JP5150759B1 - Curable coating composition - Google Patents

Abstract

Disclosed is a curable coating agent composition that exhibits excellent wear resistance and weather resistance as a coating agent for plastic substrates used outdoors.
The curable coating composition of the present invention comprises an isocyanuric ring-containing urethane (meth) acrylate compound (A), an isocyanuric ring-containing tri (meth) acrylate compound (B) having no urethane bond, and a maleimide group. 20 to 80 parts by mass of component (A), 10 to 70 parts by mass of component (B), and 100 parts by mass of component (A) with respect to a total of 100 parts by mass of component (C) comprising a reaction product of an alkoxysilane compound and colloidal silica. 1) to 35 parts by weight of component), 0.1 to 10 parts by weight of radical polymerization initiator as component (D), 1 to 12 parts by weight of UV absorber as component (E), and an organic solvent as component (F). Contains 10 to 1000 parts by mass.
[Selection figure] None

Description

  The present invention relates to a curable coating composition that is excellent in abrasion resistance and weather resistance after curing and can be preferably applied as a protective film for substrates used outdoors, particularly resin substrates.

Transparent resin materials represented by resin materials, especially polycarbonate, etc., are light in specific gravity, light in weight, easy to process, and are widely used in various applications, taking advantage of their impact resistance compared to inorganic glass. . On the other hand, resin materials are easily scratched and easily lost in luster and transparency, easily attacked by organic solvents, weather resistance (for example, light stability against ultraviolet rays), heat resistance, etc. Have Therefore, the resin material is often used by being coated with various protective films for the purpose of improving its surface characteristics.
Examples of such a protective film include a hard coat layer obtained by curing a photocurable coating agent composition.

Resin materials used outdoors require not only wear resistance but also excellent weather resistance. Colloidal silica fine particles, poly [(meth), surface-modified with a silane compound having a methacryloyloxy group, an acryloyloxy group or a vinyl group as a photocurable coating composition having both wear resistance and weather resistance. Acryloyloxyalkyl] isocyanurate and a urethane (poly) methacrylate having an alicyclic skeleton, and a wear-resistant coating composition containing a photopolymerization initiator in a specific ratio (patent) Reference 1).
In addition, 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 light 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).

  There is also an example using a thermosetting coating agent composition. Patent Document 3 discloses a first layer formed by curing a thermosetting primer composition excellent in weather resistance on the surface of a resin base material, and a thermosetting excellent in wear resistance on the first layer. A plastic article provided with a second layer obtained by curing an adhesive coating agent composition is disclosed.

Japanese Patent No. 3747065 JP 2000-063701 A JP 2001-214122 A JP 2010-254840 A

The plastic article described in Patent Document 3 achieves both wear resistance and weather resistance at a high level. However, the thermosetting composition has a problem that it requires a large amount of energy for forming a cured film and is not efficient because it requires time for heating compared to the photocurable composition. is there. Moreover, since not only a coating agent composition but an undercoat composition is used as in Patent Document 3, the number of steps increases, which is not desirable from the viewpoint of productivity. Therefore, a coating composition that can form a protective film that exhibits sufficient wear resistance and weather resistance without using an undercoat composition is eagerly desired.
If a photocurable composition is used, efficient production becomes possible. The urethane (poly) methacrylate having the alicyclic skeleton is a component that improves the weather resistance of the hard coat layer, but is insufficient in terms of wear resistance. In each Example of Patent Document 1, colloidal silica fine particles (ultraviolet curable silicone) whose surface is modified with a silane compound having a methacryloyloxy group together with this urethane (poly) methacrylate are used. However, the wear resistance is not sufficient, and the weather resistance after 2000 hours is unknown.
On the other hand, a hard coat layer obtained by curing the poly (meth) acrylate of mono- or polypentaerythritol exhibits high hardness. Therefore, in Patent Document 2, this component is used in combination with urethane poly (meth) acrylate having at least two radically polymerizable unsaturated double bonds, which is a component for improving weather resistance. However, as a result of investigations by the present inventors, it has been found that simply using a component that improves wear resistance and a component that improves weather resistance cannot withstand further accelerated tests.
Recently, an active energy ray-curable composition containing a radical polymerizable compound as described in Patent Document 4 has also been developed. This composition contains a specific urethane (meth) acrylate compound containing an isocyanurate skeleton, an acrylate compound having an isocyanurate skeleton, and radical polymerizable inorganic fine particles in a specific ratio. However, as a result of studies by the present inventors, it has been found that the adhesion after a long-time acceleration test is poor.
That is, even if a hard coat layer is formed on the surface of the resin substrate using the above-described photocurable coating agent composition, it is difficult to achieve both high wear resistance and weather resistance at a high level.

  In view of these problems, the present invention provides a curable coating agent composition that exhibits excellent wear resistance and weather resistance as a coating agent for substrates used outdoors, particularly resinous substrates. Objective.

  As a result of intensive studies, the present inventors have found that an isocyanuric ring-containing urethane (meth) acrylate compound, an isocyanuric ring-containing tri (meth) acrylate compound having no urethane bond, and a reaction between an alkoxysilane compound having a maleimide group and colloidal silica. It has been found that a composition in which a product is used in a specific ratio and an appropriate amount of an additive is added is excellent in transparency after curing, abrasion resistance, and weather resistance, and has completed the present invention. .

  That is, the curable coating composition of the present invention comprises 20 to 80 parts by mass of the (A) component with respect to 100 parts by mass in total of the following (A) component, (B) component, and (C) component. 10 to 70 parts by mass of the component (B), 1 to 35 parts by mass of the component (C), 0.1 to 10 parts by mass of a radical polymerization initiator as the component (D), and an ultraviolet absorber as the component (E). 1 to 12 parts by mass and 10 to 1000 parts by mass of an organic solvent as component (F).

(A) component:
Isocyanuric ring-containing urethane (meth) acrylate compound represented by the following general formula (1)

(In the general formula (1), R ¹ , R ² and R ³ each independently represent a divalent organic group having 2 to 10 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom. Or represents a methyl group.)

(B) component:
Isocyanuric ring-containing tri (meth) acrylate compound having no urethane bond represented by the following general formula (2)

(In the general formula (2), R ⁷ , R ⁸ and R ⁹ each independently represents a divalent organic group having 2 to 10 carbon atoms, and R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom. Or represents a methyl group, and n ¹ , n ² and n ³ each independently represents a number of 1 to 3, and n ¹ + n ² + n ³ = 3 to 9.

Component (C):
A reaction product obtained by reacting an alkoxysilane compound (c1) represented by the following general formula (3) with colloidal silica (c2) at a mass ratio of (c1) and (c2) of 9: 1 to 1: 9. A non-volatile component obtained by chemically modifying (c2) with (c1).

(In General Formula (3), R ¹³ represents a hydrogen atom or a monovalent organic group, R ¹⁴ represents a divalent hydrocarbon having 1 to 6 carbon atoms, and z is a positive number of 0.1 or more and 3 or less. In addition, when z is less than 3, (c1) contains a condensate, and R ^{13 in} one molecule of the condensate may contain two or more different groups.)

  The composition of the present invention is preferably used as a photocurable coating agent composition that uses a photoradical polymerization initiator as the component (D) and is cured by irradiation with light. By curing by irradiating light, curing in a short time with low energy becomes possible. In addition, by specifying the blending ratio of the ultraviolet absorber, and further the type of the ultraviolet absorber, curing proceeds well even when the composition is cured by irradiation with light, excellent transparency, abrasion resistance and A cured film having both weather resistance can be obtained.

  The curable coating agent composition of the present invention exhibits excellent wear resistance and weather resistance as a coating agent for substrates used outdoors, particularly resin substrates.

  Below, the best form for implementing the curable coating agent composition of this invention is demonstrated. Unless otherwise specified, the numerical range “p to q” described in this specification includes the lower limit p and the upper limit q. The numerical range can be configured by arbitrarily combining these upper limit value and lower limit value and the numerical values listed in the examples.

The curable coating agent composition of the present invention comprises 20 to 80 parts by mass of the (A) component with respect to 100 parts by mass of the following (A) component, (B) component, and (C) component. B) 10 to 70 parts by mass of component, 1 to 35 parts by mass of component (C), 0.1 to 10 parts by mass of radical polymerization initiator as component (D), and 1 UV absorber as component (E). ˜12 parts by mass and 10 to 1000 parts by mass of organic solvent as component (F). Hereinafter, the detail of each component and a composition is demonstrated.
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.

<(A) component>
The component (A) is an isocyanuric ring-containing urethane (meth) acrylate compound represented by the following general formula (1).

In the general formula (1), R ¹ , R ² , and R ³ each independently represent a divalent organic group having 2 to 10 carbon atoms. The divalent organic group having 2 to 10 carbon atoms is preferably an alkylene group having 2 to 4 carbon atoms such as ethylene group, trimethylene group, propylene group and tetramethylene group. Moreover, the compound which modified | denatured the compound of General formula (1) which has these groups to (epsilon) -caprolactone modification is also contained. In this case, the divalent organic group having 2 to 10 carbon atoms includes —OCOCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —. Among these, those in which R ¹ , R ² and R ³ are all tetramethylene groups are particularly preferred because the cured composition (cured film) is particularly excellent in wear resistance and weather resistance.

In the general formula (1), R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and a compound in which R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms has a curable composition. It is particularly preferable in that it is excellent in.

  The component (A) is synthesized by an addition reaction between a nurate type trimer of hexamethylene diisocyanate and a hydroxyalkyl (meth) acrylate or a caprolactone modified product thereof. 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.

  The content ratio of the component (A) in the composition of the present invention is 20 to 80 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C), and more preferably. 30 to 70 parts by mass. By setting the content ratio of the component (A) to 20 to 80 parts by mass, a cured film having excellent wear resistance and weather resistance can be obtained.

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

In General formula (2), R < ⁷ >, R < ⁸ > and R < ⁹ > represent a C2-C10 bivalent organic group each independently. The divalent organic group having 2 to 10 carbon atoms is preferably an alkylene group having 2 to 4 carbon atoms such as ethylene group, trimethylene group, propylene group and tetramethylene group. Moreover, the compound which modified | denatured (epsilon) -caprolactone modification | denaturation of the compound of General formula (2) which has these groups is also contained. In this case, the divalent organic group having 2 to 10 carbon atoms includes —OCOCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —. Among these, it is particularly preferable that R ⁷ , R ⁸ and R ⁹ are all ethylene groups, since a cured film having particularly excellent wear resistance and weather resistance can be obtained.

In the general formula (2), R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and a compound in which all of these are hydrogen atoms is such that the composition has excellent curability. Particularly preferred.

In the general formula ^{(2), n 1, n} 2 and n ³ are each independently a number from 1-3. However, it is ^{n 1 + n 2 + n 3} = 3~9. The n ^1, n ² and n ^3, 1 is preferred, as the ^{n 1 + n 2 + n 3} 3 are preferred.

The component (B) is preferably produced by reacting an isocyanuric acid alkylene oxide adduct with (meth) acrylic acid. n ¹ + n ² + n ³ represents the average added mole number of alkylene oxide per molecule of the component (B).

  The content ratio of the component (B) in the composition of the present invention is 10 to 70 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C), and more preferably. 20 to 60 parts by mass. (B) By making the content rate of a component into 10 parts or more, initial adhesiveness can be made favorable, and the cured film excellent in abrasion resistance and weather resistance is obtained by setting it as 10-70 mass parts. .

<(C) component>
The component (C) of the present invention comprises an alkoxysilane compound (c1) represented by the following general formula (3) and colloidal silica (c2), and a mass ratio of (c1) and (c2) of 9: 1 to 1. : A non-volatile component of the reaction product reacted in 9, which is obtained by chemically modifying (c2) with (c1).

  In addition, although the synthesis | combination of (C) component is normally performed in a solvent, (C) component is a component except the water and organic solvent which were used by reaction. Further, 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.

(In General Formula (3), R ¹³ represents a hydrogen atom or a monovalent organic group, R ¹⁴ represents a divalent hydrocarbon having 1 to 6 carbon atoms, and z is a positive number of 0.1 or more and 3 or less. In addition, when z is less than 3, (c1) contains a condensate, and R ^{13 in} one molecule of the condensate may contain two or more different groups.)

In the general formula (3), R ¹³ represents a hydrogen atom or a monovalent organic group. Specific examples of the monovalent organic group for R ¹³ include an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, and other C 1 to 6 carbon atoms composed of C, H, and O atoms. These organic groups are mentioned.

In terms of reactivity, R ¹³ is preferably a hydrogen atom or a monovalent organic group that may have an oxygen atom having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the general formula (3), R ¹⁴ represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and may be linear or branched. Examples of the linear saturated hydrocarbon group include ethylene group, 1,3-propylene group (trimethylene group), 1,4-butylene group (tetramethylene group), 1,5-pentanediyl group (pentamethylene group), 1, Examples include 6-hexanediyl group (hexamethylene group). Examples of the branched alkylene group include 1,2-propylene group, 1,2-butylene group, 1,3-butylene group, 2,3-butylene group, 1,3-pentanediyl group, 2,4-pentanediyl group, 2 , 5-hexanediyl group, 2-methyl-1,3-propylene group, 2-ethyl-1,3-propylene group, 3-methyl-1,5-pentanediyl group and the like.
R ¹⁴ is particularly preferably a linear divalent saturated hydrocarbon group having 3 to 6 carbon atoms.
Particularly preferred as R ¹⁴ is that the cured product of the composition has excellent wear resistance and weather resistance, and is a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and further has 3 carbon atoms. -6 linear divalent saturated hydrocarbon groups.

  In the general formula (3), z is a positive number and satisfies 0.1 ≦ z ≦ 3. z represents the average number of moles of remaining alkoxy groups per mole of Si atoms. (C1) 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.

  By setting z to 0.1 or more, colloidal silica is effectively surface-modified, and the cured product has excellent scratch resistance. Further, from the viewpoint of reactivity, 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 (c1).

When (c1) is a condensate, each R ¹³ may have two or more different chemical structures in one molecule.

  Incidentally, the 3,4,5,6-tetrahydrophthalimide group of the general formula (3) mainly absorbs ultraviolet rays and photodimers between the 3,4,5,6-tetrahydrophthalimide groups. is there.

  A preferred method for producing the compound of the formula (3) will be described. For example, an aminoalkyltrialkoxysilane represented by the following general formula (5) is added to a carboxylic acid anhydride having a double bond represented by the following chemical formula (4) to form an amic acid, and then 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 particularly preferable in that (c1) suitable for the curable coating agent 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 (5)

In the formula (5), 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 (3), 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 can be mentioned. It can be adjusted by removing water from the system or using a dehydrating agent.

The said manufacturing method is good to be performed in 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.

(C2) is colloidal silica, and various types can be used, but those in which spherical particles are uniformly dispersed are preferable, for example, those in which alcohol particles are uniformly dispersed are more preferable.
The average primary particle size of (c2) 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 diameter of (c2) larger than 1 nm, it can be excellent in wear resistance, and by making it a threshold smaller than 100 nm, it is excellent in dispersion stability of the colloidal solution. be able to.

In the present invention, the average primary particle diameter means a value calculated from the specific surface area by the BET method. Moreover, the specific surface area of (c2) is in the range of 30 to 3,000 m ² / g.

  The method for synthesizing the component (C) is preferably a method in which (c1) and (c2) are charged at a predetermined mass ratio in the presence of an organic solvent containing water and then heated to react. The heating temperature and time are different depending on the presence or absence of a catalyst and the like, and thus cannot be defined unconditionally.

The component (C) may contain not only the silica fine particles whose surface is modified in (c1) but also the hydrolysis condensate (c1) that does not contain silica fine particles. It is defined as
In addition to (c1), maleimide group-containing alkoxysilane synthesized from the compound represented by formula (4) and aminoalkylmethyl dialkoxysilane in the same manner as (c1), methyltrialkoxysilane, etc. A product obtained by adding an alkoxysilane compound and reacting with (c2) is also included in the concept of component (C). In this case, however, the amount of the other alkoxysilane compound charged is preferably less than half of (c1).

  The charge mass ratio of (c1) and (c2) when synthesizing the component (C) is 1: 9 to 9: 1, more preferably 2: 8 to 7: 3, still more preferably 2: 8 to 6: 4. By setting the mass ratio of (c1) and (c2) to 1: 9 to 9: 1, it is possible to achieve both wear resistance and weather resistance of the cured film.

  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 preferred 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.

The content rate of (C) component in the composition of this invention is 1-35 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component, More preferably, it is 1 -30 mass parts, More preferably, it is 3-25 mass parts, Most preferably, it is 5-20 mass parts.
By making the content rate of (C) component into 1-35 mass parts, it can be set as the composition from which the cured film excellent in abrasion resistance and a weather resistance is obtained. If the ratio of (C) component is 1 mass part or more, the abrasion resistance of a cured film will improve. However, if the component (C) is excessive, the cured film tends to shrink or the organic portion of the cured film is quickly decomposed, resulting in a decrease in weather resistance.

<(D) component: radical polymerization initiator>
The component (D) of the present invention is a radical polymerization initiator, and various compounds can be used.
If a radical photopolymerization initiator is used as the component (D), the composition serves as a photocurable coating agent composition and is cured by light irradiation. If a thermal radical polymerization initiator is used as the component (D), the composition serves as a thermosetting coating agent composition and is cured by heating.
The composition of the present invention is a photocurable coating composition using a radical photopolymerization initiator as the component (D) in that it is excellent in curability, such as being capable of curing in a short time with low energy. Preferably there is.

  Specific examples of the photo radical polymerization initiator 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-methylpropioni) ) Benzyl] phenyl} -2-methyl-propan-1-one and the like acetophenone compounds; benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-4′-methyl-diphenylsulfide, etc. Benzophenone compounds such as methylbenzoylformate, α-ketoesters such as 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid Compound; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpenty Phosphine oxide compounds such as ruphosphine oxide; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1- [4- (4-benzoylphenylsulfanyl) Acetophenone / benzophenone hybrid photoinitiators such as phenyl] -2-methyl-2- (4-methylphenylsulfinyl) propan-1-one; 2- (O-benzoyloxime) -1- [4- (phenylthio)] Oxime ester photopolymerization initiators such as -1,2-octanedione; and camphorquinone.

Specific examples of the thermal radical polymerization initiator include organic peroxides and azo compounds.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl- , 5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5 -Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butyl) Peroxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 Examples include 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.
Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane and azodi-t-butane.

  The radical polymerization initiators listed above may be used alone or in combination of two or more. Moreover, an organic peroxide can also be used as a redox catalyst by combining with a reducing agent.

The content rate of (D) component in the composition of this invention is 0.1-10 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component, and more. Preferably it is 0.5-5 mass parts, Most preferably, it is 1-3 mass parts.
When the content ratio of the component (D) is 0.1 to 10 parts by mass, the composition has excellent curability, and a cured film having excellent wear resistance and weather resistance is obtained.

<(E) component: UV absorber>
The component (E) of the present invention is an ultraviolet absorber, and various compounds or substances can be used.
Specific examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-[(2-hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyroxyphenyl) -6- (2,4-bis-butyroxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4 Triazine ultraviolet absorbers such as [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine; 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- (Meth) acryloyloxyethyl) phenyl] -2H-benzotriazole and other benzotriazole UV absorbers; 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone and other benzophenone UV absorbers, 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.

The content ratio of the component (E) in the composition of the present invention is 1 to 12 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C), and more preferably. 3 to 12 parts by mass.
(E) By making the content rate of a component into 1-12 mass parts, the abrasion resistance of a cured film and a weather resistance can be made to make compatible. When the component (E) is less than 1 part by mass, a cured film showing sufficient weather resistance cannot be obtained. On the other hand, when there is too much (E) component, not only the abrasion resistance of a cured film will fall, but also there exists a tendency for a weather resistance to fall, Therefore (E) component shall be 12 mass parts or less. In particular, by setting the content ratio of the component (E) to 3 to 12 parts by mass, a cured film having both excellent wear resistance and weather resistance can be obtained.

<(F) component: organic solvent>
The component (F) of the present invention is a solvent, and various compounds can be used.
As the component (F), those that uniformly disperse or dissolve the components (A), (B), (C), (D) and (E), and other components described later are preferable.

  Specific examples of preferred solvents 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; toluene and Aromatic compounds such as 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-methylpyrrolidone Can be mentioned. Among these, alkylene glycol monoethers such as propylene glycol monomethyl ether are not only excellent in dispersibility or solubility of various components, but also when the resin substrate to which the composition of the present invention is applied is made of a polycarbonate resin. The polycarbonate resin is particularly preferable because it does not dissolve the polycarbonate resin.

  Furthermore, by mixing a solvent that does not dissolve polycarbonate resin such as alcohol or alkylene glycol monoether and a solvent that dissolves polycarbonate resin such as ester or ketone, the substrate made of polycarbonate resin is not dissolved during coating, and the subsequent heating process Then, a method of 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 rate of (F) component in the composition of this invention is 10-1000 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component. When the blending amount of the component (F) is too small, uniform coating is difficult to perform, and when it is too large, it is difficult to obtain a cured film having a sufficient thickness. Therefore, the component (F) may be appropriately selected according to the coating method, but if it is intentionally defined, it is preferably 50 to 500 parts by mass, more preferably 50 to 300 parts by mass from the viewpoint of productivity. is there.
In addition, the organic solvent which exists with (A)-(E) component and the below-mentioned (G) component, (H) component, and other components at the time of preparation of a composition shall also be included in the content rate of (F) component. .

<(G) component: hindered amine light stabilizer>
The composition of the present invention essentially comprises the components (A) to (F), but for the purpose of improving the weather resistance, the hindered amine light stabilizer (G) (hereinafter referred to as “(G) component”). May be blended.
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.
(G) As a content rate of a component, 0.05-1.5 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component, Furthermore, 0.1-1 .5 parts by mass is preferred.

<(H) component: surface modifier>
Various surface modifiers may be added to the composition of the present invention 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. 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 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 sustainability of slipperiness.

  The preferable compounding quantity of a surface modifier is 0.01-1.0 mass part with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component. The surface smoothness of a coating film can be improved by making the compounding quantity of a surface modifier into 0.01-1.0 mass part.

<Other ingredients>
The composition of the present invention essentially comprises the components (A) to (F), but various components can be blended depending on the purpose. The above component (G), component (H) and other components listed below may be blended alone or in combination of two or more.

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 mass in total of the components (A), (B) and (C). .

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 and phosphorus 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 0 to 5 parts by mass, more preferably 0 to 3 parts by mass with respect to 100 parts by mass in total of the components (A), (B), and (C). .

You may mix | blend compounds other than (A) component and (B) component which have a 1 or more radically polymerizable unsaturated group in 1 molecule in the composition of this invention.
A compound having one radical polymerizable unsaturated group in one molecule (hereinafter referred to as “unsaturated compound”) can be blended in order to improve the adhesion between the cured film and the resin substrate.
The radically polymerizable unsaturated group in the unsaturated compound is preferably a (meth) acryloyl group.
As a compounding ratio of the unsaturated compound, from the viewpoint of preventing deterioration of wear resistance and weather resistance, 20 mass with respect to a total of 100 mass parts of the component (A), the component (B), and the component (C). Part or less.

  Specific examples of the unsaturated compound having one radical polymerizable unsaturated group in one molecule include (meth) acrylic acid, Michael addition dimer of acrylic acid, 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) (Meth) acrylate of acrylate, alkylene oxide adduct of phenol, (meth) acrylate of alkylene oxide adduct of alkylphenol, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2 Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, (meth) acrylate of alkylene oxide adduct of paracumylphenol, orthophenylphenol (meth) acrylate, alkylene oxide of orthophenylphenol Adduct (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanemethylol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- ( (Meth) acryloxyethyl) hexahydrophthalimide, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, N, N-dimethylacrylamide, acryloyl Lumorpholine, N-vinylpyrrolidone, N-vinylcaprolactam and the like can be mentioned.

In the unsaturated compound, a compound 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 resin base material 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 20 parts by mass or less with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C) from the viewpoint of preventing deterioration of weather resistance. It is preferable that

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, 1,6-hexanediol di (meth) acrylate, 1,9-nonane 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, trimethylolpropane tri (meth) ) Acrylate, tri (meth) acrylate of trimethylolpropane alkylene oxide adduct, tri- and tetra-acrylate of pentaerythritol, alkyl of pentaerythritol Trioxide and tetraacrylate of oxide adduct, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa and pentaacrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, terminal (meth) Examples thereof include silicone resins having an acryloyl group.

  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-epoch Shi cyclohexanecarboxylate (meth) acrylic acid adduct and the like.

Examples of the urethane (meth) acrylate include compounds obtained by addition reaction of organic polyisocyanate and hydroxyl group-containing (meth) acrylate, and compounds obtained by addition reaction of organic polyisocyanate, polyol and hydroxyl group-containing (meth) acrylate.
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 polyol and / or polyether polyol 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.

  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.

<Preparation method>
In the composition of the present invention, the components (A) to (F) already described, and other components such as the component (G) and the component (H), if necessary, are weighed in predetermined amounts, stirred and mixed. Can be manufactured.

<Coating method and curing method>
The curable coating agent composition of the present invention is applied to the surface of a substrate to which wear resistance and weather resistance are to be imparted.
The substrate to which the composition of the present invention can be applied is applicable to various materials used outdoors, and examples thereof include plastic, metal, and concrete. Moreover, there is no limitation in particular in the shape of a base material.
The composition of the present invention can be preferably applied particularly to plastics used outdoors. Specific examples of the plastic include polycarbonate resin, polymethyl methacrylate, polyethylene terephthalate, polyvinyl chloride, epoxy resin, and polyurethane resin. More preferred are polycarbonate resin and polymethyl methacrylate, and particularly preferred is polycarbonate resin.

What is necessary is just to follow the coating method of the curable coating agent composition of this invention in a conventional method. For example, a spray method, a spin coat method, a dip coat method, a bar coat method, a flow coat method and the like are preferable, and may be selected according to the shape of the substrate. At this time, if the surface of the base material is not exposed to the composition of the present invention for a long time, deterioration of the base material due to the organic solvent is suppressed.
What is necessary is just to set the film thickness of the coating film formed by coating suitably according to the objective. For example, the thicker the cured film, the better the weather resistance, but it is not desirable to increase the thickness from the viewpoint of the appearance and productivity of the cured film. Considering 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.
What is necessary is just to select the drying temperature of a coating film suitably according to the heat resistance of a base material, and if it is a resin-made base material, it is below the softening point of resin. For example, in the case of a polycarbonate resin, the temperature is preferably in the range of 50 to 120 ° C.

In the case where the composition of the present invention is a photocurable composition, the composition is applied to a substrate, dried, and then irradiated with light such as ultraviolet rays. A preferable production method includes a method of irradiating light with the dried substrate maintained at a high temperature.
In the case where the composition of the present invention is a photocurable composition, the temperature at which the composition is dried and then irradiated with ultraviolet rays or the like is particularly limited as long as it is below the performance maintaining temperature of the substrate material. However, the range of 50 ° C to 200 ° C is preferred. For example, in the case of a polycarbonate resin, the temperature is preferably in the range of 50 to 120 ° C, more preferably 60 to 110 ° C, still more preferably 70 to 100 ° C, and particularly preferably 80 to 100 ° C. The abrasion resistance of the cured film can be improved by maintaining the temperature of the base material in the range of 50 to 120 ° C. when irradiating with ultraviolet rays.

Examples of light include ultraviolet light and visible light, and ultraviolet light is particularly preferable.
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, and 1,000 to 6,000 mJ / cm ² is more preferable.

When the composition of the present invention is a thermosetting composition, the composition is applied to a substrate, dried, and then heated. Although it will not specifically limit if it is below the performance maintenance temperature of a board | substrate material as heating temperature, 80-200 degreeC is preferable.
As heating time, 10 minutes or more and 120 minutes or less are preferable. From the viewpoint of productivity, the time is preferably 60 minutes or less, more preferably 30 minutes or less.

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.
In this specification, the temperature of drying and heating is the surface temperature of the coating film, and is approximately equal to the atmospheric temperature of drying or heating.

  As mentioned above, although embodiment of the curable coating agent 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 more specifically with reference to examples and comparative examples. In addition, this invention is not limited by these Examples.
Hereinafter, “parts” means parts by mass, and “%” means mass%. In addition, the polyfunctional urethane (meth) acrylate other than the component (A) not corresponding to the component (A) is used as the component (A) ′, and the colloidal silica other than the component (C) not corresponding to the component (C) (dispersion medium is used). The non-volatile component removed) is referred to as (C) ′ component.

○ Production Example 1: 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), 2,6-di-tert-butyl-4-methylphenol (hereinafter referred to as “BHT”) 1.22 g, dibutyltin dilaurate (hereinafter referred to as “DBTL”) 0.73 g Was added dropwise, while stirring at a liquid temperature of 50 to 70 ° C., 1080 g (7.5 mol) of 4-hydroxybutyl acrylate (hereinafter referred to as “HBA”) 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 2: Production of component (A) ′ (IPDI-M305)
To a 2 L separable flask equipped with a stirrer and an air blowing tube, triethyl and tetraacrylate of pentaerythritol [Aronix M-305 manufactured by Toagosei Co., Ltd. Hereinafter referred to as M-305. 993 g (containing 2 moles of triacrylate), 0.61 g of BHT and 0.36 g of DBTL were charged, and 222 g (1 of IPDI) of isophorone diisocyanate (hereinafter referred to as “IPDI”) was stirred at a liquid temperature of 70 to 75 ° C. 0.0 mol) was added dropwise.
After completion of the dropwise addition, the mixture was stirred at 85 ° C. for 2 hours, and the reaction was terminated by confirming that the isocyanate group had disappeared by IR (infrared absorption) analysis of the reaction product, thereby obtaining a polyfunctional urethane acrylate.
Hereinafter, this reaction product is referred to as “IPDI-M305”.

Production Example 3: Production of component (c1) (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 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 (c1). Hereinafter, this reaction product is referred to as “THPI-alkoxysilane”.

From the 1H-NMR spectrum, the structure of the obtained THPI-alkoxysilane is represented by the general formula (3) in which 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 (c1) in Production Example 4 described later.

○ Production Example 4: Production of component (C) (THPI-silica)
In a 3 L separable flask equipped with a stirrer, 960 g of propylene glycol monomethyl ether (hereinafter referred to as PGM), 23.6 g of water, and isopropyl alcohol (hereinafter referred to as IPA) dispersed colloidal silica (IPA-manufactured by Nissan Chemical Industries, Ltd.) ST, average particle diameter of 10 to 15 nm (value calculated from specific surface area by BET method), solid content of 30%, IPA content of 70%. Hereinafter, it is simply referred to as “IPA-ST”. After adding 800 g and stirring and homogenizing, 189 g of THPI-alkoxysilane was added and stirred and dissolved at room temperature. At this time, the mass ratio of the component (c1) to the component (c2) was 44:56.
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”.

(Examples 1 to 4 and Comparative Examples 1 to 8)
The components shown in Table 1 and Table 3 were stirred and mixed according to a conventional method to produce a photocurable coating agent composition. Table 1 shows the compositions of each example (# E1 to E4), and Table 3 shows the compositions of each comparative example (# C1 to C8).
In addition, the numerical value of each component of Table 1 and Table 3 represents a mass part. Abbreviations in the table represent the following compounds.

○ Abbreviation / Component (A) “HDI3-HBA”: Reaction product of Production Example 1.
-(A) 'component "IPDI-M305": Reaction product of Production Example 2.
-(B) component "M-315": Toagosei Co., Ltd. Aronix M-315; Tris (acryloyloxyethyl) isocyanurate. In the general formula (2), R ⁷ , R ⁸ and R ⁹ are ethylene groups, R ¹⁰ , R ¹¹ and R ¹² are hydrogen atoms, n ¹ , n ² and n ³ are 1 and n ¹ Corresponds to compounds where + n ² + n ³ = 3.
Component (C) “THPI-silica”: Reaction product of Production Example 4 (nonvolatile component).
-(C) 'component "acryl-silica": Nissan Chemical Industries, Ltd. methyl ethyl ketone (hereinafter referred to as MEK) dispersed acrylic modified colloidal silica, trade name MEK-AC-2101 (average particle size 10-15 nm (ratio by BET method) Non-volatile component in the value calculated from the surface area), solid content 33%, MEK 67% contained.
Component (D) “Irg-819”: photo radical polymerization initiator manufactured by BASF Corporation, trade name Irgacure 819; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
-(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.
-(F) component "PGM": Propylene glycol monomethyl ether.
“MEK”: methyl ethyl ketone. (MEK in the component (C) ′ component “MEK-AC-2101”.)
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.
-(H) component "8019add": Toray Dow Corning Co., Ltd. silicone-type surface modifier (leveling agent), brand name 8019additive. 100% active ingredient.

In addition, the average particle diameter of colloidal silica is an average primary particle diameter, and the description “10 to 15 nm” indicates a catalog value considering the lot variation of products.
The structures of the active ingredients (E) and (G) are shown below.

The composition shown in Tables 1 and 3 was applied to the surface of a 10 cm square polycarbonate resin plate with a bar coater so that the coating thickness after drying was about 15 μm, and dried for 10 minutes with a 100 ° C. hot air dryer. After that, ultraviolet irradiation was performed immediately (at a coating 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. The lamp output, the lamp height, and the conveyor speed were adjusted so as to satisfy the following conditions, and irradiation was performed for 12 passes (total 3000 mJ / cm ² ).

  About the obtained cured film, transparency, (initial) adhesion, abrasion resistance, weather resistance (weather adhesion and presence / absence of cracks) and scratch resistance were evaluated by the following methods. The evaluation results are shown in Table 2, Table 4, and Table 5.

○ Initial adhesion A cut grid of 11 squares is formed by cutting each of the cured film with 11 mm in length and width with a cutter knife to form a 100 square grid, and cellophane tape made by Nichiban Co., Ltd. is pasted on this grid, and JIS K5400 The cellophane tape was peeled off according to the above. 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 According to JIS K7136, the haze H (%) of the cured film was measured for each substrate with a turbidimeter NDH-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The smaller the value of H, the better the transparency.

Abrasion resistance A Taber type abrasion test was conducted in accordance with ASTM D-1044. The abrasion resistance was evaluated by measuring a haze difference ΔH (%) before and after the Taber abrasion test using a Taber abrasion tester. Here, the wear wheel was CS-10F, the load was 500 g, and the rotation speed was 500 times. The smaller ΔH (%), the better the wear resistance.

○ Weather resistance According to JIS K5400, a carbon arc type sunshine weather meter was used for a 5000 hour accelerated test, and the adhesion (weather resistance adhesion) and the presence or absence of cracks were evaluated every 500 hours. 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. Moreover, the crack was determined to be good if no crack was found in the cured film by visual observation. The results are shown in Table 2 and Table 4. In each table, the longest time among the test times of the accelerated test performed on the cured film confirmed to be good with respect to adhesion and cracking was described, and the longer the number of hours, the better the weather resistance was evaluated. . Those with good evaluation after the 5000 hour accelerated test were described as “5000 <”.

Scratch resistance The samples # 02, # 04, # 23 and # 28 were evaluated for scratch resistance. The scratch resistance was evaluated by measuring the difference in gloss value (20 °) before and after the scratch test on the cured film, and evaluating the gloss retention.
The abrasion test was performed by scratching the cured film 150 times with a load of 500 g using a nylon scrubber (Scotch Bright No. 96) made of Sumitomo 3M Co., Ltd., which was wetted with water. The gloss retention of the cured film before and after the abrasion test was measured using a Gakushin dyeing dyeing fastness tester manufactured by Daiei Kagaku Seisakusho Co., Ltd. The measurement results are shown in Table 5. A higher gloss retention indicates better scratch resistance.

As shown in Table 2, the sample produced using the curable coating composition of the present invention was excellent in transparency, adhesion, abrasion resistance, and weather resistance. Of these, Example 1 had good weather resistance adhesion of 5000 hours. Further, Example 2 in which the amount of the component (B) in Example 1 was increased from 15 parts to 30 parts, and the amount of the component (A) was reduced correspondingly, the weather resistance adhesion was improved by more than 5000 hours, and the wear resistance was further increased. Also improved. In Example 3 in which the amount of the component (B) was further increased to 50 parts, the wear resistance was further improved, and the weather resistance was very excellent as in Example 2.
In order to maintain the weather resistance adhesion when the thickness of the coating film becomes thin, the wear resistance decreases when the amount of the UV absorber as the component (E) is increased. However, as shown in Example 4, when the component (E) was 7.5 parts and the component (C) was 15 parts, the wear resistance was good and the weather resistance was very good. Here, in Example 5 in which the acrylic modified colloidal silica as the (C) ′ component was used together with the (C) component, the weather resistance adhesion was slightly lowered.
On the other hand, as shown in Table 3, Comparative Example 1 which does not contain the component (A) and has an excessive amount of the component (B) had poor weather resistance adhesion. Further, Comparative Example 2 containing no component (B) has poor initial adhesion, Comparative Example 3 containing no component (C) has poor wear resistance, and Comparative Example 4 containing no component (E). The weather resistance was poor. With regard to component (C), in Comparative Example 5 in which the amount was excessively added, the wear resistance deteriorated on the contrary, and the weather resistance also deteriorated. As described above, it was important to mix the components (A), (B), (C), and (E) in appropriate amounts.
Comparative Example 6 in Table 3 is an example using polyfunctional urethane acrylate (component (A) ′) having good wear resistance without containing inorganic fine particles, but the weather resistance is poor. An example in which the component (A) ′ was used in place of the component (C) as an abrasion resistance improver was Comparative Example 7, but both the abrasion resistance and weather resistance were poor.
Comparative Example 8 in Table 3 is an example in which the component (C) (THPI-silica) in Example 4 was replaced with the component (C) ′ (acryl-silica), and the composition described in Patent Document 4 described above Corresponding to In Comparative Example 8, although the abrasion resistance was good, the weather resistance adhesion was inferior.
Table 5 shows the results of the scratch resistance test by a test method different from the Taber abrasion test. As shown in Table 5, the gloss retention of Comparative Example 3 containing no component (C) or (C) ′ is very poor. On the other hand, Example 2, Example 4 and Comparative Example 8 using surface-modified colloidal silica were good results.

The curable coating agent composition of the present invention can be suitably used as a coating agent composition for various substrates used outdoors, particularly resin substrates.
Specifically, outdoor building materials such as exterior walls and roofs of buildings; outdoor units that are always installed outdoors, instrument cases; road-related items such as plastic parts used for traffic lights, outdoor lighting, signs, guardrails, etc. Examples include: members; show windows; lenses such as telescopes and spectacles; playground equipment and toys in parks and amusement parks; food and medical articles that are irradiated with light for purposes such as sterilization.

Claims (9)

20-80 parts by mass of the (A) component, 10-70 parts by mass of the (B) component, and 100 parts by mass of the following (A) component, (B) component, and (C) component, 1 to 35 parts by mass of component (C), 0.1 to 10 parts by mass of radical polymerization initiator as component (D), 1 to 12 parts by mass of UV absorber as component (E), and organic as component (F) A curable coating agent composition comprising 10 to 1000 parts by mass of a solvent.
(A) component:
Isocyanuric ring-containing urethane (meth) acrylate compound represented by the following general formula (1)

(In the general formula (1), R ¹ , R ² and R ³ each independently represent a divalent organic group having 2 to 10 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom. Or represents a methyl group.)
(B) component:
Isocyanuric ring-containing tri (meth) acrylate compound having no urethane bond represented by the following general formula (2)

(In the general formula (2), R ⁷ , R ⁸ and R ⁹ each independently represents a divalent organic group having 2 to 10 carbon atoms, and R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom. Or represents a methyl group, and n ¹ , n ² and n ³ each independently represents a number of 1 to 3, and n ¹ + n ² + n ³ = 3 to 9.
Component (C):
A reaction product obtained by reacting an alkoxysilane compound (c1) represented by the following general formula (3) with colloidal silica (c2) at a mass ratio of (c1) and (c2) of 9: 1 to 1: 9. A non-volatile component obtained by chemically modifying (c2) with (c1).

(In General Formula (3), R ¹³ represents a hydrogen atom or a monovalent organic group, R ¹⁴ represents a divalent hydrocarbon having 1 to 6 carbon atoms, and z is a positive number of 0.1 or more and 3 or less. In addition, when z is less than 3, (c1) contains a condensate, and R ^{13 in} one molecule of the condensate may contain two or more different groups.)   The said (E) component is a curable coating agent composition of Claim 1 containing the benzotriazole type ultraviolet absorber which has a (meth) acryloyl group. The curable coating agent composition according to claim 1 or 2, wherein (c2) has an average primary particle diameter of 1 to 100 nm. In said (A) component, R < ¹ >, R < ² > and R < ³ > in General formula (1) are tetramethylene groups, and R < ⁴ >, R < ⁵ > and R < ⁶ > are hydrogen atoms. The curable coating composition as described. In the component (B), R ⁷ , R ⁸ and R ⁹ in the general formula (2) are ethylene groups, R ¹⁰ , R ¹¹ and R ¹² are hydrogen atoms, and n ¹ , n ² and n ³ are 1 and n ¹ + n ² + n ³ = 3. The curable coating composition according to claim 1.   Furthermore, 0.05-1.5 mass parts of hindered amine light stabilizers are contained as a (G) component with respect to a total of 100 mass parts of the said (A) component, (B) component, and (C) component. The curable coating agent composition in any one of 1-5.   Further, as the component (H), 0.01 to 1.0 of a silicone-based and / or fluorine-based surface modifier is added to 100 parts by mass of the total of the component (A), the component (B), and the component (C). The curable coating agent composition according to any one of claims 1 to 6, which is contained in parts by mass.   The said (D) component is radical photopolymerization initiator, The curable coating agent composition in any one of Claims 1-7. The component (C) is a step of adding aminopropyltrialkoxysilane to a carboxylic acid anhydride having a double bond represented by the following chemical formula (4) to form an amic acid,
The amic acid is cyclized by heating to form a maleimide group, and an alkoxy group is hydrolyzed and condensed using water generated by the cyclization reaction to obtain an alkoxysilane compound (c1) represented by the general formula (3). Process, and
A step of reacting the obtained (c1) with colloidal silica (c2) having an average primary particle diameter of 1 to 100 nm by heating in the presence of an organic solvent containing water;
The curable coating composition according to any one of claims 1 to 8, which is a non-volatile component of a reaction product obtained by a production method comprising: