JP6907706B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition, preferably an active energy ray-curable composition, and the cured film is preferably used as a coating agent for polypropylene coating because it has excellent adhesion to a plastic base material, particularly a polypropylene base material. Can belong to these technical fields.
In the present specification, acrylate or methacrylate is referred to as (meth) acrylate, and acrylic acid or methacrylic acid is referred to as (meth) acrylic acid.

Polypropylene is used in a variety of applications because of its high productivity, moldability, light weight and economy. Further, molded products using polypropylene are used for various purposes such as electric appliances, daily necessities such as furniture, building materials and medical treatment.

Similar to ordinary plastic, the surface of polypropylene is coated and coated with a paint called a hard coating agent for the purpose of surface protection that imparts scratch resistance and the like.
As a hard coating agent, a solvent type coating composition is known.

However, the solvent-based coating composition requires heating in order to evaporate and dry the organic solvent contained therein, which requires heat energy and equipment required for heating, and in recent years, the environment of the organic solvent has changed. There is also an increasing momentum for using paints other than solvent-based paint compositions for plastic substrates such as polypropylene.
On the other hand, the active energy ray-curable composition can be cured by irradiating with active energy rays such as ultraviolet rays, visible rays and electron beams for a very short time, and has high productivity. Widely used as a coating.

However, the active energy ray-curable composition has a problem that good adhesion cannot be obtained depending on the type of the plastic base material when the base material is a plastic base material, and the polypropylene base material is particularly difficult to adhere to. There was no preferable composition for this.
For the purpose of improving the adhesion to a polypropylene base material, an active energy ray-curable composition in which (meth) acrylate and chlorinated polyolefin are used in combination is known (Patent Documents 1 and 2).
However, the cured film in the composition has insufficient adhesion to the polypropylene base material and insufficient scratch resistance of the cured film.

Japanese Unexamined Patent Publication No. 2005-139305 Japanese Unexamined Patent Publication No. 2000-017027

The present inventors have good adhesion to a wide range of substrates, particularly excellent adhesion to plastic substrates such as polypropylene substrates, and scratch resistance that does not cause scratches even when scratched by nails. Diligent studies were conducted to find a curable composition, particularly a curable composition that can be suitably used as a coating agent.

As a result of diligent studies to solve the above problems, the present inventors have made a (meth) acrylate having a specific (meth) acryloyl group equivalent, a modified polyolefin-based polymer, and a (meth) acrylate-based polymer having a specific weight average molecular weight. We have found that the curable composition containing a polymer has good adhesion to a plastic base material, particularly a polypropylene base material, is not easily scratched by scratching with a nail, and can be suitably used as a coating agent. The invention was completed.
Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, the cured film has good adhesion to a wide range of substrates, particularly excellent adhesion to plastic substrates such as polypropylene substrates, and excellent scratch resistance.
The reason for this is that the composition of the present invention can reduce the heat of polymerization during curing, particularly the heat of polymerization generated during active energy ray curing, and alleviate the heat shrinkage generated by curing. Therefore, the stress at the interface between various base materials, particularly the plastic base material and the composition can be significantly reduced, and as a result, the adhesion between the plastic base material and the composition having a significantly different coefficient of thermal expansion can be further improved. I think it can be done.

The present invention contains the following components (A), (B) and (C) .
For a total of 100 parts by weight of the following component (A)
Cured composition containing 2 to 100 parts by weight of the component (B) and 20 to 150 parts by weight of the component (C), respectively, and 30 to 200 parts by weight in total of the component (B) and (C). Regarding things.
Component (A): A compound having one (meth) acryloyl group in one molecule and having a (meth) acryloyl group equivalent of 140 to 500 g / eq.
Component (B): Modified polyolefin polymer having a weight average molecular weight (hereinafter referred to as "Mw") of 5,000 to 100,000. Component: Alkyl (meth) acrylate as an essential constituent monomer unit. A polymer having an Mw of 5,000 to 20,000.
Hereinafter, the essential components (A) to (C), other components, usage methods, and the like will be described.

1. 1. Component (A) Component (A) is a compound having one (meth) acryloyl group in one molecule, having a (meth) acryloyl group equivalent of 140 to 500 g / eq, and is a compound of active energy rays. It is a compound that cures when irradiated or heated.
The component (A) is a component for imparting good scratch resistance to the cured film of the composition.
The component (A) is a compound having a (meth) acryloyl group equivalent of 140 to 500 g / eq. A compound having a (meth) acryloyl group equivalent of less than 140 g / eq has a large shrinkage during curing and lacks adhesion, while a compound having a (meth) acryloyl group equivalent of more than 500 g / eq has scratch resistance. It will be insufficient.

Compounds having one or more (meth) acryloyl groups in one molecule include (meth) acrylates having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylates”) and two or more. the (meth) acryloyl group-containing (meth) acrylate (hereinafter, referred to as "polyfunctional (meth) acrylate"), with the present invention to use a monofunctional (meth) acrylate which is the component (a).

Specific examples of monofunctional (meth) acrylates include butyl methacrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate. Alkyl (meth) acrylate such as;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. Monofunctional (meth) acrylate having an alicyclic group of
Glycidyl methacrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan-4) Monofunctional (meth) acrylate having a cyclic ether group such as −yl) methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate;
Aromatic monofunctional (meth) acrylates such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-phenylphenoxy (meth) acrylate and p-cumylphenol ethylene (meth) acrylate;
(Meta) Monofunctional (meth) acrylate having a maleimide group such as acryloryloxyethyl hexahydrophthalimide;
(Meta) Acryloyl morpholine;
Examples thereof include monofunctional (meth) acrylates having an alkoxyalkyl group such as alkylcarbitol (meth) acrylates such as ethylcarbitol (meth) acrylate and 2-ethylhexylcarbitol (meth) acrylate.

As a specific example of the polyfunctional (meth) acrylate, the (meth) acrylate having two (meth) acryloyl groups (hereinafter, referred to as “bifunctional (meth) acrylate”) is specifically of bisphenol A. Di (meth) acrylate of alkylene oxide adduct, di (meth) acrylate of alkylene oxide adduct of bisphenol F, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, etc. Didioli (meth) acrylate;
Di (meth) acrylate of polyols such as di (meth) acrylate of dipentaerythritol;
Di (meth) acrylates of these polyol alkylene oxide adducts Di (meth) acrylates of isocyanuric acid; and di (meth) acrylates of isocyanuric acid alkylene oxide adducts can be mentioned.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.

Specific examples of the trifunctional or higher functional (meth) acrylate include glycerin alkylene oxide adduct tri (meth) acrylate, trimethylolpropane alkylene oxide adduct tri (meth) acrylate alkylene oxide adduct, and pentaerythritol alkylene oxide adduct. Polypoly of polyols such as tri or tetra (meth) acrylates of trimethylolpropane, tri or tetra (meth) acrylates of alkylene oxide adducts of trimethylolpropane, and tetra, penta or hexa (meth) acrylates of alkylene oxide adducts of dipentaerythritol. (Meta) acrylate;
Tris (2- (meth) acryloyloxyethyl) isocyanurate and the like; and tri (meth) acrylate of the isocyanuric acid alkylene oxide adduct and the like can be mentioned.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide. However, the alkylene oxide adduct is limited to a compound satisfying a (meth) acryloyl group equivalent of 140 to 500 g / eq depending on the type of alkylene oxide and the number of moles added.

As the component (A), a (meth) acrylate having a functional group such as a hydroxyl group and an amide group can also be used.

Examples of the monofunctional (meth) acrylate having a hydroxyl group include hydroxyalkyl (meth) acrylates such as hydroxypropyl methacrylate and hydroxybutyl (meth) acrylate;
Polyol mono (meth) acrylates such as glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, ditrimethylolpropane mono (meth) acrylate and dipentaerythritol mono (meth) acrylate;
Examples thereof include mono (meth) acrylates of these polyol alkylene oxide adducts; and 2-hydroxy-3-phenoxypropyl (meth) acrylates, which are reactants of phenylglycidyl ether and (meth) acrylic acid.

Examples of the polyfunctional (meth) acrylate having a hydroxyl group include polyol poly (meth) such as diacrylate of ditrimethylolpropane, di or trimethacrylate of ditrimethylolpropane, diacrylate of dipentaerythritol, and di or trimethacrylate of dipentaerythritol. Acrylate; and di or tri (meth) acrylate of these polyol alkylene oxide adducts can be mentioned.
Examples of the alkylene oxide in the above-mentioned alkylene oxide adduct include ethylene oxide, propylene oxide and tetramethylene oxide.

Examples of the compound having an amide group include (meth) acrylamide, and specifically, Nn-butylmethacrylate, N-sec-butylmethacrylate, Nt-butylmethacrylate, and Nn-hexyl. N-alkyl (meth) acrylamide such as (meth) acrylamide; as well as N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide and N, N -N, N-dialkyl (meth) acrylamide of dihexyl (meth) acrylamide and the like can be mentioned.

Among the above-mentioned compounds, monofunctional (meth) acrylate is preferable because of its excellent adhesion to the base material.
Further, among the monofunctional (meth) acrylates, the (meth) acrylate having a glass transition point (hereinafter referred to as “Tg”) of the homopolymer is preferably 80 ° C. or higher, and more preferably the Tg of the homopolymer is 90 to 200 ° C. Is a (meth) acrylate.
For example, examples of (meth) acrylates in which the Tg of the homopolymer contains the relevant value are isobornyl acrylate (Tg of the homopolymer: 97 ° C., hereinafter, the parentheses mean the Tg of the homopolymer), acryloylmorpholin. (145 ° C.), and the like.
In the present invention, Tg means a value measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC), and is at the glass transition temperature midpoint (Tmg) in the ΔT-temperature curve. Means a value.

Further, among the monofunctional (meth) acrylates, isobornyl acrylate, acryloyl morpholine and 2-hydroxy-3-phenoxypropyl (meth) acrylate [reactant of phenylglycidyl ether and (meth) acrylic acid] are used as the base material. It is more preferable because it is more excellent in adhesion.

The content ratio of the component (A) is preferably 30 to 80% by weight, more preferably 40 to 60% by weight in the composition.
When the component (A) is 30% by weight or more, the surface hardness of the cured film of the highly transparent composition can be made excellent, while when it is 80% by weight or less, heat shrinkage in curing can be achieved. Can be suppressed, and the adhesion to the substrate can be excellent.

2. Component (B) Component (B) is a modified polyolefin-based polymer having an Mw of 5,000 to 100,000, and is a component capable of improving adhesion to a plastic substrate, particularly a polyolefin such as polypropylene. ..
The modified polyolefin constituting the component (B) means a compound in which a carboxyl group, an acid anhydride group, a hydroxyl group, or the like is introduced into the polyolefin.

Examples of the polyolefin in this case include homopolymers of olefins and copolymers of two or more types of olefins. Specific examples of the polyolefin include polyethylene, polypropylene, ethylene-propylene copolymer, polybutadiene hydride, propylene-butadiene copolymer and hydride thereof.
An example of a modified polyolefin-based polymer having a carboxyl group and / or an acid anhydride group will be described. At least one selected from unsaturated carboxylic acids and acid anhydrides thereof (hereinafter, "unsaturated carboxylic acid"). A polymer obtained by graft-polymerizing (referred to as "monomer") can be mentioned.
Examples of the unsaturated carboxylic acid monomer include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, hymicic anhydride, (meth). Examples thereof include acrylic acid and (meth) acrylic acid ester.

The component (B) is a polymer having a Mw of 5,000 to 100,000, preferably a polymer having a Mw of 10,000 to 50,000.
In the case of a polymer having a Mw of the component (B) of less than 5,000, the physical properties of the cured film of the composition such as scratch resistance are deteriorated, and in the case of a polymer having a Mw of more than 100,000, it is high. It becomes viscous, the coatability deteriorates, and the adhesion deteriorates.
In the present invention, Mw means a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”) into polystyrene.

As the component (B), a polymer in which the polymer is chlorinated (hereinafter, referred to as "chlorinated polyolefin") is preferable.
An example of a chlorinated polyolefin having a carboxyl group and / or an acid anhydride group will be described. A polymer obtained by chlorinating a modified polyolefin obtained by graft-polymerizing an unsaturated carboxylic acid monomer to a polyolefin or a polyolefin obtained by graft-polymerizing the polyolefin is chlorine. Examples thereof include a polymer obtained by graft-polymerizing an unsaturated carboxylic acid monomer to this chlorinated polymer after conversion.
In the method for producing a chlorinated polyolefin, examples of the chlorination method include a method in which a modified polyolefin or polyolefin is dissolved in a solvent such as chloroform and the chlorine is reacted under pressure.
The degree of chlorination (chlorine content) of the chlorinated polyolefin is preferably 25 to 50% by weight, more preferably 30 to 40% by weight. A polymer having a degree of chlorination of 25% by weight or more is preferable in that it is excellent in solubility with the component (A). Can be excellent.

The component (B) may be used alone or in combination of two or more.
The content ratio of the component (B) is 100 parts by weight in total of the component (A), and when the component (D) described later is blended, the content of the component (A) and the component (D) is 100 parts by weight in total. 2 to 100 parts by weight is preferable, and 5 to 50 parts by weight is more preferable.
By setting the content ratio of the component (B) to 2 or more polymerization parts, the cured film of the composition can have excellent adhesion to the plastic substrate, and by setting the content to 100 polymerization parts or less, the composition can be made. It can be excellent in coatability and curability.
Hereinafter, the component (A), or the components (A) and (D) will be referred to as a curable component.

3. 3. Component (C) Component (C) is a polymer containing an alkyl (meth) acrylate as an essential constituent monomer unit and having an Mw of 5,000 to 20,000.
The component (C) can reduce the heat of polymerization of the composition generated during curing, particularly the heat of polymerization of the composition generated during active energy ray curing, and can alleviate the heat shrinkage generated by curing. Therefore, the stress at the interface between the various base materials and the composition can be significantly reduced, and in particular, the adhesion between the polyolefin base material having a significantly different coefficient of thermal expansion and the cured film of the composition can be further improved.

Further, by using a polymer containing an alkyl (meth) acrylate as an essential constituent monomer unit as the component (C), compatibility with the component (A) and other components in the composition can be improved. ..
If a polymer that does not contain (meth) acrylate other than the component (C) as a constituent monomer unit is used, it cannot be sufficiently soluble in the component (A) and other components, and the number of copies required to suppress heat shrinkage. Cannot be used.

The Mw of the component (C) is in the range of 5,000 to 20,000, preferably 10,000 to 17,000.
A polymer having an Mw of less than 5,000 has insufficient scratch resistance of the obtained composition, and when the Mw exceeds 20,000, the compatibility with the component (A) and other components becomes incompatible. It will decrease and it will not be possible to mix in the desired blending ratio.
Further, as the component (C), a polymer having a polydispersity (Mw / Mn) of 4.50 or less, which is a ratio of Mw (weight average molecular weight) to a number average molecular weight (hereinafter referred to as “Mn”), is used. It is preferable to a polymer having a weight of 4.00 or less. The polymer having the polydispersity is preferable because the viscosity of the composition and the smoothness of the appearance of the obtained cured coating film are good.
In the present invention, Mn and Mw mean values obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”) into polystyrene.
More specifically, it means a value obtained by converting the molecular weight measured by GPC under the following conditions into polystyrene.
○ Measurement conditions Column: TSKgel SuperMultipore HZ-M (multi-dispersion type packing material) manufactured by Tosoh Corporation x 4 Column temperature: 40 ° C.
Eluent: Tetrahydrofuran Detector: RI

The Tg of the component (C) is preferably in the range of 0 ° C. to 150 ° C., and more preferably in the range of 30 to 100 ° C.
The scratch resistance of the cured film can be improved by setting the Tg of the component (C) to 0 ° C. or higher, and the component (C) can be uniformly dissolved in the composition by setting the Tg to 150 ° C. or lower. can.

1) As the monomer (C) component, various polymers can be used as long as it is a polymer containing an alkyl (meth) acrylate as an essential constituent monomer unit.
As the component (C), even if it is a homopolymer of an alkyl (meth) acrylate, it is an ethylenically unsaturated group-containing compound copolymerizable with the alkyl (meth) acrylate and the alkyl (meth) acrylate (hereinafter, “other simple compounds”). It may be a copolymer of "quantity").

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, and isobutyl (meth) acrylate. Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate , N-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate and the like.
Among these compounds, an alkyl (meth) acrylate containing an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl (meth) acrylate having a lower alkyl group having 1 to 4 carbon atoms is more preferable.
The copolymer ratio of the alkyl (meth) acrylate is preferably a polymer containing 30 to 90 mol% in the total constituent monomer units, and more preferably 40 to 85 mol%.

As the other monomer, a compound having an aromatic group and an ethylenically unsaturated compound (hereinafter, referred to as “aromatic group-containing unsaturated compound”) is preferable.
Among aromatic group-containing unsaturated compounds, examples of ethylenically unsaturated compounds include vinyl groups and (meth) acryloyl groups.
Specific examples of the aromatic group-containing unsaturated compound include aromatic vinyl compounds such as styrene and α-methylstyrene.
The copolymer ratio of the aromatic group-containing unsaturated compound is preferably a polymer containing 10 to 50 mol% in the total constituent monomer units, and more preferably 15 to 35 mol%.

Specific examples of other monomers other than the aromatic group-containing unsaturated compound include carboxyl group-containing monomers such as (meth) acrylic acid; and sulfonic acid groups such as acrylamide2-methylpropanesulfonic acid and styrenesulfonic acid. Monomer; Phosphoric acid group-containing monomer; Cyan group-containing monomer such as (meth) acrylonitrile, vinyl ester; Acid anhydride group-containing monomer; Hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate And hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate; amide group-containing monomers such as (meth) acrylamide, dimethylacrylamide, diethyl (meth) acrylamide; amino group-containing singles. Quantities; imide group-containing monomers; epoxy group-containing monomers such as glycidyl (meth) acrylate; (meth) acryloylmorpholin; and vinyl ether and the like.

The component (C) in the present invention may be a polymer having a functional group.
Examples of the functional group include a hydrophilic group such as a hydroxyl group and a carboxyl group, a radically polymerizable functional group such as an alkoxysilyl group and a (meth) acryloyl group, and a cationically polymerizable functional group such as an epoxy group.
As the component (C), among these polymers, a polymer having a hydroxyl group or a carboxyl group is preferable because it can have high adhesion to a polypropylene base material.
Further, as the component (C), a polymer having an aromatic group and a hydroxyl group and a polymer having an aromatic group and a carboxyl group are more preferable because they are more excellent in the same effects as described above.

2) Method for Producing Component (C) As the component (C), a component produced by using the above-mentioned monomer according to a conventional polymerization method can be used.
For example, a radical polymerization method, a living anion polymerization method, a living radical polymerization method and the like can be mentioned.
Moreover, as a form of polymerization, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method and the like can be mentioned.

The Mw of the component (C) is 5,000 to 20,000, but when the low molecular weight polymer is to be produced by a usual polymerization method, it is usually necessary to increase the amount of a chain transfer agent or a polymerization initiator. .. When a polymer using a large amount of chain transfer agent is used, the cured coating film is easily colored by irradiation with active energy rays, and when a polymer using a large amount of a polymerization initiator is used, the composition is stable in storage. The sex tends to decrease.
Therefore, a polymer produced by high-temperature polymerization that does not require a large amount of chain transfer agent or polymerization initiator is preferable. Further, according to the high temperature polymerization, the component (C) can be made into the above-mentioned polymer having a preferable polydispersity.

The temperature of the high temperature polymerization is preferably 160 to 350 ° C, more preferably 180 to 300 ° C.
Among the high-temperature polymerizations, the high-temperature continuous polymerization has advantages not only excellent productivity but also excellent compatibility because it is difficult to distribute the composition in the copolymer product.
That is, as the component (C), a polymer obtained by high-temperature continuous polymerization at a polymerization temperature of 160 to 350 ° C. is preferable, and a polymer obtained by high-temperature continuous polymerization at a polymerization temperature of 180 to 300 ° C. is more preferable. preferable.
If the polymerization temperature is less than 160 ° C, a branching reaction occurs to widen the molecular weight distribution and a large amount of initiator or chain transfer agent is required to reduce the molecular weight, which adversely affects weather resistance, heat resistance, and durability. give. In addition, production problems such as heat removal may occur. On the other hand, if the temperature is higher than 350 ° C., a decomposition reaction occurs, the polymer solution is colored, and the molecular weight is lowered. By polymerizing in this temperature range, it is possible to efficiently produce a polymer having an appropriate molecular weight, low viscosity, no coloring, and few impurities.
According to the high-temperature continuous polymerization method, a very small amount of a polymerization initiator may be used, and it is not necessary to use a chain transfer agent such as mercaptan or a polymerization solvent, and a high-purity polymer can be obtained. Generally, it is important to uniformly introduce a crosslinkable functional group into a polymer in order to maintain physical properties such as curability and weather resistance.

The high-temperature continuous polymerization can be carried out by a known method (for example, JP-A-57-502171, JP-A-59-6207, JP-A-60-215007, etc.).
Specifically, a pressurable reactor is filled with a solvent, the temperature is set to a predetermined temperature under pressure, and then a monomer or, if necessary, a monomer mixture composed of a polymerization solvent and a polymerization initiator is fixed. There is a method of supplying the reaction solution to the reactor at the supply rate of the above and extracting an amount of the reaction solution corresponding to the supply amount of the monomer mixture.

The case where the component (C) is a polymer having the above-mentioned functional group will be described.
In the case of a polymer containing a hydrophilic group, an alkoxysilyl group, a radically polymerizable functional group and a cationically polymerizable functional group, as a method for introducing these functional groups, for example, it is introduced at the end of living anion polymerization or living radical polymerization. A method of adding a compound having a polymerizable functional group to a functional group in the polymer, and the like.
Further, when a cationically polymerizable functional group such as an epoxy group is introduced, a (meth) acrylate having those functional groups can be copolymerized.

The polymer obtained by high-temperature continuous polymerization in the component (C) is commercially available, and a commercially available product can also be used.
Specifically, examples of the copolymer having a hydroxyl group include ARUFON UH-2170 (Mw: 14,000, Tg: 60 ° C.) and ARUFON UHE-2012 (Mw: 5,800, Tg) manufactured by Toagosei Co., Ltd. : 20 ° C.).
In addition, as the (meth) acryloyl resin having a carboxyl group, the (meth) acryloyl resin having an epoxy group, and the (meth) acryloyl resin having an alkoxysilyl group, can also be used.
Specifically, as the polymer having a carboxyl group, ARUFON UC-3000 (Mw: 10,000, Tg: 65 ° C.), ARUFON UC-3080 (Mw: 14,000, Tg: 133 ° C.), ARUFON UF. -5080 (Mw: 17,000, Tg: 75 ° C.), ARUFON UF-5022 (Mw: 14,000, Tg: 75 ° C.) and the like can be mentioned, and examples of the polymer having an epoxy group include ARUFON Ug-. 4035 (Mw: 11,000, Tg: 52 ° C.), ARUFON UG-4040 (Mw: 11,000, Tg: 63 ° C.), ARUFON UG-4070 (Mw: 9,700, Tg: 58 ° C.) and the like. be able to.

The component (C) may be used alone or in combination of two or more.
The content ratio of the component (C) is preferably 20 to 150 parts by weight, more preferably 30 to 100 parts by weight, based on 100 parts by weight of the total curable component.
By setting the content ratio of the component (C) to 20 polymerization parts or more, the cured film of the composition can have excellent adhesion to the plastic substrate, and by setting the content ratio to 150 polymerization parts or less, the composition can be made. It can be excellent in coatability and curability.

Further, the content ratio of the components (B) and (C) is preferably 30 to 200 parts by weight as the total amount of the components (B) and (C) with respect to 100 parts by weight of the total curable component. , More preferably 50 to 100 parts by weight.
By setting the content ratio of the components (B) and (C) to 30 polymerization parts or more, the cured film of the composition can have excellent adhesion to the plastic substrate, and by setting the content ratio to 200 polymerization parts or less. , The composition can be excellent in coatability and curability.

3. 3. Curable composition The present invention is a curable composition containing the components (A) to (C) as essential components.
The composition of the present invention can be used as an active energy ray-curable composition or a thermosetting composition, and can be preferably used as an active energy ray-curable composition.

As a method for producing the composition of the present invention, the essential components (A) to (C) and, if necessary, other components described later may be stirred and mixed.
In this case, it may be heated and stirred if necessary. The temperature when heating, stirring and mixing is preferably in the range of 40 to 90 ° C.

Further, as a method for producing the composition, a step of continuously polymerizing an alkyl (meth) acrylate and an unsaturated compound containing an aromatic group at a high temperature to produce the following component (C), and the obtained component (C) and ( A method for producing a curable composition, which comprises a step of mixing the components A) and (B), is preferable.
According to the production method, the component (C) can be produced in a high yield, and since the amount of the high molecular weight substance in the obtained component (C) is small, the viscosity is low and the impurities are small. It is preferable in that it can have excellent physical properties.
As the step, the method for producing the component (C) described above may be followed.

The viscosity of the composition may be appropriately set according to the intended use and purpose. The viscosity is preferably 10 to 50,000 mPa · s, more preferably 50 to 20,000 mPa · s.
In the present invention, the viscosity means a value measured at 25 ° C. with an E-type viscometer.

The composition of the present invention requires the above-mentioned components (A) to (C), but various components can be blended as needed.
Preferred other components include a compound (D) having an ethylenically unsaturated group other than the component (A) [hereinafter referred to as "component (D)"], an organic solvent [hereinafter referred to as "component (E)"], and the like. Examples include a photopolymerization initiator (F) [hereinafter referred to as "(F) component"] and a thermal polymerization initiator (G) [hereinafter referred to as "(G) component"], and other components other than these are also blended. can do.
Hereinafter, the components (D) to (G) and other components other than these will be described.
As the other components described later, only one of the illustrated compounds may be used, or two or more of them may be used in combination.

1) Component (D) The component (D) is a compound having an ethylenically unsaturated group other than the component (A).
The component (D) is an arbitrary component used for adjusting the viscosity and other physical characteristics of the composition, and various components can be used.
As the component (D), a compound having one ethylenically unsaturated group [hereinafter referred to as "monofunctional unsaturated compound"] and a compound having two or more ethylenically unsaturated groups [hereinafter, "polyfunctional unsaturated" Saturated compounds].

(1) Monofunctional unsaturated compounds Examples of monofunctional unsaturated compounds include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl acrylate; and hydroxyethyl ( Examples thereof include monofunctional (meth) acrylate having a hydroxyl group such as meta) acrylate and hydroxypropyl acrylate.
Examples of the compound having an amide group include (meth) acrylamide, and specifically, N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn. N-alkyl (meth) acrylamide such as −butylacrylamide, N-sec-butylmethacrylate, Nt-butylacrylamide; and N-hydroxyalkyl (meth) acrylamide such as N-hydroxyethyl (meth) acrylamide. Be done.

(2) Polyfunctional unsaturated compound Examples of the polyfunctional unsaturated compound include a (meth) acrylate having two (meth) acryloyl groups (hereinafter referred to as “bifunctional (meth) acrylate”) and two or more. (Meta) acrylate having a (meth) acryloyl group (hereinafter, referred to as “trifunctional or higher (meth) acrylate”) and the like can be mentioned.
Specific examples of the bifunctional (meth) acrylate include di (meth) acrylate of glycerin, di (meth) acrylate of trimethylolpropane, and di (meth) acrylate of trimethylolpropane.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.

Specific examples of the trifunctional or higher functional (meth) acrylate include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, and trimethylolpropane tri or tetra (meth) acrylate. ) Poly (meth) acrylates of polyols such as acrylates, tetra, penta or hexa (meth) acrylates of dipentaerythritol;
Di (meth) acrylates of these polyol alkylene oxide adducts;
Tris (2- (meth) acryloyloxyethyl) isocyanurate and the like; and tri (meth) acrylate of the isocyanuric acid alkylene oxide adduct and the like can be mentioned.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide. However, the alkylene oxide adduct is limited to compounds that do not satisfy the (meth) acryloyl group equivalent of 140 to 500 g / eq depending on the type of alkylene oxide and the number of moles added.

As the polyfunctional unsaturated compound, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and polyether (meth) acrylate can be used in addition to the above-mentioned compounds.
Of these, urethane (meth) acrylate is preferable, and will be described in detail below.

Urethane (meth) acrylate is obtained by a three-way reaction of polyhydric alcohol, polyhydric isocyanate and hydroxyl group-containing (meth) acrylate, or organic polyhydric isocyanate and hydroxyl group-containing (meth) acrylate without using polyhydric alcohol. ) Those obtained by two reactions with an acrylate compound (hereinafter referred to as "urethane adduct") can be mentioned.

Urethane (meth) acrylate is preferably urethane adduct because it is excellent in curability of the composition, hardness of the cured product, and scratch resistance.

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

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

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

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

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

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

The content ratio of the component (D) is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight, and 10 to 20 parts by weight with respect to 100 parts by weight of the total amount of the curable component. Is more preferable. Within the above range, the physical properties can be adjusted without impairing the excellent substrate adhesion characteristic of the composition of the present invention.

3) Component (E) The composition of the present invention can be used without a solvent, but various components (E) (organic solvent) can be used for the purpose of adjusting the coating viscosity and the film thickness. ..
Specific examples of the component (E) include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; benzene and toluene. And aromatic compounds such as xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone and the like. Can be mentioned.

The content ratio of the component (E) is preferably 0.01 to 200 parts by weight, more preferably 10 to 150 parts by weight, and 20 to 100 parts by weight with respect to 100 parts by weight of the total amount of the curable component. It is more preferably by weight.

4) Component (F) When the composition of the present invention is used as an active energy ray-curable composition and further used as an electron beam-curable composition, the component (F) (photopolymerization initiator) is not contained. , It is also possible to cure with an electron beam.
When the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays and visible rays are used as the active energy rays, the component (F) is further added from the viewpoint of easiness of curing and cost. It is preferable to contain it.
When used as an electron beam-curable composition, it is not always necessary to contain the component (F), but a small amount may be added as needed in order to improve the curability.

As the component (F) in the present invention, various known photopolymerization initiators can be used.
The component (F) is preferably a photoradical polymerization initiator.
Specific examples of the component (F) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenylpropane-1-one. , 1- [4- (2-Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1- [4- (4-( Acetphenone compounds such as 1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one ;
Benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyldiphenylsulfide;
Α-ketoester compounds such as methylbenzoylformate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid;
2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Phenyloxide compounds such as;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanosen compounds; 1- [4- (4-benzoylphenyl sulfanyl) phenyl] -2-methyl-2- (4) -Acetphenone / Benzoin hybrid photoinitiators such as -methylphenylsulfinyl) propan-1-one;
Oxime ester-based photopolymerization initiators such as 2- (O-benzoyloxime) -1- [4- (phenylthio)] -1,2-octanedione; and camphorquinone and the like can be mentioned.

Among these, acetophenone-based compounds, benzophenone-based compounds, and phosphine oxide-based compounds are preferably mentioned, and acetophenone-based compounds are particularly preferable.

The content ratio of the component (F) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, based on 100 parts by weight of the total amount of the curable components. It is particularly preferable that the amount is ~ 5 parts by weight. Within the above range, the curability of the composition is excellent, and the scratch resistance of the obtained cured film is excellent.

5) Component (G) Component (G) is a thermosetting initiator, and when the composition is used as a thermosetting composition, the component (G) can be blended.
The composition of the present invention can also be heat-cured by blending a thermal polymerization initiator.
As the thermal polymerization initiator, various compounds can be used, and organic peroxides and azo-based initiators are preferable.

Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, and 1 , 1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoleperoxy) hexane, t-butylper Oxyisopropyl monocarbonate, t-butylperoxy2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2, 2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α '-Bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-menthan hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, diisopropylbenzenehydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 , 3-Tetramethylbutylhydroperoxide, cumenehydroperoxide, t-hexylhydroperoxide, t-butylhydroperoxide and the like.

Specific examples of azo compounds include 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. , Azobis-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. In addition, the organic peroxide can be combined with a reducing agent to cause a redox reaction.

The content ratio of the component (G) is preferably 10 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component.
When the thermal polymerization initiator is used alone, it may be carried out according to the usual means of radical thermal polymerization, and in some cases, it may be used in combination with the component (E) (photopolymerization initiator), and after photocuring, the reaction rate is further increased. It is also possible to carry out thermosetting for the purpose of improving the above.

6) Other components other than the above As the other components other than the above, known additives can be used, and for example, ultraviolet absorbers, light stabilizers, acidic substances, inorganic particles, antioxidants, silane cups, etc. Examples thereof include ring agents, surface modifiers, polymers, acid generators, pigments, dyes, tackifiers and polymerization inhibitors.
Hereinafter, these components will be described.

<UV absorber>
Specific examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)-. 1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-Triazine, 2- [4-[(2-Hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bisbutyroxyphenyl) -1,3,5-triazine, 2-( Triazine-based UV absorbers such as 2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine; 2- (2H-benzo) Triazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy -5- (2- (Meta) acryloyloxyethyl) phenyl] -2H-Benzotriazole-based ultraviolet absorbers such as benzotriazole; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone Agents, cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate, octyl-2-cyano-3,3-diphenylacrylate, ultraviolet rays such as titanium oxide particles, zinc oxide particles, and tin oxide particles. Examples include inorganic particles that absorb phenyl group.

Among the compounds, a benzotriazole-based ultraviolet absorber is particularly preferable.
The content ratio of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and 0. It is more preferably 1 to 2 parts by weight.

<Light stabilizer>
As the light stabilizer, a known light stabilizer can be used, and among them, a hindered amine-based light stabilizer (HALS) is preferably mentioned.
Specific examples of hindered amine-based photostabilizers 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, bisdecanoic acid (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and the like.
Examples of commercially available hindered amine-based light stabilizers include TINUVIN 111FDL, TINUVIN123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 manufactured by BASF.

The content ratio of the ultraviolet absorber is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, and 0. It is more preferably 1 to 1 part by weight.

<Acid substances>
The composition of the present invention is excellent as an adhesive material to a base material such as plastic, but the adhesiveness can be further improved by adding an acidic substance.
Examples of the acidic substance include a photoacid generator that generates an acid by irradiation with active energy rays, sulfuric acid, nitric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid and the like.
Among these, an inorganic acid or an organic acid is preferable, an organic sulfonic acid compound is more preferable, an aromatic sulfonic acid compound is further preferable, and p-toluenesulfonic acid is particularly preferable.
The content ratio of the acidic substance is preferably 0.0001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, and 0.0005 with respect to 100 parts by weight of the total amount of the curable components. It is more preferably ~ 0.5 parts by weight. Within the above range, the adhesion to the base material is excellent, and problems such as corrosion of the base material and decomposition of other components can be prevented.

<Antioxidant>
The composition of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film.
Examples of the antioxidant used in the present invention include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like.
As the phenolic antioxidant, for example, hindered phenols such as dit-butylhydroxytoluene can be preferably mentioned. 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.
Preferred examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphite and triaryl phosphite. Commercially available products of these derivatives include, for example, ADEKA CORPORATION PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. And so on.
Examples of the sulfur-based antioxidant include thioether-based compounds, and examples of commercially available products include AO-23, AO-212S, and AO-503A manufactured by ADEKA CORPORATION.

The content ratio of the antioxidant is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of the composition of the present invention. In the above aspect, the stability of the composition is excellent, and the curability and adhesive strength are good.

<Silane coupling agent>
The composition of the present invention may further contain a silane coupling agent for the purpose of improving the adhesion to the substrate.

The silane coupling agent is not particularly limited, and known ones can be used.
Preferred specific examples of the silane coupling agent include a (meth) acryloyl group-containing silane coupling agent such as 3- (meth) acryloxipropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Vinyl group-containing silane coupling agent such as, allyl group-containing silane coupling agent such as allyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glysidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-) Dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned.

The mixing ratio of the silane coupling agent is preferably 0.05 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the curable components.
Adhesion to the substrate, especially to the inorganic substrate, can be improved by setting the ratio of the silane coupling agent to 0.05 or more, while by setting the ratio to 30 parts by weight or less, the adhesion in the composition can be improved. Due to the influence of water and the compound having a hydroxyl group, the reaction of the silane coupling agent proceeds during the storage of the composition, so that thickening and gelation can be prevented.

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

The content ratio of the surface modifier is preferably 0.01 to 1.0 parts by weight with respect to 100 parts by weight of the total amount of the composition of the present invention. Within the above range, the surface smoothness of the coating film is excellent.

4. Method of use As a method of using the composition of the present invention, a conventional method may be followed.
For example, a method of applying the composition to the applied substrate by a usual coating method and then irradiating it with active energy rays or heating it to cure it can be mentioned.
As the method of irradiating the active energy rays, a general method known as a conventional curing method may be adopted.
Further, the composition is adhered to the substrate by using the component (D) (photopolymerization initiator) and the component (E) (thermal polymerization initiator) in combination, irradiating them with active energy rays, and then heat-curing them. A method of improving the sex can also be adopted.

Examples of the base material to which the composition of the present invention can be applied include inorganic materials, plastics, paper and the like, which can be applied to various materials.
Examples of the inorganic material include glass, metal, mortar, concrete and stone, and examples of the metal include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO). Can be mentioned.
Specific examples of plastics include polyolefins such as polyethylene and polypropylene, ABS resin, polyvinyl alcohol, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resin, polyethylene terephthalate, polycarbonate, polyarylate, polyether sulfone, norbornene and the like. Examples thereof include cyclic polyolefin resins, polyvinyl chlorides, epoxy resins and polyurethane resins using the cyclic olefins of the above as monomers.

Among these base materials, the composition of the present invention has excellent adhesion to a plastic base material, and therefore can be preferably applied to a plastic base material, and further preferably to polytilene as a plastic base material.

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

The film thickness of the composition cured film with respect to the base material may be appropriately set according to the intended purpose. The thickness of the cured film may be selected depending on the use of the substrate to be used and the application of the produced substrate having the cured film, but is preferably 1 to 100 μm, more preferably 5 to 40 μm. ..

When the composition contains the component (E) (organic solvent), it is preferable that the base material is coated and then heated and dried to evaporate the organic solvent.
The drying temperature is not particularly limited as long as the applied base material is at or below a temperature at which problems such as deformation do not occur. The preferred heating temperature is 40 to 100 ° C. The drying time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 3 minutes.

When the composition of the present invention is used as an active energy ray-curable composition, examples of the active energy ray for curing include electron beam, ultraviolet ray and visible light, but ultraviolet ray or visible light ray is preferable, and ultraviolet ray is preferable. Especially preferable. Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).
The irradiation energy should be appropriately set according to the type and composition of the active energy rays. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 8,000 mJ /. cm ² is preferable, and 200 to 3,000 mJ / cm ² is more preferable.

5. Applications The composition of the present invention can be used for various purposes, and specific examples thereof include coating agents, inks and molding materials.
Among these, it can be preferably used as a coating agent.
Further, it can be more preferably used as a coating agent for a plastic base material, and more particularly preferably as a coating agent for a polypropylene base material.
Specific examples to which a coating agent for a plastic base material, preferably a polypropylene base material, is applied include electrical appliances, daily necessities such as furniture, building materials, medical treatment, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples.
Further, in the following, unless otherwise specified, "part" means a part by weight, and "%" means% by weight.

1. 1. Examples 1 to 5 and Comparative Examples 1 to 4 (preparation of composition)
Each component shown in Table 1 below was stirred and mixed at 40 ° C. to obtain a composition. The viscosity at 25 ° C. was measured with an E-type viscometer.

2. Evaluation method (evaluation for polypropylene base material)
The obtained composition was coated on polypropylene (30 mm × 150 mm × 2 mm) manufactured by Engineering Test Service Co., Ltd. using bar coater # 8 so as to have a film thickness of 10 μm.
Next, using a high-pressure mercury lamp [H06-L 41 manufactured by Eye Graphics Co., Ltd.] equipped with a conveyor, ultraviolet rays were irradiated with a ^{UV-A illuminance of 250 mW / cm2 and an irradiation energy of 600 mJ / cm 2.}
The obtained cured film was used and evaluated according to the following method. The results are shown in Table 3.

1) Adhesion The cured film was cut with a cutter knife at intervals of 2 mm in length and width to form 25 squares with a size of 2 mm x 2 mm, and Nichiban Co., Ltd. # 405 was formed on this grid. After applying the cellophane tape, it was strongly peeled off. The residual film ratio (%) after peeling was evaluated. The larger the number of residual films, the better the adhesion.

2) Scratch resistance With respect to the obtained cured film, the surface of the cured film after being rubbed with a nail was visually observed to confirm the presence or absence of scratches and dents, and evaluated on the following three levels.
○: No scratches / dents, △: No scratches, but slight dents remain on the coating film, ×: Clearly scratches are observed

3) Appearance of cured film The appearance of the obtained cured film was visually evaluated.
○: No scratches / dents, △: No scratches, but slight dents remain on the coating film, ×: Clearly scratches are observed

The abbreviations in Tables 1 and 2 mean the following. The parentheses in Tables 1 and 2 mean the number of copies of each component.
(A) Ingredients -IBXA: Isobornyl acrylate [manufactured by Osaka Organic Co., Ltd., acryloyl group equivalent 208 g / eq]
-ACMO: Acryloyl morpholine [manufactured by KJ Chemicals Co., Ltd., acryloyl group equivalent 141 g / eq]
M-120: Acrylate of 2 mol of 2-ethylhexyl ethylene oxide adduct [Aronix M-120 manufactured by Toagosei Co., Ltd., acryloyl group equivalent 155 g / eq]
(B) Ingredients -SC-390S: Chlorinated polyolefin [Supercron 390S manufactured by Nippon Paper Industries, Ltd., chlorination degree 36%, Mw: 40,000, pellet product]
-SC-814B: Chlorinated polyolefin [Supercron 814B manufactured by Nippon Paper Industries, Ltd., chlorination degree 41%, Mw: 15,000, butyl acetate 50% solution]
-SC-2030S: Chlorinated polyolefin [Supercron 2030S manufactured by Nippon Paper Industries, Ltd., chlorination degree 30%, Mw: 75,000, pellet product]
(B)'Component -HL-16P: Chlorinated polyolefin [Toyobo Co., Ltd. Hardlen 16LP, chlorination degree 32%, Mw: 150,000, pellet product]
(C) Ingredients -UH-2170: Hydroxyl-containing styrene / acrylic copolymer [ARUFON UH-2170 manufactured by Toa Synthetic Co., Ltd., Mw: 14,000, polydispersity: 3.8, Tg: 60 ° C]
UC-3080: Carboxylic group-containing styrene / acrylic copolymer [ARUFON UC-3080 manufactured by Toagosei Co., Ltd., Mw: 14,000, polydispersity: 3.8, Tg: 133 ° C]
(C)'Component -UP-1000: Acrylic copolymer [ARUFON UP-100 manufactured by Toagosei Co., Ltd., Mw: 3,000, polydispersity: 1.9, Tg: -77 ° C]
Ingredient (D) -M-305: Mixture of pentaerythritol tri and tetraacrylate [Aronix M-305 manufactured by Toa Synthetic Co., Ltd., acryloyl group equivalent 99 g / eq]
M-309: Trimethylolpropane triacrylate [Aronix M-309 manufactured by Toagosei Co., Ltd., acryloyl group equivalent 99 g / eq]
(E) Ingredients -PGM: Propylene glycol monomethyl ether
(F) Ingredients -HCPK: 1-Hydroxy-cyclohexyl-phenyl-ketone [IRGACURE 184 manufactured by BASF]

3. 3. Evaluation Results As is clear from the results of Examples 1 to 7, the composition of the present invention was excellent in adhesion to the polyprepylene base material, scratch resistance of the cured film, and appearance.
On the other hand, the composition of Comparative Example 1 is a composition containing a polyfunctional acrylate having an acryloyl group equivalent different from that of the component (A), which is less than the lower limit of the present invention, but the adhesion to the polypropylene base material cannot be obtained. Furthermore, the appearance of the cured film was also poor.
The composition of Comparative Example 2 was composed of a chlorinated polyolefin having an Mw upper limit of more than 100,000, which is different from the component (B), but the adhesion was insufficient and the appearance of the cured film was poor.
The composition of Comparative Example 3 was a composition containing a polymer having a Mw of less than the lower limit of 5,000, which was different from the component (C), but the scratch resistance of the cured film was poor.

The hard composition of the present invention can be preferably used as an active energy ray hard composition, and the obtained cured film can be used for various base materials, particularly for plastic base materials such as polypropylene base materials. It has excellent adhesion and scratch resistance, and can be particularly preferably used as a coating agent for various purposes.

Claims (20)

Contains the following components (A), (B) and (C) ,
For a total of 100 parts by weight of the following component (A)
Cured composition containing 2 to 100 parts by weight of the component (B) and 20 to 150 parts by weight of the component (C), respectively, and 30 to 200 parts by weight in total of the component (B) and (C). thing.
Component (A): A compound having one (meth) acryloyl group in one molecule and having a (meth) acryloyl group equivalent of 140 to 500 g / eq.
Component (B): Modified polyolefin polymer having a weight average molecular weight of 5,000 to 100,000 (C) Component: Alkyl (meth) acrylate as an essential constituent monomer unit, and a weight average molecular weight of 5,000 to A polymer that is 20,000. The curable composition according to claim 1, wherein the component (A) is a compound having one (meth) acryloyl group, and the glass transition point of the homopolymer is 80 ° C. or higher. The curable composition according to claim 1 or 2, wherein the component (B) is a chlorinated polyolefin resin having a degree of chlorination of 25 to 50%. The curable composition according to claim 1, wherein the component (C) is a polymer having a glass transition point of 0 ° C. to 150 ° C. The curable composition according to any one of claims 1 to 4, wherein the component (C) is a polymer having a polydispersity of 4.5 or less. The curable composition according to any one of claims 1 to 5, wherein the component (C) is a polymer further having an aromatic group and a hydroxyl group and / or a polymer having an aromatic group and a carboxyl group. thing. The curable composition according to any one of claims 1 to 6, wherein the component (C) is a polymer obtained by high-temperature continuous polymerization of a monomer containing an alkyl (meth) acrylate as an essential component. thing. The curable composition according to any one of claims 1 to 7 , further comprising a compound (D) having an ethylenically unsaturated group other than the component (A). With respect to a total of 100 parts by weight of the components (A) and (D).
The eighth aspect of the present invention, which comprises 2 to 100 parts by weight of the component (B) and 20 to 150 parts by weight of the component (C), and 30 to 200 parts by weight in total of the component (B) and (C). Curable composition. The curable composition according to any one of claims 1 to 9 , which contains an organic solvent (E). An active energy ray-curable composition comprising the composition according to any one of claims 1 to 10. The active energy ray-curable composition according to claim 11 , further containing a photopolymerization initiator (F). An active energy ray-curable coating agent composition containing the composition according to claim 12. An active energy ray-curable coating agent composition for a polypropylene base material containing the composition according to claim 13. A step of continuously polymerizing a monomer containing an alkyl (meth) acrylate as an essential component at a high temperature to produce the following component (C), and the obtained component (C) and the following components (A) and (B) .
For a total of 100 parts by weight of the following component (A)
Curing including a step of mixing so as to contain 2 to 100 parts by weight of the component (B) and 20 to 150 parts by weight of the component (C), and 30 to 200 parts by weight in total of the component (B) and (C). Method for producing mold composition.
Component (A): A compound having one (meth) acryloyl group in one molecule and having a (meth) acryloyl group equivalent of 140 to 500 g / eq.
Component (B): Modified polyolefin polymer having a weight average molecular weight of 5,000 to 100,000 (C) Component: Alkyl (meth) acrylate as an essential constituent monomer unit, and a weight average molecular weight of 5,000 to A polymer that is 20,000. The method for producing a curable composition according to claim 15 , wherein the component (A) is a compound having one (meth) acryloyl group, and the glass transition point of the homopolymer is 80 ° C. or higher. The method for producing a curable composition according to claim 15 or 16 , wherein the component (C) is a polymer having a glass transition point of 0 ° C. to 150 ° C. The method for producing a curable composition according to any one of claims 15 to 17 , wherein the component (C) is a polymer having a polydispersity of 4.5 or less. The method for producing a curable composition according to any one of claims 15 to 18 , further comprising a step of mixing the organic solvent (E). The method for producing a curable composition according to any one of claims 15 to 19 , further comprising a step of mixing the photopolymerization initiator (F).