JP2019206647A - (meth)acrylate composition and manufacturing method therefor - Google Patents

Abstract

To provide a composition capable of making a solution stable over long time even when an organic solvent easily generating peroxide is used for manufacturing a (meth)acrylate solution, and a manufacturing method therefor.SOLUTION: There is provided a (meth)acrylate composition containing following Component (A), Component (B) and Component (C), and the Component (C) of 0.0001 pts.wt. to 2 pts.wt. based on total amount of 100 pts.wt. of the Component (A) and the Component (B). Component (A): a compound having 2 or more (meth)acryloyl groups. Component (B): an organic solvent generating peroxide by receiving oxidation by oxygen. Component (C): an alkali metal compound.SELECTED DRAWING: None

Description

The present invention relates to a composition comprising a compound having two or more (meth) acryloyl groups (hereinafter referred to as “polyfunctional (meth) acrylate”), and includes a method for producing (meth) acrylate and (meth) acrylate. It belongs to the technical field of curable compositions.
In the present specification, acrylate and / or methacrylate is represented as (meth) acrylate.

Polyfunctional (meth) acrylates are used in various applications such as inks, paints, pressure-sensitive adhesives, adhesives, and electronic materials such as resists.
In these applications, an organic solvent is added to the polyfunctional (meth) acrylate to reduce the viscosity of the polyfunctional (meth) acrylate or to be mixed with an organic polymer used as a binder or filler. It may be used as a solution [hereinafter referred to as “(meth) acrylate solution”].
In the production of a (meth) acrylate solution, the polyfunctional (meth) acrylate is not dissolved in the organic solvent immediately before use in these applications, but from the viewpoint of ease of handling, the polyfunctional (meth) in the organic solvent in advance. In general, the acrylate is dissolved and stored in a (meth) acrylate solution, and good storage stability is required in the solution state.

The organic solvent used in the (meth) acrylate solution is appropriately selected according to the purpose of use and application, but for example, aromatic hydrocarbon organic solvents such as benzene and toluene do not pose a problem with air oxidation. However, when the resulting solution is applied to a substrate with low solvent resistance, such as a plastic substrate, there is a problem of eroding the substrate, and from the consideration of safety and the environment, general solvents are It's hard to say.
In addition, although aliphatic hydrocarbon organic solvents such as hexane and heptane have a low effect of eroding the base material, the solubility of polyfunctional (meth) acrylate is generally low, and in particular, polarity such as urethane (meth) acrylate is low. It cannot be used as a solvent for (meth) acrylate having a high molecular weight.
From such a background, the organic solvent used in the (meth) acrylate solution is easy to handle, excellent in compatibility with the polyfunctional (meth) acrylate, and easy to remove the solvent during drying. Organic solvents having polarity such as alcohols, ethers, and ketones are often selected for reasons such as low erosion problems.

However, it is known that these polar solvents such as alcohols, ethers, and ketones rapidly oxidize even at room temperature when they come into contact with air, and peroxides are easily generated (for example, For this reason, the peroxide value of these organic solvents increases.
On the other hand, in order to prevent oxidation of organic solvents, it can be stored under an inert gas atmosphere, but in the case of a (meth) acrylate solution, if it is stored under an inert gas atmosphere, polyfunctional (meth) acrylate will polymerize. There is a problem that it becomes easy to do.

From such a situation, it is meaningless to improve the long-term stability of using an organic solvent having a low peroxide value as the organic solvent of the (meth) acrylate solution. Sometimes a high solvent must be used.
Antioxidants are blended as stabilizers for the purpose of preventing polymerization of (meth) acrylate solutions. Specifically, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and hindered amines. A system antioxidant (HALS) or the like is generally used (for example, Patent Document 1).
However, according to the study by the present inventors, these antioxidants have an effect of suppressing an increase in peroxide when the initial peroxide concentration in the solvent is low, but once exposed to air, the peroxide is oxidized. It has been found that even when added to an organic solvent having increased prices, there is no effect of reducing peroxides, and there is no effect of imparting storage stability to polyfunctional (meth) acrylates over a long period of time.

Theoretical and Experimental Chemistry, Vol.37, No.3, 2001,185-188

International Publication No. 2016/063624 Pamphlet

  An object of the present invention is to produce a (meth) acrylate solution, even if an organic solvent that easily generates peroxide is used, a composition that can make the resulting solution stable over a long period of time and The manufacturing method is provided.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that it is effective to contain an alkali metal compound in a specific ratio in a polyfunctional (meth) acrylate solution, and completed the present invention.
Hereinafter, the present invention will be described in detail.

According to the composition and the production method of the present invention, a polar solvent is used as a solvent, which tends to generate a peroxide by air oxidation and deteriorates the storage stability when the polyfunctional (meth) acrylate is dissolved. In addition, the storage stability can be maintained over a long period of time. In addition, according to the composition and production method of the present invention, the curability is not adversely affected.
The composition and production method of the present invention are particularly acid-modified using (meth) acrylate having a large number of functional groups, such as polyfunctional urethane (meth) acrylate and dipentaerythritol acrylate, and an amine as a catalyst during the synthesis reaction. It is effective for stabilizing solutions of polyfunctional (meth) acrylates.

The present invention is a composition comprising the following component (A), component (B) and component (C), wherein the component (C) is added to 100 parts by weight of the total amount of component (A) and component (B) In a ratio of 0.0001 to 2 parts by weight.
Component (A): Compound having two or more (meth) acryloyl groups Component (B): Organic solvent component that generates peroxide by being oxidized by oxygen (C): Alkali metal compound Hereinafter, component (A) ), The component (B), the component (C), other components, the production method and use of the composition will be described.

1. Ingredient (A)
Component (A) is a polyfunctional (meth) acrylate [compound having two or more (meth) acryloyl groups].
Component (A) includes a compound having two (meth) acryloyl groups (hereinafter referred to as “bifunctional (meth) acrylate”) and a compound having three or more (meth) acryloyl groups (hereinafter referred to as “3”). Functional or more (referred to as “(meth) acrylate”).

1) 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 hexanediol di (meth). Di (meth) acrylates of divalent alkyl diols such as acrylate and nonanediol di (meth) acrylate;
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) Polyalkylene glycol di (meth) acrylates such as acrylate, ditetramethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate; and Di (meth) acrylate of bisphenol A alkylene oxide adduct and di (meth) acrylate of bisphenol F alkylene oxide adduct Di (meth) acrylate of bisphenol compounds alkylene oxide adducts such as acrylate.

  Examples of alkylene oxide adducts in the compounds exemplified above include ethylene oxide adducts, propylene oxide adducts, ethylene oxide and propylene oxide adducts, and the like.

2) Trifunctional or higher (meth) acrylates As trifunctional or higher (meth) acrylates, various compounds may be mentioned as long as they are compounds having three or more (meth) acryloyl groups. For example, glycerin tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, diglycerin tri or tetra (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, ditrimethylolpropane tri or tetra (meth) acrylate and dipentaerythritol tri, tetra Polyol, poly (meth) acrylates such as penta or hexa (meth) acrylate;
Tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, tri or tetra (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, tri, tetra, penta or hexa (meth) acrylate of dipentaerythritol alkylene oxide adduct Poly (meth) acrylates of polyol alkylene oxide adducts such as, and tri (meth) acrylates of isocyanuric acid alkylene oxide adducts.

  Examples of alkylene oxide adducts in the compounds exemplified above include ethylene oxide adducts, propylene oxide adducts, ethylene oxide and propylene oxide adducts, and the like.

3) As polyfunctional (meth) acrylate components (A) other than the above, polyfunctional (meth) acrylates other than those mentioned above can be used.
As the polyfunctional (meth) acrylate, an oligomer may be used, and examples thereof include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
In addition, a compound obtained by adding an acid anhydride to a tri- or higher functional (meth) acrylate having a hydroxyl group [hereinafter referred to as “acid-modified polyfunctional (meth) acrylate”] and the like can be mentioned.
Hereinafter, these compounds will be described.

(1) Urethane (meth) acrylate As urethane (meth) acrylate, a reaction product of polyhydric alcohol, polyhydric isocyanate and hydroxyl group-containing (meth) acrylate, and polyhydric isocyanate and hydroxyl group containing without using polyhydric alcohol A reaction product with (meth) acrylate is mentioned.

As the polyhydric alcohol, a diol is preferable.
Examples of the diol include a low molecular weight diol, a diol having a polyene skeleton, a diol having a polyester skeleton, a diol having a polyether skeleton, and a diol having a polycarbonate skeleton.
Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol and 1,6-hexanediol.
Examples of the diol having a polyene skeleton include a diol having a polybutadiene skeleton, a diol having a polyisoprene skeleton, a diol having a hydrogenated polybutadiene skeleton, and a diol having a hydrogenated polyisoprene skeleton.
Examples of the diol having a polyester skeleton include an esterification reaction product of a diol component such as the low molecular weight diol or polycaprolactone diol and an acid component such as dicarboxylic acid or an anhydride thereof. Examples of the dicarboxylic acid or anhydride thereof include adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.
Examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polyetramethylene glycol.
Examples of the polycarbonate diol include a reaction product of the low molecular weight diol or / and bisphenol such as bisphenol A and a dialkyl ester carbonate such as ethylene carbonate and dibutyl ester carbonate.

As the organic polyisocyanate, an organic diisocyanate is preferable.
Specific examples of the organic diisocyanate include hexamethylene diisocyanate, lysine methyl ester diisocyanate, and aliphatic diisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), ω, Examples include alicyclic diisocyanates such as ω′-diisocyanate dimethylcyclohexane and dimer acid diisocyanate, and aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane-4,4′-diisocyanate.

As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate and hydroxyhexyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as hydroxyoctyl (meth) acrylate (hereinafter referred to as “hydroxyl-containing monofunctional (meth) acrylate”), trimethylolpropane mono- or di (meth) acrylate, pentaerythritol mono-, di- or Hydroxyl groups such as tri (meth) acrylate, ditrimethylolpropane mono, di or tri (meth) acrylate and dipentaerythritol mono, di, tri, tetra or penta (meth) acrylate and Compounds with more than five (meth) acryloyl group [hereinafter referred to as "hydroxyl group-containing polyfunctional (meth) acrylate"] and the like.

(2) Epoxy (meth) acrylate Epoxy (meth) acrylate is a reaction product of an epoxy resin and (meth) acrylic acid.
Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and novolak type epoxy resins. Examples of the bisphenol A type epoxy resin include Epicoat 827 (trade name, the same applies hereinafter) manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 828, Epicoat 1001, Epicoat 1004, and the like. Examples of the bisphenol F type epoxy resin include Epicoat 806, Epicoat 4004P etc. are mentioned. Examples of the novolak type epoxy resin include Epicoat 152 and Epicoat 154.

(3) Polyester (meth) acrylate Polyester (meth) acrylate is a reaction product of polyester polyol and (meth) acrylic acid.
The polyester polyol is obtained by a reaction between a polyhydric alcohol and a polybasic acid.
Examples of the polyhydric alcohol include the diols described above.
Examples of the polybasic acid include succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, and tetrahydrophthalic anhydride.
.

(4) Acid-modified polyfunctional (meth) acrylate In acid-modified polyfunctional (meth) acrylate, the trifunctional or higher functional (meth) acrylate having a hydroxyl group includes ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth). Examples thereof include acrylate and dipentaerythritol penta (meth) acrylate.
Examples of the acid anhydride include the dicarboxylic acid anhydrides described above.

2. Ingredient (B)
Component (B) is an organic solvent that generates peroxide by being oxidized by oxygen.
The component (B) is specifically a compound having an oxygen atom in the chemical structure, and specifically includes alcohols, ethers, ketones, esters, carbonates, and the like. Since it is excellent in the solubility of (A), it is preferable.

Specific examples of alcohol include alkyl alcohols such as methanol, ethanol, isopropanol and butanol;
Examples include alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; and acetone alcohols such as diacetone alcohol.

Specific examples of ethers include aliphatic ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, and t-butyl methyl ether;
Cyclic alkyl group-containing ethers such as cyclopentyl methyl ether;
Acetals such as diethyl acetal and dihexyl acetal;
Cyclic ethers such as tetrahydrofuran, tetrahydropyran, dioxane and trioxane;
And aromatic ethers such as anisole and diphenyl ether; and dimethyl cellosolve, diglyme, triglyme and tetraglyme.

Specific examples of the ketone include aliphatic ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alicyclic ketones such as cyclohexanone; and aromatic ketones such as acetophenone and benzophenone.

Examples of the ester include ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate.
Examples of the carbonate include dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and 1,2-butylene carbonate.

The composition of the present invention is excellent in storage stability even when the component (B) has a high peroxide value. Is preferably used. In this case, the peroxide value is preferably 500 ppm or less, and more preferably 0 to 100 ppm.
In the present invention, the peroxide value means a value obtained by reacting component (B) with potassium iodide and titrating the produced iodine molecules with sodium sulfate.

In the present invention, the component (B) is used as an organic solvent. However, an organic solvent other than the component (B) may be used as necessary within the range not impairing the effects of the present invention [hereinafter referred to as “other organic solvent”. ] Can be used.
Other organic solvents include aliphatic hydrocarbon compounds such as n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane and n-decane, and aromatic hydrocarbon compounds such as benzene, toluene and xylene. And heterocyclic compounds such as N-methylpyrrolidone, sulfones such as sulfolane, and sulfoxides such as dimethyl sulfoxide.

3. Ingredient (C)
Component (C) is an alkali metal compound.
As the alkali metal constituting the alkali metal compound, sodium and potassium are preferable.
As the alkali metal compound, an alkali metal hydroxide is preferable, and examples thereof include sodium hydroxide and potassium hydroxide.
As the alkali metal compound, an alkali metal salt can also be used, and examples thereof include inorganic salts and organic salts, with organic salts being preferred.
Specific examples of the organic salt include organic carboxylates such as an alkali metal salt of acetic acid, an alkali metal salt of propionic acid, and an alkali metal salt of (meth) acrylic acid.
Among these, an alkali metal salt of (meth) acrylic acid is preferable because of its excellent solubility in the component (A).

Component (C) is preferably blended as an aqueous solution of an alkali metal compound because of its excellent solubility in component (A).
As a density | concentration of the alkali metal compound in the aqueous solution of an alkali metal compound, 5-45 weight% is preferable, More preferably, it is 10-40 weight%. By making the concentration of the alkali metal compound within this range, the amount of water brought into the (meth) acrylate solution can be minimized, so that the base hydrolysis during storage of the (meth) acrylate can be prevented, Furthermore, since crystallization of the aqueous alkali metal compound solution can be prevented, handling properties can be improved even at low temperatures such as in winter.

4). Other components Although the composition of this invention makes the said component (A)-(C) essential, a various component can be mix | blended as needed.
Preferable examples of other components include antioxidants and polymerization inhibitors. Hereinafter, the antioxidant and the polymerization inhibitor will be described.

1) Antioxidant Antioxidant can be made more excellent in antioxidant effect when used in combination with component (C).
Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, hindered amine antioxidants, and the like.
Examples of phenolic antioxidants include hindered phenols such as 2,6-di-t-butylhydroxytoluene. Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA Corporation.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites. Examples of commercially available products of these derivatives include ADEKA Corporation, ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, and 3010 etc. are mentioned.
Examples of the sulfur-based antioxidant include thioether-based compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA Corporation.

Hindered amine antioxidants (HALS) are components also known as light stabilizers.
Specific examples of the hindered amine antioxidant include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate. 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3 , 5-triazine, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, and the like.
Examples of commercially available hindered amine antioxidants include ADEKA AL-72, BASF, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100.

  As the antioxidant, one kind of the aforementioned compounds may be used, or two or more kinds may be used in combination. Preferred combinations of these antioxidants include the combined use of a phenolic antioxidant and a phosphorus antioxidant, and the combined use of a phenolic antioxidant and a sulfurous antioxidant.

What is necessary is just to set suitably as a content rate of antioxidant according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of total amounts of a component (A), More preferably, it is 0.1-1 weight. Part.
By making the content of the antioxidant 0.1 parts by weight or more, it is possible to prevent an increase in the peroxide of the composition during storage, while by making it 5 parts by weight or less, (meth) acrylate When a photopolymerization initiator is added and active energy rays are irradiated, a cured product with little coloring can be obtained.

2) Polymerization inhibitor In the composition of the present invention, a polymerization inhibitor can be added to the reaction solution for the purpose of preventing polymerization of acryloyl groups.
Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors.
Specific examples of the organic polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol and 4 Examples thereof include phenolic compounds such as -tert-butylcatechol, quinone compounds such as benzoquinone, phenothiazine, and N-nitroso-N-phenylhydroxylamine ammonium.
As the organic polymerization inhibitor, organic compounds having stable radicals can be used, and examples thereof include carbinoxyl and N-oxyl compounds.
N-oxyl compounds include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2 , 6,6-tetramethylpiperidine-1-oxyl and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl.
Examples of the inorganic polymerization inhibitor include copper chloride, copper sulfate, and iron sulfate.
Examples of the organic salt polymerization inhibitor include copper dibutyldithiocarbamate, N-nitroso-N-phenylhydroxylamine aluminum salt, and the like.

The polymerization inhibitor can be added to the composition or can be used as it is when it is contained in the component (A). Moreover, even when a polymerization inhibitor is contained in the component (A), a polymerization inhibitor can be further added.
As a content rate of a polymerization inhibitor, 0.0005 to 1 weight% is preferable in a composition, More preferably, it is 0.005 to 0.1 weight%. By setting the content of the polymerization inhibitor to 0.0005% by weight or more, the polymerization inhibition effect can be sufficiently exerted, and by setting it to 1% by weight or less, the curability when irradiated with active energy rays is good. Can be.

5. Manufacturing method of composition The composition of this invention contains the said component (A) -component (C) as an essential component.
What is necessary is just to stir and mix a component (A) -component (C) according to a conventional method as a manufacturing method of a composition.

The composition of this invention needs to contain 0.0001 weight part-2 weight part of a component (C) with respect to 100 weight part of total amounts of a component (A) and a component (B).
When the ratio of the component (C) is less than 0.0001 part by weight, the storage stability effect cannot be exhibited, while when it exceeds 2 parts by weight, the component (C) is uniformly dissolved in the composition. Without being deposited, or promoting the hydrolysis of (meth) acrylate, which may accelerate the decomposition of the composition.

What is necessary is just to set suitably as a content rate of a component (A) and a component (B) according to the objective. 90% by weight and 10 to 80% by weight of component (B) are preferably contained, more preferably 30 to 80% by weight of component (A) and 20 to 70% by weight of component (B).
By making the ratio of the component (A) 20% by weight or more, the drying process can be shortened, and since it does not take time to recover the volatilized component (B), it can be excellent in productivity, By making the ratio of a component (A) 90 weight% or less, a composition can be made into a low viscosity and it shall be excellent in handling property.

Moreover, the composition of this invention can also be manufactured by adding a component (B) and a component (C) in the manufacturing process of a component (A).
The reaction in the production process of component (A) may be either a dehydration esterification reaction using alcohol and (meth) acrylic acid or a transesterification reaction using alcohol and (meth) acrylate.
However, in the purification process in the production process of the component (A), for example, when the component (B) and the component (C) are added before the filtration process, these components are removed. Therefore, after the production of the component (A) is completed, it is preferable to add the component (C) in the step of adding and diluting the component (B).

6). Use of composition The composition of the present invention can be used in various applications using the component (A) as a raw material compound.
In particular, it is preferable to use the composition of the present invention as a curable composition by further blending a polymerization initiator such as a photopolymerization initiator and a thermal polymerization initiator.
The composition further containing a photopolymerization initiator in the composition of the present invention can be preferably used as an active energy ray curable composition, and the composition further containing a thermal polymerization initiator is preferably used as a thermosetting composition. can do.

When used as a curable composition, a compound having one ethylenically unsaturated group (hereinafter referred to as “monofunctional unsaturated compound”) can be blended.
As a specific example of the monofunctional unsaturated compound, a compound having one (meth) acryloyl group [hereinafter referred to as “monofunctional (meth) acrylate”] is preferable. As the monofunctional (meth) acrylate, alkyl (meth) acrylate is used. And monofunctional (meth) acrylate having an alicyclic group, monofunctional (meth) acrylate having an alkoxyalkyl group, and aromatic monofunctional (meth) acrylate.
Examples other than monofunctional (meth) acrylates include (meth) acrylamide, aromatic vinyl compounds and vinyl ethers.

The curable composition thus obtained can be used for various applications, such as adhesives, pressure-sensitive adhesives, coating agents such as paints and hard coat agents, inks such as offset and inkjet printing, resists, and photosensitive lithographic plates. Examples include patterns forming compositions such as printing plates and color resists.
When used in these applications, various components can be blended in accordance with the purpose in addition to the components described above.
When used as an adhesive, UV absorbers, light stabilizers, antioxidants, polymerization inhibitors, silane coupling agents, polyol compounds, polymers, tackifiers, fillers, metal particles, metal oxide particles, ions Examples include trapping agents, antifoaming agents, leveling agents, dyes and pigments.
When used as an adhesive, an antioxidant, a polymerization inhibitor, an ultraviolet absorber, a silane coupling agent, a leveling agent, a plasticizer, and the like can be given.
When used as a coating composition, antioxidants, ultraviolet absorbers, pigments / dyes, silane coupling agents, surface modifiers, polymers and the like can be mentioned.
When used for ink, specific examples of other components include binders, pigments, plasticizers, and anti-friction agents.
When used as a resist and pattern forming composition, antioxidants, ultraviolet absorbers, silane coupling agents, surface modifiers, alkali-soluble resins and the like can be mentioned.

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

1. Production example
1) Production Example 1 ( Production of Pentaerythritol Acrylate)
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and 5% oxygen-containing nitrogen gas inlet, 301 g of acrylic acid (4.18 mol), 167 g of pentaerythritol [manufactured by Guangei Chemical Co., Ltd.] .23 mole), 7 g of sulfuric acid as an acid catalyst, 0.14 g of hydroquinone monomethyl ether (hereinafter referred to as “MQ”) as a polymerization inhibitor, and 224 g of toluene as an organic solvent were mixed, and the reaction temperature was about 80 ° C. and 370 Torr (absolute pressure). The reaction was continued until 45% of the total hydroxyl groups in the raw material pentaerythritol had been esterified, while removing the condensed water under the above conditions.
The generated condensed water was 28 g, and 42 g of unreacted pentaerythritol was recovered. After completion of the reaction, 870 g of toluene was added.
A 20% aqueous sodium hydroxide solution corresponding to a molar amount of 1 times the molar amount of the reaction solution to which toluene was added was added with stirring to carry out a neutralization treatment to remove excess acrylic acid and sulfuric acid. The organic layer was separated, and 10 g of water was added to 100 g of the organic layer under stirring, followed by washing with water. The organic layer was separated and heated under reduced pressure to distill off toluene.
The obtained acrylate (hereinafter referred to as “PETAl”) was 185 g, and the hydroxyl value was 204 mgKOH / g.

2) Production Example 2 ( Production of Pentaerythritol Acrylate)
Using the same reaction apparatus as in Production Example 1, acrylic acid, pentaerythritol, sulfuric acid, MQ, and toluene, which are the same raw material compounds as in Production Example 1, are mixed in the same weight as in Production Example 1, and the reaction temperature is about 80 ° C. The reaction was continued until 30% of all hydroxyl groups in the raw material pentaerythritol were esterified while removing condensed water under the condition of 370 Torr (absolute pressure).
The generated condensed water was 18 g, and 83.5 g of unreacted pentaerythritol was recovered. After completion of the reaction, 870 g of toluene was added.
A 20% aqueous sodium hydroxide solution corresponding to a molar amount of 1 times the molar amount of the reaction solution to which toluene was added was added with stirring to carry out a neutralization treatment to remove excess acrylic acid and sulfuric acid. The organic layer was separated, and 10 g of water was added to 100 g of the organic layer under stirring, followed by washing with water. The organic layer was separated and heated under reduced pressure to distill off toluene.
The obtained acrylate (hereinafter referred to as “PETA2”) was 120 g, and the hydroxyl value was 224 mgKOH / g.

3) Production Example 3 [ Production of Component (A): Urethane Acrylate]
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and 5% oxygen-containing nitrogen gas inlet, 100 g of PETA1 having a hydroxyl value of 204 mgKOH / g obtained in Production Example 1, 2,6-di-tert -0.07 g of butyl cresol and 0.07 g of dibutyltin dilaurate were added, 29 g of hexamethylene diisocyanate was added dropwise at 70 ° C. over about 1 hour, and the mixture was reacted at 80 ° C. for 6 hours. This was confirmed and the reaction was completed.
The weight average molecular weight of the obtained urethane acrylate (hereinafter referred to as “UA-1”) was 2,026, and the viscosity at 50 ° C. was 13,800 mPa · s.

4) Production Example 4 [ Production of Component (A): Urethane Acrylate]
In Production Example 3, urethanization reaction was carried out in the same manner as in Production Example 3 except that 32 g of hexamethylene diisocyanate was used instead of PETA1 and 100 g of PETA2 having a hydroxyl value of 224 mgKOH / g obtained in Production Example 2 was used. It was.
The obtained urethane acrylate (hereinafter referred to as “UA-2”) had a weight average molecular weight of 2,330 and a viscosity at 50 ° C. of 23,300 mPa · s.

5) Production Example 5 [ Production of Component (A): Acid anhydride adduct of hydroxyl group-containing polyacrylate]
Using the same reactor as in Production Example 1, 400 g (1.58 mol) of dipentaerythritol, 821 g (11.4 mol) of acrylic acid, 775 g of toluene, 17 g of sulfuric acid, and 2.2 g of MQ were charged into the reactor. The esterification reaction was carried out for 6 hours.
After completion of the above reaction, 1690 g of toluene is added, the reaction solution is filtered using filter paper, then washed with 875 g of distilled water, and 800 g of 10% NaOH aqueous solution is added to the reaction solution after washing with water at room temperature for 1 hour. Neutralization was performed under the following conditions.
After the neutralization treatment, the organic layer and the aqueous layer were separated, the aqueous layer was removed, and 360 g of distilled water was added for the purpose of removing excess NaOH, followed by washing with water. Thereafter, the aqueous layer was removed after the organic layer and the aqueous layer were separated. Thereafter, toluene as a solvent was distilled off under reduced pressure of 50 mmHg or less to obtain dipentaerythritol acrylate (hydroxyl value 36 mgKOH / g).
250 g of the obtained dipentaerythritol acrylate was charged into a glass flask, 16 g of succinic anhydride and 0.13 g of MQ were added, and the temperature was raised to 85 ° C. The reaction was carried out for 4 hours after adding 1.3 g of the catalyst triethylamine. The reaction was performed in a mixed atmosphere of air / nitrogen to obtain a compound having an acid value of 34 mgKOH / g (hereinafter referred to as “DPETA-AH”).

2. Examples 1 to 6 and Comparative Examples 1 to 5
As the component (B), propylene glycol monomethyl ether (hereinafter referred to as “PGM”) and methyl ethyl ketone (hereinafter referred to as “MEK”), which had the following peroxide values by titration, were used.
・ PGM: 20ppm
・ MEK: 16ppm
Components (A), (B) and (C) shown in Table 1 below were stirred and mixed to prepare a composition.
The following stability test was done using the obtained composition. The results are shown in Table 1.

○ Stability test 10 g of the composition shown in Table 1 was added to a 50 mL screw bottle, capped, allowed to stand at 30 ° C., and the number of days until gelation was determined.
The test period was 3 months, and those that did not gel after 3 months were expressed as “> 3 months”.

The abbreviations in Table 1 mean the following. The numbers in parentheses in the table mean the number of copies. Furthermore, when an aqueous solution is used as the component (C), it means the number of solids.
20% NaOH: 20% aqueous sodium hydroxide solution 36% AANA: 36% aqueous sodium acrylate solution LA-72: HALS, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate ( ADEKA brand name ADK STAB LA-72
AS3010: Phosphorous antioxidant, triisodecyl phosphite, trade name ADEKA STAB 3010 manufactured by ADEKA Corporation
BHT: Dibutylhydroxytoluene (2,6-di-tert-butyl-p-cresol)

The compositions of Examples 1 to 6 corresponding to the composition of the present invention were excellent in storage stability that did not gel even after 3 months.
On the other hand, the storage stability of the compositions of Comparative Examples 1 to 5 not containing the component (C) was greatly reduced.

  The composition and production method of the present invention can be used in the technical field of producing a polyfunctional (meth) acrylate and in the technical field of using a polyfunctional (meth) acrylate. In particular, the curable composition comprising the composition of the present invention can be used for various applications, and examples thereof include adhesives, pressure-sensitive adhesives, coating agents, inks, and pattern forming agents.

Claims (8)

It is a composition containing the following component (A), component (B), and component (C), Comprising: 0.0001 component (C) with respect to 100 weight part of total amounts of a component (A) and a component (B) (Meth) acrylate composition contained in a ratio of 2 parts by weight to 2 parts by weight.
Component (A): Compound having two or more (meth) acryloyl groups Component (B): Organic solvent component that generates peroxide by being oxidized by oxygen (C): Alkali metal compound The (meth) acrylate composition according to claim 1, wherein the component (B) is one or more compounds selected from the group consisting of alcohols, ethers, and ketones. The (meth) acrylate composition according to claim 1 or 2, wherein the alkali metal constituting the component (C) is sodium or potassium. The (meth) acrylate composition according to any one of claims 1 to 3, wherein the component (C) is an alkali metal salt of (meth) acrylic acid. A method for producing a composition comprising the following component (A), component (B) and component (C),
Production of (meth) acrylate composition in which component (C) is added and mixed in a ratio of 0.0001 to 2 parts by weight with respect to 100 parts by weight of the total amount of component (A) and component (B). Method.
Component (A): Compound having two or more (meth) acryloyl groups Component (B): Organic solvent component that generates peroxide by being oxidized by oxygen (C): Alkali metal compound The method for producing a (meth) acrylate composition according to claim 5, wherein the component (B) is one or more compounds selected from the group consisting of alcohol, ether, and ketone. The method for producing a (meth) acrylate composition according to claim 5 or 6, wherein the alkali metal constituting the component (C) is sodium or potassium. The said component (C) is an alkali metal salt of (meth) acryl, The manufacturing method of the (meth) acrylate composition in any one of Claims 5-7.