JP2018197320A - Curable composition - Google Patents

Abstract

To provide a curable composition which has satisfactory adhesion to a wide range of substrates and shows excellent adhesion to plastic substrates, in particular, polypropylene substrates, and which has scratch resistance such that no damage is caused even by nail scratching, the curable composition being suitable for use especially in coating agents.SOLUTION: The present invention provides a curable composition which comprises components (A), (B) and (C). The component (A): a compound having one or more (meth)acryloyl groups in one molecule, with an equivalent of (meth)acryloyl groups being 140-500 g/eq. The component (B): a modified polyolefin polymer with a weight average molecular weight of 5,000-100,000. The component (C): a polymer including an alkyl(meth)acrylate as an essential constituent monomer unit, with a weight average molecular weight of 5,000-20,000.SELECTED DRAWING: None

Description

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

  Polypropylene is used in various applications because it is excellent in productivity, moldability, light weight and economy. Furthermore, molded articles using polypropylene are used in various applications such as household appliances such as electrical appliances and furniture, building materials, and medicine.

Like ordinary plastics, 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 hard coating agents, solvent-based coating compositions are known.

However, the solvent-based coating composition requires heating to evaporate and dry the organic solvent contained in the solvent-based coating composition, and requires heat energy and equipment required for heating. As a result, there is a growing momentum for using paints other than solvent-based paint compositions on plastic substrates such as polypropylene.
On the other hand, the active energy ray-curable composition can be cured by irradiating active energy rays such as ultraviolet rays, visible rays, and electron beams for a very short time and has high productivity. And is widely used as a coating.

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

JP 2005-139305 A JP 2000-017027 A

  The present inventors have good adhesion to a wide range of substrates, particularly excellent adhesion to plastic substrates such as polypropylene substrates, and have scratch resistance that does not scratch even when scratched with a nail. In order to find a curable composition, particularly a curable composition that can be suitably used for a coating agent, intensive studies were conducted.

As a result of intensive studies to solve the above problems, the present inventors have found that a (meth) acrylate having a specific (meth) acryloyl group equivalent, a modified polyolefin polymer, and a (meth) acrylate system having a specific weight average molecular weight It has been found that a curable composition containing a polymer has good adhesion to a plastic substrate, particularly a polypropylene substrate, is not easily damaged by scratching with a nail, and can be suitably used as a coating agent. Completed the invention.
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.
This is because 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 can alleviate thermal shrinkage generated by curing. Therefore, the stress at the interface between various substrates, particularly the plastic substrate and the composition, can be greatly reduced, and as a result, the adhesion between the plastic substrate and the composition having greatly different thermal expansion coefficients can be further improved. I think I can do it.

The present invention relates to a curable composition containing the following components (A), (B) and (C).
Component (A): A compound having one or more (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 140 to 500 g / eq.
Component (B): Modified polyolefin polymer (C) 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, components (A) to (C) that are essential components, other components, usage methods, and the like will be described.

1. Component (A) The component (A) is a compound having one or more (meth) acryloyl groups in one molecule and having a (meth) acryloyl group equivalent of 140 to 500 g / eq, and an active energy ray It is a compound that is cured by irradiation or heating.
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 insufficient adhesion, while a compound having a (meth) acryloyl group equivalent of more than 500 g / eq is scratch resistant. It becomes insufficient.

  As the component (A), (meth) acrylate having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) and (meth) acrylate having two or more (meth) acryloyl groups Any of them (hereinafter referred to as “polyfunctional (meth) acrylate”) can be used.

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) acrylates such as;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. A 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-dioxolane-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-cumylphenolethylene (meth) acrylate;
A monofunctional (meth) acrylate having a maleimide group such as (meth) acryloyloxyethyl hexahydrophthalimide;
(Meth) acryloylmorpholine;
Examples thereof include monofunctional (meth) acrylates having an alkoxyalkyl group such as ethyl carbitol (meth) acrylate and alkyl carbitol (meth) acrylate such as 2-ethylhexyl carbitol (meth) acrylate.

Specific examples of polyfunctional (meth) acrylates include (meth) acrylates having two (meth) acryloyl groups (hereinafter referred to as “bifunctional (meth) acrylates”). 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. Diol di (meth) acrylate;
Di (meth) acrylates of polyols such as di (meth) acrylates 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.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.

As tri- or more functional (meth) acrylates, specifically, glycerol alkylene oxide adduct tri (meth) acrylate, trimethylolpropane alkylene oxide adduct tri (meth) acrylate alkylene oxide adduct, pentaerythritol alkylene oxide addition Poly (poly) of polyols such as tri- or tetra- (meth) acrylate of a product, tri- or tetra- (meth) acrylate of an alkylene oxide adduct of ditrimethylolpropane, tetra-, penta- or hexa (meth) acrylate of an alkylene oxide adduct of dipentaerythritol (Meth) acrylate;
Examples include tris (2- (meth) acryloyloxyethyl) isocyanurate; and tri (meth) acrylates of isocyanuric acid alkylene oxide adducts.
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;
And mono (meth) acrylates of these polyol alkylene oxide adducts; and 2-hydroxy-3-phenoxypropyl (meth) acrylate, which is a reaction product of phenylglycidyl ether and (meth) acrylic acid.

Polyfunctional (meth) acrylates having a hydroxyl group include ditrimethylolpropane diacrylate, ditrimethylolpropane di- or trimethacrylate, dipentaerythritol diacrylate, dipentaerythritol di- or trimethacrylate polyol poly (meth) Acrylates; and di- or tri (meth) acrylates of these polyol alkylene oxide adducts.
Examples of the alkylene oxide in the above-described alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.

(Meth) acrylamide is mentioned as a compound which has an amide group, Specifically, Nn-butyl methacrylamide, N-sec-butyl methacrylamide, Nt-butyl methacrylamide, Nn-hexyl N-alkyl (meth) acrylamides such as (meth) acrylamide; and 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) acrylic of dihexyl (meth) acrylamide Bromide, and the like.

Among the above-mentioned compounds, monofunctional (meth) acrylate is preferable because of its excellent adhesion to the substrate.
Furthermore, among the monofunctional (meth) acrylates, (meth) acrylates having a homopolymer glass transition point (hereinafter referred to as “Tg”) of 80 ° C. or higher are preferable, and more preferably, the homopolymer Tg is 90 to 200 ° C. (Meth) acrylate.
For example, examples of (meth) acrylates in which the Tg of the homopolymer includes the value include isobornyl acrylate (Tg of the homopolymer: 97 ° C., hereinafter, parentheses indicate the Tg of the homopolymer), acryloylmorpholine (145 ° C.), and the like.
In the present invention, Tg means a value measured at a rate of temperature increase of 10 ° C./min using a differential scanning calorimeter (DSC), and at the glass transition temperature intermediate point (Tmg) in the ΔT-temperature curve. Mean value.

  Furthermore, among monofunctional (meth) acrylates, isobornyl acrylate, acryloylmorpholine, and 2-hydroxy-3-phenoxypropyl (meth) acrylate [reaction product of phenylglycidyl ether and (meth) acrylic acid] It is more preferable in that it is more excellent in adhesion.

As a content rate of (A) component, 30 to 80 weight% is preferable in a composition, and 40 to 60 weight% is more preferable.
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. On the other hand, when the component is 80% by weight or less, heat shrinkage during curing is achieved. And can be excellent in adhesion to the substrate.

2. Component (B) Component (B) is a modified polyolefin polymer having an Mw of 5,000 to 100,000, and is a component that can improve adhesion to plastic substrates, particularly polyolefins 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 an olefin homopolymer and a copolymer of two or more olefins. Specific examples of polyolefin include polyethylene, polypropylene, ethylene-propylene copolymer, polybutadiene hydride, propylene-butadiene copolymer and hydride thereof.
An example having a carboxyl group or / and an acid anhydride group will be described as the modified polyolefin polymer. At least one selected from an unsaturated carboxylic acid and an acid anhydride thereof (hereinafter referred to as “unsaturated carboxylic acid”) is used as the polyolefin. And a polymer obtained by graft polymerization of a "monomer").
Examples of unsaturated carboxylic acid monomers include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, hymic anhydride, (meth) Examples include acrylic acid and (meth) acrylic acid ester.

The component (B) is a polymer having an Mw of 5,000 to 100,000, preferably a polymer having an Mw of 10,000 to 50,000.
(B) In the case of a polymer whose component Mw is less than 5,000, the cured film physical properties of the composition such as scratch resistance are deteriorated, and in the case of a polymer whose Mw exceeds 100,000, It will become viscosity, coating property will deteriorate, or adhesiveness will fall.
In addition, in this invention, Mw means the value which converted the molecular weight measured by the gel permeation chromatography (henceforth "GPC") in polystyrene.

As the component (B), a polymer obtained by chlorinating the polymer (hereinafter referred to as “chlorinated polyolefin”) is preferable.
An example of a chlorinated polyolefin having a carboxyl group or / and an acid anhydride group will be described. A polymer obtained by chlorinating a modified polyolefin obtained by graft polymerization of an unsaturated carboxylic acid monomer to a polyolefin, or a polyolefin containing chlorine. Examples thereof include a polymer obtained by graft polymerization of an unsaturated carboxylic acid monomer to this chlorinated polymer.
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 chlorine is reacted under pressure.
The chlorination degree (chlorine content) of the chlorinated polyolefin is preferably 25 to 50% by weight, more preferably 30 to 40% by weight. A polymer having a chlorination degree of 25% by weight or more is preferable in that it has excellent solubility with the component (A). On the other hand, by setting it to 50% by weight or less, adhesion to a plastic substrate, particularly polyolefin such as polypropylene, is good. Can be excellent.

(B) A component can be used only by 1 type and can also use 2 or more types together.
(B) As a content rate of a component, when mix | blending a postscript (D) component with respect to a total of 100 weight part of (A) component, with respect to a total of 100 weight part of (A) component and (D) component. 2 to 100 parts by weight is preferable, and 5 to 50 parts by weight is more preferable.
(B) By making the content rate of a component into 2 superposition | polymerization parts or more, the cured film of a composition can be made excellent in the adhesiveness with respect to a plastic base material, By making it into 100 superposition | polymerization parts or less, a composition is made. It can be excellent in coatability and curability.
Hereinafter, the component (A), or the component (A) and the component (D) are referred to as a curable component.

3. Component (C) The component (C) is a polymer having an alkyl (meth) acrylate as an essential constituent monomer unit and 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 reduce thermal shrinkage generated by curing. Therefore, the stress at the interface between the various base materials and the composition can be greatly reduced, and in particular, the adhesion between the polyolefin base material having a greatly different thermal expansion coefficient and the cured film of the composition can be further improved.

Further, by using a polymer having an alkyl (meth) acrylate as an essential constituent monomer unit as the component (C), the compatibility with the component (A) and other components in the composition can be improved. .
When a polymer that does not contain (meth) acrylates other than the component (C) as a constituent monomer unit is used, it cannot be sufficiently soluble with the component (A) or other components, and the number of blending parts necessary to suppress thermal shrinkage. Cannot be used.

(C) Mw of a component exists in the range of 5,000-20,000, and 10,000-17,000 are preferable.
A polymer having an Mw of less than 5,000 results in insufficient scratch resistance of the resulting composition. When the Mw exceeds 20,000, the compatibility with the component (A) and other components is poor. It falls and it becomes impossible to mix | blend with a desired mixing | blending ratio.
Furthermore, as the component (C), a polymer having a polydispersity (Mw / Mn), which is a ratio of Mw (weight average molecular weight) to number average molecular weight (hereinafter referred to as “Mn”), is 4.50 or less. Preferably, it is more preferable than the polymer which is 4.00 or less. The polymer having the polydispersity is preferable because the viscosity of the composition and the smoothness of the resulting cured coating film appearance are good.
In addition, in this invention, Mn and Mw mean the value which converted the molecular weight measured by the gel permeation chromatography (henceforth "GPC") in polystyrene conversion.
More specifically, it means a value obtained by converting the molecular weight measured by GPC under the following conditions into polystyrene.
○ Measurement condition column: Tosoh Co., Ltd. TSKgel SuperMultipore HZ-M (Porous polydisperse type filler) x 4 Column temperature: 40 ° C
Eluent: Tetrahydrofuran Detector: RI

As Tg of (C) component, it is preferable that it is the range of 0 to 150 degreeC, and it is more preferable that it is the range of 30 to 100 degreeC.
By setting the Tg of the component (C) to 0 ° C. or higher, the scratch resistance of the cured film can be improved, and by setting the temperature to 150 ° C. or less, the component (C) can be uniformly dissolved in the composition. it can.

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

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, 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%, more preferably 40 to 85 mol% in all the constituent monomer units.

The other monomer is preferably a compound having an aromatic group and ethylenic unsaturation (hereinafter referred to as “aromatic group-containing unsaturated compound”).
In the aromatic group-containing unsaturated compound, examples of the ethylenic unsaturation include a vinyl group and a (meth) acryloyl group.
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%, more preferably 15 to 35 mol% in all constituent monomer units.

  Specific examples of other monomers other than the aromatic group-containing unsaturated compound include carboxyl group-containing monomers such as (meth) acrylic acid; sulfonic acid groups such as acrylamide 2-methylpropanesulfonic acid and styrenesulfonic acid Monomer; Phosphoric acid group-containing monomer; Cyano 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; Monomer; imide group-containing monomer; glycidyl (meth) acrylate, etc. Epoxy group-containing monomer, (meth) acryloyl morpholine; and vinyl ether.

The component (C) in the present invention may be a polymer having a functional group.
Examples of the functional group include hydrophilic groups such as a hydroxyl group and a carboxyl group, radical polymerizable functional groups such as an alkoxysilyl group and (meth) acryloyl group, and cationic polymerizable functional groups 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 provide high adhesion to a polypropylene base material.
Furthermore, 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 excellent in the same effect as described above.

2) Method for producing component (C) As component (C) , those produced using conventional monomers according to conventional polymerization 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.
Examples of polymerization forms include solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.

(C) Mw of a component is 5,000-20,000, However, When it is going to manufacture the said low molecular weight polymer with a normal polymerization method, it is usually necessary to increase a chain transfer agent and a polymerization initiator. . When a polymer using a large amount of a chain transfer agent is used, the cured coating film is likely to be colored by irradiation with active energy rays, and when a polymer using a large amount of a polymerization initiator is used, the composition can be stored stably. The property tends to decrease.
For this reason, the polymer manufactured by the high temperature polymerization which does not require a lot of chain transfer agents and polymerization initiators is preferable. Further, according to the high temperature polymerization, the component (C) can be made into a polymer having the preferred polydispersity described above.

As temperature of high temperature polymerization, 160-350 degreeC is preferable and 180-300 degreeC is more preferable.
Among the high temperature polymerizations, the high temperature continuous polymerization not only has excellent productivity, but also has advantages such as excellent compatibility because it is difficult to achieve a composition distribution in the copolymer product.
That is, as the component (C), a polymer obtained by continuous polymerization at a high temperature at a polymerization temperature of 160 to 350 ° C is preferable, and a polymer obtained by continuous polymerization at a high temperature at a polymerization temperature of 180 to 300 ° C is more preferable. preferable.
When the polymerization temperature is less than 160 ° C., branching reaction occurs and the molecular weight distribution is widened, and a large amount of initiator and chain transfer agent are required to lower the molecular weight, thus adversely affecting the weather resistance, heat resistance and durability. give. In addition, production problems such as heat removal may occur. On the other hand, if it is higher than 350 ° C., a decomposition reaction occurs and the polymerization solution is colored or the molecular weight is lowered. By polymerizing in this temperature range, it is possible to efficiently produce a polymer having an appropriate molecular weight, a low viscosity, no coloration and little impurities.
According to the high-temperature continuous polymerization method, a very small amount of 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 polymer having high purity can be obtained. In general, 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-T-57-502171, JP-A-59-6207, JP-A-60-215007, etc.).
Specifically, after filling a pressurizable reactor with a solvent and setting it to a predetermined temperature under pressure, a monomer or a monomer mixture consisting of a polymerization solvent and a polymerization initiator as needed is fixed. And a method of withdrawing the reaction solution in an amount commensurate with the supply amount of the monomer mixture.

The case where the component (C) is a polymer having the functional group described above will be described.
In the case of a polymer containing a hydrophilic group, an alkoxysilyl group, a radical polymerizable functional group, and a cationic polymerizable functional group, examples of the method for introducing these functional groups include introduction at the end of living anion polymerization and living radical polymerization. And a method of adding a compound having a polymerizable functional group to a functional group in the polymer.
Moreover, when introducing cationically polymerizable functional groups such as epoxy groups, (meth) acrylates having these functional groups can be copolymerized.

In the component (C), the polymer obtained by high-temperature continuous polymerization 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.), ARUFON UHE-2012 (Mw: 5,800, Tg) manufactured by Toagosei Co., Ltd. : 20 ° C.).
In addition, (meth) acryloyl resin having a carboxyl group, (meth) acryloyl resin having an epoxy group, and (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.) and ARUFON UF-5022 (Mw: 14,000, Tg: 75 ° C.) and the like. As a polymer having an epoxy group, 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.), etc. be able to.

Component (C) can be used alone or in combination of two or more.
(C) As a content rate of a component, 20-150 weight part is preferable with respect to a total of 100 weight part of a sclerosing | hardenable component, and 30-100 weight part is more preferable.
(C) By making the content rate of a component into 20 superposition | polymerization parts or more, the cured film of a composition can be made excellent in the adhesiveness with respect to a plastic base material, By making it into 150 superposition parts or less, a composition is made. It can be excellent in coatability and curability.

Furthermore, as a content rate of (B) and (C) component, it is preferable to contain 30-200 weight part as a total amount of (B) and (C) component with respect to a total of 100 weight part of a sclerosing | hardenable component. More preferably, it is 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 it to 200 polymerization parts or less. The composition can be made excellent in coatability and curability.

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 manufacturing method of the composition of this invention, what is necessary is just to stir and mix the (A)-(C) component which is an essential component, and the other component mentioned later as needed.
In this case, you may heat and stir as needed. The temperature for heating and stirring / mixing is preferably in the range of 40 to 90 ° C.

Furthermore, as a method for producing the composition, a step of continuously polymerizing an alkyl (meth) acrylate and an aromatic group-containing unsaturated compound at a high temperature to produce the following component (C), and the obtained component (C) and ( A method for producing a curable composition comprising a step of mixing components A) and (B) is preferred.
According to the production method, the component (C) can be produced in a high yield, and the amount of the high molecular weight component in the obtained component (C) is small. This is preferable in that it can be excellent in physical properties.
What is necessary is just to follow the manufacturing method of above-described (C) component as the said process.

What is necessary is just to set suitably as a viscosity of a composition according to the use, purpose, etc. to be used. 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 essentially comprises the components (A) to (C), but various components can be blended as necessary.
Preferred other components include compounds having an ethylenically unsaturated group other than component (A) (D) [hereinafter referred to as “component (D)”], organic solvents [hereinafter referred to as “component (E)”], Photopolymerization initiator (F) [hereinafter referred to as “component (F)”] and thermal polymerization initiator (G) [hereinafter referred to as “component (G)”) and the like, and other components as well are blended can do.
Hereinafter, components (D) to (G) and other components other than these will be described.
In addition, the other component mentioned later may use only 1 type of the illustrated compound, and may use 2 or more types together.

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 properties of the composition, and various components can be used.
The component (D) includes a compound having one ethylenically unsaturated group (hereinafter referred to as “monofunctional unsaturated compound”), a compound having two or more ethylenically unsaturated groups [hereinafter referred to as “polyfunctional unsaturated group”. A saturated compound).

(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 ( And monofunctional (meth) acrylates having a hydroxyl group such as (meth) acrylate and hydroxypropyl acrylate.
Examples of the compound having an amide group include (meth) acrylamide. Specifically, N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn -N-alkyl (meth) acrylamides such as butyl acrylamide, N-sec-butyl methacrylamide, Nt-butyl acrylamide; and N-hydroxyalkyl (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide It is done.

(2) Polyfunctional unsaturated compound As an example of a polyfunctional unsaturated compound, (meth) acrylate having two (meth) acryloyl groups (hereinafter referred to as “bifunctional (meth) acrylate”), and two or more (Meth) acrylate having a (meth) acryloyl group (hereinafter referred to as “trifunctional or higher (meth) acrylate”) and the like.
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 tri- or higher functional (meth) acrylates include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, and tritri or tetra (meth) ditrimethylolpropane. ) 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;
Examples include tris (2- (meth) acryloyloxyethyl) isocyanurate; and tri (meth) acrylates of isocyanuric acid alkylene oxide adducts.
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-described compounds.
Among these, urethane (meth) acrylate is preferable and will be described in detail below.

  Urethane (meth) acrylates can be obtained by a three-way reaction of a polyhydric alcohol, a polyvalent isocyanate and a hydroxyl group-containing (meth) acrylate, or an organic polyisocyanate and a hydroxyl group-containing compound (meta) ) Obtained by the two reactions with an acrylate compound (hereinafter referred to as “urethane adduct”).

  The urethane (meth) acrylate is preferably a urethane adduct in that the curability of the composition and the hardness and scratch resistance of the cured product are excellent.

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

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

As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate and hydroxyoctyl Hydroxyl group-containing mono (meth) acrylates such as (meth) acrylate, trimethylolpropane 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) acrylates.

In the urethane adduct, examples of the organic polyvalent isocyanate and the hydroxyl group-containing (meth) acrylate compound include the above compounds.
In a urethane adduct, what uses a hydroxyl-containing polyfunctional (meth) acrylate as a hydroxyl-containing (meth) acrylate is preferable.
Among these, a compound having three or more (meth) acryloyl groups and one hydroxyl group is preferable in that the cured product is superior in hardness and scratch resistance. Specifically, pentaerythritol tri (meth) is preferable. Examples include acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

Another preferred compound of the urethane adduct is 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 the same compounds as those described above.
Examples of the organic polyisocyanate having three or more isocyanate groups include the aforementioned hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.

Urethane (meth) acrylate can use what was manufactured by the conventional method.
For example, in the presence of an addition catalyst such as dibutyltin dilaurate, an organic polyvalent isocyanate and a polyvalent ol are heated and stirred to cause an addition reaction to produce an isocyanate group-containing compound, and a hydroxyl group-containing (meth) acrylate is added to the compound, followed by heating. -The method of stirring and carrying out addition reaction etc. are mentioned.
In the case of a urethane adduct, there may be mentioned a method in which an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate are heated and stirred in the presence of an addition catalyst to cause an addition reaction.

  (D) It is preferable that the content rate of a component is 1-30 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component, It is more preferable that it is 5-25 weight part, 10-20 weight part More preferably. 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) (E) Component The composition of the present invention can be used without a solvent, but various (E) components (organic solvents) can be used for the purpose of coating viscosity and film thickness adjustment. .
Specific examples of the component (E) include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; benzene and toluene And aromatic compounds such as xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone Can be mentioned.

  (E) It is preferable that the content rate of a component is 0.01-200 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component, It is more preferable that it is 10-150 weight part, 20-100 More preferably, it is part 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 included. 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 active energy rays, the component (F) is further added from the viewpoint of ease of curing and cost. It is preferable to contain.
When used as an electron beam curable composition, it is not always necessary to contain the component (F), but a small amount can be blended as necessary in order to improve curability.

As the component (F) in the present invention, various known photopolymerization initiators can be used.
The component (F) is preferably a radical photopolymerization initiator.
Specific examples of the component (F) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl Acetophenone compounds such as 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 Phosphine oxide compounds such as
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4 An acetophenone / benzophenone hybrid photoinitiator such as -methylphenylsulfinyl) propan-1-one;
Examples include oxime ester photopolymerization initiators such as 2- (O-benzoyloxime) -1- [4- (phenylthio)]-1,2-octanedione; and camphorquinone.

  Among these, acetophenone compounds, benzophenone compounds, and phosphine oxide compounds are preferable, and acetophenone 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, with respect to 100 parts by weight of the total amount of the curable components. Particularly preferred is ˜5 parts by weight. Within the above range, the composition has excellent curability and the resulting cured film has excellent scratch resistance.

5) Component (G) The component (G) is a thermal polymerization initiator. When the composition is used as a thermosetting composition, the component (G) can be blended.
The composition of this invention can mix | blend a thermal-polymerization initiator and can also be heat-hardened.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.

  Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 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- , 5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5 -Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butyl) Peroxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 Examples include 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.

Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.

As a content rate of (G) component, 10 weight part or less is preferable with respect to 100 weight part of sclerosing | hardenable component total amount.
When the thermal polymerization initiator is used singly, it may be carried out in accordance with conventional means of normal radical thermal polymerization. In some cases, it is used in combination with the component (E) (photopolymerization initiator), and after photocuring, the reaction rate is further increased. For the purpose of improving the temperature, thermosetting can also be performed.

6) Other components other than the above As other components other than the above, known additives can be used. For example, ultraviolet absorbers, light stabilizers, acidic substances, inorganic particles, antioxidants, silane cups Examples thereof include a ring agent, a surface modifier, a polymer, an acid generator, a pigment, a dye, a tackifier, and a polymerization inhibitor.
Hereinafter, these components will be described.

<Ultraviolet 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-butyroxyphenyl) -6- (2,4-bisbutyroxyphenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4- 1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine and other triazine ultraviolet absorbers; 2- (2H-benzotriazol-2-yl)- 4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-5- (2- ( Benzotriazole ultraviolet absorbers such as (meth) acryloyloxyethyl) phenyl] -2H-benzotriazole; benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, ethyl-2-cyano -3,3-diphenyl acrylate, octyl-2-cyano-3,3-diphenyl Cyanoacrylate ultraviolet absorbers such as acrylate, titanium oxide particles, zinc oxide particles, and inorganic particles, and the like to absorb the ultraviolet rays or the like tin oxide particles.

Among the compounds, benzotriazole ultraviolet absorbers are 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, with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is 1-2 parts by weight.

<Light stabilizer>
As the light stabilizer, a known light stabilizer can be used. Among them, a hindered amine light stabilizer (HALS) is preferably exemplified.
Specific examples of the hindered amine light stabilizer 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 light stabilizers include BASIN, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100.

  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 with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is 1-1 weight part.

<Acid substance>
Although the composition of this invention is excellent in the adhesive material to base materials, such as a plastics, adhesiveness can be improved further by adding an acidic substance.
Examples of the acidic substance include a photoacid generator that generates an acid upon 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, with respect to 100 parts by weight of the total amount of the curable component, More preferably, it is -0.5 weight part. Within the above range, the adhesion to the substrate is excellent, and problems such as corrosion of the substrate 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 phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
As a phenolic antioxidant, hindered phenols, such as di-t-butylhydroxytoluene, can be mentioned preferably, for example. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Preferable examples of the phosphorus antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphite, triaryl phosphite, and the like. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
Examples of sulfur-based antioxidants include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.

  The content of the antioxidant is preferably 0.01 to 5 parts by weight and more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total composition of the present invention. In the above embodiment, the composition is excellent in stability, and 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.

There is no limitation in particular as a silane coupling agent, A well-known thing can be used.
Preferable specific examples of the silane coupling agent include (meth) acryloyl group-containing silane coupling agents such as 3- (meth) acryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Vinyl group-containing silane coupling agents such as allyl group-containing silane coupling agents such as allyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, N- -(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 with respect to 100 parts by weight of the total amount of the curable component.
By making the ratio of the silane coupling agent 0.05 or more, it is possible to improve the adhesion to the substrate, particularly the adhesion to the inorganic substrate, while by making it 30 parts by weight or less, Viscosity and gelation can be prevented by the reaction of the silane coupling agent during storage of the composition under the influence of a compound having moisture or a hydroxyl group.

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

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

4). Method of Use As a method of using the composition of the present invention, a conventional method may be followed.
For example, after apply | coating a composition by the normal coating method to the base material applied, the method of irradiating an active energy ray or heating and hardening is mentioned.
The active energy ray irradiation method may be a general method known as a conventional curing method.
In addition, the (D) component (photopolymerization initiator) and the (E) component (thermal polymerization initiator) are used in combination with the composition, and this is irradiated with active energy rays and then heat-cured, thereby adhering to the substrate. A method for improving the property can also be adopted.

The substrate to which the composition of the present invention can be applied is applicable to various materials, and examples thereof include inorganic materials, plastics, and paper.
Examples of inorganic materials include glass, metal, mortar, concrete, and stone. Examples of metals 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 resins, cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, acrylic resins, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene, etc. And cyclic polyolefin resin having a cyclic olefin as a monomer, polyvinyl chloride, epoxy resin and polyurethane resin.

  Among these substrates, the composition of the present invention is excellent in adhesiveness to a plastic substrate, and therefore can be preferably applied to a plastic substrate. Further, as a plastic substrate, it can be preferably applied to polyethylene.

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

  What is necessary is just to set the film thickness of the composition cured film with respect to a base material suitably according to the objective. The thickness of the cured film may be selected according to the use of the base material to be used or the base material having the manufactured 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 organic solvent is evaporated by heating and drying after coating on the substrate.
The drying temperature is not particularly limited as long as the applied substrate is at a temperature that does not cause a problem such as deformation. A preferable heating temperature is 40 to 100 ° C. What is necessary is just to set drying time suitably with the base material to apply and heating temperature, Preferably it is 0.5 to 3 minutes.

In the case where the composition of the present invention is used as an active energy ray-curable composition, examples of the active energy rays for curing include electron beams, ultraviolet rays, and visible rays, but ultraviolet rays or visible rays are preferable, and ultraviolet rays are preferred. Particularly preferred. Examples of the ultraviolet irradiation device include a high pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).
Irradiation energy should be appropriately set according to the type and composition of the active energy ray. As an 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 applications, and specifically includes coating agents, inks and molding materials.
Among these, it can be preferably used as a coating agent.
Furthermore, it can be more preferably used as a coating agent for plastic substrates, and can be more particularly preferably used as a coating agent for polypropylene substrates.
Specific examples of the application of the coating agent for a plastic substrate, preferably a polypropylene substrate, include household appliances such as electrical appliances and furniture, building materials, and medical care.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited by these Examples.
In the following, unless otherwise specified, “part” means part by weight and “%” means percent by weight.

1. Examples 1 to 5 and Comparative Examples 1 to 4 (Preparation of compositions)
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 substrate)
The obtained composition was applied to polypropylene (30 mm × 150 mm × 2 mm) manufactured by Engineering Test Service Co., Ltd. using a bar coater # 8 so that the film thickness was 10 μm.
Next, ultraviolet rays were irradiated with UV-A illuminance of 250 mW / cm 2 and irradiation energy of 600 mJ / cm ² using a high-pressure mercury lamp equipped with a conveyor [H06-L 41 manufactured by Eye Graphics Co., Ltd.].
The obtained cured film was used and evaluated according to the following method. The results are shown in Table 3.

1) Adhesiveness The obtained cured film was cut with 2 mm vertical and horizontal intervals with a cutter knife to form 25 squares of 2 mm × 2 mm size, and Nichiban Co., Ltd. # 405 made by Nichiban Co., Ltd. After cellophane tape was applied, it was peeled off strongly. The remaining film rate (%) after peeling was evaluated. The greater the number of remaining films, the better the adhesion.

2) Scratch resistance The obtained cured film was visually observed on the surface of the cured film after being rubbed with a nail to confirm the presence or absence of scratches or dents, and evaluated according to the following three levels.
○: No scratch or dent, △: No scratch, but a slight dent remains in the coating film, ×: Clearly scratch

3) Appearance of cured film The appearance of the obtained cured film was visually evaluated.
○: No scratch or dent, △: No scratch, but a slight dent remains in the coating film, ×: Clearly scratch

Abbreviations in Table 1 and Table 2 mean the following. The brackets in Tables 1 and 2 mean the number of parts of each component.
Component (A) IBXA: Isobornyl acrylate [Osaka Organic Co., Ltd., acryloyl group equivalent 208 g / eq]
ACMO: acryloylmorpholine [manufactured by KJ Chemicals, acryloyl group equivalent 141 g / eq]
-M-120: acrylate of 2-ethylhexylethylene oxide 2 mol adduct [Aronix M-120 manufactured by Toagosei Co., Ltd., acryloyl group equivalent 155 g / eq]
(B) component SC-390S: chlorinated polyolefin [Nippon Paper Co., Ltd. Super Clone 390S, chlorination degree 36%, Mw: 40,000, pellet product]
SC-814B: Chlorinated polyolefin (Nippon Paper Co., Ltd. Super Clone 814B, chlorination degree 41%, Mw: 15,000, butyl acetate 50% solution)
SC-2030S: Chlorinated polyolefin [Nippon Paper Co., Ltd. Super Clon 2030S, chlorination degree 30%, Mw: 75,000, pellet product]
(B) ′ component HL-16P: chlorinated polyolefin [Hardlen 16LP manufactured by Toyobo Co., Ltd., chlorination degree 32%, Mw: 150,000, pellet product]
Component (C) UH-2170: hydroxyl group-containing styrene / acrylic copolymer [ARUFON UH-2170, Mw: 14,000, polydispersity: 3.8, Tg: 60 ° C., manufactured by Toagosei Co., Ltd.]
UC-3080: Carboxyl group-containing styrene / acrylic copolymer [ARUFON UC-3080, Mw: 14,000, polydispersity: 3.8, Tg: 133 ° C., manufactured by Toagosei Co., Ltd.]
Component (C) ′ UP-1000: acrylic copolymer [ARUFON UP-100 manufactured by Toagosei Co., Ltd., Mw: 3,000, polydispersity: 1.9, Tg: −77 ° C.]
Component (D) M-305: Mixture of pentaerythritol tri and tetraacrylate [Aronix M-305 manufactured by Toagosei 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) Component / PGM: Propylene glycol monomethyl ether
Component (F) HCPK: 1-hydroxy-cyclohexyl-phenyl-ketone [IRGACURE184 manufactured by BASF Corporation]

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

  The hard mold composition of the present invention can be preferably used as an active energy ray hard mold composition, and the obtained cured film can be applied to various base materials, particularly to plastic base materials including polypropylene base materials. It is excellent in adhesion and scratch resistance, and can be preferably used for various applications, particularly as a coating agent.

Claims (21)

A curable composition containing the following components (A), (B) and (C).
Component (A): A compound having one or more (meth) acryloyl groups 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 chlorination degree of 25 to 50%. The said (C) component is a polymer of glass transition point 0 degreeC-150 degreeC, The curable composition of Claims 1-3. 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 having an aromatic group and a hydroxyl group or / and a polymer having an aromatic group and a carboxyl group. object. 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. object. For a total of 100 parts by weight of the component (A),
The component (B) contains 2 to 100 parts by weight and the component (C) 20 to 150 parts by weight, and the component (B) and the component (C) total 30 to 200 parts by weight. The curable composition according to any one of the above. Furthermore, the curable composition of any one of Claims 1-8 containing the compound (D) which has ethylenically unsaturated groups other than (A) component. For a total of 100 parts by weight of the components (A) and (D),
The component according to claim 9, comprising 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). A curable composition. The curable composition according to any one of claims 1 to 10, comprising an organic solvent (E). The active energy ray hardening-type composition containing the composition of any one of Claims 1-11. Furthermore, the active energy ray hardening-type composition of Claim 12 containing a photoinitiator (F). An active energy ray-curable coating agent composition comprising the composition according to claim 13. An active energy ray-curable coating agent composition for a polypropylene substrate, comprising the composition according to claim 14. Monomer containing alkyl (meth) acrylate as an essential component is continuously polymerized at high temperature to produce the following component (C), and the obtained component (C) is mixed with the following components (A) and (B). The manufacturing method of the curable composition including the process to do.
Component (A): A compound having one or more (meth) acryloyl groups 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 16, 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 16 or 17, wherein the component (C) is a polymer having a glass transition point of 0C to 150C. The method for producing a curable composition according to any one of claims 16 to 18, wherein the component (C) is a polymer having a polydispersity of 4.5 or less. Furthermore, the manufacturing method of the curable composition of any one of Claims 16-19 including the process of mixing an organic solvent (E). Furthermore, the manufacturing method of the curable composition of any one of Claims 16-20 including the process of mixing a photoinitiator (F).