JP2013234217A - Active energy ray-curing coating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curing coating agent composition that exhibits excellent abrasion resistance and weatherability when being coated to a plastic substrate, especially the plastic substrate used in outdoor, excels in transparency, and exhibits performance of abrasion resistance or the like sufficiently even if irradiation energy of an active energy ray is small.SOLUTION: An active energy ray-curing coating agent composition includes: (A) urethane (meth)acrylate containing an isocyanuric ring of a specified structure; (B) (meth)acrylate containing an isocyanuric ring of a specified structure; (C) a reaction product of colloidal silica (c1), an alkoxysilane compound (c2) containing a (meth)acryloyl group or/and an alkoxysilane compound (c3) containing a maleimide group; (D) a (meth)acrylamide compound containing a substituent; (E) an ultraviolet absorber; and (F) an organic solvent, each of which is included in a predetermined rate.

Description

  The present invention relates to an active energy ray-curable coating composition that is excellent in abrasion resistance and weather resistance after curing and can be preferably applied as a protective film for a plastic substrate used outdoors. Is.

Conventionally, for various substrates such as metal, glass and plastic, a protective film is formed on the substrate using a coating composition for the purpose of protecting the substrate surface or imparting aesthetics or design. The forming method is used.
In particular, the plastic substrate is lightweight and excellent in impact resistance, easy moldability, and the like. However, since the surface is easily damaged and has low hardness, there is a drawback that the appearance is remarkably impaired when used as it is. For this reason, it is required that the surface of the plastic substrate is coated with a coating composition and is subjected to a so-called hard coat treatment to impart hard coat properties (such as scratch resistance and pencil hardness) to improve the surface hardness.

In plastic bases, transparent materials are small in specific gravity, light in weight, easy to process, and more resistant to impact than inorganic glass. Widely used as a substitute for glass in fields such as optical applications. Has been. On the other hand, the plastic substrate is easily damaged by the organic solvent as described above, easily damaged by organic solvents, weather resistance (for example, light stability against ultraviolet rays), and heat resistance. It has disadvantages such as inferiority. For this reason, the plastic substrate used in the application is often used by being coated with various protective films for the purpose of improving the surface characteristics.
Among the coating agent compositions used for such a protective film, the active energy ray-curable coating agent composition is widely used because it has excellent wear resistance after curing and excellent productivity.

  Plastic products used outdoors require not only wear resistance but also excellent weather resistance. As an active energy ray-curable coating composition having both wear resistance and weather resistance, colloidal silica fine particles, poly [((), which are surface-modified with a silane compound having a methacryloyloxy group, an acryloyloxy group or a vinyl group at a predetermined weight ratio (Meth) acryloyloxyalkyl] isocyanurate and a monomer mixture composed of urethane (poly) methacrylate having an alicyclic skeleton, and a wear-resistant coating forming composition containing a photopolymerization initiator in a specific ratio (Patent Document 1).

  Also, poly (meth) acrylate of mono- or polypentaerythritol, urethane poly (meth) acrylate having at least two radical polymerizable unsaturated double bonds, poly [(meth) acryloyloxyalkyl] (iso) cyanurate, ultraviolet ray A coating agent composition containing an absorbent, a hindered amine light stabilizer, and a photopolymerization initiator in a specific ratio is also known (Patent Document 2).

  Furthermore, there is also an active energy ray curable coating composition containing a specific urethane (meth) acrylate compound containing an isocyanurate skeleton, a (meth) acrylate compound having an isocyanurate skeleton, and radical polymerizable inorganic fine particles in a specific ratio. (Patent Document 3).

However, when a plastic product is used outdoors for a long period of time, particularly when a polycarbonate product requiring transparency is used outdoors for a long period of time, the current protective film cannot provide sufficient weather resistance. For example, even when a headlamp of an automobile is used for a long period of time, haze and scratches become remarkable.
Recently, there is a movement to replace the sunroof and the window of an automobile with a resin made of polycarbonate. For this purpose, wear resistance and weather resistance higher than those of the headlamp are required.
On the other hand, from the viewpoint of cost reduction of products and energy saving, it is desired that sufficient wear resistance and weather resistance are exhibited even if the irradiation energy amount of active energy rays is small.

Japanese Patent No. 3747065 JP 2000-063701 A JP 2010-254840 A

  The present inventors have demonstrated excellent abrasion resistance and weather resistance when coated on a plastic substrate, particularly a plastic substrate such as a polycarbonate substrate used outdoors, and has excellent transparency and active energy rays. It is an object of the present invention to provide an active energy ray-curable coating agent composition that sufficiently exhibits performance such as wear resistance even when the amount of irradiation energy is small.

  As a result of intensive studies to solve the above problems, the present inventors have found that an isocyanuric ring-containing urethane (meth) acrylate compound, an isocyanuric ring-containing (meth) acrylate compound having no urethane bond, a (meth) acryloyl group and / or maleimide. A composition in which a hydrolysis / condensation reaction product of an alkoxysilane compound having a group and colloidal silica and a nitrogen-substituted (meth) acrylamide monomer are used together in a specific ratio and an appropriate amount of an additive is added after curing. The present inventors have found that it is excellent in transparency, abrasion resistance, and weather resistance, and that the irradiation energy amount of active energy rays required for performance can be reduced, and the present invention has been completed.

That is, this invention is a composition containing the following (A)-(F) component, Comprising: (A) component, (B) component, (C) component, and (D) component total [Hereinafter, "(A ) To (D) total component]] with respect to 100 parts by weight, respectively, (A) to (F) components (A) component: 20 to 80 parts by weight (B) component: 5 to 60 parts by weight (C) Component: 1 to 30 parts by weight (D) Component 1 to 20 parts by weight (E) Component: 0.1 to 12 parts by weight (F) Component: Active energy ray curable coating containing 10 to 1000 parts by weight The agent composition.
Component (A): Compound represented by general formula (1) described later (B) Component: Compound (C) represented by general formula (2) described later: Colloidal silica (c1), and general formula (3) described later The (meth) acryloyl group-containing alkoxysilane compound (c2) represented by the formula (4) and / or the maleimide group-containing alkoxysilane compound (c3) represented by the following general formula (4) by weight ratio, (c1): [ (C2) + (c3)] = 9: 1 to 1: 9 non-volatile component of the reaction product subjected to hydrolysis / condensation reaction, wherein (c1) is chemically converted to (c2) and / or (c3) Includes modifications.
(D) component: (meth) acrylamide compound having at least one substituent on the nitrogen atom (E) component: ultraviolet absorber (F) component: organic solvent

Hereinafter, the present invention will be described in detail.
In the present specification, an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group, and an acrylate or methacrylate is represented as a (meth) acrylate.

  The active energy ray-curable coating agent composition of the present invention exhibits excellent wear resistance and weather resistance as a coating agent for plastic substrates used outdoors, particularly polycarbonate substrates.

The present invention relates to an active energy ray-curable coating agent composition containing the above-described components (A) to (F) at a specific ratio.
Hereinafter, the detail of each component and a composition is demonstrated.

1. (A) component (A) A component is a compound represented by following General formula (1), and is an isocyanuric ring containing urethane (meth) acrylate compound.

In the general formula (1), R ¹ , R ² and R ³ all represent an ethylene group, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group.

As the component (A), a compound in which R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms in the general formula (1), that is, a triacrylate is preferable. The compound is excellent in curability and requires a small amount of irradiation energy of active energy rays necessary for exhibiting the performance of the cured film. Furthermore, the abrasion resistance and weather resistance of the cured film are particularly excellent.

  (A) The component manufactured according to the conventional method can be used. Specific examples include an addition reaction between a nurate type trimer of hexamethylene diisocyanate and hydroxyethyl (meth) acrylate. Although this addition reaction can be performed without a catalyst, a tin-based catalyst such as dibutyltin dilaurate, an amine-based catalyst such as triethylamine, or the like may be added in order to advance the reaction efficiently.

(A) The content rate of a component is 20-80 weight part with respect to 100 weight part of (A)-(D) component total, Preferably it is 45-80 weight part, More preferably, it is 50-70 weight part. is there.
When the content ratio of the component (A) is less than 20 parts by weight, the weather resistance becomes insufficient, more specifically, it tends to cause appearance defects such as whitening in the weather resistance test, while when it exceeds 80 parts by weight, The weather resistance becomes insufficient, and more specifically, a poor adhesion is likely to occur in a weather resistance test.

2. (B) A component (B) component is a compound represented by following General formula (2), and is an isocyanuric ring containing (meth) acrylate compound which does not have a urethane bond.

In the general formula (2), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and R ⁹ represents a hydrogen atom or a (meth) acryloyl group.

The component (B) is preferably a compound in which R ⁷ and R ⁸ are hydrogen atoms and R ⁹ is a hydrogen atom or an acryloyl group in the general formula (2), that is, di- or triacrylate. The compound is particularly excellent in the curability of the composition and the abrasion resistance of the cured film.

(B) The content rate of a component is 5-60 weight part with respect to 100 weight part of (A)-(D) component total, Preferably it is 5-50 weight part, More preferably, it is 10-40 weight part, Particularly preferred is 10 to 30 parts by weight.
When the content ratio of the component (B) is less than 5 parts by weight, the weather resistance becomes insufficient, and more specifically, the adhesion resistance is likely to be generated in the weather resistance test. On the other hand, the content exceeds 60 parts by weight. And weather resistance becomes insufficient, and more specifically, appearance defects such as whitening are likely to occur in a weather resistance test.

3. Component (C) The component (C) is composed of colloidal silica (c1) [hereinafter also simply referred to as “(c1)”] and a (meth) acryloyl group-containing alkoxysilane compound (c2) represented by the following general formula (3): ) [Hereinafter simply referred to as “(c2)”] or / and a maleimide group-containing alkoxysilane compound (c3) represented by the following general formula (4) (hereinafter also simply referred to as “(c3)”), It is a non-volatile component of a reaction product obtained by hydrolysis and condensation reaction at a weight ratio of (c1): [(c2) + (c3)] = 9: 1 to 1: 9, and (c1) is converted to (c2 Or / and (c3) chemically modified.

In General Formula (3), R ¹⁰ represents a methyl group or a phenyl group, R ¹¹ represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, R ¹² represents a hydrogen atom or a methyl group, and X represents Represents an alkoxy group having 1 to 6 carbon atoms, X may be the same or different, and n is 0 or 1;

In the general formula (4), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, R ¹⁴ represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and z is 0. A positive number of 1 or more and 3 or less is represented. When z is less than 3, (c3) contains a condensate, and R ^{13 in} one molecule of the condensate may contain two or more different groups.

  In addition, although manufacture of (C) component is normally performed in an organic solvent, (C) component is a component except the water and organic solvent which were used by reaction. The component (C) is a component excluding alcohol generated by hydrolysis of alkoxysilane and water generated by condensation of silanol. That is, the component (C) means a non-volatile component in the reaction product, in other words, a Si-containing component.

Examples of the component (C) include three kinds of reactants (c1) and (c2), reactants (c1) and (c3), and reactants (c1), (c2), and (c3). , Each can be selected according to the purpose.
Hereinafter, regarding the component (C), the raw materials (c1) to (c3), the production method, and the content ratio will be described.

1) (c1)
(C1) is colloidal silica.
As (c1), various compounds can be used, but those in which spherical particles are uniformly dispersed are preferable, for example, those in which the particles are uniformly dispersed in an alcohol solvent are more preferable.
The average primary particle size of (c1) is preferably 1 to 100 nm, more preferably 5 to 60 nm, and particularly preferably 5 to 30 nm. By making the average primary particle size of (c1) larger than 1 nm, it can be excellent in abrasion resistance, and by making it smaller than 100 nm, it should be excellent in dispersion stability of the colloidal solution. Can do.
In the present invention, the average primary particle diameter means a value calculated from the specific surface area by the BET method.
The specific surface area of (c1) is preferably in the range of 30 to 3,000 m ² / g.

2) (c2)
(C2) is a compound represented by the general formula (3).
In the general formula (3), a compound in which n is 0 is preferable in that the cured film has excellent wear resistance. When n is 1, a compound in which R ¹⁰ is a methyl group is preferable in that the cured film has excellent weather resistance. R ¹¹ is preferably a compound which is a trimethylene group in that the cured film is excellent in wear resistance and weather resistance. R ¹² is preferably a hydrogen atom compound from the viewpoint of excellent curability when the composition requires curability. On the other hand, when ease of raw material production and storage stability of the composition are required, a compound that is a methyl group is preferable in terms of excellent stability during raw material production and storage of the composition. X is preferably a compound that is a methoxy group, an ethoxy group, or a propoxy group in terms of excellent reactivity.

  In (c2), a compound in which n is 0 is more preferable. Specific examples of the compound include 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, and 3- (meth) acryloyloxypropyltriethoxysilane.

3) (c3)
(C3) is a compound represented by the general formula (4) described above.
In General formula (4), as a C1-C6 monovalent organic group of R < ¹³ >, an alkyl group is preferable and a methyl group, an ethyl group, and a propyl group are especially preferable at the point which is excellent in hydrolysis reactivity. As the divalent saturated hydrocarbon group having 1 to 6 carbon atoms of R ¹⁴ , a trimethylene group is particularly preferable in that the cured film is excellent in wear resistance and weather resistance.

In the general formula (4), z represents the average number of moles of remaining alkoxy groups per mole of Si atoms. (C3) indicates an alkoxysilane monomer when z is 3, and indicates an alkoxysilane condensate or a mixture of an alkoxysilane condensate and an alkoxysilane monomer when z is less than 3. When (c3) is a condensate, each R ¹³ may have two or more different chemical structures in one molecule.

  In the general formula (4), by setting z to 0.1 or more, colloidal silica is effectively surface-modified, and the cured product has excellent scratch resistance. Further, (c1) In terms of effective reactivity with the surface, 0.4 ≦ z ≦ 3, and further preferably 0.8 ≦ z ≦ 3.

In addition, the value of z can be calculated | required from the integration ratio of a hydrogen atom by measuring the ¹ H-NMR spectrum of (c3).

A preferred method for producing the compound of the formula (4) will be described.
For example, after adding an aminoalkyltrialkoxysilane represented by the following general formula (6) to a carboxylic acid anhydride having a double bond represented by the following chemical formula (5) to form an amic acid, the ring is closed by heating. And a maleimide group, and a method of reacting water generated at this time with an alkoxy group is exemplified.
This method is preferable in that (c3) suitable for the composition of the present invention can be produced by a one-step reaction using easily available raw materials.

H ₂ N—R ¹⁴ —Si— (OR ¹³ ) ₃ (6)

In the formula (6), R ¹³ and R ¹⁴ are as defined above.
First, an amino group of an aminoalkyltrialkoxysilane is added to a carboxylic acid anhydride having a double bond to produce an amic acid (hereinafter referred to as “AMA”). Next, when the solution containing AMA is heated, the ring closure reaction proceeds and a maleimide group is generated. Since water is produced by the ring closure reaction, the hydrolysis and condensation reaction of the alkoxy group proceeds with the water.

  Here, when the ring-closing reaction is complete and all the generated water is consumed for the hydrolysis and condensation reaction of alkoxysilane, z is theoretically 1. In the formula (4), z is in the range of 0.1 to 3, and when z is less than 1, a method of adding water to the reaction system may be mentioned, while when z is more than 1, the reaction is performed. It can be adjusted by removing water from the system or using a dehydrating agent.

The above production method is preferably carried out in the presence of an organic solvent. As the organic solvent, a solvent that dissolves AMA and does not react with the raw material is preferable. Specifically, aromatic compounds such as toluene and xylene are preferable. However, since the reaction between the acid anhydride and the amino group is very fast, polar solvents such as alcohols and esters can also be used.
The temperature for the ring closure reaction is preferably in the range of 70 to 150 ° C.
When a compound that hardly dissolves water, for example, an aromatic compound, is used as the organic solvent, it is preferable to remove the solvent after completion of the reaction.
The proportion of the carboxylic acid anhydride having a double bond and the aminoalkyltrialkoxysilane is preferably equimolar. As the carboxylic acid anhydride and aminoalkyltrialkoxysilane having a double bond, a plurality of types can be used in combination.

4) Method for producing component (C) As a method for producing component (C), (c1) and (c2) or / and (c3) are mixed in a predetermined weight ratio in the presence of an organic solvent containing water. After charging, the method of heating and reacting is preferable.
The heating temperature and time may be appropriately set depending on the presence of the raw materials and the catalyst, etc., preferably 40 to 140 ° C., more preferably 60 to 120 ° C. and 0.5 to 20 hours.

The component (C) contains not only the silica fine particles surface-modified with (c2) or / and (c3), but also the hydrolysis condensate of (c2) or / and (c3) not containing silica fine particles. These may be included and defined as the component (C).
In addition to (c2) or / and (c3), a maleimide group-containing alkoxysilane synthesized from the compound represented by the formula (5) and aminoalkylmethyl dialkoxysilane in the same manner as (c3), methyl Products obtained by adding other alkoxysilane compounds such as trialkoxysilane and reacting with (c1) are also included in the concept of component (C). In this case, however, the amount of the other alkoxysilane compound charged is preferably half or less of the total amount of (c2) and (c3).

  The weight ratio of (c1): [(c2) + (c3)] when the component (C) is synthesized is 1: 9 to 9: 1, more preferably 3: 7 to 8: 2, Preferably it is 4: 6-7: 3. By setting the weight ratio of (c1): [(c2) + (c3)] to 1: 9 to 9: 1, both the wear resistance and the weather resistance of the cured film can be achieved.

  The amount of water charged into the reaction system is preferably 0.3 to 10 mol, and more preferably 0.5 to 5 mol, with respect to 1 mol of the alkoxy group. By setting the amount of water charged to 0.3 to 10 mol with respect to 1 mol of the alkoxy group, the surface of the silica fine particles can be efficiently modified without causing the silica fine particles to gel.

As the organic solvent, those that uniformly dissolve water are preferable, more preferably alcoholic solvents having a boiling point of 100 ° C to 200 ° C, and still more preferably alcoholic solvents having an ether bond and a boiling point of 100 ° C to 200 ° C. .
Specific examples of preferable organic solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol. And monobutyl ether.

  In addition, although (C) component can be manufactured without a catalyst, you may add an acid catalyst and an alkali catalyst.

  After completion of the reaction, water contained in the reaction system may be removed. The solution after the reaction may be heated or decompressed to distill off water and further the organic solvent. At this time, it is preferable to add an organic solvent having a boiling point higher than that of water to the solution after the reaction.

5) Content ratio of component (C) The content ratio of component (C) is 1 to 30 parts by weight, preferably 3 to 25 parts by weight, based on 100 parts by weight of components (A) to (D). Preferably it is 5-20 weight part.
When the content ratio of the component (C) is less than 1 part by weight, the cured film has insufficient wear resistance. On the other hand, when it exceeds 30 parts by weight, the cured film tends to shrink or the cured film Degradation of the organic part of the material becomes faster and the weather resistance decreases.

3. Component (D) The component (D) is a (meth) acrylamide compound having at least one substituent on the nitrogen atom. That is, it means a compound in which one or two hydrogen atoms bonded to the nitrogen atom of (meth) acrylamide are substituted with an organic group other than a hydrogen atom.
Examples of the substituent include an alkyl group, a hydroxyalkyl group, an aryl group, and an alkylaminoalkyl group. In the case of an alkyl group, a ring structure including a nitrogen atom may be formed.

Specific examples of the component (D) include N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-sec- N-alkyl (meth) acrylamides such as butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide;
N-aromatic group-containing alkyl (meth) acrylamides such as N-benzyl (meth) acrylamide;
N-hydroxyalkyl (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide;
N, N-dialkylaminoalkyl (meth) acrylamides such as N, N-dimethylaminoethyl (meth) acrylamide and 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, N-dialkyl (meth) acrylamides such as n-butyl (meth) acrylamide and N, N-dihexyl (meth) acrylamide;
And N, N-diaromatic group-containing alkyl (meth) acrylamides such as N, N-dibenzyl (meth) acrylamide; and (meth) acryloylmorpholine.
Among these compounds, (meth) acryloylmorpholine is preferable, and acryloylmorpholine is particularly preferable in that the cured film has excellent wear resistance and weather resistance.

(D) The content rate of a component is 1-20 weight part with respect to 100 weight part of (A)-(D) component total, Preferably it is 5-15 weight part.
When the content ratio of the component (D) is less than 1 part by weight, poor adhesion tends to occur in the weather resistance test, whereas when it exceeds 20 parts by weight, the wear resistance is insufficient.

4). (E) component (E) component of this invention is a ultraviolet absorber, and can use a various compound or substance.
Specific examples of the component (E) 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-bis-butyroxyphenyl) -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 fine particles, zinc oxide fine particles, inorganic fine particles or the like that absorbs ultraviolet light, such as tin oxide fine particles.
The ultraviolet absorbers listed above may be used alone or in combination of two or more.

  Of these, a benzotriazole-based ultraviolet absorber having a (meth) acryloyl group is particularly preferable in terms of achieving both the weather resistance and the wear resistance of the cured film.

(E) The content rate of a component is 0.1-12 weight part with respect to 100 weight part of (A)-(D) component total, Preferably it is 1-10 weight part.
When the content ratio of the component (E) is less than 0.1 parts by weight, a cured film showing sufficient weather resistance cannot be obtained. On the other hand, when the content ratio of the component (E) exceeds 12 parts by weight, not only the wear resistance of the cured film is lowered but also the weather resistance is lowered. In particular, when the content ratio of the component (E) is 1 to 10 parts by weight, a cured film having both excellent wear resistance and weather resistance can be obtained.

5. Component (F) The component (F) of the present invention is an organic solvent, and various compounds can be used.
The component (F) is preferably one that uniformly disperses or dissolves the components (A), (B), (C), (D) and (E), and other components described later.

  Preferred specific examples of component (F) include alcohols such as ethanol and isopropanol; alkylene glycol monoethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether Aromatic compounds such as toluene and xylene; esters such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dibutyl ether; diacetone alcohol; and N-methyl Examples include pyrrolidone and the like.

As the component (F), not only the dispersibility or solubility of the above components is excellent, but those that do not dissolve the substrate to be applied, particularly the plastic substrate, are preferable.
For example, when the plastic substrate is polycarbonate, an alkylene glycol monoether such as propylene glycol monomethyl ether is preferable because it does not dissolve the polycarbonate.
Furthermore, by mixing a solvent that does not dissolve the polycarbonate resin such as alcohol or alkylene glycol monoether and a solvent that dissolves the polycarbonate resin such as ester or ketone, the polycarbonate substrate is not dissolved at the time of coating. A technique for improving the adhesion of the coating film by dissolving the resin substrate surface on the micron order is also preferably applicable. Moreover, the method of improving the smoothness of the coating-film surface by mixing the solvent of various boiling points can also be applied preferably.

The content ratio of the component (F) is 10 to 1,000 parts by weight, preferably 50 to 500 parts by weight, and more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the total of the components (A) to (D). Part.
When the content ratio of the component (F) is less than 10 parts by weight, it is difficult to apply the composition uniformly. On the other hand, when the content ratio of the component (F) exceeds 1,000 parts by weight, a sufficient thickness is obtained. It is difficult to obtain a cured film. By setting it as the above-mentioned preferable ratio and a more preferable ratio, a coating process will be excellent in productivity.
Some of the components (A) to (E) and other components described below are used and sold as organic solvent solutions and dispersions. In this case, the organic solvent contained in these components is also included in the content ratio of the component (F).

6). Other components Although the composition of this invention makes the said (A)-(F) component essential, various components can be mix | blended according to the objective.
Preferable examples of other components include hindered amine light stabilizer (G) [hereinafter referred to as “(G) component”], radical photopolymerization initiator (H) [hereinafter referred to as “(H) component”]. It is done.
Other components listed below may be blended singly or in combination of two or more.

1) Component (G) The component (G) is a hindered amine light stabilizer. The component (G) is a component to be blended as desired for the purpose of improving the weather resistance of the cured film.
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, hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, etc.
Among these, those having a low basicity of hindered amine are preferable from the viewpoint of the stability of the composition, and specifically, a so-called NOR type having an amino ether group is more preferable.

  As a content rate of (G) component, 0.05-1.5 weight part is preferable with respect to 100 weight part of (A)-(D) component total, More preferably, it is 0.1-1.5 weight part is there.

2) Component (H) The component (H) is a radical photopolymerization initiator. (H) component is a component mix | blended when using an ultraviolet-ray, visible light, etc. as an active energy ray. When an electron beam is used as the active energy ray, it is not always necessary to add it. As the component (H), various compounds can be used.

  Specific examples of the component (H) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane- 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-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 Acetophenone compounds such as phenyl} -2-methyl-propan-1-one; benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4′-methyl-diphenylsulfide Compound; 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 oxides; 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] Acetophenone / benzophenone hybrid photoinitiators such as 2-methyl-2- (4-methylphenylsulfinyl) propan-1-one; 2- (O-benzoyloxime) -1- [4- (phenylthio)]-1 Oxime ester-based photopolymerization initiators such as 2-octanedione; and camphorquinone.

  The radical polymerization initiators listed above may be used alone or in combination of two or more.

As a content rate of (H) component, 0.1-10 weight part is preferable with respect to 100 weight part of (A)-(D) component total, More preferably, it is 0.5-5 weight part.
When the content ratio of the component (H) is 0.1 to 10 parts by weight, the composition has excellent photocurability, and a cured film having excellent wear resistance and weather resistance can be obtained.

3) Other components other than the above The composition of the present invention contains various surface modifiers 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. It is preferable to add.
As the surface modifier, various additives for modifying the surface physical properties, which are commercially available under the names of a surface conditioner, a leveling agent, a slipperiness imparting agent, an antifouling imparting agent and the like, 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, fluorine polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, Examples thereof include fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain. One or more of these may be used. You may use what contains a (meth) acryloyl group in a molecule | numerator for the objective of improving the slidability of a sliding property.

  The preferable amount of the surface modifier is preferably 0.01 to 1.0 part by weight with respect to 100 parts by weight of the total of the components (A) to (D). The surface smoothness of a coating film can be improved by making the compounding quantity of a surface modifier into 0.01-1.0 weight part.

In order to improve the storage stability, it is preferable to add a radical polymerization inhibitor to the composition of the present invention.
Specific examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, benzoquinone, phenothiazine. N-nitrosophenylhydroxylamine, ammonium salt of N-nitrosophenylhydroxylamine, aluminum salt of N-nitrosophenylhydroxylamine, copper dibutyldithiocarbamate, copper chloride, copper sulfate and the like.
The addition amount of the polymerization inhibitor is preferably 10 to 10,000 ppm, more preferably 100 to 3000 ppm with respect to 100 parts by weight of the total of components (A) to (D).

Various antioxidants may be added to the composition of the present invention for the purpose of improving the heat resistance and weather resistance of the cured film. Examples of the antioxidant include primary antioxidants such as hindered phenol antioxidants, and sulfur-based and phosphorus-based secondary antioxidants.
Specific examples of the primary antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert- Butyl-4-hydroxy-m-tolyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2 , 4, 6 (1H, 3H, 5H) -trione and the like.
Specific examples of secondary antioxidants include didodecyl 3,3′-thiodipropionate, 4,6-bis (octylthiomethyl) -o-cresol, tris (2,4-di-tert-butylphenyl) Phosphite etc. are mentioned.
A preferable blending amount of the antioxidant is preferably 0 to 5 parts by weight, and more preferably 0 to 3 parts by weight with respect to 100 parts by weight as a total of the components (A) to (D).

The composition of the present invention has one or more radically polymerizable unsaturated groups in one molecule, other than (A) component, (B) component, (C) component, (D) component and (E) component (Hereinafter referred to as “unsaturated compound”).
An unsaturated compound can be mix | blended in order to improve the adhesiveness of a cured film and a plastic-made base material.
The radically polymerizable unsaturated group in the unsaturated compound is preferably a (meth) acryloyl group.
The blending ratio of the unsaturated compound is preferably 20 parts by weight or less with respect to 100 parts by weight of the total of the components (A) to (D) from the viewpoint of preventing deterioration of wear resistance and weather resistance.

  Specific examples of the compound other than the (D) component having one radical polymerizable unsaturated group in one molecule and the (E) component in the unsaturated compound include (Meth) acrylic acid, Michael addition of acrylic acid Type dimer, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, (meth) acrylate of alkylphenol alkylene oxide adduct, cyclohexyl (meth) acrylate, tert-butylcyclo Xyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, (meth) acrylate of alkylene oxide adduct of paracumylphenol, orthophenylphenol (meth) Acrylate, (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanemethylol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) of alkylene oxide adduct of orthophenylphenol Acrylate, N- (2- (meth) acryloxyethyl) hexahydrophthalimide, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, N-vinyl Examples include pyrrolidone and N-vinylcaprolactam.

In unsaturated compounds, compounds other than (A) component, (B) component, and (C) component having two or more radically polymerizable unsaturated groups in one molecule (hereinafter referred to as “polyfunctional unsaturated compound”) ) May be blended. By including a polyfunctional unsaturated compound, the adhesion between the cured film and the plastic substrate and the wear resistance of the cured film may be improved.
The number of radically polymerizable unsaturated groups in the polyfunctional unsaturated compound is preferably 3 or more, more preferably 4 to 20 in one molecule so as not to lower the wear resistance.
The blending ratio of the polyfunctional unsaturated compound is preferably 20 parts by weight or less with respect to 100 parts by weight of the total of components (A) to (D) from the viewpoint of preventing the weather resistance from deteriorating.

As the polyfunctional unsaturated compound, a compound having two or more (meth) acryloyl groups in one molecule is preferable, and specific examples thereof include the following compounds.
Di (meth) acrylate of bisphenol A alkylene oxide adduct, di (meth) acrylate of alkylene oxide adduct of bisphenol F, di (meth) acrylate of alkylene oxide adduct of bisphenol Z, alkylene oxide adduct of bisphenol S Di (meth) acrylate, di (meth) acrylate of alkylene oxide adduct of thiobisphenol, di (meth) acrylate of bisphenol A, di (meth) acrylate of bisphenol F, di (meth) acrylate of bisphenol Z, bisphenol S Di (meth) acrylate, di (meth) acrylate of thiobisphenol, tricyclodecane dimethylol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth) acrylate of neopentyl glycol ester of hydroxypivalic acid, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, di (meth) acrylate of glycerin alkylene oxide adduct, dimer acid diol di (meth) acrylate, Cyclohexane dimethylol di (meth) acrylate, caprolactone modified product of poly (meth) acrylate of isocyanuric acid alkylene oxide adduct, trimethylolpropane tri (meth) acrylate Tri (meth) acrylate of trimethylolpropane alkylene oxide adduct, tri- and tetraacrylate of pentaerythritol, tri- and tetraacrylate of alkylene oxide adduct of pentaerythritol, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol Examples include hexa and pentaacrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate other than the component (A), and a silicone resin having a (meth) acryloyl group at the terminal.

  As a polyester (meth) acrylate, the dehydration condensate of a polyester polyol and (meth) acrylic acid is mentioned. Polyester polyols include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexane dimethylol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, and trimethylolpropane, and Examples include reactants from polyols such as these alkylene oxide adducts and acid components such as dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or anhydrides thereof. Moreover, the dehydration condensate of various dendrimer type polyols and (meth) acrylic acid is mentioned.

  As epoxy (meth) acrylate, (meth) acrylic acid adduct of bisphenol A type epoxy resin, (meth) acrylic acid adduct of hydrogenated bisphenol A type epoxy resin, (meth) acrylic of phenol or cresol novolac type epoxy resin Acid addition products, (meth) acrylic acid addition products of biphenyl type epoxy resins, (meth) acrylic acid addition products of diglycidyl ether of polyethers such as polytetramethylene glycol, (meth) acrylic acid addition of diglycidyl ether of polybutadiene Products, (meth) acrylic acid adducts of polybutadiene internal epoxidized products, (meth) acrylic acid adducts of silicone resins having epoxy groups, (meth) acrylic acid adducts of limonene dioxide, 3,4-epoxycyclohexylmethyl- 3,4-epoxy Cyclohexanecarboxylate (meth) acrylic acid adduct and the like.

As the urethane (meth) acrylate other than the component (A), an addition reaction between an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, or an addition reaction between an organic polyisocyanate, a polyol and a hydroxyl group-containing (meth) acrylate. Compounds.
Here, examples of the polyol include a low molecular weight polyol, a polyether polyol, a polyester polyol, and a polycarbonate polyol.
Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexane dimethylol, 3-methyl-1,5-pentanediol, and glycerin.
Examples of the polyether polyol include polypropylene glycol and polytetramethylene glycol.
As the polyester polyol, a reaction product of these low molecular weight polyols and / or polyether polyols and an acid component such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or a dibasic acid or its anhydride. Is mentioned.
Examples of the organic polyisocyanate include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, pentaerythritol tri ( Examples include hydroxyl group-containing polyfunctional (meth) acrylates such as (meth) acrylate and dipentaerythritol penta (meth) acrylate.
Further, although it is a compound similar to the component (A), the addition reaction product of a hexamethylene diisocyanate nurate-type trimer and 4-hydroxybutyl (meth) acrylate is also a polyfunctional non-functional compound belonging to “other components”. An example of a saturated compound.

  The unsaturated compounds listed above may be used alone or in combination of two or more.

  An organic polymer can also be blended with the composition of the present invention for the purpose of reducing warpage during curing while maintaining transparency. Suitable polymers include (meth) acrylic polymers, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- ( 2- (meth) acryloxyethyl) tetrahydrophthalimide and the like. In the case of a polymer copolymerized with (meth) acrylic acid, glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.

7). Method for producing and using active energy ray-curable coating agent composition In the composition of the present invention, the components (A) to (F), and other components as necessary, are weighed in predetermined amounts, stirred, Can be mixed and manufactured.

As a method of using the composition of the present invention, a method usually used in an active energy ray-curable coating agent composition may be used.
As a preferred method of use, a method of irradiating active energy rays after applying the composition to a substrate and drying it may be mentioned.

Examples of the applicable substrate include various materials such as plastic, wood, paper, cloth, metal, and concrete, but plastic and wood are preferable.
Preferable specific examples of the plastic include polycarbonate, polymethyl methacrylate, triacetyl cellulose, polyethylene terephthalate, and cycloolefin polymer. In addition, in the case of polyethylene terephthalate or cycloolefin polymer, those subjected to easy adhesion treatment are preferred. Examples of the easy adhesion treatment include those subjected to corona treatment and those formed with an easily adhesive coating layer. A particularly preferred substrate for plastic is polycarbonate.
There is no particular limitation on the shape of the substrate, and it may be flat or curved. The substrate may be in the form of a plate or a film.

  The coating method of the composition of the present invention may be in accordance with a conventional method, and may be appropriately set according to the shape of the substrate. For example, spray coat, dip coat, flow coat, spin coat, bar coat, doctor blade, die coater, comma coater, gravure coater and the like can be mentioned.

  What is necessary is just to set the film thickness of the coating film formed by coating suitably according to the objective. For example, although the weather resistance is improved when the thickness of the cured film is thick to some extent, it is not desirable to increase the thickness from the viewpoint of the appearance and productivity of the cured film. In consideration of weather resistance, appearance, and productivity, it is desirable that the film thickness of the cured film is 5 to 50 μm, more preferably 10 to 40 μm.

  The composition of the present invention contains a component (F) (organic solvent) and is dried after coating. The drying temperature in this case may be appropriately selected according to the composition to be used and the heat resistance of the substrate, and when the substrate is plastic, it is below the softening point of the plastic. For example, when the plastic is polycarbonate, the temperature is preferably in the range of 60 to 130 ° C.

Examples of active energy rays for curing the composition include light such as ultraviolet rays and visible light, electron beams, and X-rays. Ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferred.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED. In the case of a UV electrodeless lamp, a new type using a DC power supply current can also be suitably used.
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 10,000 mJ / cm ² is preferable, 200 to 5,000 mJ / cm ² is more preferable, and 500 to 3,000 mJ / cm ² is more preferable.

  The composition may be cured in the air or in a vacuum or in an inert gas atmosphere. In view of the performance of the cured film, it is preferably in a vacuum or in an inert gas atmosphere, but may be performed in the air from the viewpoint of productivity.

Irradiation of the active energy ray may be performed after the coating after drying, and then may be applied to the dry coating film at room temperature. However, it is preferable to irradiate the dry coating film in a heated state as necessary. By irradiating an active energy ray to the dried dried coating film in a heated state, the physical properties such as abrasion resistance and weather resistance of the cured film become more excellent.
The temperature of the dried coating film in this case may be set as appropriate according to the substrate used and the cured film properties such as the desired weather resistance, but is preferably 60 ° C. or higher, and the substrate is a plastic. Is below the softening point. When the temperature of the dried coating film is 60 ° C. or higher, the wear resistance of the cured film is improved as compared with the case of irradiation at room temperature. If the temperature is not raised too much, the weather resistance is also improved.
For example, when the plastic substrate is polycarbonate, the temperature is preferably 60 to 130 ° C, more preferably 70 to 120 ° C. By setting the temperature at the time of active energy ray irradiation to 60 to 130 ° C., a cured film having excellent wear resistance and weather resistance can be obtained.
In the present invention, the temperature of the dried coating film means its surface temperature, and is generally almost equal to the atmospheric temperature of drying or heating.
As a method of setting the temperature of the dried coating film to 60 ° C. or higher, a method of irradiating active energy rays immediately while maintaining a heated state after drying, a method of heating the dried coating film and irradiating active energy rays, and a heating atmosphere Examples include a method of irradiating active energy rays below.

8). Application The composition of the present invention is a coating agent composition and can be used for various coating applications, and particularly preferably for coating plastics.
Furthermore, since the cured film is excellent in weather resistance, the composition of the present invention can be suitably used for applications exposed to sunlight, particularly preferably for outdoor applications.
Specific examples of suitable applications include automotive headlamps, automotive plastic sunroofs, automotive plastic windows, train plastic windows, aircraft plastic windows, carport roofs, plastic sound barriers, signs, Guardrails, traffic lights, outdoor lighting, walls, fences and ceilings of buildings such as shops and stations, cases of machines and equipment that are always installed outdoors, helmet front plates, goggles, insect baskets, heat-reflective films that are attached to windows, etc. Optical films, touch panels, and the like.

  As mentioned above, although embodiment of the composition of this invention was described, this invention is not limited to the said embodiment. The present invention can be implemented in various forms without departing from the gist of the present invention, with modifications and improvements that can be made by those skilled in the art.

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, “parts” means parts by weight, and “%” means% by weight. In addition, the polyfunctional urethane (meth) acrylate other than the component (A) that does not correspond to the component (A) is used as the component (A) ′, and the colloidal silica other than the component (C) that does not correspond to the component (C) (dispersion medium). The non-volatile component removed) is referred to as (C) ′ component.

○ Production Example 1: Production of component (A) (HDI3-HEA)
Into a 3 L separable flask equipped with a stirrer and an air blowing tube, an isocyanate compound having a nurate trimer of hexamethylene diisocyanate as a main component [Duranate TPA-100 manufactured by Asahi Kasei Chemicals Corporation. NCO content 23%. ] 1369.5 g (NCO 7.5 mol), 2,6-di-tert-butyl-4-methylphenol (hereinafter referred to as “BHT”) 1.12 g, dibutyltin dilaurate (hereinafter referred to as “DBTL”) 0.67 g 870 g (7.5 mol) of 2-hydroxyethyl acrylate (hereinafter referred to as “HEA”) was added dropwise while stirring at a liquid temperature of 50 to 70 ° C.
After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 4 hours, and the reaction was completed by confirming that the isocyanate group had disappeared by IR (infrared absorption) analysis of the reaction product. The isocyanuric ring-containing urethane (meth) acrylate compound Got. Hereinafter, this reaction product is referred to as “HDI3-HEA”.
HDI3-HEA corresponds to the compound in which R ¹ , R ² and R ³ are all ethylene groups and R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms in the general formula (1).

○ Production Example 2: Production of component (A) ′ (HDI3-HBA)
Into a 3 L separable flask equipped with a stirrer and an air blowing tube, an isocyanate compound having a nurate trimer of hexamethylene diisocyanate as a main component [Duranate TPA-100 manufactured by Asahi Kasei Chemicals Corporation. NCO content 23%. ] 1369.5 g (NCO 7.5 mol), BHT 1.22 g, and DBTL 0.73 g were charged, while stirring the liquid temperature at 50 to 70 ° C., 1080 g of 4-hydroxybutyl acrylate (hereinafter referred to as “HBA”) (7. 5 mol) was added dropwise.
After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 4 hours, and the reaction was completed by confirming that the isocyanate group had disappeared by IR (infrared absorption) analysis of the reaction product. The isocyanuric ring-containing urethane (meth) acrylate compound Got. Hereinafter, this reaction product is referred to as “HDI3-HBA”.
HDI3-HBA corresponds to a compound in which R ¹ , R ² and R ³ are all tetramethylene groups and R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms in the general formula (1).

○ Production Example 3: Production of component (C) (methacryl-silica)
In a 0.5 L separable flask equipped with a stirrer, 120 g of propylene glycol monomethyl ether (hereinafter referred to as PGM), 6.0 g of water, 0.05 g of hydroquinone monomethyl ether, and isopropyl alcohol (hereinafter referred to as IPA) dispersed colloidal silica [ IPA-ST manufactured by Nissan Chemical Industries, Ltd., average particle size 10 to 15 nm (value calculated from specific surface area by BET method), solid content 30%, IPA 70% contained. Hereinafter, it is simply referred to as “IPA-ST”. 100 g was charged [30 g as the component (c1)] and homogenized with stirring. Next, γ-methacryloxypropyltriethoxysilane [in the general formula (3), n is 0, R ¹¹ is a 1,3-propylene group (trimethylene group), R ¹² is a methyl group, and X is an ethoxy group . (C2) component. 32.4 g was charged and dissolved at room temperature with stirring. At this time, the weight ratio of the component (c1) to the component (c2) was 48:52.
This colloidal dispersion was heated to 80 ° C. in the air and reacted for 4 hours, and then concentrated by distilling off IPA, water and the like until the non-volatile components were 35%. Next, 80 g of PGM was added, and a small amount of water remaining in the reaction system was distilled off together with PGM and the like to obtain a reaction product having a nonvolatile component of 35%. Hereinafter, among the reaction products obtained here, the non-volatile component (component (C)) excluding the solvent and the like is referred to as “methacryl-silica”.

Production Example 4: Production of component (c3) (THPI-alkoxysilane)
A 3 L separable flask equipped with a stirrer was charged with 1119 g of toluene and 456 g (3.0 mol) of 3,4,5,6-tetrahydrophthalic anhydride, and stirred at room temperature under nitrogen with 3-aminopropyltrimethyl trichloride. 663 g (3.0 mol) of ethoxysilane was added dropwise. After completion of the dropwise addition, the temperature was raised until ethanol was distilled off, and then the reaction solution was allowed to react for 4 hours while maintaining the reaction solution in the range of 85 to 110 ° C.
After completion of the reaction, low boiling point components such as toluene and ethanol were distilled off under reduced pressure while heating the flask in an oil bath at 80 ° C. to synthesize an alkoxysilane compound (c3). Hereinafter, this reaction product is referred to as “THPI-alkoxysilane”.

From the 1H-NMR spectrum, the structure of the obtained THPI-alkoxysilane has the following formula (4): R ¹³ is an ethyl group, R ¹⁴ is a 1,3-propylene group (trimethylene group), and z is 1.2. It was confirmed that
THPI-alkoxysilane was used as a raw material (c3) in Production Example 5 described later.

○ Production Example 5: Production of component (C) (THPI-silica)
In a 3 L separable flask equipped with a stirrer, 960 g of PGM, 23.6 g of water, and 800 g of IPA-ST were charged, and after stirring and homogenizing, 189 g of THPI-alkoxysilane was charged and stirred at room temperature. At this time, the weight ratio of the component (c1) to the component (c3) was 56:44.
This colloidal dispersion was heated to 80 ° C. under nitrogen and reacted for 4 hours, and then concentrated by distilling off IPA, water and the like until the non-volatile components were 35%. Next, 640 g of PGM was added, and a small amount of water remaining in the reaction system was distilled off together with PGM and the like to obtain a reaction product having a nonvolatile component of 35%. Hereinafter, among the reaction products obtained here, the non-volatile component (component (C)) excluding the solvent and the like is referred to as “THPI-silica”.

<Example 1, Example 2, Comparative Examples 1 to 3>
The components shown in Table 1 were stirred and mixed according to a conventional method to produce an active energy ray-curable coating agent composition.

In addition, the numerical value of each component of Table 1 represents a weight part. Abbreviations in the table represent the following compounds.
○ Abbreviation / Component (A) “HDI3-HEA”: Reaction product of Production Example 1.
-(A) 'component "HDI3-HBA": Reaction product of Production Example 2.
· (B) component "M-313" manufactured by Toagosei Co., Ltd. Aronix M-313; in the general formula (2), R ⁷ and R ⁸ are hydrogen atom, R ⁹ is a hydrogen atom 40 mol% Corresponds to a compound having an acryloyl group of 60 mol%.
Component (C) “Methacryl-silica”: Reaction product of Production Example 3 (nonvolatile component).
“THPI-silica”: reaction product of Production Example 5 (nonvolatile component).
-(C) 'component "IPA-ST solid content": Solid content in IPA-ST used as a raw material of manufacture example 3 and manufacture example 5. Unmodified surface colloidal silica.
Component (D) “ACMO”: ACMO manufactured by Kojin Co., Ltd., acryloylmorpholine.
-(E) component "RUVA-93": The benzotriazole type ultraviolet absorber which has a methacryloyl group made from Otsuka Chemical Co., Ltd., brand name RUVA-93; 2- [2-hydroxy-5- (2-methacryloyloxyethyl) ) Phenyl] -2H-benzotriazole.
“T-479”: hydroxyphenyltriazine-based ultraviolet absorber manufactured by BASF Corporation, trade name Tinuvin 479; 2- [2-hydroxy-4- (1-octyloxycarbonylethoxy) phenyl] -4,6-bis (4-Phenylphenyl) -1,3,5-triazine.
-(F) component "PGM": Propylene glycol monomethyl ether.
“IPA”: Isopropyl alcohol (carry-in from IPA-ST).
Component (G) “T-123”: hindered amine light stabilizer manufactured by BASF Corporation, trade name Tinuvin 123; bis (2,2,6,6-tetramethyl-1- (octyloxy) -4 decanoate -Piperidinyl) ester.
Component (H) “Irg-819”: photo radical polymerization initiator manufactured by BASF Corporation, trade name Irgacure 819; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
Other components “8019add”: Silicone surface modifier (leveling agent) manufactured by Toray Dow Corning Co., Ltd., trade name 8019additive. 100% active ingredient.

<Evaluation method>
The composition shown in Table 1 was applied to the surface of a polycarbonate plate with a bar coater so that the coating thickness after drying was about 15 μm, dried for 10 minutes with a hot air dryer at 100 ° C. UV irradiation was performed (at a film surface temperature of 90 ° C.) to prepare a sample having a cured film on the surface of the resin plate.
Ultraviolet irradiation uses a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., and has a peak illuminance of 400 mW / cm ² and irradiation energy of 250 mJ / cm ^{2 in} one pass in the UV-A region of UV POWER PUCK manufactured by EIT. and so as lamp output, lamp height, and to adjust the conveyor speed, two-pass (total 500 mJ / cm ²⁾ or 12-pass (total 3000 mJ / cm ²⁾ was performed by irradiating.

  About the obtained cured film, initial stage adhesiveness, transparency, abrasion resistance, and weather resistance were evaluated by the method shown below. The evaluation results are shown in Table 1.

○ Initial adhesion A grid of 100 squares is formed on a cured film with an ultraviolet irradiation amount of 3000 mJ / cm ² by cutting with a cutter knife every 11 mm in length and width, and a grid of 100 squares is made on this grid. The cellophane tape was affixed, and the cellophane tape was peeled off according to JIS K5600. Adhesion was evaluated by the ratio of the remaining film after peeling of the cellophane tape (that is, the number of remaining cells, unit:%).

○ Transparency The haze H (%) of the cured film having an ultraviolet irradiation amount of 3000 mJ / cm ² was measured for each substrate with a turbidimeter NDH-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K7136. The smaller the value of H, the better the transparency.

○ abrasion resistance UV irradiation dose 500 mJ / cm ² of the cured film, and to the cured film of the ultraviolet irradiation amount 3000 mJ / cm ^2, conforms to ASTM D-1044, it was Taber abrasion test. Here, the wear wheel was CS-10F, the load was 500 g, and the rotation speed was 500 times. The haze difference ΔH (%) before and after the Taber abrasion test was measured, and the smaller the ΔH (%), the better the abrasion resistance.
Further, a composition having a small ΔH (%) even with an ultraviolet irradiation amount of 500 mJ / cm ² was evaluated as a composition that requires a small amount of irradiation energy of active energy rays necessary for performance.

-Weather resistance A weather resistance test was conducted according to SAE J1960 using an ATLAS xenon weatherometer Ci4000. Appearance observation (presence of cracking, peeling, whitening) and adhesion were evaluated every 1000 kJ / m ² at a wavelength of 340 nm, and this was continued up to 5000 kJ / m ² . In addition, the adhesiveness determined that the film | membrane did not peel when the cellophane tape was affixed and peeled off to the cured film. Appearance and adhesion were evaluated by the final energy amount that was confirmed to be good, and the numerical values are shown in Table 1.

<Evaluation results>
The compositions of Examples 1 and 2 which are the compositions of the present invention are excellent in transparency, adhesion, abrasion resistance, and weather resistance, and are active energy rays necessary for exhibiting the performance of the cured film. The composition required only a small amount of irradiation energy. Also, comparing Example 1 and Example 2, the composition of Example 2 using THPI-silica as the component (C) was more weathered than the composition of Example 1 using methacryl-silica. The adhesion of was good.
On the other hand, the composition of Comparative Example 1 was changed in the composition of Example 2 component (A) to HDI3-HBA, while the cured film of the radiation amount 3000 mJ / cm ² is excellent in performance, the dose 500 mJ / cm ² The wear resistance was significantly deteriorated. The composition of Comparative Example 2 in which the component (D) of Example 1 was omitted and the amount of the component (B) was increased by that amount was poor in adhesion after the weather resistance test. The composition of Comparative Example 3 in which the component (C) in the compositions of Example 1 and Example 2 was replaced with non-surface-modified colloidal silica was inferior in wear resistance and weather resistance.

The composition of the present invention can be suitably used as a coating composition for various substrates used outdoors, preferably a plastic substrate, particularly a polycarbonate substrate.
Specifically, automotive headlamps, automotive plastic sunroofs, automotive plastic windows, train plastic windows, aircraft plastic windows, carport roofs, plastic sound barriers, signs, guardrails, traffic lights, Outdoor lighting, walls and fences and ceilings of buildings such as stores and stations, cases of machines and equipment that are always installed outdoors, front plates of helmets, goggles, insect baskets, optical films such as heat-reflective films attached to windows, Examples include touch panels.

Claims (16)

A composition comprising the following components (A) to (F), the sum of the components (A), (B), (C) and (D) [hereinafter referred to as “components (A) to (D)” (A total)] With respect to 100 parts by weight, the components (A) to (F) are respectively (A) component: 20 to 80 parts by weight (B) component: 5 to 60 parts by weight (C) component: 1 to 30 parts by weight Part (D) Component: 1 to 20 parts by weight (E) Component: 0.1 to 12 parts by weight (F) Component: An active energy ray-curable coating agent composition contained in a proportion of 10 to 1000 parts by weight.
(A) Component: Compound represented by the following general formula (1)

[In the general formula (1), R ¹ , R ² and R ³ all represent an ethylene group, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group. ]
(B) Component: Compound represented by the following general formula (2)

[In General Formula (2), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and R ⁹ represents a hydrogen atom or a (meth) acryloyl group. ]
Component (C): Colloidal silica (c1) and (meth) acryloyl group-containing alkoxysilane compound (c2) represented by the following general formula (3) or / and a maleimide group represented by the following general formula (4) A non-volatile component of a reaction product obtained by subjecting an alkoxysilane compound (c3) to hydrolysis / condensation reaction at a weight ratio of (c1): [(c2) + (c3)] = 9: 1 to 1: 9 And (c1) is chemically modified with (c2) and / or (c3).

[In General Formula (3), R ¹⁰ represents a methyl group or a phenyl group, R ¹¹ represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, R ¹² represents a hydrogen atom or a methyl group, X Represents an alkoxy group having 1 to 6 carbon atoms, X may be the same or different, and n is 0 or 1. ]

[In General Formula (4), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, R ¹⁴ represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and z is 0 . Represents a positive number from 1 to 3. When z is less than 3, (c3) contains a condensate, and R ^{13 in} one molecule of the condensate may contain two or more different groups. ]
(D) component: (meth) acrylamide compound having at least one substituent on the nitrogen atom (E) component: ultraviolet absorber (F) component: organic solvent The active energy ray-curable coating composition according to claim 1, wherein the component (A) is a compound in which R ⁴ , R ⁵ and R ⁶ in the general formula (1) are all hydrogen atoms. The active energy ray according to claim 1, wherein the component (B) is a compound in which R ⁷ and R ⁸ in the general formula (2) are hydrogen atoms, and R ⁹ is a hydrogen atom or an acryloyl group. A curable coating agent composition.   The component (C) is the reaction product of (c1) and (c2), or the reaction product of (c1) and (c3). The active energy ray-curable coating agent composition described in 1.   The active energy ray-curable coating agent composition according to any one of claims 1 to 4, wherein (c1) has an average primary particle diameter of 1 to 100 nm. The component (C) is a step of adding an aminopropyltrialkoxysilane to a carboxylic acid anhydride having a double bond represented by the following chemical formula (5) to form an amic acid;
The amic acid is cyclized by heating to form a maleimide group, and the alkoxy group is partially hydrolyzed and condensed using water generated by the cyclization reaction to obtain an alkoxysilane compound (c3) represented by the general formula (4) ), And
A step of reacting the obtained (c3) with colloidal silica (c1) having an average primary particle diameter of 1 to 100 nm by heating in the presence of an organic solvent containing water,
The active energy ray-curable coating agent composition according to any one of claims 1 to 5, which is a non-volatile component of a reaction product obtained by a production method comprising:

  The active energy ray-curable coating agent composition according to any one of claims 1 to 6, wherein the component (D) is acryloylmorpholine.   The active energy ray-curable coating agent composition according to any one of claims 1 to 7, wherein the component (E) includes a benzotriazole ultraviolet absorber having a (meth) acryloyl group. (A) component: 45-80 weight part (B) component: 5-50 weight part (C) with respect to said (A)-(D) component total 100 weight part, respectively. ) Component: 1-30 parts by weight (D) Component: 1-20 parts by weight (E) Component: 0.1-12 parts by weight (F) Component: 10 to 1000 parts by weight The total amount of (D) component total accounts for 70 weight% or more of the quantity remove | excluding the weight of (F) component from the weight of the whole composition, The any one of Claims 1-8 characterized by the above-mentioned. The active energy ray-curable coating agent composition described in 1.   Furthermore, 0.05-1.5 weight part of hindered amine light stabilizer is contained as (G) component with respect to 100 weight part of said (A)-(D) component total. The active energy ray-curable coating agent composition according to any one of the above.   Furthermore, 0.1-10 weight part of photoradical polymerization initiators are contained as (H) component with respect to 100 weight part of said (A) component-(D) component total, Any of Claims 1-10. The active energy ray-curable coating agent composition according to claim 1.   The active energy ray-curable coating composition according to claim 11, wherein 50% by weight or more of the component (H) is an acylphosphine oxide-based initiator.   It is a coating agent for plastics, The active energy ray hardening-type coating agent composition of any one of Claims 1-12 characterized by the above-mentioned.   The active energy ray-curable coating composition according to claim 13, wherein the plastic is polycarbonate.   The active energy ray-curable coating agent composition according to any one of claims 1 to 14 is applied to a plastic substrate, heated and dried, and then the dried coating film is brought to a temperature of 60 or more. A method for producing a plastic article having a protective layer on a surface irradiated with active energy rays in a state.   The method for producing a plastic article having a protective layer on the surface according to claim 15, wherein the plastic base material is polycarbonate and the active energy ray is irradiated in a state where the dry coating film is at 60 to 130 ° C.