JP6863291B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition, preferably an active energy ray-curable composition. The cured film of the composition of the present invention is excellent in adhesion to an inorganic base material and a plastic base material, and is particularly excellent in adhesion to a glass base material as an inorganic base material. , A coating agent for coating a glass substrate, and a coating agent for coating a plastic, which can be preferably used and belong to these technical fields.

The active energy ray-curable composition can be cured by irradiating it with active energy rays such as ultraviolet rays, visible rays, and electron beams for a very short time, and is widely used as an ink or coating for various substrates because of its high productivity. Has been done.

However, when the base material is a plastic material, the desired base material adhesion can be obtained relatively easily, but there is a problem that good adhesion cannot be obtained with an inorganic material such as glass.
As a method for imparting adhesion to an inorganic substrate such as a metal or glass, a polyfunctional (meth) excluding phosphate esters (A) and (A) having two or more (meth) acryloyl groups in one molecule. ) An active energy ray-curable composition containing an acrylate (B) and a photoinitiator (C) is known (Patent Document 1).
However, since the component (A) in the composition has strong acidity, there is a problem that the vapor-deposited film deteriorates when it is applied to a base material having a metal-deposited film. Moreover, sufficient adhesion to glass could not be obtained.

As an active energy ray-curable composition for the purpose of improving adhesion to a glass substrate, a single compound (A) having one or more (meth) acryloyloxy groups and an ethylenically unsaturated compound are homopolymerized. An active energy ray-curable composition containing a (co) polymer (B), a silane coupling agent (C), and a photopolymerization initiator (D) obtained by copolymerizing ethylene or a mixture thereof is known. (Patent Document 2).
It is stated that the component (B) in the composition preferably has a weight average molecular weight [hereinafter referred to as “Mw”] of 10,000 or more in order to make the coating appearance suitable.
However, according to the study by the present inventors, in the case of a solvent-free composition, when a polymer having an Mw of more than 10,000 is used, the compatibility with various components is lowered and the composition becomes cloudy. In addition, it has been found that the coatability is lowered because the viscosity of the composition is increased. Further, in order to exhibit good adhesion to the substrate, the number of parts of the polymer to be blended is preferably 30 parts by weight or more, but the number of copies that can be blended with a high molecular weight polymer in consideration of compatibility and coatability. There was a problem that the upper limit of the above was only about 25 parts by weight.

In order to solve the above problems, it is conceivable to use a solvent-type composition containing an organic solvent, and in Patent Document 2, all of the compositions are solvent-type compositions in the examples.
However, according to the studies by the present inventors, in the case of the solvent-type composition, although the above-mentioned compatibility problem can be solved, the adhesion to the glass substrate and the scratch resistance are insufficient. there were.

Examples other than the above include an acrylic resin (A), an unsaturated compound (B) containing two or more ethylenically unsaturated groups, a phosphoric acid group-containing ethylenically unsaturated compound (C), and a silane coupling agent ( An active energy ray-curable composition containing D) and a fluorine-based compound (E) is known (Patent Document 3).
However, since the condensation reaction of the component (D) in the composition is promoted under acidic conditions, there is a problem that the storage stability of the composition is significantly impaired by the coexistence of the component (C) having an acidity.

Further, in the active energy ray-curable composition, with respect to a base material having poor adhesiveness such as polyethylene terephthalate which has not been surface-treated among plastic materials, the adhesion and scratch resistance to the base material are the same as described above. Had the problem of.

Japanese Unexamined Patent Publication No. 2009-155470 JP-A-2015-93893 Japanese Unexamined Patent Publication No. 2015-83658

The present inventors have good adhesion to a wide range of substrates, particularly excellent adhesion to inorganic materials such as glass and plastic materials, and scratch resistance that does not cause scratches even when scratched by a nail. In order to find a curable composition that can be suitably used for a coating agent, an ink, or the like, a diligent study was conducted.

As a result of diligent studies to solve the above problems, the present inventors have found that the compound has one or more (meth) acryloyl groups and one or more hydroxyl groups in one molecule, and the number of (meth) acryloyl groups. A curable composition containing a compound having the same number of hydroxyl groups and a (meth) acrylate-based polymer having an Mw of 1,000 to 30,000 has good adhesion to an inorganic substrate, particularly glass. The present invention has been completed by finding that it is not easily scratched by scratching with a claw and can be suitably used not only as a coating agent but also as an ink because of its excellent pigment dispersibility.
Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, the heat of polymerization during curing, particularly the heat of polymerization generated during active energy ray curing, can be reduced, and the heat shrinkage generated by curing can be alleviated. Therefore, the stress at the interface between various base materials, particularly the inorganic base material and the plastic material and the composition can be significantly reduced, and as a result, the adhesion between the inorganic base material and the composition having significantly different thermal expansion coefficients is further improved. Can be made to.

The present invention is a compound having one or more (meth) acryloyl groups and one or more hydroxyl groups in one molecule, and the number of (meth) acryloyl groups is equal to the number of hydroxyl groups in the molecule. A compound (A1) containing one (meth) acryloyl group and one hydroxyl group and a compound (A2) containing two or more (meth) acryloyl groups and a compound (A2) having two or more hydroxyl groups in the molecule. [hereinafter as "component (a)" hereinafter], and (meth) acrylate and the essential constituent monomer units, the polymer weight average molecular weight of 1,000 to 30,000 (B) [hereinafter, "(B ) Ingredients].
Hereinafter, the essential components (A), (B), other components, usage and the like will be described.

1. 1. Component (A) Component (A) is a compound having one or more (meth) acryloyl groups and one or more hydroxyl groups in one molecule, and the number of (meth) acryloyl groups is equal to the number of hydroxyl groups. It is a compound that is cured by irradiation with active energy rays 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 hydroxyl group, and a compound having no hydroxyl group even if it is a polyfunctional (meth) acrylate that simply increases the surface hardness is a cured film even if the component (B) is blended. Does not have sufficient substrate adhesion.

The component (A) includes a compound having one (meth) acryloyl group and one hydroxyl group in the molecule [hereinafter referred to as “(A1) component”] and two or more (meth) acryloyl groups in the molecule. And any compound having two or more hydroxyl groups [hereinafter referred to as "(A2) component"] can be used.

The component (A1) is a reaction product of hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, phenylglycidyl ether and (meth) acrylic acid. Examples thereof include 2-hydroxy-3-phenoxypropyl (meth) acrylate.

Specific examples of the component (A2) include epoxy (meth) acrylate obtained by adding (meth) acrylic acid to an epoxy resin, transesterification reaction of polyhydric alcohol and (meth) acrylic acid, and polyhydric alcohol (). Examples thereof include hydroxyl group-containing poly (meth) acrylate obtained by transesterification reaction of meta) acrylate.
Examples of the epoxy (meth) acrylate include bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, ethylene glycol type epoxy (meth) acrylate, diethylene glycol type epoxy (meth) acrylate, and polyethylene glycol type epoxy (meth). Acrylic, propylene glycol type epoxy (meth) acrylate, dipropylene glycol type epoxy (meth) acrylate, polypropylene glycol type epoxy (meth) acrylate, neopentyl glycol type epoxy (meth) acrylate, 1,6-hexanediol type epoxy (meth) ) Examples include acrylate.
Examples of the compound containing three or more (meth) acryloyl groups in the molecule include novolac type epoxy (meth) acrylate and the like.

As the hydroxyl group-containing poly (meth) acrylate, di (meth) acrylate of pentaerythritol and di (meth) acrylate of ditrimethylolpropane;
Di (meth) acrylates of these polyol alkylene oxide adducts Poly (meth) acrylates of polyols such as dipentaerythritol tri (meth) acrylates;
Examples thereof include tri (meth) acrylate of a dipentaerythritol alkylene oxide adduct.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.

Among these compounds, epoxy (meth) acrylate is preferable as the component (A2), and further, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, neopentyl glycol type epoxy (meth) acrylate and the like are used. Is preferable.

The component (A1) has the effect of improving the adhesion to the inorganic substrate, but is preferable because the surface hardness of the cured film can be improved by using the component (A2) in combination.
When the (A1) component and the (A2) component are used in combination, the (A1) component and the (A2) component are 3 to 70% by weight, respectively, in the total amount of 100% by weight of the (A1) component and the (A2) component. It is preferably 30 to 97% by weight, more preferably 10 to 30% by weight and 70 to 90% by weight, respectively.

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 composition can be made excellent, while when it is 80% by weight or less, heat shrinkage in curing can be suppressed. And can be made to have excellent adhesion to the substrate.

2. Component (B) Component (B) is a polymer containing (meth) acrylate as an essential constituent monomer unit and having an Mw of 1,000 to 30,000.
The component (B) 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 inorganic 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 (meth) acrylate as an essential constituent monomer unit as the component (B), the 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 (B) 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 (B) is in the range of 1,000 to 30,000, preferably 2,000 to 20,000.
A polymer having an Mw of less than 1,000 has insufficient scratch resistance of the obtained composition, and when the Mw exceeds 30,000, 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.
The Mw of the component (B) is preferably 1,000 to 10,000 in the case of a composition targeting an inorganic base material, and 2,000 to 30,000 in the case of a composition targeting a plastic base material. The polymer is preferable.

Further, as the component (B), a polymer having a polydispersity (Mw / Mn) of 4.00 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 molecular weight of 3.70 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.
The degree of polydispersity of the component (B) is preferably 3.00 or less in the case of a composition targeting an inorganic base material, and preferably 4.00 or less in the case of a composition targeting a plastic base material.
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 glass transition point (hereinafter referred to as “Tg”) of the component (B) is preferably in the range of −85 ° C. to 120 ° C., and more preferably in the range of −80 ° C. to 100 ° C.
The scratch resistance of the cured film can be improved by setting the Tg of the component (B) to −85 ° C. or higher, and the component (B) can be uniformly dissolved in the composition by setting the temperature to 120 ° C. or lower. Can be done.
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 a value at the glass transition temperature midpoint (Tmg) in the ΔT-temperature curve. Means.
The Tg of the component (B) is preferably −85 ° C. to 40 ° C. in the case of a composition targeting an inorganic base material, and preferably −50 ° C. to 120 ° C. in the case of a composition targeting a plastic base material. ..

1) As the monomer (B) 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 (B), even if it is a homopolymer of an alkyl (meth) acrylate, it may be a copolymer of an ethylenically unsaturated group-containing compound (hereinafter, referred to as “other monomer”) copolymerizable with the (meth) acrylate. It may be a polymer.
When a copolymer is used as the component (B), a polymer containing 50 mol% or more of alkyl (meth) acrylate as a constituent monomer unit is preferable, and a polymer containing 80 mol% or more is more preferable.

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.

Specific examples of other monomers include carboxyl group-containing monomers such as (meth) acrylic acid; sulfonic acid group-containing monomers such as acrylamide2-methylpropanesulfonic acid and styrenesulfonic acid; and phosphate group-containing simple compounds. Quantities; cyano group-containing monomers such as (meth) acrylonitrile, vinyl esters; aromatic vinyl compounds such as styrene and α-methylstyrene; acid anhydride group-containing monomers; hydroxyethyl (meth) acrylates, hydroxyethyl Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates such as (meth) acrylates and hydroxybutyl (meth) acrylates; Amide group-containing monomers such as (meth) acrylamide, dimethylacrylamide and diethyl (meth) acrylamide; Examples thereof include an amino group-containing monomer; an imide group-containing monomer; an epoxy group-containing monomer such as glycidyl (meth) acrylate; (meth) acryloylmorpholin; and vinyl ether.

The component (B) 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 (B), among these polymers, the polymer containing a hydroxyl group improves the adhesion to the base material, and particularly enhances the interaction with the interface of the inorganic base material to improve the adhesion to the inorganic base material. It can be expensive and is preferable.

2) Method for Producing Component (B) As the component (B), 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 (B) is 1,000 to 30,000, 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 (B) 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 (B), 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 away. 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, Japanese Patent Application Laid-Open No. 57-502171, Japanese Patent Application Laid-Open No. 59-6207, Japanese Patent Application Laid-Open No. 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 a monomer mixture composed of a polymerization solvent and a polymerization initiator, if necessary, is fixed. 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 can be mentioned.

The case where the component (B) 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 (B) is commercially available, and a commercially available product can also be used.
Specifically, ARUFON UP-1000 (Mw: 3,000, Tg: -77 ° C), ARUFON UP-1010 (Mw: 1,700, Tg: -31 ° C), ARUFON UP-, manufactured by Toa Synthetic Co., Ltd. 1020 (Mw: 2,000, Tg: -80 ° C), ARUFON UP-1021 (Mw: 1,600, Tg: -71 ° C), ARUFON UP-1061 (Mw: 1,600, Tg: -60 ° C) , ARUFON UP-1080 (Mw: 6,000, Tg: -61 ° C), ARUFON UP-1110 (Mw: 2,500, Tg: -64 ° C), ARUFON UP-1170 (Mw: 8,000, Tg: −57 ° C.), ARUFON UP-1190 (Mw: 1,700, Tg: −50 ° C.).
Further, as a copolymer having a hydroxyl group, ARUFON UH-2041 (Mw: 2,500, Tg: -50 ° C.), ARUFON UH-2190 (Mw: 6,000, Tg: -47 ° C.), ARUFON UHE-2012 (Mw: 6,000, Tg: -47 ° C.) Mw: 5,800, Tg: 20 ° C.) and ARUFON UH-2170 (Mw: 14,000, polydispersity: 3.5, Tg: 60 ° C.) and the like.
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, ARUFON UC-3510 (Mw: 2,000, Tg: -50 ° C), ARUFON UG-4010 (Mw: 2,900, Tg: -57 ° C), ARUFON US-6100 (Mw: 2,) 500, Tg: −58 ° C.) and the like.

The component (B) may be used alone or in combination of two or more.
As for the content ratio of the component (B), the total weight of the component (A) is 100 parts by weight, and when the component (D) described later is blended, the content of the component (A) and the component (D) is 100 parts by weight. 20 to 70 parts by weight is preferable, and 30 to 60 parts by weight is more preferable.
By setting the content ratio of the component (B) to 20 polymerization parts or more, the cured film of the composition can have excellent adhesion to the inorganic substrate, and by setting the content ratio to 70 polymerization parts or less, the composition can be made. It can be excellent in curability.
Hereinafter, the component (A), or the components (A) and (D) will be referred to as a curable component.

3. 3. Curable composition The present invention is a curable composition containing the components (A) and (B) 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) and (B) and, if necessary, other components described later may be stirred and mixed.
Further, as a method for producing the composition, a step of polymerizing a monomer containing (meth) acrylate as an essential component by high-temperature continuous polymerization to produce the component (B), and the obtained component (B) and (A). ) Is preferably included in the method for producing a curable composition.
As the step of producing the component (B), the method for producing the component (B) described above may be followed.
The obtained component (B) and component (A) may be mixed by stirring and mixing according to a conventional method.

When the components (A) and (B) and other components described later are mixed as necessary, they may be heated and stirred as necessary. The temperature when heated, stirred and mixed is preferably in the range of 40 to 90 ° C.

The viscosity of the composition may be appropriately set according to the intended use and purpose. The viscosity is preferably 100 to 50,000 mPa · s, more preferably 200 to 30,000 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) and (B), but various components can be blended as needed.
Preferred other components include the silane coupling agent (C) [hereinafter referred to as "component (C)"], the compound (D) having an ethylenically unsaturated group other than the components (A) and (C) [hereinafter, "component"). "(D) component"], photopolymerization initiator (E) [hereinafter referred to as "(E) component"] and thermal polymerization initiator [hereinafter referred to as "(F) component"], and other than these. Other ingredients can also be blended.
Hereinafter, the components (C) to (F) 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 (C) The composition of the present invention may further contain the component (C) (silane coupling agent) for the purpose of improving the adhesion to the substrate.

The component (C) is not particularly limited, and known components 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 component (C) can be preferably used for the purpose of further improving the adhesion to the base material, particularly the adhesion to the inorganic base material.
The component (C) is preferably blended in an amount of 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 component.
Adhesion to the base material, particularly to the inorganic base material, can be improved by setting the ratio of the component (C) to 0.05 or more, while adhering to the inorganic base material can be improved by setting the ratio to 30 parts by weight or less in the composition. Due to the influence of water and the compound having a hydroxyl group, the reaction of the component (C) proceeds during storage of the composition, so that thickening and gelation can be prevented.

2) Component (D) The component (D) is a compound having an ethylenically unsaturated group other than the components (A) and (C).
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 referred to as "polyfunctional unsaturated compound"]. Saturated compounds].

(1) Monofunctional unsaturated compound Examples of the monofunctional unsaturated compound include a (meth) acrylate having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) and one. Examples thereof include (meth) acrylamide compounds having a (meth) acryloyl group (hereinafter, referred to as “monofunctional (meth) acrylamide”).

Specific examples of monofunctional (meth) acrylates include
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, lauryl ( Alkyl (meth) acrylates such as meta) acrylates and stearyl (meth) acrylates;
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 (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolane) Monofunctional (meth) acrylate having a cyclic ether group such as -4-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.

Specific examples of the monofunctional (meth) acrylamide include N-methyl (meth) acrylamide, N-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-n-butyl (meth) acrylamide. N-alkyl (meth) acrylamide such as N-sec-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide; N such as N-hydroxyethyl (meth) acrylamide -Hydroxyalkyl (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-dihexyl (meth) acrylamide N, N-dialkyl (meth) acrylamide and the like.

(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 an alkylene oxide adduct of bisphenol A, di (meth) acrylate of an alkylene oxide adduct of bisphenol F, and butanediol di (meth) acrylate. Diol di (meth) acrylates such as hexane diol di (meth) acrylate and nonane diol di (meth) acrylate;
Di (meth) acrylate of polyols such as di (meth) acrylate of glycerin and 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 tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, and trimethylolpropane tri or tetra (meth) acrylate. ) Poly (meth) acrylate of polyols such as acrylate, dipentaerythritol tetra, penta or hexa (meth) acrylate;
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.

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) 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 (E) (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 (E) 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 (E), but a small amount may be added as needed in order to improve the curability.

As the component (E) in the present invention, various known photopolymerization initiators can be used.
The component (E) is preferably a photoradical polymerization initiator.
Specific examples of the component (E) 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 (E) 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.

4) Component (F) The component (F) is a thermal polymerization initiator, and when the composition is used as a thermosetting composition, the component (F) 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. , Azodi-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 (F) 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.

5) Other components other than the above As the other components other than the above, known additives can be used, and for example, organic solvents, ultraviolet absorbers, light stabilizers, acidic substances, inorganic particles, antioxidants, etc. , Silane coupling agents, surface modifiers, polymers, acid generators, pigments, dyes, tackifiers, polymerization inhibitors and the like.

<Organic solvent>
The composition of the present invention can be used without a solvent, but various organic solvents can be used for the purpose of adjusting the coating viscosity and the film thickness. Specifically, 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; aromatics such as benzene, toluene and xylene. Group compounds; 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.

The content ratio of the organic solvent 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 composition. Is even more preferable.

<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 the hindered amine-based 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, bisdecanoic acid (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and the like.
Examples of commercially available products of the hindered amine-based light stabilizer 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 phosphine. 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.

<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 (E) (photopolymerization initiator) and the component (F) (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 inorganic materials and plastics, and therefore can be preferably applied to inorganic materials and plastics. Further, the inorganic material can be preferably applied to glass and metal, and the plastic can be preferably applied to polyethylene terephthalate, polycarbonate, poly (methyl) methacrylate and a copolymer containing the same as a main component.

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 an 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 compounding 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 and an ink.

Specific examples of the coating agent include glass and plastic coatings, woodworking paints, topcoat paints such as mortar and slate, and protective coats on metal surfaces.
Specific examples of the use of the coating agent include coating of a glass container, an electrode insulating coating of a lithium ion battery, and coating of an automobile interior member.

Further, the composition of the present invention can also be used as an ink by blending a pigment or a dye. Examples of inks include printing inks for glass bottles, printing inks on metal surfaces, and the like.

The cured film of the composition of the present invention can be preferably used depending on the application requiring scratch resistance, and can be preferably used as a coating on furniture glass or as a printing ink for glass bottles.

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.
In Example 5, the components (A) to (E) were stirred and mixed to obtain a composition, which was then kneaded with a three-roll mill to obtain an ink composition.

2. Evaluation of glass substrate The obtained compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were cut using a doctor blade into a float plate glass (150 mm × 70 mm × 3 mm) manufactured by Nippon Sheet Glass Co., Ltd. with a film thickness of 20 μm. It was coated so that it became a test piece.
Next, the specimen was irradiated with ultraviolet rays under the conditions of ^{UV-A illuminance of 80 W / cm and irradiation energy of 800 mJ / cm 2} using a high-pressure mercury lamp [H06-L 41 manufactured by Eye Graphics Co., Ltd.] equipped with a conveyor. ..
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 1 mm intervals to form 100 squares with a size of 1 mm x 1 mm, and Nichiban Co., Ltd. # 405 was formed on this grid. After applying the cellophane tape, it was strongly peeled off. The number of residual films 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 cured 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) Ingredient
(A1) Ingredients -M-5700: 2-Hydroxy-3-phenoxypropyl (meth) acrylate [Aronix M-5700 manufactured by Toagosei Co., Ltd.]
(A2) Ingredients・ OT-2501: Bisphenol A type epoxy acrylate [Aronix OT-2501 manufactured by Toagosei Co., Ltd.]
(B) Component -UH-2041: (Meta) acryloyl-based polymer having a hydroxyl group [ARUFON UH-2041 manufactured by Toagosei Co., Ltd., Mw: 2,500, polydispersity: 1.50, Tg: -50 ° C. ]
-UP-1000: Copolymer composed of aliphatic (meth) acrylate [ARUFON UP-1000 manufactured by Toagosei Co., Ltd., Mw: 3,000, polydispersity: 1.88, Tg: -77 ° C]
(C) Ingredients -KBM-5103: 3- (meth) acryloxypropyltrimethoxysilane [KBM-5103 manufactured by Shin-Etsu Silicone Co., Ltd.]
Component (D) -M-402: Mixture product of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [Aronix M-402 manufactured by Toagosei Co., Ltd.]
-M-408: Ditrimethylolpropane tetraacrylate [Aronix M-408 manufactured by Toagosei Co., Ltd.]
(E) Ingredients -HCPK: 1-Hydroxy-cyclohexyl-phenyl-ketone [IRGACURE 184 manufactured by BASF]
-TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCUR TPO manufactured by BASF]
-BAMB: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369 manufactured by BASF)
Other Ingredients -FA5380: Blue Pigment [FASTOGEN Blue FA5380 manufactured by DIC Corporation]
BL-1H: Polyvinyl butyral [BL-1H manufactured by Sekisui Chemical Co., Ltd., Mw: 50,000, Tg: 63 ° C]

3. 3. Evaluation of Metal Substrate The compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were dropped on an aluminum plate with a dropper so as to have a diameter of about 5 mm and a film thickness of 3 mm.
Next, ultraviolet rays were irradiated with a Spot Cure SP-9 manufactured by Ushio, Inc. at a UV-A illuminance of 250 W / cm and an irradiation energy of 1,000 mJ / cm ^2.
The obtained cured film was used and evaluated according to the following method. The results are shown in Table 4.

1) Adhesion Lightly hooked from the side surface of the cured film with a spatula, and evaluated whether the cured film was peeled off.
2) Scratch resistance The same method as for "scratch resistance" in the above "evaluation of glass substrate" was carried out.

4. Evaluation Results As is clear from the results of Examples 1 to 5 in Tables 3 and 4, the composition of the present invention is excellent in adhesion to inorganic substrates such as glass substrate and metal substrate and scratch resistance. Met.
On the other hand, since the compositions of Comparative Examples 1 and 2 do not contain the component (B), they have a large thermal shrinkage due to the heat of polymerization during curing, and the linear expansion coefficient is significantly different from that of the polymer material. Adhesion was not obtained.
The composition of Comparative Example 3 uses a polyfunctional acrylate instead of the component (A). Since the composition of Comparative Example 3 had a low interaction with the surface of the base material, sufficient adhesion could not be obtained even if the component (B) was used. Moreover, since the adhesion is low, the cured film is easily peeled off just by scratching with a nail.
The composition of Comparative Example 4 uses polyvinyl butyral instead of (B). Although the composition of Comparative Example 4 has sufficient scratch resistance, the number of copies that can be used is limited due to its low compatibility, so that heat shrinkage cannot be reduced to a sufficient level, and adhesion can be obtained. There wasn't.

5. Example 6 (Preparation of composition)
As a component (A), 20 parts of OT-2501, 10 parts of M-5700, and as a component (B), UH-2170 [(meth) acryloyl polymer having a hydroxyl group, ARUFON UH- manufactured by Toa Synthetic Co., Ltd. 2170, Mw: 14,000, polydispersity: 3.5, Tg: 60 ° C.] 40 parts, M-306 [pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Toa Synthetic Co., Ltd.] as component (D) Aronix M-306] 30 parts, HPPK 3 parts, TPO 1 part and 60 parts of propylene glycol monomethyl ether (hereinafter referred to as "PGM") as an organic solvent are stirred and mixed at 40 ° C. to obtain a composition. It was.
The viscosity of the obtained composition at 25 ° C. was measured with an E-type viscometer and found to be 492 mPa · s.

6. Evaluation of plastic and glass substrates
1) Plastic base material The composition of Example 6 and Comparative Examples 1 to 4 was applied to a polyethylene terephthalate film [Lumirror T-60 manufactured by Toray Industries, Inc., 200 mm x 120 mm x 0.05 mm] using a bar coater to obtain a film thickness. It was coated to 25 μm and used as a test body.
For the composition of Example 6, after coating, the composition was heated to 85 ° C. to evaporate the PGM of the organic solvent.
Next, the test piece was irradiated with ultraviolet rays under the same method and irradiation conditions as in the above-mentioned "evaluation of the glass substrate".
The obtained cured film was used and evaluated according to the method of the above-mentioned "evaluation for metal substrate". The results are shown in Table 5.

2) Glass substrate Using the composition of Example 6, a test piece was prepared by the same method as in the above-mentioned "evaluation of glass substrate" and irradiated with ultraviolet rays under the same method and irradiation conditions.
The obtained cured film was used and evaluated by the same method as in the above-mentioned "evaluation of glass substrate". The results are shown in Table 5.

The hard composition of the present invention can be preferably used as an active energy ray hard composition, and the obtained cured film is suitable for various base materials, particularly inorganic base materials such as glass and plastic base materials. On the other hand, it has excellent adhesion and scratch resistance, and can be preferably used as a coating for furniture glass, a protective coating agent for lithium ion battery electrodes, and a printing ink or paint for glass bottles.

Claims (20)

A compound having one or more (meth) acryloyl groups and one or more hydroxyl groups in one molecule, and having the same number of (meth) acryloyl groups and hydroxyl groups , and one (1) in the molecule. meth) acryloyl group and a compound having one hydroxyl group (A1) and two or more in the molecule (meth) acryloyl group and a compound comprising a compound having two or more hydroxyl groups (A2) (a), and (meth ) A curable composition containing acrylate as an essential constituent monomer unit and a polymer (B) having a weight average molecular weight of 1,000 to 30,000. The curable composition according to claim 1, wherein the component (A2) is an epoxy (meth) acrylate. According to claim 1 or 2, the total amount of the component (A1) and the component (A2) is 100% by weight, and the component (A1) and the component (A2) are contained in an amount of 3 to 70% by weight and 30 to 97% by weight, respectively. The curable composition according to the description. The (B) component, curable composition according to any one of claims 1 to 3 which is a polymer of a glass transition point -85 ° C. to 120 ° C.. The curable composition according to any one of claims 1 to 4 , wherein the component (B) is a polymer having a hydroxyl group. The curable composition according to any one of claims 1 to 5 , wherein the component (B) is a polymer having a polydispersity of 4.00 or less. The curable composition according to any one of claims 1 to 6, wherein the component (B) is contained in an amount of 20 to 70 parts by weight based on a total of 100 parts by weight of the component (A). The curable composition according to any one of claims 1 to 7, further comprising a silane coupling agent (C). The curable composition according to any one of claims 1 to 8, further comprising a compound (D) having an ethylenically unsaturated group other than the components (A) and (C). The curable composition according to claim 9, wherein the component (B) is contained in an amount of 20 to 70 parts by weight based on a total of 100 parts by weight of the components (A) and (D). 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 comprising a photopolymerization initiator (E). An active energy ray-curable ink composition containing the composition according to claim 12. An active energy ray-curable ink composition for an inorganic base material or a plastic base material containing the composition according to claim 13. An active energy ray-curable coating agent composition containing the composition according to claim 12. An active energy ray-curable coating agent composition for an inorganic base material or a plastic base material containing the composition according to claim 15. A monomer containing (meth) acrylate as an essential component is polymerized by high-temperature continuous polymerization at a temperature of 160 to 350 ° C., and (meth) acrylate is used as an essential constituent monomer unit, and the weight average molecular weight is 1,000 to 30, A step of producing the polymer (B) of 000, the obtained component (B), and a compound having one or more (meth) acryloyl groups and one or more hydroxyl groups in one molecule. A compound having the same number of meta) acryloyl groups and hydroxyl groups, a compound (A1) having one (meth) acryloyl group and one hydroxyl group in the molecule, and two or more (meth) acryloyls in the molecule. A method for producing a curable composition, which comprises a step of mixing a compound (A) containing a compound (A2) having a group and two or more hydroxyl groups. The method for producing a curable composition according to claim 17, wherein the component (A2) is an epoxy (meth) acrylate. The curable composition according to claim 17 or 18, wherein the component (B) is a polymer having a glass transition point of −85 ° C. to 120 ° C. and a hydroxyl group having a polydispersity of 4.00 or less. Production method. The method for producing a curable composition according to any one of claims 17 to 19, further comprising a step of mixing the photopolymerization initiator (E).