TW201800381A - Curable composition - Google Patents

Abstract

An object of the present invention is to provide a curable composition that can make a cured layer having high hardness, and that has low water contact angle and excellent wettability by an adhesive, and a method for producing the same. The curable composition of the present invention includes a mixture of (meth)acrylates of pentaerythritol, wherein the content of pentaerythritol di(meth)acrylate in the mixture measured by high performance liquid chromatography using a reversed phase silica column and aqueous phosphoric acid/methanol type mobile phase is 15 to 40 area %, and the mixture has a hydroxy value of 190 to 400 mgKOH/g.

Description

Hardened composition

The present invention relates to a curable composition, preferably an active energy ray curable composition. The composition of the present invention can be used for various applications such as coating agents for hard coats, inks for inkjet printing, pattern forming agents and adhesives for photosensitive lithographic printing plates, color resists, etc., especially It is preferable to use it as a coating agent, which belongs to these technical fields.

In addition, in this specification, any one or both of an acryloyl group and a methacryloyl group is represented by (meth) acryloyl group, and any one of acrylate and methacrylate Either or both are represented by (meth) acrylate, and either or both of acrylic acid and methacrylic acid are represented by (meth) acrylic acid.

As for the active energy ray-curable composition, a composition containing a compound having two or more (meth) acryloyl groups is used in various applications, especially neopentyl tetraol triacrylate and neopentyl tetraol A mixture of tetraacrylates (hereinafter referred to as "PETTA") as a main component is used for various purposes due to its excellent physical properties.

For example, it is known that a composition containing PETTA has high surface hardness and good adhesion to acrylic adhesives. As a hard coating agent for plastic films used in touch sensors of touch panel type image display devices (Patent Document 1).

Prior technical literature Patent Literature

Patent Literature 1 Japanese Patent Application Publication No. 2013-155219

However, the previous cured film containing PETTA has a problem of insufficient wettability of the adhesive such as an ultraviolet-curable adhesive (Optically Clear Resin: hereinafter, referred to as "OCR") due to the high water contact angle.

The inventors of the present invention conducted an in-depth review in order to develop a curable composition, preferably an active energy ray curable composition, which has a high hardness of a cured film, a low water contact angle, and excellent wettability of an adhesive such as OCR.

The inventors of the present invention conducted various reviews based on the concept of whether PETTA having a higher hydroxyl value can solve the aforementioned problem.

As a result, a hardening type composition was found, which is a (meth) acrylate mixture of neopentyl alcohol, which contains a mixture having a specific content of neopentyl alcohol diacrylate and hydroxyl value, in addition to the high hardness of the hardened film The contact angle of water is low, and the wettability of the adhesive is excellent, so the present invention has been completed.

Hereinafter, the present invention will be described in detail.

According to the present invention, in addition to the high hardness of the cured film, the water contact angle is low, and a hardened composition excellent in the wettability of adhesives such as OCR can be provided.

[Appearance for implementing invention]

The present invention relates to a hardening type composition comprising a mixture (A), which is a mixture of (meth) acrylates of neopentyl alcohol, wherein the content of neopentyl alcohol diacrylate is determined by The value obtained by high-speed liquid chromatography (hereinafter referred to as "HPLC") analysis is 15 to 40 area%, and the hydroxyl value of the mixture (A) is 190 to 400 mgKOH / g.

Hereinafter, the component (A), the curable composition, the use, and the method of use will be described.

1. (A) Ingredients

(A) The component is a mixture of (meth) acrylic esters of neopentaerythritol, and the content of neopentaerythritol di (meth) acrylates (hereinafter referred to as "PEDM") is obtained by HPLC analysis In terms of value, it is 15 to 40 area%, and the hydroxyl value of the component (A) is 190 to 400 mgKOH / g.

(A) "(Meth) acrylate mixture of neopentaerythritol" in the ingredients means mono (meth) acrylate and di (meth) acrylate of neopentaerythritol (PEDM), a mixture of tri (meth) acrylate and tetra (meth) acrylate.

(A) The hydroxyl value of the component is 190 ~ 400mgKOH / g, preferably 200 ~ 380mgKOH / g, more preferably 200 ~ 360mgKOH / g.

If 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 poor. On the other hand, if the hydroxyl value of the component (A) exceeds 400 mgKOH / g, the compatibility with other components becomes poor.

Furthermore, in the present invention, "hydroxyl value" means the number of milligrams of potassium hydroxide equivalent to the hydroxyl group in 1 g of the sample.

In the present invention, the content of PEDM in the component (A) is preferably 15 to 40% by area in terms of the value of HPLC analysis using a reverse-phase silicone column and a phosphoric acid aqueous solution / methanol-based eluate, and more preferably It is preferably 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 poor. When it exceeds 40 area%, the compatibility with other components may be deteriorated.

The more detailed definition of the case of measuring the content of PEDM in the component (A) means a value measured using HPLC under the following conditions.

. Device: HPLC (High Speed Liquid Chromatography)

. Type of column: reverse phase silicone rubber column for HPLC (silica gel modified with C 18 alkyl group, particle size: 3.5μm, 2.1mm × 50mm)

. Column temperature: 40 ℃

. Composition of eluate: 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 ratio of (A) component to high molecular weight body is small, the obtained (A) component can be adjusted to a low viscosity, and the cured film of the obtained composition can be further adjusted to a high hardness This is preferable.

The ratio of the high molecular weight body in this case is measured by gel permeation chromatography (hereinafter, referred to as "GPC"), and the area% of the high molecular weight body obtained can be expressed by the following formula (P1).

Area of high molecular weight% = [(R-I-L) / R] × 100… (P1)

The symbols and terms in formula (P1) have the following meanings.

. R: (A) the total area of the detected peak in the component

. I: Area of detection peaks including PEDM, neopentaerythritol tri (meth) acrylate and neopentaerythritol tetra (meth) acrylate

. L: The weight-average molecular weight (hereinafter referred to as "Mw") is smaller than the detection peaks including PEDM, neopentaerythritol tri (meth) acrylate, and neopentaerythritol tetra (meth) acrylate. Total area of detected peaks

In the present invention, Mw means a value converted from polystyrene molecular weight based on the molecular weight measured by GPC using tetrahydrofuran (hereinafter, referred to as "THF") as a solvent.

In addition, the molecular weight measured by GPC in this invention means the value measured under the following conditions.

. Detector: Differential refractometer (RI detector)

. Types of columns: cross-linked polystyrene columns

. Column temperature: within the range of 25 ~ 50 ℃

. Eluent: THF

(A) As a component, the compound obtained by the dehydration esterification reaction of neopentyl alcohol and (meth) acrylic acid, and the compound which makes neopentyl alcohol and a (meth) acryloyl group [hereinafter, said "Monofunctional (meth) acrylate"] Any of the compounds obtained by transesterification.

As for the component (A), the compound obtained by transesterification of neopentaerythritol with a monofunctional (meth) acrylate can produce the aforementioned component (A) having a specific hydroxyl value with high yield, and The obtained (A) component has few high molecular weight bodies, and is preferable from the viewpoint of low viscosity and high hardness of the cured film of the obtained composition.

1-1. Dehydration esterification reaction

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

As the (meth) acrylic acid used in the dehydration esterification reaction, either acrylic acid or methacrylic acid, or both acrylic acid and methacrylic acid may be used, however, it is preferred to use only acrylic acid.

In addition, in the production of the component (A), (meth) acryloyl halide, (meth) acrylic anhydride, or the like may be used as the (meth) acrylic acid equivalent instead of (meth) acrylic acid.

In the case where the component (A) is produced by the dehydration esterification reaction of neopentyl alcohol and (meth) acrylic acid, the use ratio of (meth) acrylic acid is as long as the The hydroxyl value may be 190 to 400 mgKOH / g, and is not particularly limited.

The molar amount of (meth) acrylic acid used is preferably less than the molar amount of the hydroxyl groups of neopentyl alcohol used. The total molar number of the hydroxyl groups of neopentyl alcohol is 0.75 to 1.25 Ear equivalent is preferred, with 0.85 to 1.15 molar equivalent being more preferred.

The method of producing the component (A) is not particularly limited, and a well-known dehydration esterification reaction can be used, however, it is preferable to use a catalyst or a stabilizer.

As for the catalyst, an acid catalyst is preferably mentioned.

Moreover, as a stabilizer, a well-known polymerization inhibitor, such as hydroquinone monomethyl ether, is preferable. Moreover, oxygen can also be used as a stabilizer, especially a polymerization inhibitor. For example, by manufacturing the (A) component in an oxygen-containing environment, unnecessary polymerization of (meth) acrylic acid or (meth) acrylate can be prevented. In addition, the content ratio of oxygen in the environment is preferably 1 to 20% by volume, and more preferably 1 to 10% by volume.

In addition, the method of manufacturing the component (A) preferably includes a method of refining at least liquid-liquid extraction (liquid separation). With the above-mentioned aspect, the compound having a hydroxyl value of 190 to 400 mgKOH / g can be easily produced.

1-2. Transesterification reaction

The component (A) can also be produced by transesterification of neopentaerythritol and monofunctional (meth) acrylate in the presence of a transesterification catalyst.

If the transesterification reaction of neopentaerythritol and monofunctional (meth) acrylate using the aforementioned catalysts X and Y is compared with the dehydration esterification reaction of neopentaerythritol and (meth) acrylic acid, because ( A) The polymer in the composition The volume is small, the viscosity is low, and there are few impurities. Therefore, the aforementioned multifunctional (meth) acrylate mixture having excellent physical properties can be produced.

Hereinafter, the method for producing the monofunctional (meth) acrylate, catalyst X, catalyst Y, and (A) component will be described.

1-2-1. Monofunctional (meth) acrylate

The monofunctional (meth) acrylate used as the raw material of the component (A) is a compound having one (meth) acryloyl group in the molecule, and examples thereof include compounds represented by the following formula (1).

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, ethyl, n- or isopropyl, n-, iso-or tertiary butyl, n-, secondary or tertiary pentyl, and neopentyl Radical, normal, secondary or tertiary hexyl, normal, secondary or tertiary heptyl, normal, secondary or tertiary octyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, Lauryl, thirteen, myristyl, fifteen, cetyl, heptadecyl, stearyl, nineteen, aralkyl, 26, 30, beesyl, vinyl, Allyl, methallyl, crotonyl, 1,1-dimethyl-2propenyl, 2-methylbutenyl, 3-methyl-2-butenyl, 3-methyl-3 -Butenyl, 2-methyl-3-butenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, deca Dienyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, oleoyl, linoleoyl, linoleyl, cyclopentyl, cyclopentylmethyl Group, cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, 4-tertiary butylcyclohexyl, tricyclodecyl, isobornyl, adamantyl Dicyclopentyl, dicyclopentenyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-tertiary butylphenyl, benzyl, diphenylmethyl, di Phenylethyl, triphenylmethyl, cinnamyl, naphthyl, anthracenyl, methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methyl Oxybutyl, ethoxyethyl, ethoxyethoxyethyl, cyclopentyloxyethyl, cyclohexyloxyethyl, cyclopentyloxyethoxyethyl, cyclohexyloxyethoxy Ethyl, dicyclopentenyloxyethyl, phenoxyethyl, phenoxyethoxyethyl, glycidyl, β-methylglycidyl, β-ethylglycidyl, 3 , 4-epoxycyclohexylmethyl, 2-oxetanylmethyl, 3-methyl-3-oxetanylmethyl, 3-ethyl-3-oxetanylmethyl, tetrahydrofuranyl, tetrahydrofurfuryl Group, tetrahydropiperanyl, dioxolyl, dioxanyl, N, N-dimethylaminoethyl, N, N-diethylaminoethyl, N, N-di Methylaminopropyl, N, N-diethylaminopropyl, N-benzyl-N-methylaminoethyl, N-benzyl-N-methylaminopropyl Wait.

As far as R ^{2 is} concerned, among these functional groups, methyl, ethyl, propyl, pentyl, butyl, heptyl, octyl, heptyl and 2-ethylhexyl have a carbon number of 1 to 8. Alkyl; alkoxyalkyl such as 2-methoxyethyl, 2-ethoxyethyl and 2-methoxybutyl; N, N-dimethylaminoethyl, N, N-di Dialkylamino groups such as ethylaminoethyl, N, N-dimethylaminopropyl, and N, N-diethylaminopropyl are preferred.

In the present invention, these monofunctional (meth) acrylates can be used alone or in any combination of two or more.

Among these monofunctional (meth) acrylates, preferred are methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate Alkyl (meth) acrylate such as ester and 2-ethylhexyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms, 2-methoxyethyl acrylate, etc. Alkyl esters and N, N-dimethylaminoethyl (meth) acrylate, especially showing good reactivity with neopentyl alcohol, easy to obtain (meth) acrylic acid with a C 1-4 alkyl group The ester and the alkoxyalkyl (meth) acrylate having a C 1-2 alkyl group are more preferable.

Furthermore, in order to promote the dissolution of neopentaerythritol, alkoxyalkyl (meth) acrylate having a C 1-2 alkyl group exhibiting very good reactivity is more preferable, and (meth) acrylic acid 2- Methoxyethyl is particularly preferred.

Furthermore, monofunctional (meth) acrylates are particularly preferred because of their excellent reactivity.

(A) The use ratio of neopentyl alcohol to monofunctional (meth) acrylate in the production method of the component is not particularly limited, but the total amount of hydroxyl groups in neopentyl alcohol is 1 mole, so that the monofunctional ( It is better to adjust the meth) acrylate to 0.4 to 10.0 moles, and more preferably to 0.6 to 5.0 moles. By adjusting the monofunctional (meth) acrylate to 0.4 mole or more, the side reaction can be suppressed. In addition, if it is adjusted to 10.0 mol or less, the amount of component (A) produced can be increased to improve productivity.

1-2-2. Catalyst

As the transesterification catalyst in the production method of the component (A), for example, tin-based catalysts, titanium-based catalysts, sulfuric acid, and the like can be used.

In the present invention, from the viewpoint of efficiently and efficiently producing the component (A), it is preferable to use the following catalysts X and Y together as a catalyst.

Catalyst X: selected from cyclic tertiary amines having a azabicyclic structure or salts or complexes thereof (hereinafter, referred to as "azabicyclic system compounds"), amidine or salts or complexes thereof (hereinafter, It is called "amidine compound", a compound having a pyridine ring or its salt or complex (hereinafter, referred to as "pyridine compound"), and a phosphine or its salt or complex (hereinafter, referred to as "phosphine") More than one compound in the group of "compounds")

Catalyst Y: 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 azabicyclic compounds, amidine-based compounds, pyridine-based compounds, and phosphine-based compounds.

For catalyst X, among the aforementioned compound groups, one or more compounds selected from the group consisting of azabicyclic compounds, amidine-based compounds, and pyridine-based compounds are preferred. These compounds have excellent catalyst activity and can preferably produce component (A). After the reaction is completed, they form a complex with the catalyst Y described later. Since the complex is difficult to dissolve in the reaction solution, it can be borrowed It is easily removed from the reaction liquid after the reaction by simple methods such as filtration and adsorption. In particular, the nitrogen heterocyclic compound is difficult to dissolve in the reaction solution due to the complex with the catalyst Y, and can be more easily removed by filtration, adsorption, and the like.

On the other hand, although the phosphine-based compound is excellent in catalyst activity, it is difficult to form a complex with the catalyst Y, or in the case of forming a complex, it is easily soluble in the reaction solution, because most of it dissolves at the end of the reaction In the subsequent reaction liquid, it is difficult to remove from the reaction liquid by simple methods such as filtration and adsorption.

啶(quinolizidine)、3-羥基奎寧環、3-奎寧酮、喹核(quincorine)、喹核醇(quincoridine)、辛可尼丁(cinchonidine)、辛可寧(cinchonine)、奎尼丁(quinidine)、奎寧(quinine)、銅色樹鹼(cupreine)、伊博格鹼(ibogain)、苦馬豆素(swaisonin)、栗籽豆精胺(castanospermine)、米安色林(mianserin)、米氯平(mirtazapine)、坎那定(canadine)、朝格氏鹼(Tröger’s base)、1-氮雜雙環[2.2.2]辛-3-羧酸、三伸乙基二胺(別名：1,4-二氮雜雙環[2.2.2]辛烷，以下，稱為「DABCO」)、六亞甲基四胺、3-喹啉啶酮鹽酸鹽、3-氯-1-氮雜雙環[2.2.2]辛烷鹽酸鹽、辛可尼丁二鹽酸鹽、辛可寧鹽酸鹽水合物、辛可尼丁硫酸鹽二水合物、氫奎尼丁鹽酸鹽、辛可寧硫酸鹽二水合物、奎寧鹽酸鹽二水合物、硫酸奎寧二水合物、奎寧磷酸鹽、奎尼丁硫酸鹽二水合物、米安色林鹽酸鹽、1,1’-(丁-1,4-二基)雙[4-氮雜-1-氮鎓雙環[2.2.2]辛烷]二溴化物、1,1’-(癸-1,10-二基)雙[4-氮雜-1-氮鎓雙環[2.2.2]辛烷]二溴化 物、雙(三甲基鋁)-1,4-二氮雜雙環[2.2.2]辛烷加成物、氫化鉍(bismuthine)、奎寧環鹽酸鹽、3-奎寧酮鹽酸鹽、3-羥基奎寧環鹽酸鹽、DABCO鹽酸鹽、奎寧環乙酸鹽、3-奎寧酮乙酸鹽、3-羥基奎寧環乙酸鹽、DABCO乙酸鹽、奎寧環丙烯酸鹽、3-奎寧酮丙烯酸鹽、3-羥基奎寧環丙烯酸鹽、DABCO丙烯酸鹽等。 Specific examples of azabicyclic compounds include 1-azabicyclo [1.1.0] butane, 1,3-diazabicyclo [1.1.0] butane, and 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 Alkanes, 1,3-diazabicyclo [2.2.0] hexane, 1-azabicyclo [2.1.1] hexane, 1,3-diazabicyclo [2.1.1] hexane, 1-nitrogen Heterobicyclo [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 [3.2.0] 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-aza Bicyclo [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-diazabicyclo [4.2.0] octane, 1,4-diazabicyclo [4.2.0] octane, 1,5-bis Azabicyclo [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-diaza Heterobicyclo [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- Diaza Cyclo [5.2.0] nonane, 1,3-diazabicyclo [5.2.0] nonane, 1,4-diazabicyclo [5.2.0] nonane, 1,5-diazabicyclo [ 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] nonane, 1,8-diazabicyclo [6.1.0] non Alkanes, 1-azabicyclo [7.1.0] decane, 1,9-diazabicyclo [7.1.0] decane, 1-azabicyclo [6.2.0] decane, 1,8-diaza Heterobicyclo [6.2.0] decane, 1-azabicyclo [6.1.1] decane, 1,8-diazabicyclo [6.1.1] decane, 1-azabicyclo [5.3.0] decane Alkanes, 1,7-diazabicyclo [5.3.0] decane, 1-azabicyclo [5.2.1] decane, 1,7-diazabicyclo [5.2.1] decane, 1-nitrogen Heterobicyclic [ 4.3.1] Decane, 1,6-diazabicyclo [4.3.1] decane, 1-azabicyclo [4.2.2] decane, 1,6-diazabicyclo [4.2.2] decane Alkane, 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, lupinane, lupinine (lupinine), quin

Quinolizidine, 3-hydroxyquinine ring, 3-quininone, quincorine, quincoridine, quincoridine, cinchonidine, cinchonine, quinidine ( quinidine, quinine, cupreine, ibogain, swaisonin, castanospermine, mianserin, Mirtazapine, canadine, Tröger's base, 1-azabicyclo [2.2.2] octan-3-carboxylic acid, triethylidene diamine (alias: 1 , 4-diazabicyclo [2.2.2] octane, hereinafter referred to as "DABCO"), hexamethylenetetramine, 3-quinolinidone hydrochloride, 3-chloro-1-azabicyclo [2.2.2] Octane hydrochloride, cinchonidine dihydrochloride, cinchonine hydrochloride hydrate, cinchonidine sulfate dihydrate, hydroquinidine hydrochloride, cinchonine sulfate Salt dihydrate, Quinine hydrochloride dihydrate, Quinine sulfate dihydrate, Quinine phosphate, Quinidine sulfate dihydrate, Mianserin hydrochloride, 1,1 '-(D -1,4-diyl) bis [4-aza-1-azonium bicyclo [2.2.2] octane] dibromide, 1,1 '-(dec- 1,10-diyl) bis [4-aza-1-azonium bicyclo [2.2.2] octane] dibromide, bis (trimethylaluminum) -1,4-diazabicyclo [2.2. 2) Octane adduct, bismuthine, quinine ring hydrochloride, 3-quinine hydrochloride, 3-hydroxyquinine hydrochloride, DABCO hydrochloride, quinine cyclic acetate , 3-quininone acetate, 3-hydroxyquinine ring acetate, DABCO acetate, quinine ring acrylate, 3-quininone acrylate, 3-hydroxyquinine ring acrylate, DABCO acrylate, etc.

Specific examples of the amidine-based 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.

Specific examples of the pyridine-based compound include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, 4-propylpyridine, 4-isopropylpyridine, 4-tertiary butylpyridine, 4-pentylpyridine, 4- (1-ethylpropyl) pyridine, 4- (5- Nonyl) pyridine, 2-vinylpyridine, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4 -Dimethylpyridine, 3,5-dimethylpyridine, 3,5-diethylpyridine, N, N-dimethyl-4-aminopyridine (hereinafter referred to as "DMAP"), 2,4 , 6-Trimethylpyridine, 2,6-Di-tertiary butylpyridine, N, N-dimethyl-2-aminopyridine, 4-piperidinylpyridine, 4-pyrrolidinylpyridine, 4- Phenylpyridine, quine Porphyrin, 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-methoxypyridine, 2,6-dimethoxypyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, 1,8-naphthalene Pyridine, 2,6-naphthyridine, 2,7-naphthyridine, 2,2'-bipyridine, 3,3'-bipyridine, 4,4'-bipyridine, 2,3'-bipyridine, 2, 4'-bipyridine, 3,4'-bipyridine, 4,4'-ethylidene dipyridine, 1,3-bis (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, boron Alkane-2-picoline complex, pyridinium p-toluenesulfonate, etc.

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

[In formula (2), R ³ , R ⁴ and R ⁵ mean a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, and carbon Aryl groups having 6 to 24 or cycloalkyl groups having 5 to 20 carbon atoms; as for R ³ , R ⁴ and R ⁵ , they may be the same or different].

嗪、雙[2-(二苯基膦基)苯基]醚、(2-溴苯基)二苯基膦、雙(五氟苯基)苯基膦、二苯基膦基苯-3-磺酸鈉、二苯基-1-芘基膦、二苯基-2-吡啶基膦、4-(二甲基胺基)苯基二苯基膦、1,1’-雙(二苯基膦基)二茂鐵、(R,R”)-2,2”-雙(二苯基膦基)-1,1”-聯二茂鐵、(R)-N,N-二甲基-1-[(S)-2-(二苯基膦基)二茂鐵基]乙基胺、(S)-N,N-二甲基-1-[(R)-2-(二苯基膦基)二茂鐵基]乙基胺、(R)-N,N-二甲基-1-[(S)-1’,2-雙(二苯基膦基)二茂鐵基]乙基胺、(S)-N,N-二甲基-1-[(R)-1’,2-雙(二苯基膦基)二茂鐵基]乙基胺、4-二苯基膦基甲基聚苯乙烯樹脂、(R)-(+)-2-二苯基膦基-2’-甲氧基-1,1’-聯萘、(S)-(-)-2-二苯基膦基-2’-甲氧基-1,1’-聯萘、2-(二苯基膦基)苯甲酸、4-(二苯基膦基)苯甲酸、2-(二苯基膦基)苄醛、(S)-(-)-5,5’-雙[二(3,5-二甲苯基)膦基]-4,4’-聯-1,3-苯并二氧雜環戊烯、(R)-(+)-5,5’-雙[二(3,5-二甲苯基)膦基]-4,4’-聯-1,3-苯并二氧雜環戊烯、(S)-(+)-5,5’-雙[二(3,5-二-三級丁基-4-甲氧基苯基)膦基]-4,4’-聯-1,3-苯并二氧雜環戊烯、(R)-(-)-5,5’-雙[二(3,5-二-三級丁基-4-甲氧基苯基)膦基]-4,4’-聯-1,3-苯并二氧雜環戊烯、(五氟苯基)二苯基膦、(S)-(-)-5,5’-雙(二苯基膦基)-4,4’-聯-1,3-苯并二氧雜環戊烯、(R)-(+)-5,5’-雙(二苯基膦基)-4,4’-聯-1,3-苯并二氧雜環戊烯、參(4-甲氧基苯基) 膦、三(對-甲苯基)膦、三(鄰-甲苯基)膦、三(間-甲苯基)膦、參(2,6-二甲氧基苯基)膦、三苯基硼烷-三苯基膦錯合物、三苯基膦硼烷、參(五氟苯基)膦、參[3,5-雙(三氟甲基)苯基]膦、參(4-氟苯基)膦、對苯乙烯基二苯基膦、四苯基鏻溴化物、甲基三苯基鏻溴化物、正丁基三苯基鏻溴化物、甲氧基甲基三苯基鏻氯化物、苄基三苯基鏻氯化物、四苯基鏻四苯基硼酸鹽、四苯基鏻四-對-甲苯基硼酸鹽、乙基三苯基鏻乙酸酯．乙酸錯合物、乙基三苯基鏻碘化物、參(4-甲氧基-3,5-二甲基苯基)膦、(+)-DIOP(2,3-O-亞異丙基-2,3-二羥基-1,4-雙(二苯基膦基)丁烷)、(-)-DIOP、1,2-雙(二苯基膦基)乙烷、1,3-雙(二苯基膦基)丙烷、1,2-雙(二甲基膦基)乙烷、1,4-雙(二苯基膦基)丁烷、1,6-雙(二苯基膦基)己烷、1,5-雙(二苯基膦基)戊烷、雙(二苯基膦基)甲烷、反式-1,2-雙(二苯基膦基)乙烯、(S,S)-Chiraphos((2S,3S)-(-)-貳(二苯基膦基)丁烷)、(R,R)-DIPAMP(乙-1,2-二基雙[(2-甲氧基苯基)苯基膦])、(S,S)-DIPAMP、1,2-雙[雙(五氟苯基)膦基]乙烷、(2R,3R)-(-)-Norphos(2,3-雙(二苯基膦基)雙環[2.2.1]庚-5-烯)、(2S,3S)-(+)-Norphos、2-丁烯基(二-三級丁基)膦、環己基二苯基膦、二環己基(1,1-二苯基-1-丙烯-2-基)膦、二乙基苯基膦、二環己基苯基膦、二苯基丙基膦、2-(二-三級丁基膦基)聯苯、2-(二環己基膦基)聯苯、2-(二環己基膦基)-2’-(二甲基胺基)聯苯、1-[2-(二-三級丁基膦基)苯基]-3,5-二苯基-1H-吡唑、二-三級丁基苯基膦、(4-二甲基胺基苯基)二-三級丁基膦、二-三級丁基(3-甲基-2- 丁烯基)膦、乙基二苯基膦、異丙基二苯基膦、甲基二苯基膦、三環己基膦、三(2-呋喃基)膦、三(2-噻吩基)膦、三-三級丁基膦、三環戊基膦等。 Specific examples of phosphine compounds include triphenylphosphine, (S)-(-)-BINAP, (R)-(+)-BINAP (2,2'-bis (diphenylphosphino) -1,1'-binaphthalene), (±) -BINAP, 2,2'-bis (diphenylphosphino) biphenyl, Xantphos, 4,6-bis (diphenylphosphino) phen

Azine, bis [2- (diphenylphosphino) phenyl] ether, (2-bromophenyl) diphenylphosphine, bis (pentafluorophenyl) phenylphosphine, diphenylphosphinobenzene-3- Sodium sulfonate, diphenyl-1-pyrenephosphine, diphenyl-2-pyridylphosphine, 4- (dimethylamino) phenyldiphenylphosphine, 1,1'-bis (diphenyl Phosphono) 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- (diphenyl (Phosphino) ferrocenyl] ethylamine, (R) -N, N-dimethyl-1-[(S) -1 ', 2-bis (diphenylphosphino) ferrocenyl] ethyl Amine, (S) -N, N-dimethyl-1-[(R) -1 ', 2-bis (diphenylphosphino) ferrocenyl] ethylamine, 4-diphenylphosphine Methyl polystyrene resin, (R)-(+)-2-diphenylphosphino-2'-methoxy-1,1'-binaphthalene, (S)-(-)-2-bis Phenylphosphino-2'-methoxy-1,1'-binaphthalene, 2- (diphenylphosphino) benzoic acid, 4- (diphenylphosphino) benzoic acid, 2- (diphenyl (Phosphino) benzaldehyde, (S)-(-)-5,5'-bis [bis (3,5-xylyl) phosphino] -4,4'-bi-1,3-benzodioxane Heterocyclopentene, (R)-(+)-5,5'-bis [bis (3,5-xylyl) phosphino] -4,4'-bi-1,3-benzo Oxacyclopentene, (S)-(+)-5,5'-bis [bis (3,5-di-tertiarybutyl-4-methoxyphenyl) phosphino] -4,4 ' -Bi-1,3-benzodioxole, (R)-(-)-5,5'-bis [di (3,5-di-tert-butyl-4-methoxybenzene (Phosphino)]-4,4'-bi-1,3-benzodioxole, (pentafluorophenyl) diphenylphosphine, (S)-(-)-5,5'- Bis (diphenylphosphino) -4,4'-bi-1,3-benzodioxole, (R)-(+)-5,5'-bis (diphenylphosphino) -4,4'-Bi-1,3-benzodioxole, ginseng (4-methoxyphenyl) phosphine, tri (p-tolyl) phosphine, tri (o-tolyl) phosphine , Tris (m-tolyl) phosphine, ginseng (2,6-dimethoxyphenyl) phosphine, triphenylborane-triphenylphosphine complex, triphenylphosphine borane, ginseng (pentafluoro Phenyl) phosphine, ginseng [3,5-bis (trifluoromethyl) phenyl] phosphine, ginseng (4-fluorophenyl) phosphine, p-styryl diphenylphosphine, tetraphenylphosphonium bromide, methyl Triphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, tetraphenylphosphonium tetraphenylborate, tetra Phenylphosphonium tetra-p-tolylborate, ethyltriphenylphosphonium acetate. Acetate complex, Triphenylphosphonium iodide, ginseng (4-methoxy-3,5-dimethylphenyl) phosphine, (+)-DIOP (2,3-O-isopropylidene-2,3-di Hydroxy-1,4-bis (diphenylphosphino) butane), (-)-DIOP, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) ) Propane, 1,2-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) -Chiraphos ((2S , 3S)-(-)-Two (diphenylphosphino) butane), (R, R) -DIPAMP (ethane-1,2-diylbis ((2-methoxyphenyl) phenylphosphine ]), (S, S) -DIPAMP, 1,2-bis [bis (pentafluorophenyl) phosphino] ethane, (2R, 3R)-(-)-Norphos (2,3-bis (diphenyl Phosphinyl) bicyclo [2.2.1] hept-5-ene), (2S, 3S)-(+)-Norphos, 2-butenyl (di-tertiary butyl) phosphine, cyclohexyl diphenyl phosphine , Dicyclohexyl (1,1-diphenyl-1-propen-2-yl) phosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, diphenylpropylphosphine, 2- (di-tris Grade butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2- (dicyclohexylphosphino) -2 '-(dimethylamino) biphenyl, 1- [2- ( Two-three (Butylphosphino) phenyl) -3,5-diphenyl-1H-pyrazole, di-tertiary butyl phosphine, (4-dimethylaminophenyl) di-tertiary butyl phosphine , Di-tertiary butyl (3-methyl-2-butenyl) phosphine, ethyl diphenyl phosphine, isopropyl diphenyl phosphine, methyl diphenyl phosphine, tricyclohexyl phosphine, tri ( 2-furyl) phosphine, tri (2-thienyl) phosphine, tri-tertiary butylphosphine, tricyclopentylphosphine, etc.

In the present invention, these catalysts X can be used alone or in any combination of two or more. These catalysts X are selected from the group consisting of quinine ring, 3-quininone, 3-hydroxyquinine ring, DABCO, N-methylimidazole, DBU, DBN, DMAP, triphenylphosphine, tri (p -Tolyl) phosphine, tri (m-tolyl) phosphine, ginseng (4-methoxyphenyl) phosphine and ginseng (4-methoxy-3,5-dimethylphenyl) phosphine At least one compound is preferred, especially exhibits good reactivity with neopentaerythritol, easy to obtain at least one selected from the group consisting of 3-hydroxyquinine ring, DABCO, N-methylimidazole, DBU and DMAP One compound is better.

(A) The use ratio of the catalyst X in the production method of the component is not particularly limited. However, it is preferable to use the catalyst X of 0.0001 to 0.5 mol relative to the total amount of hydroxyl groups in neopentyl alcohol of 1 mol. It is preferably 0.0005 to 0.2 mole. By using a catalyst X of 0.0001 mole or more, the amount of target (A) component can be increased, and by using 0.5 mole or less, the generation of by-products or the coloring of the reaction liquid can be suppressed and the reaction can be completed. The refining step becomes simple.

1-2-4. Catalyst Y

Catalyst Y is a compound containing zinc.

As for the catalyst Y, as long as it is a zinc-containing compound, various compounds can be used. However, in terms of excellent reactivity, zinc organic acid and zinc diketoenolate are preferred.

Examples of the organic acid zinc include zinc dibasic acid such as zinc oxalate and compounds represented by the following formula (3).

[In formula (3), R ⁶ and R ⁷ mean a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms. The aryl group of 24, or a cycloalkyl group having 5 to 20 carbon atoms; as far as R ⁶ and R ⁷ are concerned, they may be the same or different].

As for the compound of the aforementioned formula (3), a compound in which R ⁶ and R ^{7 have} a linear or branched alkyl group having 1 to 20 carbon atoms is preferred. In R ⁶ and R ⁷ , the linear or branched alkyl group having 1 to 20 carbon atoms is a functional group that does not have halogen atoms such as fluorine and chlorine. The catalyst Y having this functional group can provide high yields The component (A) is preferably produced.

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

[In formula (4), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ mean a linear or branched alkyl group having 1 to 20 carbon atoms and a linear chain having 1 to 20 carbon atoms. Or branched alkenyl group, aryl group having 6-24 carbon atoms, or cycloalkyl group having 5-20 carbon atoms; as far as R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are concerned, Same or different.]

Specific examples of the zinc-containing compound represented by the above formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octoate, zinc neodecanoate, zinc laurate, and myristic acid Zinc, zinc stearate, zinc cyclohexanoate, zinc 2-ethylhexanoate, zinc benzoate, zinc tertiary butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, zinc methacrylate, etc. .

Furthermore, regarding these zinc-containing compounds, in the presence of hydrates or solvates or complexes with catalyst X, the hydrates, solvates and complexes with catalyst X are also It can be used as catalyst Y in the manufacturing method of (A) component.

Specific examples of the zinc-containing compound represented by the above formula (4) include acetyl, acetylacetonated zinc hydrate, bis (2,6-dimethyl-3,5-heptane Dione) zinc, bis (2,2,6,6-tetramethyl-3,5-heptanedione) zinc, bis (5,5-dimethyl-2,4-hexanedione) zinc, etc. Furthermore, regarding these zinc-containing compounds, in the presence of hydrates, solvates or complexes with catalyst X, the hydrates, solvates and complexes with catalyst X may also be Used as catalyst Y in the manufacturing method of (A) component.

As for the organic acid zinc and zinc diketoenolate in the catalyst Y, the aforementioned compounds can be used directly, however, these compounds can also be generated and used in the reaction system.

For example, zinc compounds such as metallic zinc, zinc oxide, zinc hydroxide, zinc chloride, and zinc nitrate (hereinafter, referred to as "raw zinc compounds") are used as raw materials. In the case of zinc organic acid, raw zinc compounds are combined with The method of organic acid reaction, in the case of zinc diketoenolate, the method of reacting the raw material zinc compound with 1,3-diketone, etc.

In the present invention, these catalysts Y can be used alone or in any combination of two or more. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferred, especially acetic acid, which exhibits good reactivity with neopentaerythritol and is easy to obtain Zinc, zinc acrylate, and zinc acetylacetonate are particularly preferred.

(A) The use rate of the catalyst Y in the method of manufacturing the component is not particularly limited. However, relative to the total amount of hydroxyl groups in neopentaerythritol is 1 mole, it is preferable to use the catalyst Y of 0.0001 to 0.5 mole, more It is preferably 0.0005 to 0.2 mole. By using catalyst Y of 0.0001 mole or more, the amount of target (A) component can be increased. By using 0.5 mole or less, the generation of by-products or the coloring of the reaction solution can be suppressed, and the The refining steps are simplified.

1-2-5. Transesterification reaction

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

(A) The use ratio of the catalyst X and the catalyst Y in the production method of the component is not particularly limited, but for the catalyst Y of 1 mol, it is better to use the catalyst X of 0.005 ~ 10.0 mol, more preferably It is 0.05 to 5.0 moles. By using 0.005 mol or more, the amount of target (A) component can be increased. By adjusting it to 10.0 mol or less, the generation of by-products or the coloring of the reaction liquid can be suppressed, and the purification step after the reaction can be completed Simplify.

As for the combination of the catalyst X and the catalyst Y used in the present invention, the combination of the catalyst X series azabicyclic compound and the catalyst Y series compound represented by the aforementioned formula (3) is preferred. For the DABCO azabicyclic compound, the compound represented by the above formula (3) is preferably a combination of at least one compound selected from the group consisting of zinc acetate and zinc acrylate.

In addition to obtaining the component (A) in good yield, this combination is suitable for various industrial applications where color tone is important because the color tone after the reaction is excellent. Furthermore, it is an economically advantageous manufacturing method because it is a catalyst that can be obtained relatively cheaply.

The catalyst X and catalyst Y used in the present invention may be added at the initial stage of the above reaction or may be added on the way. In addition, the desired amount of use may be added together, or may be added in portions.

(A) The reaction temperature in the production method of the component is preferably 40 to 180 ° C, more preferably 60 to 160 ° C. By adjusting the reaction temperature to above 40 ° C, the reaction speed can be accelerated, and by adjusting to below 180 ° C, the thermal polymerization of (meth) acryloyl groups in the raw materials or products can be suppressed, and the coloring of the reaction liquid can be suppressed. Simplify the purification steps after the reaction.

(A) The reaction pressure in the production method of the component can be carried out in a reduced pressure state or a pressurized state as long as the set reaction temperature can be maintained without any particular limitation. It is preferably 0.000001 to 10 MPa (absolute pressure).

(A) In the production method of the component, as the transesterification reaction proceeds, the by-product monohydric (meth) acrylate monohydric alcohol is produced. Although the monohydric alcohol can coexist in the reaction system, the transesterification reaction can be further promoted by discharging the monohydric alcohol out of the reaction system.

(A) In the production method of the component, the reaction may be carried out without using a solvent, however, a solvent may be used if necessary.

、二

、苯甲醚、二苯基醚、乙二醇二甲醚、二乙醇二甲醚、三乙醇二甲醚及四乙醇二甲醚等醚類；18-冠-6-醚等冠醚類；苯甲酸甲酯及γ-丁內酯等酯類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮、乙醯苯及二苯酮等酮類；碳酸二甲酯、碳酸二乙酯、碳酸伸乙酯、碳酸伸丙酯、碳酸1,2-伸丁酯等碳酸酯化合物；環丁碸等碸類；二甲基亞碸等亞碸類；尿素類或其衍生物；三丁基膦氧化物等膦氧化物類、咪唑鎓鹽、哌啶鎓鹽及吡啶鎓鹽等離子液體；聚矽氧油；及水等。 Specific examples of the solvent include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene , Diethylbenzene, cumene, pentylbenzene, dipentylbenzene, tripentylbenzene, dodecylbenzene, di-dodecylbenzene, pentyltoluene, isopropyltoluene, decalin and tetrahydronaphthalene Class; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, diethyl acetal, dihexyl acetal, tertiary butyl methyl ether, cyclopentyl methyl Ether, tetrahydrofuran, tetrahydropiperan, three

,two

, Anisole, diphenyl ether, ethylene glycol dimethyl ether, diethanol dimethyl ether, triethanol dimethyl ether, and tetraethanol dimethyl ether; ethers such as 18-crown-6-ether; Esters such as methyl benzoate and γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and benzophenone; dimethyl carbonate and carbonic acid Carbonate compounds such as diethyl ester, ethyl carbonate, propyl carbonate, 1,2-butylene carbonate; citric acid such as cyclobutadiene; citric acid such as dimethyl sulfony; urea or its derivatives ; Ionic liquids such as phosphine oxides such as tributylphosphine oxide, imidazolium salts, piperidinium salts and pyridinium salts; polysiloxane oils; and water.

Among these solvents, hydrocarbons, ethers, carbonate compounds and ionic liquids are preferred.

These solvents may be used alone, or any combination of two or more of them may be used as a mixed solvent.

(A) In the method for producing the component, although inert gas such as argon, helium, nitrogen, and carbon dioxide can be introduced into the system for the purpose of maintaining the color tone of the reaction liquid well, it can also prevent (meth) acryloyl For the purpose of polymerization, oxygen-containing gas is introduced into the system. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. As for the introduction method containing oxygen, there is a method of dissolving it in the reaction liquid or blowing it into the reaction liquid (so-called bubbling).

In the production method of the component (A), for the purpose of preventing the polymerization of the (meth) acryloyl group, it is preferable to add a polymerization inhibitor to the reaction liquid.

、N-亞硝基-N-苯基羥基胺銨鹽、2,2,6,6-四甲基哌啶-1-氧化物、4-羥基-2,2,6,6-四甲基哌啶-1-氧化物等有機系聚合抑制劑；氯化銅、硫酸銅及硫酸鐵等無機系聚合抑制劑；及二丁基二硫基胺甲酸銅、N-亞硝基-N-苯基羥基胺鋁鹽等有機鹽系聚合抑制劑。 Specific examples of polymerization inhibitors include hydroquinone, tertiary butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di-tertiary butyl-4-methylphenol, 2,4 , 6-Tri-tertiary butylphenol, 4-tertiary butyl catechol, benzoquinone, phenothiol

, N-nitroso-N-phenylhydroxylamine ammonium salt, 2,2,6,6-tetramethylpiperidine-1-oxide, 4-hydroxy-2,2,6,6-tetramethyl Organic polymerization inhibitors such as piperidine-1-oxide; inorganic polymerization inhibitors such as copper chloride, copper sulfate, and iron sulfate; and copper dibutyldithiocarbamate, N-nitroso-N-benzene Organic salt-based polymerization inhibitors such as aluminum hydroxylamine salts.

The polymerization inhibitor may be added alone, or may be added in any combination of two or more, and may be added from the initial stage of the present invention, or it may be on the way Add to. In addition, the desired amount of use may be added together, or may be added in portions. In addition, it can be continuously added via a rectification tower.

Regarding the addition ratio of the polymerization inhibitor, in the reaction liquid, 5 to 30,000 wtppm is preferred, and more preferably 25 to 10,000 wtppm. By adjusting the ratio to 5wtppm or more, the polymerization inhibitory effect can be exerted. By adjusting to 30,000wtppm or less, the coloring of the reaction liquid can be suppressed, the purification step after the reaction can be simplified, and the obtained ( A) The hardening rate of the component decreases.

(A) The reaction time in the method of manufacturing the component varies with the type and amount of catalyst, the reaction temperature, the reaction pressure, etc. However, it is preferably 0.1 to 150 hours, and more preferably 0.5 to 80 hours.

(A) The manufacturing method of the component can be implemented by any of batch method, semi-batch method, and continuous method. As an example of the batch formula, by adding neopentaerythritol, monofunctional (meth) acrylate, catalyst and polymerization inhibitor to the reactor, the oxygen-containing gas is bubbled into the reaction liquid, Simultaneously stirring at the set temperature; then, with the progress of the transesterification reaction, the by-produced monohydric alcohol is taken out of the reactor at the set pressure and the target (A) component is generated.

For the reaction product obtained in the method of manufacturing component (A), separation is carried out. The purification operation is preferable because the target (A) component can be obtained with high purity.

Just separate. As for the refining operation, crystallization operation, filtration operation, distillation operation, extraction operation, etc. may be mentioned, and such combination is preferable. The crystallization operation includes cooling crystallization and concentrated crystallization, and the filtration operation includes pressure filtration, suction filtration and centrifugal filtration. For the distillation operation, simple distillation, fractional distillation, molecular distillation, and steam distillation can be cited, and for the extraction operation, solid-liquid extraction, liquid-liquid extraction, etc. can be cited.

Solvents can also be used in this separation and purification operation.

In addition, it can also be used in the present invention: a neutralizing agent for neutralizing either or both of the catalyst and polymerization inhibitor used, or an adsorbent for adsorbing and removing The acid or alkali that the product decomposes or removes, the activated carbon used to improve the hue, and the diatomite used to improve the filtration efficiency and filtration speed.

2. Hardened composition

The present invention relates to a hardened composition containing the aforementioned component (A).

The manufacturing method of the composition includes a step of performing transesterification reaction of neopentyl alcohol and monofunctional (meth) acrylate in the presence of the aforementioned catalysts X and Y to produce a (meth) acrylate mixture Is preferred.

According to this production method, the (A) component having a specific hydroxyl value can be produced with high yield, and because the obtained (A) component has few high-molecular weight bodies and becomes low in viscosity, the resulting composition can be formed Those having excellent coatability or even coatability are also preferable in that the cured film of the obtained composition can be formed with high hardness.

For this step, it is only necessary to follow the manufacturing method of the aforementioned (A) component.

As far as the viscosity of the composition is concerned, it may be set appropriately according to the purpose.

When the component (A) is used for a better application such as a coating agent, printing ink, and pattern forming agent, the viscosity of the composition may be appropriately set according to the purpose, and is 1 to 100,000 mPa. s is better, more preferably 5 ~ 50,000mPa. s. By adjusting to this viscosity range, the composition can be applied with excellent uniformity in coating and the appearance of the hardened product.

In addition, the viscosity in this invention means the value measured at 25 degreeC using the E-type viscometer.

The composition of the present invention may use any one of an active energy ray-curable composition and a thermosetting composition, however, the active energy ray-curable composition is preferred.

The composition of the present invention contains the aforementioned (A) as an essential component, but various components can be blended according to the purpose.

Specific examples of the other components include a photopolymerization initiator [hereinafter, referred to as "(B) component"], a thermal polymerization initiator [hereinafter, referred to as "(C) component"], and the aforementioned (A) component Compounds other than ethylenically unsaturated groups [hereinafter referred to as "(D) component"] and organic solvents [hereinafter referred to as "(E) component"] etc.

Hereinafter, these components will be described.

In addition, for other components described below, only one exemplified compound may be used, or two or more kinds may be used in combination.

2-1. (B) ingredients

When the composition of the present invention is used as an active energy ray-curable composition and further used as an electron-ray-curable composition, it may not contain the component (B) (photopolymerization initiator) and may be cured by electron beam.

In the case where the composition of the present invention is used as an active energy ray-curable composition, in particular, when ultraviolet rays and visible rays are used as the active energy ray, from the viewpoint of ease of curing or cost, it further contains (B) Ingredients are preferred.

With regard to active energy rays, when electron beams are used, it is not necessary to blend, but in order to improve the hardenability, a small amount of blending may be necessary.

Specific examples of the component (B) include: benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl -1- [4-1- (methylvinyl) phenyl] acetone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio)] phenyl] -2-N-morpholinylpropan-1-one, 2-benzyl- 2-dimethylamino-1- (4-N-morpholinylphenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4 -Morpholin-4-ylphenyl) butan-1-one and 3,6-bis (2-methyl-2-N-morpholinylpropionyl) -9-n-octylcarbazole and other acetophenones Compounds; benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds; benzophenone, 2-methylbenzophenone, 3-methyl Benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1- [4- (4-Benzylacetylphenylthio) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and 4-methoxy-4'-dimethylamino benzophenone and other benzophenone series Compounds; bis (2,4,6-trimethylbenzyl) phenylphosphine oxide, 2,4,6-trimethylbenzyl diphenylphosphine oxide, and bis (2,6-di Methoxybenzyl)) 2,4,4-trimethylpentylphosphine oxide and other acetylphosphine oxide; and thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone Ketone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-pentoxy-9H-thioxanthone-2-yl-oxy ] 2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone and other thioxanthone-based compounds.

Examples of compounds other than the foregoing include benzil diketone (benzil), methyl phenylglyoxylate, (2,4,6-trimethylbenzyl) phenylphosphonic acid ethyl ester, ethyl Anthraquinone, phenanthrenequinone, camphorquinone, etc.

Among these compounds, α-hydroxyphenyl ketones are preferred even if they are thin-film coatings in the atmosphere, and their surface hardenability is good. Specifically, 1-hydroxycyclohexyl phenyl ketone, and 2-Hydroxy-2-methyl-1-phenylpropan-1-one is more preferred.

In addition, when the film thickness of the cured product must be increased, for example, it must be adjusted to 50 μm or more, in order to improve the hardenability of the cured product, or in combination with an ultraviolet absorber or a pigment, the double (2,4 , 6-trimethylbenzyl) phenylphosphine oxide, 2,4,6-trimethylbenzyl diphenylphosphine oxide and bis (2,6-dimethoxybenzyl) 2,4,4-trimethylpentylphosphine oxide and other acetylphosphine oxide compounds, or 2-methyl-1- [4- (methylthio) phenyl] -2-N-morpholine Propan-1-one, 2-benzyl-2-dimethylamino -1- (4-N-morpholinylphenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl Phenyl) -butan-1-one and the like are preferably used in combination.

(B) The content ratio of the components is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 8 parts by weight relative to 100 parts by weight of the total amount of the hardenable components. By adjusting the ratio of the component (B) to 0.1 parts by weight or more, the photocurability of the composition becomes good, and those with excellent adhesion can be formed. By adjusting to 10 parts by weight or less, the internal curability of the cured film can be It becomes good, and the adhesiveness with a base material can be made good.

In addition, in the present invention, the "curable component" means a component hardened by heat or active energy rays, which means the component (A), and when the component (D) is blended later, it means (A) and (D )ingredient.

2-2. (C) ingredients

When using the composition of the present invention as a thermosetting composition, a thermal polymerization initiator may be blended.

As for the thermal polymerization initiator, various compounds can be used, and organic peroxides and azo-based initiators are preferred.

Specific examples of organic peroxides include 1,1-bis (tertiary butylperoxy) -2-methylcyclohexane and 1,1-bis (tertiary hexylperoxy)- 3,3,5-trimethylcyclohexane, 1,1-bis (tertiary hexylperoxy) cyclohexane, 1,1-bis (tertiary butylperoxy) -3,3,5 -Trimethylcyclohexane, 1,1-bis (tertiary butylperoxy) cyclohexane, 2,2-bis (4,4-di-butylperoxycyclohexyl) propane, 1, 1-bis (tertiary butylperoxy) cyclododecane, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxymaleate, peroxy-3,5,5-trimethyl Tertiary butyl hexanoate, tertiary butyl peroxylaurate, 2,5- Dimethyl-2,5-bis (m-tall oil peroxy) hexane, tert-butyl peroxyisopropyl monocarbonate, tert-butyl 2-ethylhexyl monocarbonate, peroxy Tertiary hexyl benzylate, 2,5-dimethyl-2,5-bis (benzyl peroxy) hexane, tertiary butyl peroxyacetate, 2,2-bis (tertiary butyl peroxide) Oxy) butane, tertiary butyl peroxybenzate, n-butyl 4,4-bis (tertiary butylperoxy) valerate, di-tertiary butyl peroxyisophthalate, α, α '-Bis (tertiary butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (tertiary butylperoxy) Alkane, tertiary butyl cumyl peroxide, di-tertiary butyl peroxide, p-menthane hydrogen peroxide, 2,5-dimethyl-2,5-di (tertiary butyl peroxide) Oxy) hexyne-3, diisopropylbenzene hydroperoxide, tertiary butyl trimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene Hydrogen peroxide, tertiary hexyl hydrogen peroxide, tertiary butyl hydrogen peroxide, etc.

Specific examples of the azo compound include 1,1'-azobis (cyclohex-1-carbonitrile), 2- (aminomethylazo) isobutyronitrile, and 2-phenylazo Nitrogen-4-methoxy-2,4-dimethylvaleronitrile, azobis-tertiary octane, azobis-tertiary butane, etc.

These can be used alone or in combination of two or more. In addition, the organic peroxide can also be combined with a reducing agent to perform a redox reaction.

The amount of these thermal polymerization initiators used is preferably 10 parts by weight or less based on 100 parts by weight of the total amount of the curable components.

When the thermal polymerization initiator is used alone, it may be carried out in accordance with the usual methods of free radical thermal polymerization, and it may be used together with the component (B) (photopolymerization initiator) as needed, and after it is hardened by light, Further, for the purpose of increasing the reaction rate, thermal curing is performed.

2-3. (D) ingredients

The component (D) is an ethylenically unsaturated compound other than the component (A) described above, 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 the component (D) include (meth) acryloyl group, (meth) acrylamide group, vinyl group and (meth) allyl group, etc. Radical) acrylamide is preferred.

Furthermore, in the following, "monofunctional" means a compound having one ethylenically unsaturated group, "X functional" means a compound having X ethylenically unsaturated groups, and "multifunctional" means having two The above ethylenically unsaturated group compounds.

(D) In the component, specific examples of the monofunctional ethylenically unsaturated compound include the same compounds as the aforementioned monofunctional (meth) acrylate, and the methyl (meth) acrylate, (methyl ) Ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate and (meth ) 2-Methoxyethyl acrylate is preferred.

Compounds other than the aforementioned monofunctional (meth) acrylates include (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, ( Methacrylic acid monohydroxy ethyl phthalate, ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, (Meth) acrylic acid benzyl ester, (meth) acrylic acid phenyl ester, phenol alkylene oxide adduct (meth) acrylic acid ester, alkylphenol alkylene oxide adduct Of (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, alkylene oxide of p-cumylphenol (Meth) acrylate, o-phenylphenol (meth) acrylate, o-phenylphenol alkylene oxide adduct (meth) acrylate, (meth) acrylic acid tetrahydrofurfur Ester, isobornyl (meth) acrylate, tricyclodecylhydroxymethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (methyl) Acryloyloxyethyl) hexahydrophthalimide, N- (2- (meth) acryloyloxyethyl) tetrahydrophthalamide, N, N-dimethylacrylamide, propylene amide Morpholine, N-vinylpyrrolidone, N-vinylcaprolactam, etc.

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, and hexyl. Alkanediol di (meth) acrylates such as alkanediol di (meth) acrylate and nonanediol di (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate Poly (alkyl) glycol di (meth) acrylates such as meth) acrylate and polytetramethylene glycol di (meth) acrylate; di (meth) acrylate of trimethylolpropane, Glycerol di (meth) acrylate, II trimethylolpropane di (meth) acrylate, diglycerol di (meth) acrylate, and dipentaerythritol di (meth) acrylate Polyhydric alcohol di (meth) acrylate; Glyceryl alkylene oxide adduct di (meth) acrylate, neopentyl alcohol alkylene oxide adduct di (meth) acrylate, two trimethylolpropane alkylene oxide Adduct bis (meth) acrylate, diglycerin alkylene oxide adduct bis (meth) acrylate and dipentaerythritol alkylene oxide adduct bis (meth) Bis (meth) acrylates of polyol alkylene oxide adducts such as acrylates; and di (meth) acrylates and bisphenol F alkylene oxide adducts of bisphenol A Alkyl oxide adduct bis (meth) acrylate, etc.

In addition, epoxy (meth) acrylates having a bisphenol skeleton, polyether skeleton, or polyalkylene skeleton, and carbamates having a polyester skeleton, polyether skeleton, or polycarbonate skeleton ( Methacrylate and polyester (meth) acrylate etc.

Examples of the trifunctional or higher ethylenically unsaturated compound include compounds having three or more (meth) acryloyl groups [hereinafter, referred to as "trifunctional or more (meth) acrylate"].

As for the trifunctional or more (meth) acrylate, if it is a compound having 3 or more (meth) acryloyl groups, various compounds are possible, for example, tri (meth) acrylic acid of trimethylolpropane Ester, tri (meth) acrylate of glycerol, tri or tetra (meth) acrylate of two trimethylolpropane, tri or tetra (meth) acrylate of diglyceride, and tri , Four, five or six (meth) acrylate and other polyol poly (meth) acrylate; and trimethylol propane alkylene oxide adduct tri (meth) acrylate, glycerol alkylene Tri (meth) acrylate of base oxide adduct, tri or tetra (meth) acrylic acid of neopentyl alcohol alkylene oxide adduct Ester, two or three (meth) acrylates of trimethylolpropane alkylene oxide adducts, three or four (meth) acrylates of diglycerin alkylene oxide adducts, two new Poly (meth) acrylates of polyalkylene oxide adducts of pentaerythritol alkylene oxide adducts three, four, five or six (meth) acrylates; isocyanuric acid Tri (meth) acrylates of acid alkylene oxide adducts; and neopentaerythritol tri (meth) acrylates, dipentaerythritol penta (meth) acrylates, etc. have hydroxyl groups and have Three or more (meth) acryloyl compounds, and urethane (meth) acrylates that are reactants of organic polyisocyanates.

Examples of the alkylene oxide adducts mentioned above include ethyl oxide adducts, propylene oxide adducts, and ethyl oxide and propylene oxide adducts. Wait.

(D) The content ratio of the component is preferably 0 to 60% by weight in the total amount of 100 parts by weight of the curable component, and more preferably 0 to 30% by weight.

When the content ratio of the component (D) is 60% by weight or less, especially when the component (D) is a polyfunctional ethylenically unsaturated compound, the cured film can be prevented from becoming brittle.

2-4. (E) ingredients

The composition of the present invention may contain the organic solvent of the component (E) for the purpose of improving the applicability to the substrate and the like.

Specific examples of the component (E) include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether Compounds; acetone alcohol such as diacetone alcohol; aromatic compounds such as benzene, toluene and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate; acetone, methyl ethyl ketone Ketone compounds such as methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone.

Among these, alkylene glycol monoether compounds and ketone compounds are preferred, and alkylene glycol monoether compounds are more preferred.

(E) The content ratio of the component is preferably 10 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, and more preferably 50 to 300 parts by weight relative to 100 parts by weight of the total amount of the curable component. good. If it is in the above range, it can be an appropriate viscosity when the composition is applied, and the composition can be easily applied by a well-known coating method described later.

3. Use

The composition of the present invention can be used for various applications such as coating agents, printing inks, pattern forming agents, and adhesives, and more preferably, it can be used for coating applications such as hard coat layers.

Hereinafter, the coating composition will be described.

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

The composition for coating is preferably used as a hard coat. As the substrate, plastic films used for touch sensors, Plastic film used in polarizer protective film or antireflection film, resin molded product used in home appliances or automotive interior and exterior parts, etc.

The case where the composition of the present invention is used for a hard coat layer of a polarizer protective film (hereinafter, simply referred to as "protective film") will be described.

As for the protective film, it is suitable for general users, and examples include cellulose acetate resins such as triethyl acetyl cellulose and diethyl acetyl cellulose, acrylic resins, polyethylene terephthalate, and poly Carbonates, cyclic polyolefin resins using cyclic olefins such as norbornene as monomers, etc.

Silica particles can also be blended into the composition to form a hardened film into an anti-glare layer.

In addition, the cured film of the composition may be formed as a protective film, which is used as the outermost surface of the polarizing plate, and may also be used as an undercoat layer of the protective film to form a cured film between the protective film and the polarizer.

Specific examples of the case where it is used as the outermost surface of the polarizing plate include a cured film / protective film / adhesive / polarizer, or a cured film / protective film / adhesive / polarizer / adhesive / protective film / Examples of the composition of the cured film.

Specific examples of the case where the protective film is used as the undercoat layer include the configuration of the protective film / cured film / adhesive / polarizer, or the protective film / cured film / adhesive / polarizer / adhesive / curing Examples of film / protective film configurations.

Although the coating composition contains the aforementioned (A) as an essential component, various components may be blended according to the purpose.

The other components are specifically, in addition to the aforementioned (B), (C), (D) and (E) components, examples include antioxidants, ultraviolet absorbers, pigments. Dyes, silane coupling agents, surface modifiers, polymers, etc.

Hereinafter, these components will be described.

In addition, for other components described below, only one exemplified compound may be used, or two or more kinds may be used in combination.

3-1. Antioxidant

The antioxidant is blended for the purpose of improving the durability of the cured film such as heat resistance and weather resistance.

Examples of antioxidants include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

Examples of the phenol-based antioxidant include blocking phenols such as tertiary butylhydroxytoluene. Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeka Corporation.

Examples of phosphorus-based antioxidants include phosphines such as trialkylphosphine and triarylphosphine; trialkylphosphite and triarylphosphite. Examples of commercially available products for these derivatives include Adekastab PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, and 329K manufactured by Adeka Co., Ltd. , 1178, 1500, 135A, 3010, etc.

Examples of sulfur-based antioxidants include thioether-based compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.

One of these may be used, or two or more may be used. Preferred combinations of these antioxidants include the combined use of phenol-based antioxidants and phosphorus-based antioxidants, and the combined use of phenol-based antioxidants and sulfur-based antioxidants.

The content ratio of the antioxidant may be appropriately set according to the purpose, and it is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight relative to 100 parts by weight of the total amount of the hardenable components.

By adjusting the content ratio to 0.1 parts by weight or more, the durability of the composition can be improved. On the other hand, by setting it to 5 parts by weight or less, the curability and adhesion can be improved.

3-2. Ultraviolet absorber

The ultraviolet absorber is blended for the purpose of improving the light resistance of the cured film.

系紫外線吸收劑；或TINUVIN 900、TINUVIN 928、TINUVIN 1130等苯并三唑系紫外線吸收劑。 As for the ultraviolet absorber, there are three such as TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 manufactured by BASF, etc.

UV absorbers; or benzotriazole UV absorbers such as TINUVIN 900, TINUVIN 928, TINUVIN 1130, etc.

The content ratio of the ultraviolet absorber may be appropriately set according to the purpose. However, it is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the total amount of the hardenable components. . By adjusting the content ratio to 0.01% by weight or more, the light resistance of the cured film can be improved. On the other hand, by adjusting it to 5% by weight or less, the curability of the composition can be excellent.

3-3. Pigments and dyes

Examples of pigments include organic pigments and inorganic pigments.

紫等。 Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine chestnut, hansa yellow, benzidine yellow, and pyrazolone red; Liso Red and Bordeaux red wine pigments ( helio bordeaux), scarlet pigments and permanent red 2B and other soluble azo pigments; alizarin, indanthrene and thioindigo and other derivatives derived from vat dyes; phthalocyanine blue and phthalocyanine green and other phthalocyanine-based organic pigments; Quinacridone-based organic pigments such as acridone red and quinacridone magenta; perylene-based organic pigments such as perylene red and perylene scarlet; isoindolinone such as isoindolinone yellow and isoindolinone orange Series organic pigments; skin anthrone organic pigments such as picanthrone red and picanthrone orange; thioindigo-based organic pigments; condensed azo-based organic pigments; benzimidazolone-based organic pigments; quinophthalone yellow and other quinophthalone Organic pigments; isoindoline yellow and other isoindoline organic pigments; and as other pigments flavanthrone yellow (flavanthrone yellow), acylamide yellow (acylamide yellow), nickel azo yellow, copper azomethine Yellow, pyrone orange, anthrone orange, dianthraquinonyl red (dianthraquinonyl red) and di

Purple etc.

In addition, specific examples of the aforementioned inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron (III) oxide), and cadmium red , Ultramarine, cyanine, chrome oxide green, cobalt green, amber, titanium black and synthetic iron black, etc. In addition, the carbon black exemplified in the filler can also be used as an inorganic pigment.

As for the dye, various compounds known before can be used.

3-4. Silane coupling agent

The silane coupling agent is blended for the purpose of improving the bonding strength of the interface between the cured film and the substrate.

The silane coupling agent is not particularly limited as long as the adhesion to the substrate can be improved.

Examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidyl. Oxypropylmethyl diethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane , N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane-N- (1,3-dimethylbutylene) propylamine, N-phenyl- 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

The blending ratio of the silane coupling agent may be appropriately set according to the purpose, and it is preferably 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight relative to 100 parts by weight of the total amount of the hardenable components.

By adjusting the blending ratio to 0.1 parts by weight or more, the adhesive strength of the composition can be improved. On the other hand, by adjusting to 10 parts by weight or less, the adhesive force can be prevented from changing with time.

3-5. Surface modifier

The composition of the present invention may be added with a surface modifier for the purpose of improving the uniformity of coating at the time of coating, or for the purpose of improving the lubricity of the cured film and increasing the scratch resistance.

Examples of surface modifiers include surface modifiers, surfactants, leveling agents, defoamers, slip imparting agents, and antifouling imparting agents. These known surface modifiers can be used.

Among these, preferably, a silicone-based surface modifier and a fluorine-based surface modifier are mentioned. Specific examples include polysiloxane-based polymers and oligomers having polysiloxane chains and polyalkylene oxide chains, and polysiloxane-based polymers having polysiloxane chains and polyester chains and Oligomers, fluoropolymers and oligomers with perfluoroalkyl and polyalkylene oxide chains, and fluoropolymers and oligomers with perfluoroalkyl ether chains and polyalkylene oxide chains Polymer etc.

In addition, for the purpose of improving the durability of lubricity and the like, a surface modifier having an ethylenically unsaturated group in the molecule, preferably a (meth) acryloyl group, may also be used.

The content ratio of the surface modifier is preferably 0.01 to 1.0 part by weight relative to 100 parts by weight of the total amount of the hardening component. Within the above range, the surface smoothness of the coating film is excellent.

3-6. Polymer

The composition of the present invention may further contain a polymer for the purpose of further improving curl resistance of the obtained cured film.

Preferred polymers include (meth) acrylic polymers, and preferred constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) Acrylic acid, glycidyl (meth) acrylate, N- (2- (meth) acryloyloxyethyl) tetrahydrophthalimide, etc. In the case of a polymer copolymerized with (meth) acrylic acid, glycidyl (meth) acrylate can be added to introduce a (meth) acryloyl group into the polymer chain.

The content ratio of the polymer is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the total amount of the curable components. Within the above range, the obtained cured film has more excellent curl resistance.

4. How to use

As for the method of using the composition of the present invention, it suffices to follow the usual method.

For example, a method of hardening by applying active energy rays or heating after applying the composition to the substrate can be cited.

Specifically, after the composition is applied on a suitable substrate by a common coating method, in the case of an active energy ray-curable composition, a method of irradiating the active energy ray to harden it is applied to a thermosetting composition. The case is the method of hardening by heating. In the case of applications such as molding materials, after the composition is injected into the set mold frame, in the case of the active energy ray-curable composition, the method of curing it by irradiating the active energy ray, and in the thermosetting composition The case is the method of hardening by heating.

The irradiation method or heating method of the active energy ray may be any conventional method known in the previous curing method.

Alternatively, the component (B) component (photopolymerization initiator) and (C) component (thermal polymerization initiator) in the composition may be used in combination, after irradiating it with active energy rays, it may be hardened by heating A method to improve the adhesion to the substrate.

As for the base material to which the composition of the present invention is applicable, various materials are applicable, including plastic, wood, metal, inorganic materials, paper, and the like.

Specific examples of plastics include cellulose acetate resins such as polyvinyl alcohol, triethyl cellulose and diethyl cellulose, acrylic resins, polyethylene terephthalate, and polycarbonate , Polyarylate, polyether ash, cyclic polyolefin resin with norbornene and other cyclic olefins as monomers, polyvinyl chloride, epoxy resin and polyurethane resin, etc.

For wood, natural wood, synthetic wood, etc. may be mentioned.

Examples of metals include metals such as steel plates, aluminum, and chromium; metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).

Examples of inorganic materials include glass, plaster, concrete, and stone.

Among these, plastic substrates are particularly preferred.

The thickness of the cured film of the composition relative to the base material may be appropriately set according to the purpose. As far as the thickness of the cured film is concerned, it can be selected according to the use of the substrate used or the substrate with the cured film produced, and preferably 1 to 500 μm, more preferably 5 to 200 μm.

The method for applying the composition of the present invention to the substrate may be appropriately set according to the purpose, and examples thereof include bar coaters, cloth coaters, blade coaters, dip coaters, roller coaters, and spin coaters. , Flow coater, knife coater, corner wheel coater, reverse wheel coater, die coater, lip coater, gravure coater, micro gravure coater, inkjet and other methods of coating.

The active energy rays used to harden the composition of the present invention include ultraviolet rays, visible rays, and electron rays. However, ultraviolet rays are preferred.

Examples of the ultraviolet irradiation device include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, and light-emitting diodes (LEDs).

The irradiation energy may be appropriately set according to the type of active energy ray and the blending composition. If a high-pressure mercury lamp is used as an example, the irradiation energy in the UV-A region (315 ~ 380nm) is 100 ~ 5,000mJ cm ² is preferred, and 200 to 1,000 mJ / cm ² is more preferred.

[Example]

Examples and comparative examples are shown below to explain the present invention more specifically.

Furthermore, the following "parts" means parts by weight.

1. Manufacturing Example 1) Production Example 1 [ Production of (A) component by dehydration esterification method]

In a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a blowing inlet, blow in 5 vol% oxygen-containing nitrogen, and at the same time, 301 parts (4.18 mol) of acrylic acid and 167 parts (1.23 mol) of neopentyl Tetraol [made by Guangrong Chemical Co., Ltd., hereinafter referred to as "PE"], 7 parts of sulfuric acid, 0.14 parts of hydroquinone monomethyl ether (hereinafter, referred to as "MEHQ") and 224 parts of toluene are mixed The reaction temperature was about 80 ° C and 370 Torr (absolute pressure). The condensation water was removed and the reaction was continued until 45 mol% of all hydroxyl groups in PE were esterified.

The produced condensation water was 28 parts, and 42 parts of unreacted PE were recovered. After the reaction was completed, 870 parts of toluene was added.

With respect to the acid content of the reaction liquid to which this toluene was added, a 20% aqueous solution of sodium hydroxide equivalent to one-fold molar amount was added with stirring, and neutralization treatment was performed to remove excess acrylic acid and sulfuric acid. The organic layer was separated, and under stirring, 10 parts of water was added to 100 parts of the organic layer to perform water washing treatment. The organic layer was separated and heated under reduced pressure, and toluene was distilled off to obtain 185 parts of the purified processed product.

As a result of HPLC analysis of the purified product, it was confirmed that it contained neopentyl alcohol monoacrylate, neopentyl alcohol diacrylate (hereinafter, referred to as "PEDA"), neopentyl alcohol triacrylate and neopentyl alcohol tetra Acrylate.

The PEDA content in the resulting refined treatment was 21 area%, the hydroxyl value was 204 mgKOH / g, and the viscosity was 570 mPa. s (hereinafter, referred to as "DE-PETA1"). The results are shown in Table 1.

◆ HPLC measurement conditions

. HPLC device: LC10AD [made by Shimadzu Corporation]

. Column: Reverse-phase silicone column for HPLC [Sunfire C18 manufactured by Japan Waters Co., Ltd., particle size 3.5 μm, 4.6 mm × 20 mm]

. Column temperature: 40 ℃

. Composition of eluate: 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

◆ Measurement method of hydroxyl value

Acetylation reagent was added to the sample, and heat treatment was performed in a warm bath at 92 ° C for 1 hour. After cooling, a small amount of water was added and heat treatment was performed in a warm bath at 92 ° C for 10 minutes. After cooling, the phenolphthalein solution was used as an indicator, and the acid was titrated with a potassium hydroxide ethanol solution to determine the hydroxyl value.

◆ Viscosity

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

2) Production Example 2 [ Production of (A) component by dehydration esterification method]

Except for using 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, the condensation was removed under the same conditions as in Raw Material Production Example 1. Water reacts at the same time until 30% of all hydroxyl groups in PET are esterified.

The resulting condensation water was 18 parts, and 83.5 parts of unreacted PE were recovered. After the reaction was completed, 870 parts of toluene was added.

By the same operation as in Production Example 1, using the same amount of sodium hydroxide aqueous solution and water, after performing the neutralization treatment and the water washing treatment, toluene was distilled off to obtain 120 parts of a purified processed product.

The PEDA content in the resulting refined treatment was 23 area%, the hydroxyl value was 224 mgKOH / g, and the viscosity was 630 mPa. s (hereinafter referred to as "DE-PETA2"). The results are shown in Table 1.

3) Production Example 3 [ Production of (A) component by dehydration esterification method]

Except for using 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, the condensation water was removed under the same conditions as in Raw Material Production Example 1. At the same time, 15% of all hydroxyl groups in the PET are esterified.

The condensation water produced was 10 parts, and 101 parts of unreacted PE were recovered. After the reaction was completed, 870 parts of toluene was added.

By performing the same operation as in Production Example 1, using the same amount of aqueous sodium hydroxide solution and water, after performing neutralization treatment and water washing treatment, toluene was distilled off to obtain 50 parts of a purified processed product.

The PEDA content in the resulting refined treatment was 29 area%, the hydroxyl value was 240 mgKOH / g, and the viscosity was 678 mPa. s (hereinafter, referred to as "DE-PETA3"). The results are shown in Table 1.

4) Production Example 4 [ Production of (A) component by dehydration esterification method]

In the same flask as in Production Example 1, 55% by volume of oxygen-containing nitrogen gas was blown in, while 1163 parts (16.2 mol) of acrylic acid, 732 parts (5.4 mol) of PE, p-toluenesulfonic acid (29 parts), Mix copper chloride (4 parts) under the conditions of reaction temperature about 90 ℃, external temperature 102 ℃, internal and external temperature difference △ T12 ℃, and 101kPa (absolute pressure), and do not remove the condensation water, react to all hydroxyl groups in PE 48% has been esterified.

After the reaction was completed, it was cooled and 20% aqueous sodium hydroxide solution (32 parts) was added to the reaction solution to neutralize the strong acid catalyst.

The reaction solution (1,959 parts) was added to the separatory funnel, followed by cyclohexane (600 parts), methyl ethyl ketone (2,400 parts), and further water (1,250 After mixing), the liquid-liquid separation is carried out by standing, the lower layer is taken out, and the organic phase is separated. Then, a 20% aqueous solution of sodium hydroxide (840 parts) in equal molar amount with the acid component of the organic phase was added with stirring, and neutralization treatment was performed. The organic phase was separated and washed with water. After washing with water, the organic phase was separated again, heated under reduced pressure, and the solvent was distilled off to obtain 874 parts of the purified processed product.

The PEDA content in the resulting refined treatment was 36 area%, the hydroxyl value was 280 mgKOH / g, and the viscosity was 799 mPa. s (hereinafter referred to as "DE-PETA4"). The results are shown in Table 1.

5) Production Example 5 ( Production of (A) component by transesterification method)

Add 90.24 parts (0.66 mol) of neopentaerythritol and 621.04 parts (4.77 mol) of 2-methoxyacrylic acid to a 1 liter flask equipped with a stirrer, thermometer, gas introduction tube, rectification tower and cooling tube Ethyl acetate, 0.85 parts (0.01 mol) of N-methylimidazole of catalyst X, 2.16 parts (0.01 mol) of zinc acrylate of catalyst Y, 0.30 parts (equivalent to the total weight of the added raw materials 413wtppm) of hydroquinone monomethyl ether, and the oxygen-containing gas (containing 5 volume% oxygen and 95 volume% nitrogen) is bubbled into the liquid.

The reaction solution is heated and stirred at a temperature of 105 to 130 ° C, and the pressure in the reaction system is adjusted to the range of 120 to 760 mmHg, and 2-methoxyethanol and acrylic acid 2- which are by-products accompanied by the transesterification reaction are produced. The mixed liquid of methoxyethyl is taken out of the reaction system through a rectification tower and a cooling pipe. In addition, 2-methoxyethyl acrylate is added to the reaction system at the same weight as the withdrawn liquid at any time. After 18 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the withdrawal was terminated. After cooling the reaction solution to room temperature, 40.0 parts of aluminum silicate (Kyowa Kyoward 700 (trade name) manufactured by Chemical Industry Co., Ltd., 4.5 parts of activated carbon (Tahe S (trade name) manufactured by Nimura Chemical Co., Ltd.), heated and stirred at an internal temperature in the range of 95 to 105 ° C under normal pressure 3 hour. After separating the solid components by pressure filtration, dry air is bubbled into the filtrate, and at the same time, the vacuum distillation is carried out at a temperature of 70 to 95 ° C and a pressure of 0.001 to 100 mmHg for 8 hours to separate unreacted acrylic acid. Distillate of 2-methoxyethyl ester. To the bottom liquid of the kettle, 2.0 parts of diatomaceous earth (Radolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.) was added, and pressure filtration was carried out, 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.

Furthermore, the purification yield of the component (A) by the transesterification method is to use the neopentyl content obtained by performing distillation, crystallization, filtration, and other separation and purification operations on the reaction product after the completion of the transesterification reaction. Calculate the mass of the purified product of the acrylate of tetraol.

Purification yield (%) = Refined treatment of acrylate containing neopentyl alcohol (parts) / (Molecular weight of neopentyl alcohol tetraacrylate × Molar number of neopentyl alcohol used as raw material) × 100

6) Production Example 6 ( Production of (A) component by transesterification method)

The component (A) was produced in the same manner as in Production Example 5 except that the compound shown in Table 1 below was used as a catalyst and the heating and stirring time of the transesterification reaction was adjusted to 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 (A) component by transesterification method)

The component (A) was produced in the same manner as in Production Example 5 except that the compound shown in Table 1 below was used as a catalyst and the heating and stirring time of the transesterification reaction was adjusted to 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 (A) component by transesterification method)

The component (A) was produced in the same manner as in Production Example 5 except that the compound shown in Table 1 below was used as a catalyst, and the heating and stirring time of the transesterification reaction was adjusted to 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 (A) component by transesterification method)

The component (A) was produced in the same manner as in Production Example 5 except that the compound shown in Table 1 below was used as a catalyst and the heating and stirring time of the transesterification reaction was adjusted to 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.

In addition, Table 1 also collectively describes the acrylate mixtures of neopentyl alcohol used in the comparative examples. The meaning of the abbreviation is as follows.

. M305: A mixture composed of neopentaerythritol triacrylate (PEDA content of 2 area%, hydroxyl value of 115 mgKOH / g, viscosity of 610 mPa · s), Aronix M-305 manufactured by East Asia Synthetic Co., Ltd.

. M306: A mixture composed of neopentaerythritol triacrylate (PEDA content of 8 area%, hydroxyl value of 154 mgKOH / g, viscosity of 692 mPa · s), Aronix M-306 manufactured by East Asia Synthetic Co., Ltd.

. HCPK: 1-hydroxycyclohexyl phenyl ketone, IRGACURE 184 manufactured by BASF Corporation

Comparing each other with approximately the same hydroxyl value, the acrylic acid ester mixture obtained by the transesterification method of Manufacturing Example 5 to Manufacturing Example 8 relative to the acrylic acid ester mixture obtained by the dehydration esterification of Manufacturing Example 1 to Manufacturing Example 4 The mixture has a lower viscosity.

2. Examples and Comparative Examples 1) Manufacture of active energy ray hardening composition

The compounds shown in Table 2 below were stirred and mixed at the ratios shown in Table 2 to produce active energy ray-curable compositions.

The obtained composition was used for evaluation described below. In addition, the viscosity of the composition was measured according to the same method as described above. The results of this are shown in Table 2.

Furthermore, the numbers in Table 2 mean the number of copies. In addition, the abbreviations in Table 2 are as described above.

2) Evaluation method (1) Pencil hardness

The obtained composition was coated on a polyethylene terephthalate film [manufactured by Toyobo Co., Ltd., Cosmo Shine A4300 (thickness 100 μm)] with a bar coater so that the film thickness became 5 μm.

Using the high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., the obtained test body was adjusted to an irradiation energy of 800 mJ / cm ² per time with an intensity of 500 mW / cm ^{2 in} the ultraviolet region (UV-A) centered at 365 nm. The conveyor belt is transported in an air environment and irradiated with ultraviolet rays.

According to JISK5600-5-4, the pencil hardness of the obtained cured film was evaluated with a load of 750 g.

(2) Water contact angle

For the cured film obtained by the same method as (1), a contact angle measuring device [SCA20 manufactured by Inhiro Seiki Co., Ltd.] was used at a room temperature of 23 ° C. and a 50% RH environment, with a dropping amount of 4 μl Measure the water contact angle.

From the results of Example 1 to Example 9, the composition of the present invention has a PEDA content of 15 to 40 area% and a hydroxyl value of 190 to 400 mgKOH / g in the component (A). Obviously, except for the high hardness of the cured film, The water contact angle is low, and the wettability of the adhesive is excellent.

If the (A) components with approximately the same hydroxyl value are compared with each other, as shown below, the compositions of Examples 1 to 4 containing the (A) component obtained by dehydration and esterification, including the transesterification method The resulting compositions of Example 5 to Example 8 of component (A) have a lower viscosity.

Example 1 (204mgKOH / g): 480mPa. s

Example 5 (200mgKOH / g): 357mPa. s, Example 6 (205mgKOH / g): 366mPa. s

Example 4 (280mgKOH / g): 671mPa. s, Example 8: (284mgKOH / g): 469mPa. s

In contrast, the compositions of Comparative Example 1 and Comparative Example 2 have a PEDA content of less than 15 area% in component (A) and a hydroxyl value of less than 190 mgKOH / g. Compared with the composition of the example, the cured film The water contact angle is higher.

[Industry availability]

The composition of the present invention is preferably used as an active energy ray-curable composition, and in terms of its use, it can be used for various applications such as coating agents, printing inks, pattern forming agents, and adhesives, especially It is better for coating applications.

Claims (14)

A hardening type composition comprising a mixture (A) which is a mixture of (meth) acrylates of neopentyl alcohol, wherein the content of neopentyl alcohol di (meth) acrylate is borrowed The value obtained by high-speed liquid chromatography analysis using a reverse-phase silicone column and using a phosphoric acid aqueous solution / methanol-based eluate is 15 to 40 area%, and the hydroxyl value of the mixture (A) is 190 to 400 mgKOH / g. The hardening composition according to claim 1, wherein the (A) component is a mixture of (meth) acrylates obtained by transesterification of neopentyl alcohol with a compound having one (meth) acryloyl group . The hardening type composition according to claim 2, wherein the (A) component is in the presence of the following catalysts X and Y, and the transesterification reaction of neopentaerythritol with a compound having a (meth) acryloyl group The resulting mixture of (meth) acrylates; Catalyst X: selected from the group consisting of cyclic tertiary amines having a azabicyclic structure or salts or complexes thereof, amidines or salts or complexes thereof, having a pyridine ring One or more compounds in the group of compounds or their salts or complexes, and phosphines or their salts or complexes; Catalyst Y: compounds containing zinc. The hardening composition according to claim 3, wherein the catalyst X is the following compound: Catalyst X: selected from the group consisting of cyclic tertiary amines having an azabicyclic structure or salts or complexes thereof, amidine or One or more compounds in the group of salts or complexes, and compounds having a pyridine ring or salts or complexes thereof. The hardening composition according to claim 2, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The hardening composition according to claim 3, wherein the catalyst Y is a compound selected from the group consisting of zinc organic acid and zinc diketoenolate. An active energy ray hardening type composition comprising the composition according to any one of claim 1 to claim 6. The active energy ray-curable composition according to claim 7, which further contains a photopolymerization initiator (B). An active energy ray-curable composition for coating, which comprises the composition according to claim 7. A method for manufacturing a hardened composition, comprising neopentaerythritol and a compound having one (meth) acryloyl group, performing a transesterification reaction in the presence of the following catalysts X and Y to produce a mixture (A) Step; wherein the mixture (A) is a mixture of (meth) acrylates of neopentyl alcohol, where the content of neopentyl alcohol di (meth) acrylate is obtained by using a reverse phase silicone column and using phosphoric acid The value obtained by high-speed liquid chromatography analysis of the aqueous solution / methanol-based eluate is 15 to 40 area%, and the hydroxyl value of the mixture (A) is 190 to 400 mgKOH / g; Catalyst X: selected from Cyclic tertiary amine with azabicyclic structure or its salt or complex, amidine or its salt or complex, compound with pyridine ring or its salt or complex, and phosphine or its salt or complex More than one compound in the group; Catalyst Y: compounds containing zinc. The method for manufacturing a hardened composition according to claim 10, wherein the catalyst X uses the following compounds: Catalyst X: selected from the group consisting of a cyclic tertiary amine having a azabicyclic structure or a salt or complex thereof, amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof More than one compound in the group. The method for producing a hardened composition according to claim 10, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The method for producing a hardened composition according to any one of claims 10, wherein the catalyst Y is a compound selected from the group consisting of an organic acid zinc and zinc diketoenolate. The method for manufacturing a hardened composition according to any one of claim 10 to claim 13 includes the step of mixing the photopolymerization initiator (B) after manufacturing the component (A).