmethacrylate.
The mold is preferably made of metal in terms of long life in the lens sheet manufacturing application, and is preferably a transparent plastic in the nanoimprint application described later.

When the composition of the present invention is used for nanoimprint application, a conventional method may be followed.
For example, after applying the composition to the base material, a mold having a fine processing pattern and having transparency is pressed.
Next, a method of irradiating the transparent mold with active energy rays to cure the composition and then removing the mold can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, "part" means a part by weight.

1. 1. Manufacturing example
1) Production Example 1 (Production of GLY-TA1 by transesterification method)
63.60 parts (0.69 mol) of glycerin and 700.99 parts (5) of 2-methoxyethyl acrylate in a 1 liter flask equipped with a stirrer, thermometer, gas introduction tube, rectification tower and cooling tube. .39 mol), 5.47 parts (0.05 mol) of DABCO as catalyst X, 8.94 parts (0.05 mol) of zinc acetate as catalyst Y, 1.56 parts (charged raw material) of hydroquinone monomethyl ether (2000 wtppm based on the total weight of the flask) was charged, and an oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled in the liquid.
The pressure in the reaction system was adjusted in the range of 110 to 760 mmHg while heating and stirring in the reaction solution temperature range of 105 to 130 ° C., and 2-methoxyethanol and 2-methoxyethyl acrylate produced as by-products as the transesterification reaction proceeded. The mixed solution of the above was withdrawn from the reaction system via a rectification column and a cooling tube. In addition, 2-methoxyethyl acrylate in the same weight as the withdrawal solution was added to the reaction system at any time. Thirty hours after the start of heating and stirring, the pressure in the reaction system was returned to normal pressure to complete the extraction.
After cooling the reaction solution to room temperature and filtering and separating the precipitate, 1.0 part of aluminum silicate [Kyoward 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.] and activated charcoal [Futamura Chemical Co., Ltd.] were added to the filtrate. 1. The distillate containing −methoxyethyl acrylate was separated. 2.0 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Co., Ltd.] was added to the kettle liquid and pressure filtration was performed, and the obtained filtrate was used as a purified product.
As a result of composition analysis of the purified product using a high performance liquid chromatograph equipped with a UV detector, it was confirmed that glycerin triacrylate was contained as a main component (hereinafter referred to as "GLY-TA1"). The yield of the purified product was 90%. As a result of measuring the hydroxyl value of the obtained purified product according to the following method, it was 17 mgKOH / g. The results are shown in Table 1.

2) Production Examples 2 to 4 (Production of GLY-TA2 to 4 by transesterification method)
GLY-TA2-4 was produced according to the same method as in Production Example 1 except that the compounds shown in Table 1 below were used as the catalysts X and Y. The results are shown in Table 1.

3) Evaluation method of purified product The obtained purified product was measured in terms of high molecular weight GPC area, viscosity and hydroxyl value according to the method shown below. The results are shown in Table 1.

(1) High molecular weight GPC area%
For the purified product obtained in the above production example, the area% of the high molecular weight body was calculated by GPC measurement under the following conditions.
◆ GPC measurement conditions / equipment: Waters Co., Ltd. GPC system name 1515 2414 717P RI
-Detector: Differential refractive index (RI) detector-Column: Guard column Showa Denko Co., Ltd. Shodex KFG (8 μm 4.6 x 10 mm), 2 types of this column Waters Co., Ltd. stylel HR 4E THF (7. 8 x 300 mm) + stylel HR 1 THF (7.8 x 300 mm)
-Column temperature: 40 ° C
-Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL / min-Calculation method of high molecular weight body area (%) Based on the following formula (1) from the GPC measurement results Calculated.
Area% of high molecular weight body = [(RIL) / R] × 100 ... (1)
The symbols and terms in the formula (1) are as described above.

(2) Viscosity The viscosity of the obtained purified product was measured with an E-type viscometer (25 ° C.).

(3) Hydroxylity value An acetylation reagent is added to the obtained purified product, and the product is heat-treated in a warm bath at 92 ° C. for 1 hour. After allowing to cool, a small amount of water is added and heat treatment is performed in a warm bath at 92 ° C. for 10 minutes. After allowing to cool, the acid was titrated with a potassium hydroxide ethanol solution using a phenolphthalein solution as an indicator to determine the hydroxyl value.

4) Comparative production example 1 (Production of GLY-TA5 by dehydration ester method)
61.17 parts (0.66 mol) of glycerin and 172.18 parts (2.39) of acrylic acid in a flask equipped with a stirrer, thermometer, gas introduction pipe, rectification tower, cooling pipe and water separator. Mol), 129.50 parts of toluene, 6.40 parts of 78 wt% sulfuric acid aqueous solution, 0.37 parts of copper sulfate (1000 wtppm with respect to the total weight of the charged raw materials), oxygen-containing gas (5 volumes of oxygen) %, 95% by volume of nitrogen) was bubbled in the liquid. The mixture was stirred while being heated under reflux at a pressure of 370 mmHg in the reaction system, and water produced as a by-product as the dehydration esterification reaction proceeded was extracted from the reaction system via a rectification column and a cooling tube. During this period, the temperature of the reaction solution changed in the range of 80 to 90 ° C. Six hours after the start of heating and stirring, the heating of the reaction solution was completed, and the pressure in the reaction system was returned to normal pressure to complete the extraction.
After cooling the reaction solution to room temperature, 133 parts of toluene and 55 parts of water were added, and the mixture was stirred and then allowed to stand to separate the lower layer (aqueous layer). Then, 52 parts of a 20% sodium hydroxide aqueous solution was added to the upper layer (organic layer), stirred, and then allowed to stand to separate the lower layer (aqueous layer). Then, 38 parts of water was added to the upper layer (organic layer), stirred, and then allowed to stand to separate the lower layer (aqueous layer). 0.018 parts of hydroquinone monomethyl ether is added to the upper layer (organic layer), and while bubbling dry air, vacuum distillation is performed at a temperature of 60 to 90 ° C. and a pressure of 0.001 to 100 mmHg for 8 hours to contain toluene. The distillate was separated. 2.0 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Co., Ltd.] was added to the kettle liquid and pressure filtration was performed, and the obtained filtrate was used as a purified product.
As a result of composition analysis of the purified product using a high performance liquid chromatograph equipped with a UV detector, it was confirmed that it contained glycerin triacrylate (hereinafter referred to as "GLYTA5"). The yield of the purified product was 8%. As a result of measuring the hydroxyl value of the obtained reaction product in the same manner as described above, it was 52 mgKOH / g.

5) Production Example 5 (Preparation of component (B) dispersed in GLY-TA1)
200 parts of GLY-TA1 and MEK-AC-2140Z [Methyl ethyl ketone (hereinafter referred to as "MEK") of surface-treated silica fine particles are dispersed in a flask equipped with a stirrer, a thermometer, a gas introduction tube, a cooling tube and a eggplant-shaped flask. 500 g of sol, particle content = 46% by weight, particle size = 10 to 15 nm, manufactured by Nissan Chemical Industry Co., Ltd.] was charged, and oxygen-containing gas (oxygen content 5% by volume, nitrogen content 95% by volume) was bubbled into the liquid. rice field. The flask was immersed in a temperature-controlled oil bath, the temperature was raised to an internal temperature of 50 ° C., and then MEK was desolvated at a pressure of 5 mmHg in the system. After heating for 30 minutes, the pressure was once returned to normal pressure, the MEK distilled out in the eggplant flask was taken out, the solvent was removed again at an internal temperature of 50 ° C. and an internal pressure of 5 mmHg, and the mixture was heated for 1 hour to eliminate the distillate. After confirming that, the pressure in the system was returned to normal pressure and the silica preparation solution in the flask was withdrawn.
The MEK remaining in the obtained silica preparation solution was quantified by gas chromatography and found to be 0.1% by weight. The fine particle content of the component (B) was 53% by weight (calculated from the measured value of the distilled volatile matter), and the viscosity was 1,254 mPa · s (hereinafter referred to as “Si-1)”).

6) Production Examples 6 to 8 (Preparation of component (B) dispersed in GLY-TA2 to 4)
A silica preparation liquid was produced according to the same method as in Production Example 1 except that GLY-TA2-4 was used instead of GLY-TA1 as the component (A) (hereinafter referred to as "Si-2-4").

7) Comparative Production Example 2 (Preparation of component (B) dispersed in GLY-TA5)
140 parts of GLY-TA5, MEK-AC-2140Z [MEK dispersion sol of surface-treated silica fine particles, particle content = 46% by weight, particle size = 10 to 15 nm, Nissan Chemical Industry Co., Ltd. Made by Co., Ltd.] was charged, and a silica preparation solution was produced in the same manner as in Production Example 5 and extracted.
The MEK remaining in the obtained silica preparation solution was quantified by gas chromatography and found to be 0.2% by weight. The fine particle content of the component (B) was 33% by weight (calculated from the measured value of the distilled volatile matter), and the viscosity was 4,650 mPa · s (hereinafter referred to as “Si-5”).

8) Comparative Production Example 3 (Preparation of component (B) dispersed in TMPTA)
200 parts of TMPTA (“Aronix M-309” manufactured by Toagosei), MEK-AC-2140Z [MEK dispersion sol of surface-treated silica fine particles, particle content = 46% by weight, particles, in a flask equipped with the same equipment as in Production Example 5 Diameter = 10 to 15 nm, manufactured by Nissan Chemical Industry Co., Ltd.] was charged in an amount of 500 g, and a silica preparation solution was produced in the same manner as in Production Example 5 and extracted.
The MEK remaining in the obtained silica preparation solution was quantified by gas chromatography and found to be 0.1% by weight. The fine particle content of the component (B) was 53% by weight (calculated from the measured value of the distilled volatile matter), and the viscosity was 3,821 mPa · s (hereinafter referred to as "Si-6").

Table 3 shows the viscosities, fine particle content, and residual MEK content of the silica preparation liquids obtained in Production Examples 5 to 8 and Comparative Production Example 2.

2. Examples and Comparative Examples
1) Production of active energy ray-curable composition 100 parts of Si-1 and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, "IRGACURE907" manufactured by BASF Japan Ltd. 5 parts and 2,4-diethylthioxanthone, and 0.2 part of "Kayacure DETX-S" manufactured by Nippon Kayaku Co., Ltd. were stirred and mixed to prepare an active energy ray-curable composition.
In the same manner, the compounds shown in Table 4 below were stirred and mixed at the ratios shown in Table 4 to prepare an active energy ray-curable composition.
In Table 4, the silica preparation liquid contains the components (A) and (B) in Examples 1 to 9, and contains the components (B) and (C) in Comparative Examples 2 and 3. The number of copies of the components (A), (B) and (C) in parentheses is the amount brought into the composition from the silica preparation solution, that is, the components (A), (B) and (C) contained in the composition. Means proportion.

The numbers in Table 4 mean the number of copies, and the abbreviations mean the following.
-ACMO: Acryloyl morpholine, "ACMO" manufactured by KJ Chemicals Co., Ltd., 25 ° C viscosity 12 mPa · s
-NVP: N-vinylpyrrolidone, manufactured by Nippon Catalyst Co., Ltd.-UA306H: Polyfunctional urethane acrylate (urethane adduct, which is a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), "UA306H" manufactured by Kyoeisha Chemical Co., Ltd.
-TMPTA: Trimethylolpropane triacrylate, "Aronix M-309" manufactured by Toagosei Co., Ltd., 25 ° C. viscosity 90 mPa · s
-IRG907: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, "IRGACURE907" manufactured by BASF Japan Ltd.
-DETX: 2,4-diethylthioxanthone, "Kayacure DETX-S" manufactured by Nippon Kayaku Co., Ltd.
-TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, "Lucillin TPO" manufactured by BASF Japan Ltd.

2) Evaluation method The following evaluation was performed using the obtained composition. The results are shown in Table 5.
(1) Viscosity The viscosity of the obtained composition was measured with an E-type viscometer (25 ° C.).
(2) Transferability A hemispherical uneven shape having a height of 10 μm is formed on a triacetyl cellulose film “TD80UL” manufactured by FUJIFILM Corporation, which has a thickness of 80 μm, after applying the composition obtained above to a thickness of 10 μm with a bar coater. The composition was cured by laminating it on a nickel mold having the same material and irradiating it with ultraviolet rays through a triacetyl cellulose film.
As the ultraviolet irradiation device, a metal halide lamp manufactured by Eye Graphics Co., Ltd. was used, and the intensity of the ultraviolet region (UV-V) centered on 405 nm was set to 500 mW / cm ² and 500 mJ / cm ² through the PET film. After irradiation with ultraviolet rays, the triacetyl cellulose film was released from the mold to obtain an optical film.
The obtained transferred fine concavo-convex structure was observed with an electron microscope at a magnification of 10000 times, and it was confirmed whether the tip of the protrusion was not chipped and the stamper shape could be transferred, and evaluated in two stages according to the following criteria.
〇: No chipping ×: There is a chipping

(3) After applying the composition obtained above to a scratch-resistant 100 μm-thick easy-adhesive polyethylene terephthalate (hereinafter referred to as “PET”) film [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.] to a thickness of 10 μm with a bar coater. , 100 μm thick untreated polyethylene terephthalate film [Lumirror T50 manufactured by Toray Industries, Inc. Hereinafter referred to as Lumirer. ] Was laminated, and the composition was cured by irradiating with ultraviolet rays through the rumirror.
As the ultraviolet irradiation device, a metal halide lamp manufactured by Eye Graphics Co., Ltd. was used, and the intensity of the ultraviolet region (UV-V) centered on 405 nm was set to 500 mW / cm ² and 500 mJ / cm ² through the PET film.
After irradiation with ultraviolet rays, the rumirror was peeled off to obtain an optical film. The scratch resistance of the obtained optical film was evaluated using steel wool # 0000 after 100 reciprocations under a load of 500 g on the following five levels.
◎: No scratches 〇: 1 or more scratches and less than 10 △: 10 or more scratches and less than 50 ×: 50 or more and less than 100 scratches × ×: 100 or more scratches

(4) Plastic deformation hardness (3) The hardened product obtained in the scratch resistance test is subjected to the maximum load of the Vickers indenter at room temperature using an ultrafine hardness tester (Fisher Instruments Co., Ltd., H-100C). The surface hardness was measured under the condition that the hardness was 10 mN, and evaluated by the plastic deformation hardness.

(5) Adhesion (3) The optical film obtained with scratch resistance is cut into 25 squares of 5 × 5 with a cutter knife, and then Nichiban cellophane tape is attached, and the peeling speed is about 1 cm / sec. The tape was peeled off vigorously at the speed of.
A similar test was carried out on the following films instead of easy-adhesive PET. The abbreviations in Table 5 mean the following.
-Acrylic: Acrylic resin film "Clarity HI50-75" manufactured by Kuraray Co., Ltd. (thickness 75 μm)
-TAC: Triacetyl cellulose film "TD80UL" manufactured by FUJIFILM Corporation (thickness 80 μm)
The adhesion to the base material was evaluated on a three-point scale based on the following criteria by confirming the number of squares of the cured product remaining after the above operation.
〇: 25 to 21 squares △: 20 to 10 squares ×: 10 squares or less

3) Discussion As is clear from the results of Examples 1 to 9, the composition of the present invention was excellent in transferability, hardness of the cured product, scratch resistance, and substrate adhesion.
On the other hand, in Comparative Example 1, since the composition did not contain the component (B), both the plastic deformation hardness and the adhesion to the acrylic were inferior. Further, since Comparative Examples 2 and 3 were compositions using different polyfunctional acrylates instead of the component (A), they were inferior in transferability, scratch resistance, and adhesiveness to acrylic and TAC.

The composition of the present invention can be used for various purposes, and can be preferably used as a shaping material and a hard coating agent. Specific examples of the shaping material include fine concavo-convex structures such as a lens sheet, a moth-eye film, an antiglare film, a light extraction film for organic EL / LED, a light confinement film for solar cells, and a heat ray retroreflective film. It can be used for producing a fixed-form film, and as a hard coating agent, it can be used for improving the surface hardness and scratch resistance of various plastics.

Claims (21)

A composition containing the following components (A), (B) and (C).
In the total of 100% by weight of the components (A), (B) and (C), the component (A) is 40 to 95% by weight, the component (B) is 5 to 60% by weight, and the component (C) is 0 to 0. An active energy ray-curable composition containing 55% by weight.
Component (A): A (meth) acrylate mixture containing glycerin tri (meth) acrylate as a main component, wherein the high molecular weight compound in the component (A) is an area% by gel permeation chromatography based on the formula (1). Area% of the high molecular weight compound of the mixture which is less than 30% = [(RIL) / R] × 100 ... (1)
The symbols and terms in formula (1) mean the following.
-R: Total area of detection peak in component (A) -I: Area of detection peak containing glycerin tri (meth) acrylate-L: Detection having a smaller weight average molecular weight than detection peak containing glycerin tri (meth) acrylate Total area of peak (B) component: Filler (C) component: Compound having an ethylenically unsaturated group other than the component (A) Claim 1 that the component (A) is a (meth) acrylate mixture containing glycerin tri (meth) acrylate as a main component, which is obtained by transesterifying a compound having one (meth) acryloyl group with glycerin. The active energy ray-curable composition according to the above. The component (A) contains glycerin tri (meth) acrylate as a main component, which is obtained by transesterifying a compound having glycerin and one (meth) acryloyl group in the presence of the following catalysts X and Y. The active energy ray-curable composition according to claim 2, which is a (meth) acrylate mixture.
Catalyst X: One or more selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or salts or complexes thereof, amidin or salts or complexes thereof, compounds having a pyridine ring or salts or complexes thereof, and phosphine or salts or complexes thereof. Compound.
Catalyst Y: A compound containing zinc. The active energy ray-curable resin composition according to claim 3, wherein the following compound is used as the catalyst X.
Catalyst X: One or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, amidin or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof. The active energy ray-curable composition according to any one of claims 3 or 4, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The active energy ray-curable composition according to any one of claims 3 to 5, wherein the catalyst Y is zinc organic acid and / or zinc diketone enolate. The active energy ray-curable composition according to any one of claims 1 to 6, wherein the hydroxyl value of the component (A) is 60 mgKOH / g or less. Any of claims 1 to 7, wherein the component (C) contains a compound (C-1) having a homopolymer having a glass transition temperature of 70 ° C. or higher and having one ethylenically unsaturated group in the molecule. The active energy ray-curable composition according to item 1. The compound (C-1-N) in which the component (C-1) contains nitrogen in the molecule and has a glass transition temperature of the homopolymer of 70 ° C. or higher and has one ethylenically unsaturated group in the molecule. The active energy ray-curable composition according to claim 8. The active energy ray-curable composition according to any one of claims 1 to 9, which contains urethane (meth) acrylate (C-2) as the component (C). The active energy ray-curable composition according to any one of claims 1 to 10, wherein the component (B) is inorganic oxide fine particles having an average particle diameter equal to or less than the wavelength of visible light. The active energy ray-curable composition according to claim 11, wherein the component (B) is silica having an average particle size equal to or less than the wavelength of visible light. Claims 1 to claim further include a photopolymerization initiator and / or a sensitizer as the component (D) in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the total amount of the components (A) and (C). 12. The active energy ray-curable composition according to any one of 12. The active energy ray-curable type according to any one of claims 1 to 13, further comprising 0.1 to 1000 parts by weight of an organic solvent with respect to 100 parts by weight of the total amount of the components (A) and (C). Composition. An active energy ray-curable composition for a shaping material, which comprises the composition according to any one of claims 1 to 14. An active energy ray-curable composition for hard coating, which comprises the composition according to any one of claims 1 to 14. Glycerin and a compound having one (meth) acryloyl group are subjected to an ester exchange reaction in the presence of the following catalysts X and Y to form a (meth) acrylate mixture containing glycerin tri (meth) acrylate as a main component, which is a mixture. A step of producing a mixture (A) in which the high molecular weight compound in the mixture is less than 30% in area% by gel permeation chromatography based on the above formula (1), and the obtained component (A) and the following (B). ) And (C) components are 40 to 95% by weight of (A) component and 5 to 60% by weight of (B) component in a total of 100% by weight of (A), (B) and (C) components. A method for producing an active energy ray-curable composition, which comprises a step of mixing the component (C) so as to contain 0 to 55% by weight.

Catalyst X: One or more selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or salts or complexes thereof, amidin or salts or complexes thereof, compounds having a pyridine ring or salts or complexes thereof, and phosphine or salts or complexes thereof. Compound.
Catalyst Y: A compound containing zinc.

Component (B): Filler Component (C): Compound having an ethylenically unsaturated group other than the component (A) The method for producing an active energy ray-curable composition according to claim 17, wherein the catalyst X uses the following compound.
Catalyst X: One or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, amidin or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof. The method for producing an active energy ray-curable composition according to claim 17 or 18, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The method for producing an active energy ray-curable composition according to any one of claims 17 to 19, wherein the catalyst Y is zinc organic acid and / or zinc diketone enolate. The method for producing an active energy ray-curable composition according to any one of claims 17 to 20, further comprising a step of mixing the photopolymerization initiator (D).