JPWO2017141970A1 - Curable composition - Google Patents

Abstract

To provide a curable composition having a high hardness of a cured film, a low water contact angle, and excellent wettability of an adhesive, and a method for producing the same.
Pentaerythritol di (meth) acrylate as a value obtained by high performance liquid chromatographic analysis using a reverse phase silica column and using an aqueous solution of phosphoric acid / methanol as an eluent. A curable composition comprising a mixture (A) having a content of 15 to 40 area% and a hydroxyl value of 190 to 400 mgKOH / g.

Description

The present invention relates to a curable composition, and preferably to an active energy ray curable composition. The composition of the present invention can be used in various applications such as coating agents such as hard coats, inks such as inkjet printing, pattern forming agents such as photosensitive lithographic printing plates and color resists, and adhesives. It can be preferably used for the use of agents and belongs to these technical fields.
In the present specification, either or both of an acryloyl group and a methacryloyl group are represented as a (meth) acryloyl group, and either one or both of an acrylate and a methacrylate are represented as a (meth) acrylate, and an acrylic. Either or both of acid and methacrylic acid are represented as (meth) acrylic acid.

  As an active energy ray-curable composition, a composition containing a compound having two or more (meth) acryloyl groups is used in various applications. In particular, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (hereinafter referred to as “PETTA”). ")" As a main component is used for various purposes by utilizing its excellent physical properties.

  For example, as a hard coating agent for a plastic film used for a touch sensor of a touch panel type image display device, a composition containing PETTA is known because of its high surface hardness and good adhesion to an acrylic adhesive (patent) Reference 1).

JP 2013-155219 A

  However, a conventional cured film made of PETTA has a problem that wettability of an adhesive such as an ultraviolet curable adhesive (hereinafter referred to as “OCR”) is insufficient because of a high water contact angle. .

  The inventors of the present invention have made extensive studies in order to find a curable composition, preferably an active energy ray curable composition, having a high hardness of the cured film, a low water contact angle, and excellent wettability of an adhesive such as OCR. I went there.

The present inventors have made various studies based on the idea that the above problem can be solved if PETTA has a higher hydroxyl value.
As a result, a curable composition containing a pentaerythritol (meth) acrylate mixture having a specific pentaerythritol diacrylate content and a hydroxyl value has a high cured film hardness and a low water contact angle. The present inventors have found that the adhesive has excellent wettability and completed the present invention.
Hereinafter, the present invention will be described in detail.

  ADVANTAGE OF THE INVENTION According to this invention, the hardness of a cured film is high, a water contact angle is low, and the curable composition excellent in the wettability of adhesive agents, such as OCR, can be provided.

The present invention is a mixture of (meth) acrylates of pentaerythritol, which has a pentaerythritol diacrylate content of 15 to 40 area% and a hydroxyl value as a value obtained by high performance liquid chromatograph (hereinafter referred to as HPLC) analysis. Relates to a curable composition comprising a mixture (A) having a molecular weight of 190 to 400 mgKOH / g.
Hereinafter, (A) component, a curable composition, a use, and a usage method are demonstrated.

1. Component (A) The component (A) is a mixture of pentaerythritol (meth) acrylate, and has a pentaerythritol di (meth) acrylate (hereinafter referred to as “PEDM”) content of 15 as a value obtained by HPLC analysis. It is a mixture having ˜40 area% and a hydroxyl value of 190 to 400 mg KOH / g.

In the component (A), “a (meth) acrylate mixture of pentaerythritol” means a mixture of mono (meth) acrylate, di (meth) acrylate (PEDM), tri (meth) acrylate and tetra (meth) acrylate of pentaerythritol. means.
The hydroxyl value of the component (A) is 190 to 400 mgKOH / g, preferably 200 to 380 mgKOH / g, and more preferably 200 to 360 mgKOH / g.
When the hydroxyl value of the component (A) is less than 190 mgKOH / g, the water contact angle of the cured film is high and the wettability of the adhesive is inferior. On the other hand, when the hydroxyl value of the component (A) exceeds 400 mgKOH / g, the compatibility with other components becomes poor.
In the present invention, the hydroxyl value means the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of a sample.

In the present invention, the PEDM content in the component (A) is preferably 15 to 40 area% as a value by HPLC analysis using a reverse phase silica column and using an eluent of an aqueous phosphoric acid solution / methanol system. Preferably it is 20-40 area%.
When the content of PEDM is less than 15 area%, the water contact angle of the cured film is high and the wettability of the adhesive is inferior, and when it exceeds 40 area%, the compatibility with other components is deteriorated. There is a thing.

(A) As a more detailed definition in the case of measuring PEDM content in a component, the value measured according to the following conditions using HPLC is meant.
・ Apparatus: HPLC (high performance liquid chromatograph)
Column type: HPLC reversed phase silica column (silica gel modified with an alkyl group having 18 carbon atoms, particle size: 3.5 μm, 2.1 mm × 50 mm)
Column temperature: 40 ° C
Eluent composition: 0.015 wt% phosphoric acid aqueous solution / methanol = 50/50 (0-25 minutes) → 30/70 (25-30 minutes) → 0/100 (30-45 minutes)
・ UV detector: wavelength 210nm
・ Flow rate: 0.8mL / min

Furthermore, in the present invention, the component (A) having a small proportion of the high molecular weight component can reduce the viscosity of the resulting component (A), and the cured film of the resulting composition can have a high hardness. It is preferable at the point which can be made.
The ratio of the high molecular weight in this case can be expressed by the following formula (P1) as the area% of the high molecular weight obtained by gel permeation chromatography (hereinafter referred to as “GPC”) measurement.
High molecular weight area% = [(R−I−L) / R] × 100 (P1)
The symbols and terms in formula (P1) mean the following.
R: Total area of detection peaks in component (A) I: Area of detection peaks containing PEDM, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate L: PEDM, pentaerythritol tri (meta ) The total area of the detection peak having a smaller weight average molecular weight (hereinafter referred to as “Mw”) than the detection peak containing acrylate and pentaerythritol tetra (meth) acrylate. In the present invention, Mw is tetrahydrofuran (hereinafter referred to as “Mw”) as a solvent. This is a value obtained by converting the molecular weight measured by GPC with reference to the molecular weight of polystyrene.
In addition, 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: within 25-50 ° C-Eluent: THF

The component (A) is a compound obtained by dehydration esterification reaction of pentaerythritol and (meth) acrylic acid, and a compound having pentaerythritol and one (meth) acryloyl group [hereinafter referred to as monofunctional (meth) acrylate] Any of the compounds obtained by transesterification can be used.
As the component (A), a compound obtained by transesterification of pentaerythritol and a monofunctional (meth) acrylate can produce the component (A) having the specific hydroxyl value described above in a high yield, and is obtained ( A) Since the high molecular weight body in the component is small, the viscosity is low, and the cured film of the resulting composition is preferable in that it has high hardness.

1-1. The dehydration esterification (A) component can be produced by subjecting pentaerythritol and (meth) acrylic acid to a dehydration esterification reaction.

(Meth) acrylic acid used in the dehydration esterification reaction may be either acrylic acid or methacrylic acid, or both acrylic acid and methacrylic acid, but only acrylic acid is used. It is preferable to do.
In addition, in the production of the component (A), instead of (meth) acrylic acid, (meth) acrylic acid equivalent, (meth) acrylic acid halide, (meth) acrylic anhydride, etc. may be used. Good.

In the case where the component (A) is produced by a dehydration esterification reaction of pentaerythritol and (meth) acrylic acid, the proportion of (meth) acrylic acid used is such that the hydroxyl value of the resulting (meth) acrylic acid ester is 190 to If it is the quantity used as 400 mgKOH / g, there will be no restriction | limiting in particular.
The molar amount of (meth) acrylic acid used is preferably less than the molar amount of the hydroxyl group of pentaerythritol to be used, preferably 0.75 to 1.25 molar equivalents relative to the total number of hydroxyl groups of pentaerythritol, More preferably, it is 0.85-1.15 molar equivalent.

There is no restriction | limiting in particular as a manufacturing method of (A) component, Although well-known dehydration esterification reaction can be used, It is preferable to use a catalyst and a stabilizer.
As the catalyst, an acid catalyst can be preferably exemplified.
Moreover, as a stabilizer, well-known polymerization inhibitors, such as hydroquinone monomethyl ether, can be mentioned suitably. It is also preferable to use oxygen as a stabilizer, particularly a polymerization inhibitor. For example, unnecessary polymerization of (meth) acrylic acid or (meth) acrylate can be prevented by producing the component (A) in an oxygen-containing atmosphere. Moreover, it is preferable that it is 1-20 volume%, and, as for the content rate of oxygen in atmosphere, it is more preferable that it is 1-10 volume%.
Moreover, it is preferable that the manufacturing method of (A) component includes the method of refine | purifying at least liquid-liquid extraction (separation). In the above embodiment, a compound having a hydroxyl value of 190 to 400 mgKOH / g can be easily produced.

1-2. The transesterification (A) component can also be produced by transesterification of pentaerythritol and monofunctional (meth) acrylate in the presence of a transesterification catalyst.
According to the transesterification reaction of pentaerythritol and monofunctional (meth) acrylate using the catalysts X and Y together, compared with the dehydration esterification reaction of pentaerythritol and (meth) acrylic acid, Since the molecular weight is small, it is possible to produce a polyfunctional (meth) acrylate mixture having low viscosity and few impurities, and thus excellent physical properties.
Hereinafter, the manufacturing method of a monofunctional (meth) acrylate, the catalyst X, the catalyst Y, and the (A) component is demonstrated.

1-2-1. 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 the following formula (1), for example. Compounds.

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.

Specific examples of R ² in the above formula (1) include methyl group, ethyl group, n- or i-propyl group, n-, i- or t-butyl group, n-, s- or t-amyl group, Neopentyl group, n-, s- or t-hexyl group, n-, s- or t-heptyl group, n-, s- or t-octyl group, 2-ethylhexyl group, capryl group, nonyl group, decyl group, Undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, aralkyl group, seryl group, myricyl group, melicyl group, vinyl group, allyl group, methallyl group, crotyl group 1,1-dimethyl-2-propenyl group, 2-methylbutenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 2-methyl-3-butenyl group, butenyl , Pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, oleyl group, linol group, linolene group, cyclopentyl Group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group, tricyclodecanyl group, isobornyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group, Phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, 4-t-butylphenyl group, benzyl group, diphenylmethyl group, diphenylethyl group, triphenylmethyl group, cinnamyl group, Butyl, anthranyl, methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, ethoxyethoxyethyl, cyclopentoxyethyl, cyclohexyloxyethyl, cyclopent Toxiethoxyethyl group, cyclohexyloxyethoxyethyl group, dicyclopentenyloxyethyl group, phenoxyethyl group, phenoxyethoxyethyl group, glycidyl group, β-methylglycidyl group, β-ethylglycidyl group, 3,4-epoxycyclohexylmethyl group 2-oxetanemethyl group, 3-methyl-3-oxetanemethyl group, 3-ethyl-3-oxetanemethyl group, tetrahydrofuranyl group, tetrahydrofurfuryl group, tetrahydropyranyl group, dioxazolanyl Group, dioxanyl group, N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, N, N-dimethylaminopropyl group, N, N-diethylaminopropyl group, N-benzyl-N-methylaminoethyl group, N-benzyl-N-methylaminopropyl group etc. are mentioned.
Among these functional groups, R ² is alkyl having 1 to 8 carbon atoms such as methyl, ethyl, propyl, pentyl, butyl, heptyl, octyl, heptyl and 2-ethylhexyl. Group, alkoxyalkyl group such as 2-methoxyethyl group, 2-ethoxyethyl group and 2-methoxybutyl group, N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, N, N-dimethylaminopropyl group A dialkylamino group such as N, N-diethylaminopropyl group is preferred.

In the present invention, these monofunctional (meth) acrylates can be used alone or in combination of two or more.
Among these monofunctional (meth) acrylates, carbon such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and i-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate Preferred examples include alkyl (meth) acrylates having a number 1 to 8 alkyl group, alkoxyalkyl (meth) acrylates such as 2-methoxyethyl acrylate, and N, N-dimethylaminoethyl (meth) acrylate, particularly pentaerythritol. More preferable examples include (meth) acrylates having an alkyl group having 1 to 4 carbon atoms, which are excellent in reactivity and easily available, and alkoxyalkyl (meth) acrylates having an alkyl group having 1 to 2 carbon atoms. .
Furthermore, an alkoxyalkyl (meth) acrylate having a C1-C2 alkyl group that promotes dissolution of pentaerythritol and exhibits extremely good reactivity is more preferred, and 2-methoxyethyl (meth) acrylate is particularly preferred.
Furthermore, as monofunctional (meth) acrylate, monofunctional acrylate is particularly preferable because of its excellent reactivity.

  Although there is no restriction | limiting in particular in the usage-amount of the pentaerythritol and monofunctional (meth) acrylate in the manufacturing method of (A) component, 0.4-10 is monofunctional (meth) acrylate with respect to 1 mol of total hydroxyl groups in pentaerythritol. 0.0 mol is preferable, and 0.6 to 5.0 mol is more preferable. By making the monofunctional (meth) acrylate 0.4 mol or more, side reactions can be suppressed. Moreover, the production amount of (A) component can be increased by making it 10.0 mol or less, and productivity can be improved.

1-2-2. As the transesterification catalyst in the method for producing the catalyst (A) component, conventionally known ones such as a tin-based catalyst, a titanium-based catalyst, and sulfuric acid can be used.
In the present invention, the following catalysts X and Y are preferably used in combination as a catalyst in that the component (A) can be efficiently produced in high yield.
Catalyst X: a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof (hereinafter referred to as “azabicyclo compound”), an amidine or a salt or complex thereof (hereinafter referred to as “amidine compound”), a compound having a pyridine ring, or One or more compound catalysts selected from the group consisting of salts or complexes thereof (hereinafter referred to as “pyridine compounds”) and phosphines or salts or complexes thereof (hereinafter referred to as “phosphine compounds”): a compound containing zinc.
Hereinafter, the catalyst X and the catalyst Y will be described.

1-2-3. Catalyst X
The catalyst X is one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, pyridine compounds and phosphine compounds.
The catalyst X is preferably one or more compounds selected from the group consisting of an azabicyclo compound, an amidine compound, and a pyridine compound, among the compound groups described above. These compounds are excellent in catalytic activity and can preferably produce the component (A), and also form a complex with the catalyst Y described later after completion of the reaction. Since the complex is hardly soluble in the reaction solution, it can be easily filtered and adsorbed. By this method, it can be easily removed from the reaction solution after completion of the reaction. In particular, since the complex with the catalyst Y becomes hardly soluble in the reaction solution, the azacyclo compound can be more easily removed by filtration and adsorption.
On the other hand, although the phosphine compound is excellent in catalytic activity, it is difficult to form a complex with the catalyst Y, or when the complex is formed, the phosphine compound is easily soluble in the reaction solution, and most of the phosphine compound is present in the reaction solution after completion of the reaction. Since it remains dissolved, it is difficult to remove it from the reaction solution by a simple method such as filtration and adsorption.

  Specific examples of the azabicyclo compounds include 1-azabicyclo [1.1.0] butane, 1,3-diazabicyclo [1.1.0] butane, 1-azabicyclo [2.1.0] heptane, 1,3 -Diazabicyclo [2.1.0] heptane, 1,4-diazabicyclo [2.1.0] heptane, 1-azabicyclo [2.2.0] hexane, 1,3-diazabicyclo [2.2.0] hexane 1-azabicyclo [2.1.1] hexane, 1,3-diazabicyclo [2.1.1] hexane, 1-azabicyclo [2.2.1] heptane, 1,3-diazabicyclo [2.2.1]. ] Heptane, 1,4-diazabicyclo [2.2.1] heptane, 1-azabicyclo [3.2.0] heptane, 1,3-diazabicyclo [3.2.0] heptane, 1,4-diazabicyclo [ .2.0] heptane, 1,6-diazabicyclo [3.2.0] heptane, 1,3-diazabicyclo [2.2.2] octane, 1-azabicyclo [3.2.1] octane, 1,3 -Diazabicyclo [3.2.1] octane, 1,4-diazabicyclo [3.2.1] octane, 1,5-diazabicyclo [3.2.1] octane, 1,6-diazabicyclo [3.2.1] ] Octane, 1-azabicyclo [4.1.1] octane, 1,3-diazabicyclo [4.1.1] octane, 1,4-diazabicyclo [4.1.1] octane, 1,5-diazabicyclo [4] 1.1] octane, 1,6-diazabicyclo [4.1.1] octane, 1,7-diazabicyclo [4.1.1] octane, 1-azabicyclo [4.2.0] octane, 1,3 -Diazabi B [4.2.0] octane, 1,4-diazabicyclo [4.2.0] octane, 1,5-diazabicyclo [4.2.0] octane, 1,7-diazabicyclo [4.2.0] Octane, 1-azabicyclo [3.3.1] nonane, 1,3-diazabicyclo [3.3.1] nonane, 1,4-diazabicyclo [3.3.1] nonane, 1,5-diazabicyclo [3. 3.1] Nonane, 1-azabicyclo [3.2.2] nonane, 1,3-diazabicyclo [3.2.2] nonane, 1,4-diazabicyclo [3.2.2] nonane, 1,5- Diazabicyclo [3.2.2] nonane, 1,6-diazabicyclo [3.2.2] nonane, 1,8-diazabicyclo [3.2.2] nonane, 1-azabicyclo [4.3.0] nonane, 1,3-diazabicyclo [4.3.0] Nonane, 1,4-diazabicyclo [4.3.0] nonane, 1,5-diazabicyclo [4.3.0] nonane, 1,6-diazabicyclo [4.3.0] nonane, 1,7-diazabicyclo [ 4.3.0] nonane, 1,8-diazabicyclo [4.3.0] nonane, 1-azabicyclo [4.2.1] nonane, 1,3-diazabicyclo [4.2.1] nonane, 1, 4-diazabicyclo [4.2.1] nonane, 1,5-diazabicyclo [4.2.1] nonane, 1,6-diazabicyclo [4.2.1] nonane, 1,7-diazabicyclo [4.2. 1] nonane, 1-azabicyclo [5.2.0] nonane, 1,3-diazabicyclo [5.2.0] nonane, 1,3-diazabicyclo [5.2.0] nonane, 1,4-diazabicyclo [ 5.2.0] Nonane, 1,5-di Zabicyclo [5.2.0] nonane, 1,6-diazabicyclo [5.2.0] nonane, 1,7-diazabicyclo [5.2.0] nonane, 1,8-diazabicyclo [5.2.0] Nonane, 1-azabicyclo [5.1.1] nonane, 1,3-azabicyclo [5.1.1] nonane, 1,4-azabicyclo [5.1.1] nonane, 1,5-azabicyclo [5. 1.1] nonane, 1,6-azabicyclo [5.1.1] nonane, 1,7-azabicyclo [5.1.1] nonane, 1-azabicyclo [6.1.0] nonane, 1,3- Diazabicyclo [6.1.0] nonane, 1,4-diazabicyclo [6.1.0] nonane, 1,5-diazabicyclo [6.1.0] nonane, 1,6-diazabicyclo [6.1.0] Nonane, 1,7-diazabicyclo [6.1.0] no 1,8-diazabicyclo [6.1.0] nonane, 1-azabicyclo [7.1.0] decane, 1,9-diazabicyclo [7.1.0] decane, 1-azabicyclo [6.2. 0] decane, 1,8-diazabicyclo [6.2.0] decane, 1-azabicyclo [6.1.1] decane, 1,8-diazabicyclo [6.1.1] decane, 1-azabicyclo [5. 3.0] decane, 1,7-diazabicyclo [5.3.0] decane, 1-azabicyclo [5.2.1] decane, 1,7-diazabicyclo [5.2.1] decane, 1-azabicyclo [ 4.3.1] decane, 1,6-diazabicyclo [4.3.1] decane, 1-azabicyclo [4.2.2] decane, 1,6-diazabicyclo [4.2.2] decane, 1- Azabicyclo [5.4.0] undecane, 1 , 7-diazabicyclo [5.4.0] undecane, 1-azabicyclo [5.3.1] undecane, 1,7-diazabicyclo [5.3.1] undecane, 1-azabicyclo [5.2.2] undecane. 1,7-diazabicyclo [5.2.2] undecane, 1-azabicyclo [4.4.1] undecane, 1,7-diazabicyclo [4.4.1] undecane, 1-azabicyclo [4.3.2]. ] Undecane, 1,7-diazabicyclo [4.3.2] undecane, 1-azabicyclo [3.3.0] octane, 1-azabicyclo [4.3.0] nonane, quinuclidine, lupinan, lupinin, quinolizidine, 3 -Hydroxyquinuclidine, 3-quinuclidinone, quincholine, quincolidine, cinchonidine, cinchonine, quinidine, quinine, cupurein, warts In, swainsonine, castanospermine, mianserin, mirtazapine, canazine, Trager base, 1-azabicyclo [2.2.2] octane-3-carboxylic acid, triethylenediamine (also known as 1,4-diazabicyclo [2.2 .2] Octane. Hereinafter referred to as “DABCO”), hexamethylenetetramine, 3-quinolidinone hydrochloride, 3-chloro-1-azabicyclo [2.2.2] octane hydrochloride, cinchonidine dihydrochloride, cinchonine hydrochloride hydrate, cinchonidine sulfate Dihydrate, hydroquinidine hydrochloride, cinchonine sulfate dihydrate, quinine hydrochloride dihydrate, quinine sulfate dihydrate, quinine phosphate, quinidine sulfate dihydrate, mianserin hydrochloride, 1 , 1 ′-(butane-1,4-diyl) bis [4-aza-1-azoniabicyclo [2.2.2] octane] dibromide, 1,1 ′-(decane-1,10-diyl) bis [4 -Aza-1-azoniabicyclo [2.2.2] octane] dibromide, bis (trimethylaluminum) -1,4-diazabicyclo [2.2.2] octane adduct, Sumtin, quinuclidine hydrochloride, 3-quinuclidinone hydrochloride, 3-hydroxyquinuclidine hydrochloride, DABCO hydrochloride, quinuclidine acetate, 3-quinuclidinone acetate, 3-hydroxyquinuclidine acetate, DABCO acetate, quinucli Examples thereof include gin acrylate, 3-quinuclidinone acrylate, 3-hydroxyquinuclidine acrylate, and DABCO acrylate.

  Specific examples of the amidine compound include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 1-allylimidazole, 1 , 8-diazabicyclo [5.4.0] undec-7-ene (hereinafter referred to as “DBU”), 1,5-diazabicyclo [4.3.0] non-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, phthalimide DBU etc. are mentioned.

  Specific examples of the pyridine compound include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, and 4-propylpyridine. 4-isopropylpyridine, 4-tert-butylpyridine, 4-amylpyridine, 4- (1-ethylpropyl) pyridine, 4- (5-nonyl) pyridine, 2-vinylpyridine, 2,3-dimethylpyridine, 2 , 4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 3,5-diethylpyridine, N, N-dimethyl-4-amino Pyridine (hereinafter referred to as “DMAP”), 2,4,6-trimethylpyridine, 2,6-di-ter -Butylpyridine, N, N-dimethyl-2-aminopyridine, 4-piperidinopyridine, 4-pyrrolidinopyridine, 4-phenylpyridine, quinoline, 2-methylquinoline, 3-methylquinoline, 4-methylquinoline, 6-methylquinoline, 7-methylquinoline, 8-methylquinoline, isoquinoline, 1-methylisoquinoline, acridine, 3,4-benzoquinoline, 5,6-benzoquinoline, 7,8-benzoquinoline, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,6-dihydroxypyridine, 2- (hydroxymethyl) pyridine, 3- (hydroxymethyl) pyridine, 4- (hydroxymethyl) pyridine, 5-hydroxyisoquinoline, 2-methoxypyridine , 3-methoxypyridine, 4-methoxy Pyridine, 2,6-dimethoxypyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, 1,8-naphthyridine, 2,6-naphthyridine, 2,7-naphthyridine, 2,2′- Bipyridyl, 3,3′-bipyridyl, 4,4′-bipyridyl, 2,3′-bipyridyl, 2,4′-bipyridyl, 3,4′-bipyridyl, 4,4′-ethylenedipyridine, 1,3- Di (4-pyridyl) propane, 1,10-phenanthroline monohydrate, 2- (trimethylsilyl) pyridine, DMAP hydrochloride, DMAP acetate, DMAP acrylate, 1-methylpyridinium chloride, 1-propylpyridinium chloride, Borane-pyridine complex, borane-2-picoline complex, pyridinium paratoluenesulfonate, etc. And the like.

  Examples of the phosphine compound include compounds having a structure represented by the following formula (2).

[In Formula (2), R < ³ >, R < ⁴ > and R < ⁵ > are a C1-C20 linear or branched alkyl group, a C1-C20 linear or branched alkenyl group, carbon number 6 Means an aryl group of ˜24 or a cycloalkyl group of 5 to 20 carbon atoms. R ³ , R ⁴ and R ⁵ may be the same or different. ]
Represent. )

  Specific examples of the phosphine compound include triphenylphosphine, (S)-(−)-BINAP, (R)-(+)-BINAP (2,2′-bis (diphenylphosphino) -1,1′-binaphthyl) , (±) -BINAP, 2,2′-bis (diphenylphosphino) biphenyl, xanthophos, 4,6-bis (diphenylphosphino) phenoxazine, bis [2- (diphenylphosphino) phenyl] ether, (2 -Bromophenyl) diphenylphosphine, bis (pentafluorophenyl) phenylphosphine, sodium diphenylphosphinobenzene-3-sulfonate, diphenyl-1-pyrenylphosphine, diphenyl-2-pyridylphosphine, 4- (dimethylamino) phenyldiphenyl Phosphine, 1,1′-bis (diphenylphosphino) ferrocene, (R R ")-2,2" -bis (diphenylphosphino) -1,1 "-biferrocene, (R) -N, N-dimethyl-1-[(S) -2- (diphenylphosphino) ferrocenyl] ethylamine , (S) -N, N-dimethyl-1-[(R) -2- (diphenylphosphino) ferrocenyl] ethylamine, (R) -N, N-dimethyl-1-[(S) -1 ′, 2 -Bis (diphenylphosphino) ferrocenyl] ethylamine, (S) -N, N-dimethyl-1-[(R) -1 ', 2-bis (diphenylphosphino) ferrocenyl] ethylamine, 4-diphenylphosphinomethylpolystyrene Resin, (R)-(+)-2-diphenylphosphino-2′-methoxy-1,1′-binaphthyl, (S)-(−)-2-diphenylphosphino-2′-methoxy-1 1'-binaphthyl, 2- (diphenylphosphino) benzoic acid, 4- (diphenylphosphino) benzoic acid, 2- (diphenylphosphino) benzaldehyde, (S)-(-)-5,5'-bis [di (3,5-xylyl) phosphino] -4,4′-bi-1,3-benzodioxole, (R)-(+)-5,5′-bis [di (3,5-xylyl) phosphino ] -4,4'-bi-1,3-benzodioxole, (S)-(+)-5,5'-bis [di (3,5-di-tert-butyl-4-methoxyphenyl) Phosphino] -4,4′-bi-1,3-benzodioxole, (R)-(−)-5,5′-bis [di (3,5-di-tert-butyl-4-methoxyphenyl) Phosphino] -4,4′-bi-1,3-benzodioxole, (pentafluoroph Enyl) diphenylphosphine, (S)-(−)-5,5′-bis (diphenylphosphino) -4,4′-bi-1,3-benzodioxole, (R)-(+)-5 , 5′-bis (diphenylphosphino) -4,4′-bi-1,3-benzodioxole, tris (4-methoxyphenyl) phosphine, tri (p-tolyl) phosphine, tri (o-tolyl) Phosphine, tri (m-tolyl) phosphine, tris (2,6-dimethoxyphenyl) phosphine, triphenylborane-triphenylphosphine complex, triphenylphosphineborane, tris (pentafluorophenyl) phosphine, tris [3,5-bis (Trifluoromethyl) phenyl] phosphine, tris (4-fluorophenyl) phosphine, parastyryl dipheny Phosphine, tetraphenylphosphonium bromide, methyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate , Ethyltriphenylphosphonium acetate / acetic acid complex, ethyltriphenylphosphonium iodide, tris (4-methoxy-3,5-dimethylphenyl) phosphine, (+)-DIOP (2,3-O-isopropylidene-2,3-dihydroxy -1,4-bis (diphenylphosphino) butane), (−)-DIOP, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1, -Bis (dimethylphosphino) ethane, 1,4-bis (diphenylphosphino) butane, 1,6-bis (diphenylphosphino) hexane, 1,5-bis (diphenylphosphino) pentane, bis (diphenylphosphino) ) Methane, trans-1,2-bis (diphenylphosphino) ethylene, (S, S) -kiraphos, (R, R) -DIPAMP (Ethane-1,2-diylbis [(2-methoxyphenyl) phenylphosphane]), (S, S) -DIPAMP, 1,2-bis [bis (pentafluorophenyl) phosphino] ethane, (2R, 3R)-(−)-Norphos, (2S, 3S)-(+)-Norphos, 2- Butenyl (di-tert-butyl) phosphine, cyclohexyl diphenylphosphine, dicyclohexyl (1,1-diphenyl-1-propen-2-yl ) Phosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, diphenylpropylphosphine, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2- (dicyclohexylphosphino) -2 ′-(dimethyl) Amino) biphenyl, 1- [2- (di-tert-butylphosphino) phenyl] -3,5-diphenyl-1H-pyrazole, di-tert-butylphenylphosphine, (4-dimethylaminophenyl) di-tert- Butylphosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, ethyldiphenylphosphine, isopropyldiphenylphosphine, methyldiphenylphosphine, tricyclohexylphosphine, tri (2-free E) phosphine, tri (2-thienyl) phosphine, tri-tert-butylphosphine, tricyclopentylphosphine and the like.

  In this invention, these catalysts X can be used individually or in combination of 2 or more types. Among these catalysts X, quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN, DMAP, triphenylphosphine, tri (p-tolyl) phosphine, tri (m- At least one compound selected from the group consisting of (tolyl) phosphine, tris (4-methoxyphenyl) phosphine and tris (4-methoxy-3,5-dimethylphenyl) phosphine is preferable, and particularly good for pentaerythritol More preferable is at least one compound selected from the group consisting of 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP, which shows reactivity and is easily available.

  (A) Although there is no restriction | limiting in particular in the usage-amount of the catalyst X in the manufacturing method of a component, It is preferable to use 0.0001-0.5 mol of catalyst X with respect to 1 mol of total hydroxyl groups in pentaerythritol. Preferably it is 0.0005-0.2 mol. By using the catalyst X in an amount of 0.0001 mol or more, the amount of the target component (A) can be increased, and by setting it to 0.5 mol or less, by-products can be generated and the reaction liquid can be colored. It can suppress and the purification process after completion | finish of reaction can be simplified.

1-2-4. Catalyst Y
The catalyst Y is a compound containing zinc.
As the catalyst Y, various compounds can be used as long as they contain zinc, but organic acids zinc and zinc diketone enolate are preferable because of excellent reactivity.
Examples of the organic acid zinc include dibasic acid zinc such as zinc oxalate and a compound represented by the following formula (3).

[In Formula (3), R < ⁶ > and R < ⁷ > are C1-C20 linear or branched alkyl groups, C1-C20 linear or branched alkenyl groups, C6-C24 An aryl group or a C5-C20 cycloalkyl group is meant. 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 the component (A) can be produced.

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

[In Formula (4), R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R < ¹¹ >, R < ¹² > and R < ¹³ > are C1-C20 linear or branched alkyl groups, C1-C20 linear Or a branched alkenyl group, a C6-C24 aryl group, or a C5-C20 cycloalkyl group is meant. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different. ]

Specific examples of the compound containing zinc represented by the above formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octylate, zinc neodecanoate, zinc laurate, zinc myristate, stearin. Examples include zinc oxide, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc t-butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.
In addition, about these compounds containing zinc, when the complex with the hydrate, solvate, or catalyst X exists, this complex with the hydrate, solvate, and catalyst X is also component (A). It can be used as the catalyst Y in the production method.

  Specific examples of the compound containing zinc represented by the above formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, bis (2,6-dimethyl-3,5-heptanedionato) zinc, bis ( 2,2,6,6-tetramethyl-3,5-heptanedionato) zinc, bis (5,5-dimethyl-2,4-hexanedionato) zinc and the like. In addition, about these compounds containing zinc, when the complex with the hydrate, solvate, or catalyst X exists, this complex with the hydrate, solvate, and catalyst X is also component (A). It can be used as the catalyst Y in the production method.

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

  In this invention, these catalysts Y can be used individually or in combination of 2 or more types. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, zinc acetylacetonate are preferable, particularly zinc acetate which shows good reactivity with pentaerythritol and is easily available, Zinc acrylate and zinc acetylacetonate are preferred.

  (A) Although the usage-amount of the catalyst Y in the manufacturing method of a component does not have a restriction | limiting in particular, it is preferable to use 0.0001-0.5 mol of catalyst Y with respect to 1 mol of total hydroxyl groups in pentaerythritol. Preferably it is 0.0005-0.2 mol. By using 0.0001 mol or more of catalyst Y, the production amount of the target component (A) can be increased, and by setting it to 0.5 mol or less, by-product formation and reaction liquid coloring can be achieved. It can suppress and the purification process after completion | finish of reaction can be simplified.

1-2-5. Transesterification Reaction As described above, the production method by the transesterification reaction of component (A) is preferably a production method in which the catalysts X and Y are used in combination as a catalyst. The production method will be described below.

  (A) Although the usage-amount of the catalyst X and the catalyst Y in the manufacturing method of a component does not have a restriction | limiting in particular, It is preferable to use 0.005-10.0 mol of catalyst X with respect to 1 mol of catalyst Y, Preferably it is 0.05-5.0 mol. By using 0.005 mol or more, the production amount of the target (A) component can be increased, and by making it 10.0 mol or less, generation of by-products and coloring of the reaction solution are suppressed, The purification process after completion of the reaction can be simplified.

As a combination of the catalyst X and the catalyst Y used in the present invention, the catalyst X is an azabicyclo compound, the catalyst Y is preferably a compound represented by the formula (3), and the azabicyclo compound is DABCO. A combination in which the compound represented by the formula (3) is at least one compound selected from the group consisting of zinc acetate and zinc acrylate is most preferable.
In addition to being able to obtain the component (A) with good yield, this combination is excellent in color tone after completion of the reaction, and therefore can be suitably used for various industrial applications in which color tone is regarded as important. Furthermore, since the catalyst is available at a relatively low cost, it is an economically advantageous production method.

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

  (A) It is preferable that the reaction temperature in the manufacturing method of a component is 40-180 degreeC, More preferably, it is 60-160 degreeC. By setting the reaction temperature to 40 ° C. or higher, the reaction rate can be increased, and by setting it to 180 ° C. or lower, thermal polymerization of (meth) acryloyl groups in raw materials and products is suppressed, and coloring of the reaction liquid is performed. And the purification process after completion of the reaction can be simplified.

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

  In the manufacturing method of (A) component, the monohydric alcohol derived from monofunctional (meth) acrylate byproduces with progress of transesterification. Although the monohydric alcohol may be allowed to coexist in the reaction system, 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 as 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, 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 Ethers such as tellurium, dimethylcellosolve, diglyme, triglyme and tetraglyme; crown ethers such as 18-crown-6; esters such as methyl benzoate and γ-butyrolactone; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone And ketones such as benzophenone; carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and 1,2-butylene carbonate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; ureas or derivatives thereof Ionic liquids such as phosphine oxides such as tributylphosphine oxide, imidazolium salts, piperidinium salts and pyridinium salts; silicon oil; and water Is mentioned.
Of 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 and carbon dioxide may be introduced into the system for the purpose of maintaining a good color tone of the reaction solution, but a (meth) acryloyl group For the purpose of preventing polymerization of oxygen, an oxygen-containing gas may be introduced into the system. 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 in which the oxygen-containing gas is dissolved in the reaction solution or blown into the reaction solution (so-called bubbling).

In the manufacturing method of (A) component, it is preferable to add a polymerization inhibitor in the reaction liquid for the purpose of preventing the polymerization of the (meth) acryloyl group.
Specific examples of the polymerization inhibitor include hydroquinone, tert-butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-tert -Butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, 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 salt systems such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt A polymerization inhibitor is mentioned.
A polymerization inhibitor may be added individually by 1 type, or may be added in combination of 2 or more types, may be added from the beginning of this invention, and may be added from the middle. Moreover, a desired use amount may be added all at once, or may be added in divided portions. Moreover, you may add continuously via a rectification column.
The addition ratio of the polymerization inhibitor is preferably 5 to 30,000 wtppm in the reaction solution, and more preferably 25 to 10,000 wtppm. By setting this ratio to 5 wtppm or more, the polymerization inhibition effect can be exerted, and by setting it to 30,000 wtppm or less, coloring of the reaction solution can be suppressed, and the purification step after completion of the reaction can be simplified. Moreover, the fall of the cure rate of the (A) component obtained can be prevented.

  Although the reaction time in the manufacturing method of (A) component changes with the kind and usage-amount of a catalyst, reaction temperature, reaction pressure, etc., Preferably it is 0.1 to 150 hours, More preferably, it is 0.5 to 80 hours.

  The method for producing the component (A) can be carried out by any of batch, semi-batch and continuous methods. As an example of a batch system, pentaerythritol, monofunctional (meth) acrylate, a catalyst and a polymerization inhibitor are charged into a reactor, and stirred at a predetermined temperature while bubbling oxygen-containing gas into the reaction solution. Then, it can implement by the method of producing | generating the target (A) component by extracting the monohydric alcohol byproduced with progress of transesterification from a reactor by predetermined | prescribed pressure.

For the reaction product obtained by the method for producing the component (A), it is preferable to carry out a separation / purification operation because the desired component (A) can be obtained with high purity.
Examples of the separation / purification operation include a crystallization operation, a filtration operation, a distillation operation, and an extraction operation, and these are preferably combined. Examples of the crystallization operation include cooling crystallization and concentration crystallization. Examples of the filtration operation include pressure filtration, suction filtration, and centrifugal filtration. Examples of the distillation operation include single distillation, fractional distillation, and molecular distillation. And steam distillation, and the extraction operation includes solid-liquid extraction and liquid-liquid extraction.
A solvent may be used in the separation and purification operation.
Further, a neutralizing agent for neutralizing either or both of the catalyst and polymerization inhibitor used in the present invention, an adsorbing agent for removing by adsorption, and an acid or alkali for decomposing or removing by-products Further, activated carbon for improving the color tone, diatomaceous earth for improving the filtration efficiency and filtration speed, and the like may be used.

2. Curable composition TECHNICAL FIELD This invention relates to the curable composition containing the said (A) component.
As a method for producing the composition, a production method including a step of producing a (meth) acrylate mixture by transesterifying pentaerythritol and a monofunctional (meth) acrylate in the presence of the catalysts X and Y is preferable.
According to the production method, the component (A) having a specific hydroxyl value can be produced in a high yield, and since the high molecular weight product in the component (A) obtained is small, the viscosity becomes low, and the resulting composition is applied. It is preferable in that it can be excellent in workability and leveling properties, and the cured film of the resulting composition can have high hardness.
What is necessary is just to follow the manufacturing method of above-described (A) component as the said process.

What is necessary is just to set suitably as a viscosity of a composition according to the objective.
When the component (A) is used for a preferred application such as a coating agent, an ink and a pattern forming agent, the viscosity of the composition may be appropriately set according to the purpose, and is preferably 1 to 100,000 mPa · s. Preferably, it is 5 to 50,000 mPa · s. By setting it as the said viscosity range, it is excellent in the leveling property at the time of the coating of a composition, and shall be excellent in the external appearance of hardened | cured material.
The viscosity in the present invention means a value measured at 25 ° C. using an E-type viscometer.

Although the composition of this invention can be used for both an active energy ray hardening-type composition and a thermosetting type composition, an active energy ray hardening-type composition is preferable.
The composition of the present invention contains (A) as an essential component, but various components can be blended depending on the purpose.
Specific examples of other components include a photopolymerization initiator (hereinafter referred to as “component (B)”), a thermal polymerization initiator (hereinafter referred to as “component (C)”), and ethylene other than the component (A). And a compound having an unsaturated group (hereinafter referred to as “component (D)”) and an organic solvent (hereinafter referred to as “component (E)”).
Hereinafter, these components will be described.
In addition, the other component mentioned later may use only 1 type of the illustrated compound, and may use 2 or more types together.

2-1. (B) Component 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 does not contain the component (B) (photopolymerization initiator) and is an electron. It can also be cured by a wire.
In the case where 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 active energy rays, the component (B) is further added from the viewpoint of ease of curing and cost. It is preferable to contain.
When an electron beam is used as the active energy ray, it is not always necessary to add it, but a small amount can be added as necessary in order to improve curability.

Specific examples of the component (B) include benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl 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-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- Such as 4-methylbenzyl) -1- (4-morpholin-4-ylphenyl) butan-1-one and 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole Acetophenone compounds;
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-benzoylphenylsulfanyl) 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;
Such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Acylphosphine oxide compounds; and thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2 -Yl-oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and thioxanthone compounds such as fluorothioxanthone.
Examples of the compound other than the above include benzyl, methyl phenylglyoxylate, ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, ethyl anthraquinone, phenanthrenequinone and camphorquinone.

Among these compounds, α-hydroxyphenyl ketones are preferable because they have good surface curability even in the case of thin film coating in the atmosphere. Specifically, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2 -Methyl-1-phenylpropan-1-one is more preferred.
In addition, 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, the purpose of improving the curability inside the cured product, or when using an ultraviolet absorber or a pigment together, Acylphosphines such as (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Oxide compounds, 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-morpholine-4 Yl phenyl) - is preferably used in combination with butan-1-one and the like.

As for the content rate of (B) component, 0.1-10 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.5-8 weight part. (B) By making the ratio of a component into 0.1 weight part or more, the photocurability of a composition can be made favorable and it can be excellent in adhesiveness, and a cured film can be made into 10 weight part or less. The internal curability can be improved, and the adhesion to the substrate can be improved.
In the present invention, the “curable component” is a component that is cured by heat or active energy rays, and means the component (A). When the component (D) described later is blended, (A) and ( D) means a component.

2-2. (C) component When using the composition of this invention as a thermosetting type composition, a thermal-polymerization initiator can be mix | blended.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) 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-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, 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-butylperoxide Id, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 Examples include 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.
Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.

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 in accordance with conventional means of normal radical thermal polymerization. In some cases, it is used in combination with the component (B) (photopolymerization initiator). For the purpose of improving the temperature, thermosetting can also be performed.

2-3. Component (D) The component (D) is an ethylenically unsaturated compound other than the component (A), and is blended for the purpose of imparting various physical properties to the cured product of the composition.
Examples of the ethylenically unsaturated group in component (D) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, and a (meth) allyl group, and a (meth) acryloyl group is preferred.
In the following, “monofunctional” means a compound having one ethylenically unsaturated group, “X function” means a compound having X ethylenically unsaturated groups, and “polyfunctional”. Means a compound having two or more ethylenically unsaturated groups.

In the component (D), specific examples of the monofunctional ethylenically unsaturated compound include compounds similar to the monofunctional (meth) acrylate described above, and include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate and 2-methoxyethyl (meth) acrylate are preferred.
As compounds other than the monofunctional (meth) acrylate described above, (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate , Ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate of alkylene oxide adduct of phenol , (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate of alkylene oxide adduct of alkylphenol (Meth) acrylates of alkylene oxide adducts of paraxamylphenol, orthophenylphenol (meth) acrylates, (meth) acrylates of alkylene oxide adducts of orthophenylphenol, tetrahydrofurfuryl (meth) acrylates, isobornyl (meth) acrylates, Tricyclodecanemethylol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (meth) acryloxyethyl) hexahydrophthalimide, N- (2- (meth) acryloxyethyl) Examples include tetrahydrophthalimide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone and N-vinylcaprolactam.

Examples of the bifunctional ethylenically unsaturated compound include compounds having two (meth) acryloyl groups (hereinafter referred to as “bifunctional (meth) acrylate”).
Specific examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate and nonanediol di (meth). Alkanediol di (meth) acrylates such as acrylates;
Polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate;
Polyols such as di (meth) acrylate of trimethylolpropane, di (meth) acrylate of glycerin, di (meth) acrylate of ditrimethylolpropane, di (meth) acrylate of diglycerin, and di (meth) acrylate of dipentaerythritol Di (meth) acrylate;
Di (meth) acrylate of glycerine alkylene oxide adduct, di (meth) acrylate of pentaerythritol alkylene oxide adduct, di (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, di (meth) of diglycerin alkylene oxide adduct Di (meth) acrylates of polyol alkylene oxide adducts such as di (meth) acrylate of acrylate and dipentaerythritol alkylene oxide adducts; and di (meth) acrylates of bisphenol A alkylene oxide adducts and alkylene oxide additions of bisphenol F And di (meth) acrylate of the product.
In addition, epoxy (meth) acrylate having a bisphenol skeleton, polyether skeleton, polyalkylene skeleton, polyester skeleton, urethane (meth) acrylate having a polyether skeleton or a polycarbonate skeleton, and polyester (meth) acrylate may also be used. Can do.

Examples of the trifunctional or more ethylenically unsaturated compound include compounds having three or more (meth) acryloyl groups [hereinafter referred to as “trifunctional or more (meth) acrylates”].
Examples of the tri- or higher functional (meth) acrylate include various compounds as long as the compound has three or more (meth) acryloyl groups. For example, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) Polyol poly (meth) acrylates such as acrylate, tritrimethylolpropane tri or tetra (meth) acrylate, diglycerin tri or tetra (meth) acrylate, and dipentaerythritol tri, tetra, penta or hexa (meth) acrylate; And tri (meth) acrylate of trimethylolpropane alkylene oxide adduct, tri (meth) acrylate of glycerol alkylene oxide adduct, tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct Ditrimethylolpropane alkylene oxide adduct tri- or tetra (meth) acrylate, diglycerol alkylene oxide adduct tri- or tetra (meth) acrylate, dipentaerythritol alkylene oxide adduct tri-, tetra-, penta- or hexa- ( Poly (meth) acrylates of polyol alkylene oxide adducts such as (meth) acrylates;
Tris (meth) acrylates of isocyanuric acid alkylene oxide adducts; and compounds having 3 or more (meth) acryloyl groups and hydroxyl groups, such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate Examples thereof include urethane (meth) acrylate that is a reaction product with polyisocyanate.

  Examples of the alkylene oxide adduct include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.

(D) It is preferable that the content rate of a component is 0-60 weight% in 100 weight part of total amounts of a sclerosing | hardenable component, More preferably, it is 0-30 weight%.
By making the content rate of (D) component 60 weight% or less, especially when (D) component is a polyfunctional ethylenically unsaturated compound, it can prevent that a cured film becomes weak.

2-4. (E) Component The composition of this invention can contain the organic solvent of (E) component for the purpose of improving the coating property to a base material.

Specific examples of the component (E) include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; benzene and toluene And aromatic compounds such as xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone Can be mentioned.
Among these, alkylene glycol monoether compounds and ketone compounds are preferable, and alkylene glycol monoether compounds are more preferable.

  (E) It is preferable that the content rate of a component is 10-1,000 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component, It is more preferable that it is 50-500 weight part, 50-300 More preferably, it is part by weight. Within the above range, the composition can have a viscosity suitable for coating, and the composition can be easily applied by a known application method described later.

3. Applications The composition of the present invention can be used for various applications such as coating agents, inks, patterning agents, and adhesives, and can be preferably used particularly for coating applications such as hard coats.
Hereinafter, the coating composition will be described.

  The composition of the present invention can be preferably used as a coating composition because the cured film has a high hardness, a low water contact angle, and excellent adhesive wettability.

  The coating composition can be preferably used for hard coat applications, and the substrate is used for plastic films used for touch sensors, plastic films used for polarizer protective films and antireflection films, home appliances and automotive interior and exterior parts. Resin molded products, and the like.

The case where the composition of the present invention is used for a hard coat application of a polarizer protective film (hereinafter simply referred to as “protective film”) will be described.
The protective film can be applied to those usually used, and examples thereof include cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, cyclic polyolefin resins having cyclic olefins such as acrylic resin, polyethylene terephthalate, polycarbonate and norbornene as monomers. .
Silica particles can be blended in the composition to make the cured film an antiglare layer.
Moreover, a cured film of the composition is formed on a protective film, and this is used as the outermost surface of the polarizing plate or as a primer for the protective film, and a cured film is formed between the protective film and the polarizer. Also good.
Specific examples of use as the outermost surface of the polarizing plate include the configuration of a cured film / protective film / adhesive / polarizer, and a cured film / protective film / adhesive / polarizer / adhesive / protective film / cured film. An example of the configuration is given.
Specific examples of use as a primer for a protective film include the configuration of protective film / cured film / adhesive / polarizer, and protective film / cured film / adhesive / polarizer / adhesive / cured film / protective film. An example of the configuration is given.

The coating composition contains the component (A) as an essential component, but various components can be blended depending on the purpose.
Specifically, as other components, in addition to the components (B), (C), (D) and (E) described above, antioxidants, ultraviolet absorbers, pigments / dyes, silane coupling agents, surface modification Examples include a quality agent and a polymer.
Hereinafter, these components will be described.
In addition, the other component mentioned later may use only 1 type of the illustrated compound, and may use 2 or more types together.

3-1. Antioxidant Antioxidant is mix | blended in order to improve durability, such as the heat resistance of a cured film, and a weather resistance.
Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
Examples of the phenolic antioxidant include hindered phenols such as di-t-butylhydroxytoluene. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010 etc. are mentioned.
Examples of sulfur-based antioxidants include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include the combined use of phenolic antioxidants and phosphorus antioxidants, and the combined use of phenolic antioxidants and sulfurous antioxidants.
What is necessary is just to set suitably as content rate of antioxidant according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is.
When the content ratio is 0.1 parts by weight or more, the durability of the composition can be improved. On the other hand, when the content ratio is 5 parts by weight or less, curability and adhesion can be improved.

3-2. Ultraviolet absorber An ultraviolet absorber is mix | blended in order to improve the light resistance of a cured film.
Examples of the UV absorber include triazine UV absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole UV absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
What is necessary is just to set suitably as a content rate of a ultraviolet absorber according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is. When the content ratio is 0.01% by weight or more, the light resistance of the cured film can be improved, and when it is 5% by weight or less, the curability of the composition is excellent. be able to.

3-3. Examples of pigments and dye pigments include organic pigments and inorganic pigments.
Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, benzidine yellow and pyrazolone red; soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet and Permanent Red 2B; Alizarin, Indantron And derivatives from vat dyes such as thioindigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; Isoindolinone organic pigments such as indolinone yellow and isoindolinone orange; pyranthrone organic pigments such as pyranthrone red and pyranthrone orange Thioindigo organic pigments; condensed azo organic pigments; benzimidazolone organic pigments; quinophthalone organic pigments such as quinophthalone yellow; isoindoline organic pigments such as isoindoline yellow; and other pigments such as flavanthrone yellow and acylamide Examples include yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, and dioxazine violet.
Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and oxidation. Examples include chrome green, cobalt green, amber, titanium black, and synthetic iron black. The carbon black exemplified as the filler can also be used as an inorganic pigment.
Various conventionally known compounds can be used as the dye.

3-4. Silane coupling agent A silane coupling agent is mix | blended in order to improve the interface adhesive strength of a cured film and a base material.
The silane coupling agent is not particularly limited as long as it can contribute to improvement in adhesion to the substrate.

  Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, 3-mercaptopropylmethyl Dimethoxysilane, 3-mercaptopropyl trimethoxy silane and the like.

The blending ratio of the silane coupling agent may be appropriately set according to the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component. .
When the blending ratio is 0.1 parts by weight or more, the adhesive strength of the composition can be improved. On the other hand, when the blending ratio is 10 parts by weight or less, it is possible to prevent the adhesive force from changing over time.

3-5. Surface modifier For the composition of the present invention, a surface modifier may be added for the purpose of increasing the leveling property at the time of coating, the purpose of increasing the slipping property of the cured film and improving the scratch resistance, and the like.
Examples of the surface modifier include a surface modifier, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and these known surface modifiers can be used. .
Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, and fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain. And a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
Further, for the purpose of increasing the slidability, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.

  It is preferable that the content rate of a surface modifier is 0.01-1.0 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component. It is excellent in the surface smoothness of a coating film as it is the said range.

3-6. Polymer The composition of the present invention may further contain a polymer for the purpose of further improving the curl resistance of the resulting cured film.
Suitable polymers include (meth) acrylic polymers, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- ( 2- (meth) acryloxyethyl) tetrahydrophthalimide and the like. In the case of a polymer copolymerized with (meth) acrylic acid, glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.
It is preferable that the content rate of a polymer is 0.01-10 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component. It is excellent in the curl resistance of the cured film obtained as it is the said range.

4). Method of Use As a method of using the composition of the present invention, a conventional method may be followed.
For example, after apply | coating a composition to a base material, the method of making it harden | cure by irradiating an active energy ray or heating, etc. are mentioned.
Specifically, after applying the composition to the substrate to be applied by an ordinary coating method, in the case of an active energy ray curable composition, a method of irradiating and curing active energy rays, or a thermosetting composition In the case of a thing, the method of heating and hardening etc. is mentioned. In the case of applications such as molding materials, the composition is injected into a predetermined mold and then cured in the case of an active energy ray curable composition by irradiation with active energy rays, or a thermosetting composition. In the case of a thing, the method of heating and hardening etc. is mentioned.
A general method known as a conventional curing method may be adopted as the active energy ray irradiation method and heating method.
In addition, the component (B) (photopolymerization initiator) and the component (C) (thermal polymerization initiator) are used in combination with the composition, irradiated with active energy rays, and then heat-cured, thereby adhering to the substrate. A method for improving the property can also be adopted.

The substrate to which the composition of the present invention can be applied is applicable to various materials, and examples thereof include plastic, wood, metal, inorganic material, and paper.
Specific examples of plastics include cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, cyclic polyolefin resins having cyclic olefins such as acrylic resin, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene as monomers. , Polyvinyl chloride, epoxy resin, polyurethane resin and the like.
Examples of the wood include natural wood and synthetic wood.
Examples of the metal include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
Examples of inorganic materials include glass, mortar, concrete, and stone.
Among these, a plastic substrate is particularly preferable.

  What is necessary is just to set the film thickness of the composition cured film with respect to a base material suitably according to the objective. The thickness of the cured film may be selected according to the substrate to be used and the use of the substrate having the produced cured film, but is preferably 1 to 500 μm, more preferably 5 to 200 μm. .

  The method of applying the composition of the present invention to the substrate may be appropriately set according to the purpose, and is a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma. Examples of the coating method include a coater, a reverse roll coater, a die coater, a lip coater, a gravure coater, a micro gravure coater, and an ink jet.

Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, and ultraviolet rays are preferred.
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).
Irradiation energy may be appropriately set according to the type and composition of the active energy ray. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region (315 to 380 nm) is 100 to 5 1,000 mJ / cm ² is preferable, and 200 to 1,000 mJ / cm ² is more preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, “parts” means parts by weight.

1. Production example
1) Production Example 1 [Production of Component (A) by Dehydration Esterification Method]
Since nitrogen gas containing 5% by volume of oxygen was not blown into a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a blower, 301 parts (4.18 mol) of acrylic acid, pentaerythritol [Kouei Chemical Co., Ltd. ) Made. Hereinafter, it is referred to as “PE”. 167 parts (1.23 mol), 7 parts of sulfuric acid, 0.14 part of hydroquinone monomethyl ether (hereinafter referred to as “MEHQ”) and 224 parts of toluene were mixed, and the reaction temperature was about 80 ° C. and the conditions were 370 Torr (absolute pressure). The reaction was continued until 45 mol% of all hydroxyl groups in the PE had been esterified while removing the condensed water.
The generated condensed water was 28 parts, and 42 parts of unreacted PE was recovered. After completion of the reaction, 870 parts of toluene was added.
A 20% aqueous sodium hydroxide solution corresponding to a molar amount of 1 times the molar amount of the reaction solution to which toluene was added was added with stirring to carry out a neutralization treatment to remove excess acrylic acid and sulfuric acid. The organic layer was separated, and 10 parts of water was added to 100 parts of the organic layer under stirring, followed by washing with water. The organic layer was separated and heated under reduced pressure to distill off the toluene to obtain 185 parts of a purified product.
As a result of HPLC analysis of the purified product, it was confirmed that pentaerythritol monoacrylate, pentaerythritol diacrylate (hereinafter referred to as PEDA), pentaerythritol triacrylate, and pentaerythritol tetraacrylate were contained.
The PEDA content in the purified product thus obtained was 21 area%, the hydroxyl value was 204 mgKOH / g, and the viscosity was 570 mPa · s (hereinafter referred to as “DE-PETAl”). The results are shown in Table 1.

◆ HPLC measurement conditions / HPLC apparatus: LC10AD [manufactured by Shimadzu Corporation]
Column: Reversed-phase silica column for HPLC (Sunwater C18 manufactured by Japan Waters Co., Ltd., particle size 3.5 μm, 4.6 mm × 20 mm)
-Column temperature: 40 ° C
Eluent composition: 0.015 wt% phosphoric acid aqueous solution / methanol = 50/50 (0-25 minutes) → 30/70 (25-30 minutes) → 0/100 (30-45 minutes)
・ UV detector: wavelength 210nm
・ Flow rate: 0.8mL / min

◆ Method for measuring hydroxyl value Add an acetylating reagent to the sample and heat-treat in a warm bath at 92 ° C for 1 hour. After standing to cool, a small amount of water is added and heat-treated in a warm bath at 92 ° C. for 10 minutes. After allowing to cool, the hydroxyl value was determined by titrating the acid with a potassium hydroxide ethanol solution using a phenolphthalein solution as an indicator.

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

2) Production Example 2 [Production of Component (A) by Dehydration Esterification Method]
Condensed water was used under the same conditions as in Raw Material Production Example 1 except that 301 parts (4.18 mol) of acrylic acid, 167 parts (1.23 mol) of PE, 7 parts of sulfuric acid, 0.14 part of MEHQ and 224 parts of toluene were used. While removing, the reaction was continued until 30% of all hydroxyl groups in the PET were esterified.
The generated condensed water was 18 parts, and 83.5 parts of unreacted PE was recovered. After completion of the reaction, 870 parts of toluene was added.
By the same operation as in Production Example 1, the same amount of aqueous sodium hydroxide solution and water were used for neutralization treatment and water washing treatment, and then toluene was distilled off to obtain 120 parts of a purified treated product.
The purified product obtained had a PEDA content of 23 area%, a hydroxyl value of 224 mgKOH / g, and a viscosity of 630 mPa · s (hereinafter referred to as “DE-PET A2”). The results are shown in Table 1.

3) Production Example 3 [Production of Component (A) by Dehydration Esterification Method]
Condensation under the same conditions as in Raw Material Production Example 1 except that 301 parts (4.18 moles) of acrylic acid, 167 parts (1.23 moles) of PE, 7 parts of sulfuric acid, 0.14 parts of MEHQ and 224 parts of toluene are used. While removing water, the reaction was continued until 15% of all hydroxyl groups in the PET were esterified.
The generated condensed water was 10 parts, and 101 parts of unreacted PE was recovered. After completion of the reaction, 870 parts of toluene was added.
By the same operation as in Production Example 1, the same amount of aqueous sodium hydroxide solution and water were used for neutralization treatment and water washing treatment, and then toluene was distilled off to obtain 50 parts of a purified product.
The purified product obtained had a PEDA content of 29 area%, a hydroxyl value of 240 mg KOH / g, and a viscosity of 678 mPa · s (hereinafter referred to as “DE-PET A3”). The results are shown in Table 1.

4) Production Example 4 [Production of Component (A) by Dehydration Esterification Method]
Since 5% by volume oxygen-containing nitrogen gas was not blown into the same flask as in Production Example 1, 1163 parts (16.2 moles) of acrylic acid, 732 parts (5.4 moles) of PE, and p-toluenesulfonic acid (29 parts) Then, cupric chloride (4 parts) was mixed, and all the water in PE was removed without removing condensed water under the conditions of reaction temperature of about 90 ° C., external temperature of 102 ° C., internal / external temperature difference ΔT 12 ° C., and 101 kPa (absolute pressure). The reaction was continued until 48% of the hydroxyl groups were esterified.
After completion of the reaction, the reaction mixture was cooled and a 20% aqueous sodium hydroxide solution (32 parts) was added to the reaction solution to neutralize the strong acid catalyst.
Put the reaction liquid (1,959 parts) into a separatory funnel, then add cyclohexane (600 parts), methyl ethyl ketone (2,400 parts), and further water (1,250 parts), mix, and leave the liquid to stand. Separation was performed and the lower layer was extracted to separate the organic phase. Next, an equimolar amount of 20% aqueous sodium hydroxide solution (840 parts) was added with stirring to the acid content of the organic phase to carry out neutralization treatment. The organic phase was separated and washed with water. After washing with water, the organic phase was separated again and heated under reduced pressure to distill off the solvent to obtain 874 parts of a purified product.
The purified product obtained had a PEDA content of 36 area%, a hydroxyl value of 280 mg KOH / g, and a viscosity of 799 mPa · s (hereinafter referred to as “DE-PET A4”). The results are shown in Table 1.

5) Production Example 5 (Production of component (A) by transesterification method)
In a 1-liter flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectifying column and a cooling tube, 90.24 parts (0.66 mol) of pentaerythritol and 621.04 parts of 2-methoxyethyl acrylate ( 4.77 mol), 0.85 parts (0.01 mol) of N-methylimidazole as catalyst X, 2.16 parts (0.01 mol) of zinc acrylate as catalyst Y, 0.30 of hydroquinone monomethyl ether Parts (413 wtppm with respect to the total weight of the charged raw materials) were charged, and oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid.
2-methoxyethanol and 2-methoxyethyl acrylate by-produced as the transesterification progresses while adjusting the pressure in the reaction system in the range of 120-760 mmHg while heating and stirring the reaction liquid at a temperature of 105-130 ° C. Was extracted from the reaction system via a rectification column and a cooling tube. Further, 2-methoxyethyl acrylate in the same weight part as the extracted liquid was added to the reaction system as needed. 18 hours after the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the extraction was completed. After cooling the reaction liquid to room temperature, 40.0 parts of aluminum silicate (Kyowa Kagaku Co., Ltd. Kyodo 700 (trade name)) and activated carbon (Futamura Chemical Co., Ltd. Taiko S (trade name)) are used for the filtrate. ) Was added, and the mixture was heated and stirred at an internal temperature of 95 to 105 ° C. under normal pressure for 3 hours. After separating the solids by pressure filtration, vacuum distillation was performed for 8 hours at a temperature of 70 to 95 ° C. and a pressure of 0.001 to 100 mmHg while bubbling dry air through the filtrate, and unreacted 2-methoxy A distillate containing ethyl acrylate was separated. 2.0 parts of diatomaceous earth (Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.) was added to the kettle and subjected to pressure filtration, and the obtained filtrate was used as a purified product.
The yield of the purified product obtained was 70%, the PEDA content was 17 area%, the hydroxyl value was 200 mgKOH / g, and the viscosity was 421 mPa · s (hereinafter referred to as “EX-PETA5”). The results are shown in Table 1.
The purification yield of component (A) by the transesterification method is that of pentaerythritol obtained after subjecting the reaction product after the transesterification reaction to separation and purification operations such as distillation, crystallization and filtration. It calculated using the mass of the refinement | purification processed material containing an acrylated product.
Purification yield (%) = Purified product containing acrylated pentaerythritol (part) / (Molecular weight of pentaerythritol tetraacrylate × Mole number of pentaerythritol used as raw material) × 100

6) Production Example 6 (Production of component (A) by transesterification method)
The component (A) was produced in the same manner as in Production Example 5, except that the compounds shown in Table 1 below were used as the catalyst and the heating and stirring time for the transesterification reaction was 15 hours.
The yield of the purified product obtained was 69%, the PEDA content was 18 area%, the hydroxyl value was 205 mgKOH / g, and the viscosity was 432 mPa · s (hereinafter referred to as “EX-PETA6”). The results are shown in Table 1.

7) Production Example 7 (Production of component (A) by transesterification method)
The component (A) was produced in the same manner as in Production Example 5, except that the compounds shown in Table 1 below were used as the catalyst and the heating and stirring time for the transesterification reaction was 15 hours.
The yield of the purified product obtained was 60%, the PEDA content was 24 area%, the hydroxyl value was 261 mgKOH / g, and the viscosity was 539 mPa · s (hereinafter referred to as “EX-PETA7”). The results are shown in Table 1.

8) Production Example 8 (Production of component (A) by transesterification method)
The component (A) was produced in the same manner as in Production Example 5 except that the compounds shown in Table 1 below were used as the catalyst and the heating and stirring time for the transesterification reaction was 13 hours.
The yield of the purified product obtained was 56%, the PEDA content was 26 area%, the hydroxyl value was 284 mgKOH / g, and the viscosity was 556 mPa · s (hereinafter referred to as “EX-PETA8”). The results are shown in Table 1.

9) Production Example 9 (Production of Component (A) by Transesterification Method)
The component (A) was produced in the same manner as in Production Example 5 except that the compounds shown in Table 1 below were used as the catalyst and the heating and stirring time for the transesterification reaction was 10 hours.
The yield of the purified product obtained was 67%, the PEDA content was 33 area%, the hydroxyl value was 342 mgKOH / g, and the viscosity was 733 mPa · s (hereinafter referred to as “EX-PETA9”). The results are shown in Table 1.

Table 1 also shows the acrylate mixture of pentaerythritol used in the comparative example. The abbreviations mean the following:
M305: Mixture mainly composed of pentaerythritol triacrylate (PEDA content 2 area%, hydroxyl value 115 mgKOH / g, viscosity 610 mPa · s), ARONIX M-305 manufactured by Toagosei Co., Ltd.
M306: Mixture mainly composed of pentaerythritol triacrylate (PEDA content: 8 area%, hydroxyl value: 154 mgKOH / g, viscosity: 692 mPa · s), Aronix M-306 manufactured by Toagosei Co., Ltd.
HCPK: 1-hydroxycyclohexyl phenyl ketone, IRGACURE184 manufactured by BASF

  Compared with the almost same hydroxyl value, the acrylate mixtures obtained by the transesterification methods of Production Examples 5 to 8 are lower in viscosity than the acrylate mixtures obtained by Dehydration Esterification of Production Examples 1 to 4. Met.

2. Examples and Comparative Examples
1) Production of active energy ray-curable composition The compounds shown in Table 2 below were stirred and mixed in the proportions shown in Table 2 to produce an active energy ray-curable composition.
The obtained composition was used and evaluated as described later. Further, the viscosity of the composition was measured according to the same method as described above. The results are shown in Table 2.
The numbers in Table 2 mean the number of copies. The abbreviations in Table 2 are as described above.

2) Evaluation method
(1) Pencil hardness The obtained composition was applied to a polyethylene terephthalate film [manufactured by Toyobo Co., Ltd., Cosmo Shine A4300 (thickness: 100 μm)] with a bar coater so as to have a film thickness of 5 μm.
Using the high-pressure mercury lamp manufactured by iGraphics Co., Ltd., the obtained test specimen was irradiated with an irradiation energy of 800 mJ / cm ² per pass at an ultraviolet region (UV-A) intensity of 500 mW / cm ² centered at 365 nm. In the conveyor adjusted so that it might become, it conveyed in the air atmosphere and irradiated with the ultraviolet-ray.
According to JISK5600-5-4, the pencil hardness of the obtained cured film was evaluated under a load of 750 g.

(2) About the cured film obtained by the same method as water contact angle (1), the water contact angle was measured at a room temperature of 23 ° C. and 50% RH using a contact angle measuring device [SCA20 manufactured by Eihiro Seiki Co., Ltd.]. Under the environment, the measurement was performed with a dropping amount of 4 microliters.

As is clear from the results of Examples 1 to 9, the composition of the present invention is cured because the PEDA content in the component (A) is 15 to 40 area% and the hydroxyl value is 190 to 400 mgKOH / g. The film had a high hardness, a low water contact angle, and excellent adhesive wettability.
When the (A) components having substantially the same hydroxyl value are compared with each other, as shown below, the compositions of Examples 1 to 4 containing the component (A) obtained by dehydration esterification are obtained by the transesterification method. In Examples 5 to 8 including the obtained component (A), the viscosity was low.
Example 1 (204 mgKOH / g): 480 mPa · s
Example 5 (200 mgKOH / g): 357 mPa · s, Example 6 (205 mgKOH / g): 366 mPa · s
Example 4 (280 mgKOH / g): 671 mPa · s, Example 8: (284 mgKOH / g): 469 mPa · s
On the other hand, the compositions of Comparative Examples 1 and 2 have a PEDA content in the component (A) of less than 15% by area and a hydroxyl value of less than 190 mgKOH / g. Also, the water contact angle of the cured film was high.

  The composition of the present invention can be preferably used as an active energy ray-curable composition, and can be used for various applications such as coating agents, inks, pattern forming agents and adhesives. In particular, it can be preferably used for coating applications.

Claims (14)

  Pentaerythritol di (meth) acrylate as a value obtained by high performance liquid chromatographic analysis using a reverse phase silica column and using an aqueous solution of phosphoric acid / methanol as an eluent. A curable composition comprising a mixture (A) having a content of 15 to 40 area% and a hydroxyl value of 190 to 400 mgKOH / g.   The curable composition according to claim 1, wherein the component (A) is a mixture of (meth) acrylate obtained by transesterification of a compound having pentaerythritol and one (meth) acryloyl group. 3. The (A) component is a mixture of (meth) acrylates obtained by transesterification of a compound having pentaerythritol and one (meth) acryloyl group in the presence of the following catalysts X and Y. The curable composition described in 1.
Catalyst X: One or more selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex thereof Compound.
Catalyst Y: Compound containing zinc. The curable composition according to claim 3, 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, an amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof.   The curable composition according to any one of claims 2 to 4, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate.   The curable composition according to any one of claims 3 to 5, wherein the catalyst Y is a compound selected from the group consisting of an organic acid zinc and a zinc diketone enolate.   The active energy ray hardening-type composition containing the composition of any one of Claims 1-6.   Furthermore, the active energy ray hardening-type composition of Claim 7 containing a photoinitiator (B).   The active energy ray hardening-type composition for coating containing the composition of Claim 7 or Claim 8. A compound having pentaerythritol and one (meth) acryloyl group is transesterified in the presence of the following catalysts X and Y,
Pentaerythritol di (meth) acrylate as a value obtained by high performance liquid chromatographic analysis using a reverse phase silica column and using an aqueous solution of phosphoric acid / methanol as an eluent. Mixture (A) having a content of 15 to 40% by area and a hydroxyl value of 190 to 400 mgKOH / g
The manufacturing method of the curable composition including the process of manufacturing.
Catalyst X: One or more selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex thereof Compound.
Catalyst Y: Compound containing zinc. The method for producing a curable composition according to claim 10, 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, an amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof.   The method for producing a curable composition according to claim 10 or 11, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate.   The method for producing a curable composition according to any one of claims 10 to 12, wherein the catalyst Y is a compound selected from the group consisting of an organic acid zinc and a zinc diketone enolate.   (A) The manufacturing method of the curable composition of any one of Claims 10-13 including the process of mixing a photoinitiator (B), after manufacturing a component.