JP4973072B2 - Active energy ray-curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition, capable of effectively improving the storage stability by a simple method without problems of coloring, and the like. <P>SOLUTION: The active energy ray-curable composition containing a compound (A) having an ethylenically unsaturated group has the peroxide content in the composition of less than 2 ppm based on the oxygen equivalent. As the (A) component, an N-vinyl-pyrrolidone (A-1) is preferable. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to an active energy ray-curable composition, and the composition of the present invention can be used for various applications such as coating agents such as inks and paints, adhesives, binders and molded products. It will be used in the field.

  The active energy ray-curable composition is excellent in curability and is used in various fields because it has a low environmental load because it does not use a solvent.

In the active energy ray-curable composition, N-vinylpyrrolidone (hereinafter referred to as NVP) is used as a reactive diluent for high-viscosity (meth) acrylate because it is fast-curing and has excellent adhesion to a substrate. Is often blended (for example, Patent Documents 1 and 2).
However, compositions containing NVP (hereinafter referred to as NVP-based compositions) often have poor storage stability. That is, when the NVP-based composition is stored for a long time, there is a problem that the viscosity increases with time.

JP-B-1-53312 (6th column, lines 6-11)

Japanese Patent No. 2525647 (Claims)

  In order to solve the storage stability of the NVP-based composition, the storage stability has been improved by blending a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, which has been conventionally blended with the active energy ray-curable composition. However, it has a problem that the composition is colored (Patent Documents 3 and 4, etc.).

  The present inventors have intensively studied to find an active energy ray-curable composition that can effectively improve storage stability by a simple method and has no problems such as coloring.

Japanese Patent Laid-Open No. 10-017877 (paragraph number 0032)

JP 09-272707 A (paragraph number 0011)

As a result of various studies, the present inventors have found that in order to solve the above problems, the storage stability of the resulting composition can be improved by a simple method of managing the amount of peroxide in the composition. The headline and the present invention were completed.
Hereinafter, the present invention will be described in detail. In the present specification, (meth) acrylate means acrylate and / or methacrylate.

1. Active energy ray-curable composition The present invention is a composition comprising an ethylenically unsaturated group-containing compound (A) [hereinafter simply referred to as component (A)], wherein N-vinylpyrrolidone is used as the component (A). The present invention relates to an active energy ray-curable composition containing (A-1) and having a peroxide content of less than 2 ppm in terms of oxygen.
Hereinafter, the component (A) will be described.

1-1. Component (A) Component (A) used in the present invention contains N-vinylpyrrolidone (A-1) [hereinafter referred to as component (A-1)], and (A) other than component (A-1) As the component, various compounds can be used as long as they have an ethylenically unsaturated group.
Examples of the component (A) include compounds having a vinyl group such as (meth) acrylate, vinyl ether and N-vinylpyrrolidone, and (meth) allyl compounds.
Hereinafter, (meth) acrylate and vinyl ether will be described.

1-1-1. (Meth) acrylate
As the (meth) acrylate, a compound having one (meth) acryloyl group (hereinafter referred to as mono (meth) acrylate) and a compound having two or more (meth) acryloyl groups (hereinafter referred to as poly (meth) acrylate), etc. Is mentioned.

  Examples of the mono (meth) acrylate include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and 1,4-butanediol mono (meth) acrylate; phenol ethylene oxide modified (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate and nonylphenol Aromatic mono (meth) acrylates such as ethylene oxide-modified (meth) acrylate; alicyclic mono (meth) acrylates such as isobornyl acrylate, and the like. In addition to these, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, (meth) acryloylmorpholine, maleimide (meth) acrylate, glycidyl (meth) acrylate, and the like can be given.

Examples of the poly (meth) acrylate include directional group di (meth) such as bisphenol A alkylene oxide modified di (meth) acrylate, bisphenol F alkylene oxide modified di (meth) acrylate and bisphenol Z alkylene oxide modified di (meth) acrylate. Acrylate; alkylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) Polyalkylene glycol di (meta) such as acrylate, polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate Acrylate; (meth) acrylate having two (meth) acryloyl groups such as isocyanuric acid ethylene oxide-modified di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, polyethylene glycol di (meth) acrylate, and penta It has three (meth) acryloyl groups such as erythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, isocyanuric acid alkylene oxide modified tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, etc. A (meth) acrylate etc. can be mentioned. In addition to these, (meth) acrylates having four or more (meth) acryloyl groups such as dipentaerythritol hexa (meth) acrylate and di (trimethylolpropane) tetra (meth) acrylate can also be used.
In the above, examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.

  In addition, oligomers such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate can also be used.

Examples of the urethane (meth) acrylate oligomer include a reaction product obtained by further reacting a hydroxyl group-containing (meth) acrylate with a polyol and an organic polyisocyanate reaction product.
Here, examples of the polyol include a low molecular weight polyol, a polyether polyol, and a polyester polyol.
Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexane dimethanol and 3-methyl-1,5-pentanediol.
Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
As the polyester polyol, a reaction product of these low molecular weight polyols and / or polyether polyols and acid components such as dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or anhydrides thereof. Is mentioned.
Examples of the organic polyisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

As a polyester (meth) acrylate oligomer, the dehydration condensate of a polyester polyol and (meth) acrylic acid is mentioned.
Examples of the polyester polyol include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol and trimethylolpropane, and these And a reaction product from a polyol such as an alkylene oxide adduct and an acid component such as a dipic acid such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or an anhydride thereof.

  Epoxy acrylate is obtained by addition reaction of (meth) acrylic acid to epoxy resin, (meth) acrylate of bisphenol A type epoxy resin, (meth) acrylate of phenol or cresol novolac type epoxy resin and diglycidyl ether of polyether (Meth) acrylic acid adducts and the like.

1-1-2. As vinyl ether vinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, 2- (2′-vinyloxyethoxy) ethyl acrylate and 2- (2′-vinyloxyethoxy) ethyl methacrylate and the like can be mentioned.

1-1-3. Preferred component (A)
As the component (A) other than the component (A-1) , a compound having a (meth) acrylate and a vinyl group is preferable among those described above.
The component (A) In this case, preferably a combination of compounds having a component (A-1) and other ethylenically unsaturated groups [hereinafter called component (A-2)].

As the component (A-2), any compound other than the component (A-1) may be arbitrarily selected from the above-mentioned compounds, preferably a (meth) acrylate, more preferably a high viscosity (meth). Acrylate.
As the high viscosity (meth) acrylate, a (meth) acrylate having a viscosity at 25 ° C. of 10,000 mPa · s or more is preferable.
Examples of the high viscosity (meth) acrylate include urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate.

  The ratio of the component (A-1) and the component (A-2) may be appropriately set according to the purpose and application, but is preferably based on the total amount of the component (A-1) and the component (A-2). As (A-1) component 1-50 mass% and (A-2) component 50-99 mass% are preferable, More preferably, (A-1) component 5-40 mass% and (A-2) component 60 It is -95 mass%.

1-2. Other Components When the composition of the present invention is cured by ultraviolet rays, a photopolymerization initiator can be blended as necessary.
Photopolymerization initiators include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenyl Acetophenones such as acetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2 -Anthraquinones such as methyl anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxa Thioxanthone such as benzene, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,6-trimethylbenzoyl diphenylphosphine oxide Monoacylphosphine oxide or bisacylphosphine oxide; benzophenones such as benzophenone; and xanthones.
These photopolymerization initiators can be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiation accelerator.
A preferable blending ratio of the photopolymerization initiator is 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the composition.

In addition to the above, various components can be blended according to the use and necessity.
For example, various additives such as fillers such as barium sulfate, silicon oxide, talc, clay and calcium carbonate, coloring pigments such as phthalocyanine blue, phthalocyanine green, titanium oxide and carbon black, adhesion imparting agents and leveling agents And polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, and N-nitrosophenylhydroxylamine aluminum salt.

1-3. Composition The composition of the present invention has a peroxide content of less than 2 ppm in terms of oxygen. If this amount exceeds 2 ppm, the viscosity will increase with time, and the storage stability will decrease.
The peroxide content in the present invention can be measured by a method of titrating liberated iodine with sodium thiosulfate using potassium iodide.

  Examples of the method for reducing the peroxide content of the composition to less than 2 ppm include a method in which the raw material (A) component has a peroxide content of less than 2 ppm. In addition, after the composition is manufactured, a method such as nitrogen sealing may be used so that the peroxide content does not increase.

  Furthermore, the acid value of the composition is preferably less than 0.2 mg KOH / g because the increase in viscosity over time can be suppressed. As a method for obtaining such an acid value, a compound having no acid group is used as the component (A), or an unreacted (meth) acrylic acid or a compound having a reduced amount of an acid catalyst is used as a final product. It ’s fine.

2. Production Method The composition of the present invention can be produced by stirring and mixing a plurality of types of component (A) and other components as necessary according to a conventional method.
When the component (A) and / or other components are poor in solubility, heating can be performed during or after the blending of each component, if necessary.

In the present invention, since the composition contains the component (A-1), a method in which the composition is not heated at 60 ° C. or higher after the blending of the component (A-1) is preferable because the increase in viscosity can be suppressed.

3. Applications and methods of use The composition of the present invention can be used in various applications, and examples thereof include coating agents such as inks and paints, adhesives, binders and molded articles. Among these, it can be preferably used for ink, coating agent and adhesive.

As a method for using the composition of the present invention, for example, in the case of uses such as inks, coating agents, adhesives and binders, ultraviolet rays and electrons are applied to the base material to be applied by a normal coating method. In the case of applications such as molding materials, etc. by irradiating active energy rays such as lines, the composition is injected into a predetermined mold and cured by irradiating with active energy rays. A general method such as a method can be employed.
As the irradiation method of the active energy ray, a general method conventionally known as a curing method of the active energy ray curable composition may be employed.

  According to the active energy ray-curable composition of the present invention, the storage stability can be effectively improved by a simple method, and there is no problem such as coloring.

The present invention relates to an active energy ray-curable composition comprising a component (A), wherein the peroxide content in the composition is less than 2 ppm in terms of oxygen.
The acid value of the composition is preferably less than 0.2 mgKOH / g.
As the composition of the present invention, the component (A) preferably contains N-vinylpyrrolidone (A-1).
Furthermore, as a method for producing a composition containing the component (A-1), a method in which the composition is not heated at 60 ° C. or higher after the blending of the component (A-1) is preferable.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following, “part” means part by mass.

○ Example 1
Among the compounds shown in Table 1, compounds other than N-vinylpyrrolidone (hereinafter referred to as NVP) and Irgacure 651 (benzyldimethyl ketal; hereinafter referred to as IC-651) manufactured by Ciba Specialty Chemicals are stirred and dissolved at 80 ° C. for 2 hours. I let you.
After the mixture was cooled to 50 ° C., NVP was added and dissolved, and finally IC-651 was added and dissolved.
The resulting composition was a transparent light yellow liquid of APHA 40. Further, the peroxide content of the composition was measured by a method of titrating liberated iodine with sodium thiosulfate using potassium iodide and found to be 0.2 ppm or less.
The composition remained liquid even when heated at 90 ° C. for 3 hours.

NVP: N-vinylpyrrolidone M-1600: urethane acrylate, Aronix M-1600 manufactured by Toagosei Co., Ltd. Peroxide amount = 0.8ppm
M-1600-2: Heated at 80 ° C. for 48 hours while bubbling air through M-1600. Peroxide content = 12.4ppm
M-313: Mixture of diacrylate and triacrylate of isocyanuric acid ethylene oxide modified product, Aronix M-313 manufactured by Toagosei Co., Ltd.
M-6100: Polyester acrylate, Aronix M-6100 manufactured by Toagosei Co., Ltd.
M-210: Bisphenol A ethylene oxide 2 mol modified acrylate, Aronix M-210 manufactured by Toagosei Co., Ltd.
IC-651: benzyldimethyl ketal, Irgacure 651, manufactured by Ciba Specialty Chemicals

○ Comparative Example 1
A composition was produced in the same manner as in Example 1 except that the compounds shown in Table 1 were used.
The resulting composition was a transparent light yellow liquid of APHA 40.
When the composition was heated at 90 ° C., it gelled in 1 hour.

The composition of this invention can be used for various uses, such as coating agents, such as ink and a coating material, an adhesive agent, a binder, and a molded article.

Claims (6)

A composition comprising an ethylenically unsaturated group-containing compound (A) [hereinafter referred to as “component (A)”] , wherein N-vinylpyrrolidone (A-1) [hereinafter referred to as “(A -1) component ” and an active energy ray-curable composition having a peroxide content of less than 2 ppm in terms of oxygen. The active energy ray-curable composition according to claim 1, wherein the acid value is less than 0.2 mgKOH / g. The component (A) includes (A-1) component and a compound (A-2) having an ethylenically unsaturated group other than the component (A-1) [hereinafter referred to as “component (A-2)”], The component (A-1) and the component (A-2) containing 1 to 50% by mass of the component (A-1) and 50 to 99% by mass of the component (A-2) based on the total amount of the component (A-2). 2. The active energy ray-curable composition according to 2. The active energy ray-curable composition according to claim 3, wherein the component (A-2) is (meth) acrylate. Furthermore, the activity of any one of Claims 1-4 which contains a photoinitiator and contains the said photoinitiator in 0.1 mass part or more and 10 mass parts or less with respect to 100 mass parts of compositions. Energy ray curable composition. A composition comprising N-vinylpyrrolidone (A-1), wherein the peroxide content in the composition is less than 2 ppm in terms of oxygen, comprising: (A -1) A method for producing an active energy ray-curable composition in which the composition is not heated at 60 ° C. or higher after blending the components.