Active energy ray-curable coating composition and molded article

Abstract

The purpose of the present invention is to provide: an active-energy-ray-curable coating composition capable of forming a cured coating film having exceptional weather resistance, abrasion resistance, and chemical resistance; and a molded article having a cured coating film. The present invention relates to an active-energy-ray-curable coating composition containing a compound of formula (1) as component (A), a compound of formula (2) as component (B), and a compound containing six or more (meth)acryloyl groups per molecule as component (C) (in the formulas, R1, R2, and R3 represent an oxyalkylene group, etc.; X1, X2, and X3 represent CH2=CR4-CO-, CH2=CR4-CO(O(CH2)5-CO)a1-, H, or an alkyl group; R4 represents H or a methyl group; a1 is an integer equal to or greater than 1; R21 to R25 represent a group having a polymerizable group; Z21 to Z23 represent a group of formula (2z); L21 to L22 represent a divalent linking group; n1 to n2 represent 0 or 1; X21 represents an alkylene group; * represents a bond; Z1 represents O or N; and Z2 represents H or -C(=O)-).

Description

Technical Field

[0001] The present invention relates to an active energy ray curable coating composition and a molded article.

Background Art

[0002] Resin materials, especially transparent resin materials typified by polycarbonate, etc., have a small specific gravity, are lightweight, are easy to process, and take advantage of the characteristic of being more resistant to impact than inorganic glass, and are widely used in various applications. On the other hand, resin materials have various drawbacks such as being easily scratched on the surface, easily losing gloss and transparency, being easily invaded by organic solvents, being inferior in weather resistance (for example, light resistance to ultraviolet rays, etc.), and being inferior in heat resistance. Therefore, resin materials are often used after being coated with various protective films for the purpose of improving their surface characteristics. Examples of such a protective film include a hard coat layer formed by curing an active energy ray curable coating composition.

[0003] Resin materials used outdoors require excellent weather resistance as well as abrasion resistance. As an active energy ray curable coating composition having both abrasion resistance and weather resistance, an active energy ray curable composition in which a mono- or poly-pentaerythritol poly(meth)acrylate compound modified with caprolactone, a urethane (meth)acrylate containing an isocyanurate ring, and poly[(meth)acryloyloxyalkyl]isocyanurate are used in combination at a specific ratio is known (see Patent Document 1). In Patent Document 2, a urethane acrylate having 4 to 9 acryloyl groups in the molecule, a urethane acrylate having 1 to 3 acryloyl groups in the molecule and a polyester skeleton in the resin skeleton, a urethane acrylate having 1 to 3 acryloyl groups in the molecule and no polyester skeleton in the resin skeleton, an acetophenone-based photopolymerization initiator, a phosphine oxide-based photopolymerization initiator, an ultraviolet absorber, and a light stabilizer are combined in a specific ratio to disclose an ultraviolet curable coating composition excellent not only in transparency, abrasion resistance, and weather resistance but also in hot water resistance.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, resin materials and active energy ray curable coating compositions that can be used in harsh environments such as outdoors and around automobiles have been required to have not only weather resistance and abrasion resistance but also resistance to acid rain and automotive battery fluid, that is, excellent chemical resistance. However, in the inventions described in Patent Documents 1 and 2 above, no consideration has been given to chemical resistance, and the inventions described in Patent Documents 1 and 2 cannot solve all the problems of chemical resistance, weather resistance, and abrasion resistance.

[0006] The present invention has been made in view of the above problems, and an object thereof is to provide an active energy ray curable coating composition capable of forming a cured film having high chemical resistance while having weather resistance and abrasion resistance, and a molded article having the cured film.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors (A) As a component, a (meth)acrylate compound having an isocyanurate bond represented by the following formula (1) described later, (B) As a component, a compound having an isocyanurate bond or an allophanate bond and one or more urethane bonds different from these bonds, represented by the following formula (2) described later, and (C) As a component, an active energy ray-curable coating composition containing a compound containing 6 or more (meth)acryloyl groups in one molecule has been found to solve the above problems, and the present invention has been completed.

[0008] That is, the present invention provides the following inventions. (1) An active energy ray-curable coating composition containing the following components (A) to (C), (A) As a component, it contains a compound represented by the following formula (1), (B) As a component, it contains a compound represented by the following formula (2), (C) As a component, an active energy ray-curable coating composition characterized by containing a compound containing 6 or more (meth)acryloyl groups in one molecule.

[0009] [Chemical formula]

[0010] (In the formula, R 1 , R 2 and R 3 each independently represent an oxyalkylene group or a polyoxyalkylene group, X 1 , X 2 and X 3 each independently represent CH2=CR 4 -CO-, CH2=CR 4 -CO(O(CH2)5-CO) a1 -, a hydrogen atom or an alkyl group, R 4 represents a hydrogen atom or a methyl group, a plurality of R 4 may be the same or different, and a1 is an integer of 1 or more. However, X 1~X 3 At least two of them are CH2=CR 4 -CO- or CH2=CR 4 -CO(O(CH2)5-CO) a1 -).

[0011]

Chemical formula

[0012] (In the formula, R 21 ~R 25 each independently represents a group having a polymerizable group, Z 21 ~Z 23 each independently represents a group represented by the following formula (2z), L 21 ~L 22 each independently represents a divalent linking group, n1 to n2 are each independently 0 or 1.).

[0013]

Chemical formula

[0014] (In the formula, X 21 represents an alkylene group having 2 to 17 carbon atoms, * is a bond, Z 1 represents an oxygen atom or a nitrogen atom, Z 2 represents a hydrogen atom or -C(=O)-. However, when Z 1 is an oxygen atom, Z 2 is a hydrogen atom. On the other hand, when Z 1 is a nitrogen atom, Z 2 is -C(=O)- and the nitrogen atom of Z 1 and the -C(=O)- of Z 2 are bonded to form a ring.). When the formula (2z) is Z 21 in the formula (2), the bond * represented by B1 is R 21 , the bond represented by B2 is L 21 or R 22, the bond represented by B3 is L 22 or R 23 and binds; when formula (2z) is Z in the above formula (2) 22 , the bond * represented by B1 is L 22 , the bond represented by B2 is R 24 , the bond represented by B3 is R 23 and binds; when formula (2z) is Z in the above formula (2) 23 , the bond * represented by B1 is L 21 , the bond represented by B2 is R 22 , the bond represented by B3 is R 25 and binds.)

[0015] (2) The active energy ray-curable coating composition according to (1) above, wherein the compound represented by the above formula (2) is any one of the compounds represented by the following formulas (2-1) to (2-4).

[0016]

Chemical formula

[0017]

Chemical formula

[0018]

Chemical formula

[0019]

Chemical formula

[0020] (3) In the total solid content of the components (A) to (C), the content of the component (A) is 1% by mass or more and 85% by mass or less, the content of the component (B) is 14% by mass or more and 98% by mass or less, and the content of the component (C) is 1% by mass or more and 20% by mass or less. The active energy ray-curable coating composition according to (1) or (2) above. (4) The active energy ray-curable coating composition according to any one of (1) to (3) above, wherein the component (C) is a polyfunctional urethane acrylate obtained by reacting a diisocyanate compound or a triisocyanate compound with a compound represented by the following formula (3-1) or (3-2).

[0021]

Chemical formula

[0022] [Chemical formula] (In the formula, X 31 ~X 32 each independently represents an alkylene group having 2 to 17 carbon atoms, R 33 is -R C -O-CO-CH=CH2, or represents a structure obtained by removing a hydroxyl group from the compound represented by the formula (3-1) or (3-2), and R C represents an alkylene group. A plurality of X 31 , X 32 in the formula may be the same as or different from each other.)

[0023] (6) The component (B) contains a component (B-1) and a component (B-2), the component (B-1) contains a compound in which at least one of R 27 in the formula (2-1) or (2-3) is R A -(O-CO-(CH2)5) n -, or R A -(O-(CH2)4) n -, or a compound in which A1 in the formula (2-2) or (2-4) has a structure obtained by removing a hydroxyl group from the terminal of polytetramethylene glycol or polycaprolactone diol, the component (B-2) is R 27A compound in which the group is an alkylene group, or a compound having a structure obtained by removing a hydroxyl group from the end of an alkylene diol in the formula (2-2) or (2-4), In the total solid content of the components (A) to (C), the content of the component (B-1) is 9% by mass or more and 90% by mass or less, and the content of the component (B-2) is 5% by mass or more and 60% by mass or less. The active energy ray-curable coating composition according to any one of (2) to (5). (7) A molded article having a cured film of the active energy ray-curable coating composition according to any one of (1) to (6) and a substrate. (8) The molded article according to (7), wherein the substrate is a polycarbonate resin. (9) A molded article obtained by bending the molded article according to (7) or (8) by thermoforming. (10) A molded article according to any one of (7) to (9), which is used for automotive headlamp lenses, automotive glazing, automotive body exterior, plastic for building materials, and steel plates for building materials. [Effect of the Invention]

[0024] According to the active energy ray-curable coating composition of the present invention, a cured film having excellent chemical resistance, high weather resistance and abrasion resistance can be formed. This cured film has excellent adhesion to resin materials such as polycarbonate and has excellent adhesion even in a high temperature and high humidity environment. Therefore, the active energy ray-curable coating composition of the present invention can be suitably used as a hard coat for resin materials in automotive applications and building materials applications. [Embodiments for Carrying Out the Invention]

[0025] [Active Energy Ray-Curable Coating Composition] The active energy ray-curable coating composition of the present invention (hereinafter sometimes simply referred to as "coating composition" or "composition") contains components (A) to (C). In this specification, the compound represented by formula (1) is referred to as "compound (1)", and compounds represented by other formulas are also referred to in the same way. Further, "acrylate" and "methacrylate" are collectively referred to as "(meth)acrylate". The same applies to "acrylic acid" and "methacrylic acid", "acryloyl group" and "methacryloyl group", and "acryloyloxy group" and "methacryloyloxy group", and they are explained as concepts that include both by using "(meth)".

[0026] [Component (A)] Component (A) is a compound represented by the following formula (1), and when the coating composition contains component (A), the wear resistance and adhesion of the cured film are improved.

[0027] [Chemical formula]

[0028] In formula (1), R 1 , R 2 and R 3 are each independently an oxyalkylene group or a polyoxyalkylene group. The number of carbon atoms of the oxyalkylene group is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. The number of carbon atoms of the polyoxyalkylene group per repeating unit is also preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. Further, the number of repeating units of the oxyalkylene group in the polyoxyalkylene group is preferably in the range of 1 to 10. Note that the oxygen atom of the oxyalkylene group and the terminal oxygen atom in the polyoxyalkylene group are bonded to X 1 , X 2 or X 3 in the formula.

[0029] X 1 , X 2 and X 3 are each independently CH2=CR 4 -CO-, CH2=CR 4 -CO(O(CH2)5-CO) a1- represents a hydrogen atom or an alkyl group, where X 1 ~X 3 At least two of them are CH2=CR 4 -CO- or CH2=CR 4 -CO(O(CH2)5-CO) a1 -. That is, compound (1) is a bifunctional or trifunctional (meth)acrylate. R 4 represents a hydrogen atom or a methyl group, and a plurality of R 4 may be the same or different, but a hydrogen atom is preferred. a1 is an integer of 1 or more, preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1. Among them, X 1 , X 2 and X 3 are preferably CH2=CR 4 -CO-, CH2=CR 4 -CO(O(CH2)5-CO) a1 - or a hydrogen atom, and it is more preferable that at least two of X 1 ~X 3 are CH2=CR 4 -CO-, and it is particularly preferable that all three are CH2=CR 4 -CO-.

[0030] Particularly preferred compound (1) includes a compound represented by the following formula (1-1). In the following formula, R 4 is the same as above, and R 1’ ~R 3’ is an alkylene group having 1 to 5 (preferably 1 to 3) carbon atoms.

[0031]

Chemical formula

[0032] Specific structures of component (A) include bis(2-acryloyloxyethyl)hydroxyethyl isocyanurate, tris(2-acryloyloxyethyl) isocyanurate (manufactured by Toagosei Co., Ltd., trade names Aronix M-313, Aronix M-315, manufactured by Shin-Nakamura Chemical Co., Ltd., trade names NK Ester A9300, A9300S, manufactured by Arkema, SR368, SR368NS), bis(2-acryloyloxypropyl)hydroxyethyl isocyanurate, tris(2-acryloyloxypropyl) isocyanurate, tris(2-acryloyloxyethyl) isocyanurate modified with one caprolactone per molecule (manufactured by Toagosei Co., Ltd., trade name Aronix M-325), tris(2-acryloyloxyethyl) isocyanurate modified with three caprolactones per molecule (manufactured by Toagosei Co., Ltd., trade name Aronix M-327), and the like.

[0033] Component (A) may be used alone as one kind of compound, or in combination of two or more kinds. The content of component (A) is preferably 1 to 85% by mass, more preferably 2.5 to 70% by mass, still more preferably 5 to 50% by mass, and particularly preferably 8 to 20% by mass in 100% by mass of the total solid content of components (A) to (C). By setting it above the above lower limit value, the wear resistance and adhesion are further improved, and by setting it below the above upper limit value, the weather resistance and chemical resistance are further improved.

[0034] [Component (B)] Component (B) is a compound represented by formula (2), and the weather resistance and adhesion of the cured film are improved by the coating composition containing component (B).

[0035] [Chemical formula]

[0036] In formula (2), R 21 ~R 25 are each independently a group having a polymerizable group. R 21 ~R 25The polymerizable group it has is preferably a (meth)acryloyl group (CH2=CR 4 -CO-(R 4 is the same as described above).), and R 21 ~R 25 is preferably a combination of a (meth)acryloyl group and a divalent linking group. R 21 ~R 25 Examples of the divalent linking group that R

[0037] has include an alkylene group having 1 to 30 carbon atoms which may have a substituent, an oxyalkylene group having 1 to 30 carbon atoms which may have a substituent, -O-, -C(=O)-O-, -O-C(=O)-, -C(=O)-, -O-C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-, -C(=NH)-NH- and -NH-C(=NH)-, and combinations thereof. Note that the hydrogen atoms of the groups listed as the divalent linking group may be substituted with an alkyl group, an alkoxy group, an acyl group, etc.

[0037] [[ID=********]] n1 to n2 are each independently 0 or 1. L 21 ~L 22 are each independently a divalent linking group. L 21 ~L 22 The divalent linking group of L Examples of caprolactone-modified diols include "Placcel 205", a polycaprolactone diol with a mass average molecular weight of 530; "Placcel 205BA", a polycaprolactone diol with a mass average molecular weight of 530 and a carboxyl group in its side chain; "Placcel L205AL", a polycaprolactone diol with a mass average molecular weight of 500 that is a liquid at room temperature; "Placcel 205H", a polycaprolactone diol with a mass average molecular weight of 530 and improved water resistance compared to Placcel 205; "Placcel 205U", a polycaprolactone diol with a mass average molecular weight of 530 and lower viscosity and acid value compared to Placcel 205; "Placcel 208", a polycaprolactone diol with a mass average molecular weight of 830; "Placcel L208AL", a polycaprolactone diol with a mass average molecular weight of 830 that is a liquid at room temperature; "Placcel 210", a polycaprolactone diol with a mass average molecular weight of 1000; "Placcel 210BA", a polycaprolactone diol with a mass average molecular weight of 1000 and a carboxyl group in its side chain; "Placcel 210CP", a polycaprolactone diol with a mass average molecular weight of 1000, lower acid value and improved water resistance compared to Placcel 210; "Placcel 210N", a polycaprolactone diol with a mass average molecular weight of 1000 and a narrower molecular weight distribution compared to Placcel 210; "Placcel 212", a polycaprolactone diol with a mass average molecular weight of 1250; "Placcel L212AL", a polycaprolactone diol with a mass average molecular weight of 1250 that is a liquid at room temperature; "Placcel 220", a polycaprolactone diol with a mass average molecular weight of 2000; "Placcel 220BA", a polycaprolactone diol with a mass average molecular weight of 2000 and a carboxyl group in its side chain; "Placcel 220CPB", a polycaprolactone diol with a mass average molecular weight of 2000, lower acid value and improved water resistance compared to Placcel 220; "Placcel 220N", a polycaprolactone diol with a mass average molecular weight of 2000 and a narrower molecular weight distribution compared to Placcel 220; "Placcel 220NP1", a polycaprolactone diol with a mass average molecular weight of 2000 and lower crystallinity compared to Placcel 220."Placcel L220AL", which is a polycaprolactone diol with a mass average molecular weight of 2,000 for a normal temperature liquid; "Placcel 230", which is a polycaprolactone diol with a mass average molecular weight of 3,000; "Placcel L230AL", which is a polycaprolactone diol with a mass average molecular weight of 3,000 for a normal temperature liquid; "Placcel 230CP", which is a polycaprolactone diol with a mass average molecular weight of 3,000 and a lower acid value and improved water resistance compared to Placcel 230; "Placcel 240", which is a polycaprolactone diol with a mass average molecular weight of 4,000; "Placcel 240CP", which is a polycaprolactone diol with a mass average molecular weight of 4,000 and a lower acid value and improved water resistance compared to Placcel 240; "Placcel 220EB", which is a polycaprolactone diol with a mass average molecular weight of 2,000 and improved hydrolysis resistance compared to Placcel 220; "Placcel 220EC", which is a polycaprolactone diol with a mass average molecular weight of 2,000 and excellent elastic recovery compared to Placcel 220EB (all are trade names, manufactured by Daicel Chemical Industries, Ltd.), etc. can be mentioned. Among them, from the viewpoints of the weather resistance and abrasion resistance of the obtained cured film, polycaprolactone diols with a mass average molecular weight in the range of 500 to 1,500 are preferred, and those in the range of 500 to 1,000 are more preferred. Furthermore, L 21 ~L 22 preferably has another linking group in addition to any one of the structures obtained by removing a hydroxyl group from either end of an alkylene diol, a caprolactone-modified diol, or polytetramethylene glycol. As the other linking group, those exemplified as "the divalent linking group that R 21 ~R 25 has" are preferred.

[0038] Z 21 ~Z 23 each independently has a structure represented by the following formula (2z).

[0039]

Chemical formula

[0040] In formula (2z), X 21 is an alkylene group having 2 to 17 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and even more preferably an alkylene group having 2 to 6 carbon atoms.

[0041] The * shown in formula (2z) is a bond, and when formula (2z) is Z in the above formula (2) 21 the bond * represented by B1 is R 21 the bond represented by B2 is L 21 or R 22 the bond represented by B3 is L 22 or R 23 and directly binds; when formula (2z) is Z in the above formula (2) 22 the bond * represented by B1 is L 22 the bond represented by B2 is R 24 the bond represented by B3 is R 23 and directly binds; when formula (2z) is Z in the above formula (2) 23 the bond * represented by B1 is L 21 the bond represented by B2 is R 22 the bond represented by B3 is R 25 and directly binds.

[0042] Z 1 is an oxygen atom or a nitrogen atom, and Z 2 is a hydrogen atom or -C(=O)-. However, when Z 1 is an oxygen atom (-O-), Z 2 becomes a hydrogen atom (-H). On the other hand, when Z 1 is a nitrogen atom, Z 2 becomes -C(=O)-, and the nitrogen atom of Z 1 and -C(=O)- of Z 2 combine to form a ring. That is, when Z 1 is an oxygen atom, formula (2z) has a structure having an allophanate bond, and when Z 1 is a nitrogen atom, formula (2z) has a structure having an isocyanurate bond.

[0043] Among them, as the compound (2), compounds represented by the following formulas (2-1) to (2-4) are preferred.

[0044] [Chemical]

[0045] [Chemical]

[0046] [Chemical]

[0047] [Chemical]

[0048] In formulas (2-1) to (2-4), R 26 is independently a hydrogen atom or a methyl group. In formulas (2-1) to (2-4), R 27 is independently an alkylene group having 2 to 10 carbon atoms (preferably 2 to 4 carbon atoms), R A -(O-CO-(CH2)5) n - or R A -(O-(CH2)4) n . R A represents an alkylene group, and an alkylene group having 2 to 4 carbon atoms is preferred. n independently represents an integer from 1 to 10, and an integer from 1 to 5 is preferred.

[0049] In formulas (2-1) to (2-4), X 22 is independently an alkylene group having 2 to 17 carbon atoms, preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 2 to 6 carbon atoms. In formulas (2-2) and (2-4), A1 is a structure obtained by removing a hydroxyl group from either end of alkylene diol, caprolactone-modified diol, or polytetramethylene glycol, and L 21 ~L22 is the same as that described above. A plurality of Rs in formulas (2-1) to (2-4) 26 , R 27 , X 22 may be the same as or different from each other.

[0050] Component (B) may be used alone as one kind of compound, or may be used in combination of two or more kinds. Among them, from the viewpoint of achieving a good balance of various properties, it is preferable to use two or more kinds of component (B) in combination. When using two or more kinds, it is preferable that component (B) contains component (B-1) and component (B-2). As component (B-1), at least one of the Rs in formula (2-1) or formula (2-3) is R 27 -(O-CO-(CH2)5) A -, or R n -(O-(CH2)4) A -, or a compound in which A1 in formula (2-2) or formula (2-4) has a structure obtained by removing a hydroxyl group from the end of polytetramethylene glycol or polycaprolactone diol. Examples of component (B-2) include a compound in which R in formula (2-1) or formula (2-3) is an alkylene group, or a compound in which A1 in formula (2-2) or formula (2-4) has a structure obtained by removing a hydroxyl group from the end of an alkylenediol. n Among them, a combination of component (B-1) represented by formula (2-1) and component (B-2) represented by formula (2-1) or (2-3), or a combination of component (B-1) represented by formula (2-2) and having a polycaprolactone structure for A1 and component (B-2) represented by formula (2-1) or formula (2-3) is preferable. 27 is an alkylene group, or a compound in which A1 in formula (2-2) or formula (2-4) has a structure obtained by removing a hydroxyl group from the end of an alkylenediol. Among them, a combination of component (B-1) represented by formula (2-1) and component (B-2) represented by formula (2-1) or (2-3), or a combination of component (B-1) represented by formula (2-2) and having a polycaprolactone structure for A1 and component (B-2) represented by formula (2-1) or formula (2-3) is preferable. When the (B) component contains the (B-1) component and the (B-2) component, the content of the (B-1) component is preferably 9 to 90% by mass, more preferably 20 to 70% by mass, still more preferably 30 to 60% by mass, and particularly preferably 45 to 60% by mass in 100% by mass of the total solid content of the (A) to (C) components. Further, the content of the (B-2) component is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, still more preferably 15 to 40% by mass, and particularly preferably 20 to 30% by mass in 100% by mass of the total solid content of the (A) to (C) components.

[0051] The content of the whole (B) component is preferably 14 to 98% by mass, more preferably 30 to 95% by mass, still more preferably 45 to 93% by mass, particularly preferably 60 to 90% by mass, and most preferably 70 to 85% by mass in 100% by mass of the total solid content of the (A) to (C) components. By setting the lower limit value or more, the weather resistance is improved, and by setting the upper limit value or less, the abrasion resistance is improved.

[0052] [(C) component] The (C) component is a compound containing 6 or more (meth)acryloyl groups in one molecule, and when the coating composition contains the (C) component, the abrasion resistance and chemical resistance of the cured film are improved. The (C) component is not particularly limited as long as it has 6 or more (meth)acryloyl groups in one molecule. For example, polyfunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and polypentaerythritol poly(meth)acrylate; urethane (meth)acrylate obtained by reacting an isocyanate compound with a (meth)acrylate compound, etc. may be mentioned.

[0053] As the polyfunctional (meth)acrylate as the (C) component, a compound represented by the following formula (3-0) is preferable.

[0054] [Chemical formula]

[0055] In formula (3-0), among the plurality of Rs 30 at least 6 represent CH2=CR B -COO-, and the remaining Rs 30 represent a hydroxyl group or CH2=CR B -COO-. R B represents a hydrogen atom or a methyl group. When R B is a hydrogen atom, the polymerizable unsaturated group is an acryloyl group, and when R B is a methyl group, it is a methacryloyl group. That is, the compound (3-0) has a pentaerythritol skeleton and is a polymerizable compound having six or more (meth)acryloyloxy groups, which are polymerizable unsaturated groups, in its structure. By having three or more polymerizable unsaturated groups, the crosslink density upon curing becomes high, and as a result, the abrasion resistance and chemical resistance can be improved. n30 represents an integer from 1 to 4, preferably an integer from 1 to 3, more preferably 1 or 2, and it is particularly preferred that n30 = 1 and the compound (3-0) has a dipentaerythritol skeleton. The compound (3-0) may be used alone or in combination of two or more.

[0056] The urethane (meth)acrylate as the component (C) can be obtained by reacting a (meth)acrylate compound having a hydroxyl group with an isocyanate compound.

[0057] As the (meth)acrylate compound having a hydroxyl group used in the production of urethane (meth)acrylate, a compound represented by the following formula (3-1) or (3-2) is preferred. In the following formula, R 31 ~R 32 each independently represents a hydrogen atom or a methyl group, and a plurality of Rs 31 , R 32 in the formula may be the same or different from each other.

[0058]

Chemical formula

[0059] In addition, as the isocyanate compound used in the production of urethane (meth) acrylate, an aliphatic polyisocyanate or an alicyclic polyisocyanate having two or more isocyanate groups is preferable. Specifically, aliphatic polyisocyanates such as 1,4-butanediisocyanate, 1,5-pentanediisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, etc., or dimers or trimers thereof; norbornane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, hydrogenated xylylene diisocyanate, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, etc. alicyclic polyisocyanates, or dimers or trimers thereof, etc. may be mentioned.

[0060] Among them, as the isocyanate compound, a triisocyanate compound represented by the following formula (3-3) or a diisocyanate compound represented by the following formula (3-4) is particularly preferable.

[0061]

Chemical formula

[0062] In the formula, X 31 ~X 32 each independently represents an alkylene group having 2 to 17 carbon atoms, and an alkylene group having 2 to 6 carbon atoms is preferable. A plurality of Xs 31 and X 32 in the formula may be the same as or different from each other. R 33 represents -R C -O-CO-CH=CH2, or the structure obtained by removing a hydroxyl group from the compound represented by the above formula (3-1) or (3-2), RC represents an alkylene group, and the number of carbon atoms in the alkylene group is preferably from 1 to 30, more preferably from 1 to 20, and particularly preferably from 1 to 10.

[0063] (C) The content of the whole component is preferably 1.0 to 20% by mass, more preferably 2.5 to 17.5% by mass, still more preferably 5.0 to 15% by mass, and particularly preferably 5.5 to 13% by mass in 100% by mass of the total solid content of the components (A) to (C). By setting it to be not less than the above lower limit value, the chemical resistance is improved, and by setting it to be not more than the above upper limit value, the weather resistance is improved.

[0064] [Other components] The composition of the present invention may optionally contain other components other than the above components (A) to (C) within the range where the effects of the present invention can be obtained. Examples of the other components include reactive compounds, organic solvents, various resins, fillers, polymerization initiators, stabilizers, ultraviolet absorbers, leveling agents. Further, it may also contain inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, catalysts, surfactants, flow regulators, coupling agents, dyes, rheology control agents, antioxidants, plasticizers, etc.

[0065] As the reactive compound, a (meth)acrylate compound other than the components (A) to (C) or a compound having a double bond such as a vinyl group may be blended. Examples of the (meth)acryloyl-based compound include monofunctional (meth)acrylate and 2- to 5-functional (meth)acrylate that do not correspond to the components (A) to (C).

[0066] Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates having an alkyl group with 1 to 22 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc.; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc.; ω-alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, etc.; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate (e.g., trade name "Placcel" manufactured by Daicel Chemical Industries, Ltd.), polycarbonate-modified hydroxy (meth)acrylate, mono(meth)acrylate of polyester diol obtained from phthalic acid and propylene glycol, mono(meth)acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, (meth)acrylic acid adducts of various epoxy esters, and the like.

[0067] Examples of bifunctional to pentafunctional (meth)acrylates include Di(meth)acrylates of dihydric alcohols such as 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate; Polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di(meth)acrylate of tris(2-hydroxyethyl) isocyanurate, di(meth)acrylate of diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol, di(meth)acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, di(meth)acrylate or tri(meth)acrylate obtained by reacting 2 - 3 moles of acrylic acid with 1 mole of tris(2-hydroxyethyl) isocyanurate, trimethylolpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate modified with ethylene oxide, polypropylene glycol di(meth)acrylate modified with propylene oxide, polytetramethylene glycol di(meth)acrylate modified with tetramethylene oxide, glycerol tri(meth)acrylate modified with ethylene oxide, glycerol tri(meth)acrylate modified with propylene oxide, ditrimethylolpropane tetra(meth)acrylate, hydroxypivalic acid-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate modified with ethylene oxide, trimethylolpropane tri(meth)acrylate modified with propylene oxide, tri(meth)acrylate phosphate modified with ethylene oxide, pentaerythritol tetra(meth)acrylate modified with ethylene oxide, pentaerythritol tetra(meth)acrylate modified with propylene oxide, pentaerythritol tetra(meth)acrylate modified with tetraethylene oxide, polyester (meth)acrylate compound synthesized by condensation reaction of polyhydric alcohol, (meth)acrylic acid and polyfunctional carboxylic acidExamples of the epoxy (meth)acrylate compound, acrylate acrylate compound, etc. synthesized by the addition reaction of a novolac type epoxy resin, a glycidyl group-containing acrylic polymer, and (meth)acrylic acid are given.

[0068] The reactive compound may be used alone or in combination of two or more. The amount of the reactive compound used is preferably 0 to 300% by mass based on 100% by mass of the total solid content of components (A) to (C).

[0069] Examples of the organic solvent include ester solvents, ketone solvents, ether solvents, aliphatic solvents, aromatic solvents, and alcohol solvents. Specifically, examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate, examples of the ketone solvent include acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, etc., examples of the ether solvent include tetrahydrofuran, dioxolane, etc., examples of the aliphatic solvent include hexane, cyclohexane, etc., examples of the aromatic solvent include toluene, xylene, etc., and examples of the alcohol solvent include ethanol, methanol, propanol, butanol, propylene glycol monomethyl ether, etc. The composition of the present invention may be a solventless composition containing no organic solvent or a high solid content composition with a relatively low content of the organic solvent. By making it solventless or low solvent / high solid content, reduction of the environmental load due to reduction of the volatile organic compound (VOC) amount can be achieved. Here, the high solid content composition refers to, for example, a composition in which the content of the organic solvent is 30% by mass or less in the total amount of the composition.

[0070] Also, a liquid organic polymer may be used for viscosity adjustment. The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction. For example, carboxyl group-containing polymer modified products (Floren G-900, NC-500: Kyoeisha), acrylic polymers (Floren WK-20: Kyoeisha), amine salts of special modified phosphate esters (HIPLAAD ED-251: Kusumoto Chemicals), modified acrylic block copolymers (DISPERBYK2000; BYK Chemie), and the like can be mentioned.

[0071] As various resins, thermosetting resins and thermoplastic resins can be used. A thermosetting resin is a resin having a property that it can be substantially insolubilized and infusibilized when cured by heating or by means such as radiation or a catalyst. Specific examples thereof include phenol resins, urea resins, melamine resins, benzoguanamine resins, alkyd resins, unsaturated polyester resins, vinyl ester resins, diallyl terephthalate resins, epoxy resins, silicone resins, urethane resins, furan resins, ketone resins, xylene resins, thermosetting polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, styrene maleic anhydride (SMA) resins, and the like. These thermosetting resins can be used alone or in combination of two or more.

[0072] A thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyetheretherketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndiotactic polystyrene resin, cyclic polyolefin resin, and the like. These thermoplastic resins can be used alone or in combination of two or more.

[0073] As the filler, for example, silica can be blended for the purpose of improving wear resistance. There is no limitation on the silica, and known silica fine particles such as powdery silica, colloidal silica, and nanosilica can be used. Examples of commercially available powdery silica fine particles include Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., E220A, E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Chemical Ltd., SG Flake manufactured by Nippon Sheet Glass Co., Ltd., and the like. Examples of commercially available colloidal silica include methanol silica sol, IPA-ST, MEK-ST, PGM-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. manufactured by Nissan Chemical Industries, Ltd.

[0074] Silica may be reactive silica. Examples of the reactive silica include reactive compound-modified silica. Examples of the reactive compound include reactive silane coupling agents having a hydrophobic group, compounds having a (meth)acryloyl group, compounds having a maleimide group, and compounds having a glycidyl group. Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50, R711, etc. manufactured by Nippon Aerosil Co., Ltd., and examples of commercially available colloidal silica modified with a compound having a (meth)acryloyl group include MIBK-SD, MIBK-SD-L, MIBK-AC-2140Z, MEK-AC-2140Z, etc. manufactured by Nissan Chemical Industries, Ltd. Also, silica obtained by adding acrylic acid after modification with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane, and silica modified with a product obtained by urethanization reaction of 3-isocyanatopropyltriethoxysilane, a hydroxyl group, and a compound having a (meth)acryloyl group are also mentioned as reactive silica.

[0075] The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or irregularly shaped ones can be used. For example, as commercially available hollow silica fine particles, Silanax manufactured by Nippon Steel Mining Co., Ltd. etc. can be used. Also, the primary particle diameter is preferably in the range of 5 to 200 nm. When it is 5 nm or more, the dispersion of the inorganic fine particles in the composition becomes sufficient, and when it is 200 nm or less, sufficient strength of the cured product can be maintained. The compounding amount of silica is preferably 3 to 60% by mass in 100% by mass of the composition.

[0076] Examples of fillers other than silica include inorganic fillers and organic fillers. The filler shape is not limited, and particulate, plate-shaped, or fibrous fillers can be mentioned. Examples of fillers with excellent heat resistance include alumina, magnesia, titania, zirconia, etc.; examples of those with excellent heat conductivity include boron nitride, aluminum nitride, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc.; examples of those with excellent conductivity include metallic fillers and / or metal-coated fillers using simple metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); examples of those with excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, etc., and potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; examples of those with a high refractive index include barium titanate, zirconia oxide, titanium oxide, etc.; examples of those exhibiting photocatalytic properties include photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, ruthenium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc., composites of the above metals, and their oxides, etc.; examples of those with excellent abrasion resistance include metals such as alumina, zirconia, magnesium oxide, etc., and their composites and oxides, etc.; examples of those with excellent conductivity include metals such as silver, copper, etc., tin oxide, indium oxide, etc.; examples of those with excellent ultraviolet shielding properties include titanium oxide, zinc oxide, etc. These inorganic fine particles may be appropriately selected according to the application and may be used alone or in combination of multiple types. In addition, since the above inorganic fine particles have various properties other than the properties listed in the examples, they may be selected according to the application in a timely manner.

[0077] Examples of inorganic fibers include carbon fibers, glass fibers, boron fibers, alumina fibers, silicon carbide fibers (silicon carbide fibers), etc., as well as activated carbon fibers, graphite fibers, tungsten carbide fibers, ceramic fibers, natural fibers, mineral fibers such as basalt, boron nitride fibers, boron carbide fibers, and metal fibers. Examples of the above metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

[0078] Examples of the organic fiber include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate; natural fibers such as cellulose, pulp, cotton, wool, and silk; and regenerated fibers such as protein, polypeptide, and alginic acid.

[0079] The blending amount of the filler is preferably 3 to 60% by mass in 100% by mass of the composition.

[0080] Since the composition of the present invention is cured by active energy rays, it is preferable to use a polymerization initiator, particularly a photopolymerization initiator. Known photopolymerization initiators may be used. For example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used.

[0081] Specific examples of the photoinitiator include acetophenone compounds such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-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]phenyl}-2-methyl-propan-1-one; benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, and 4-benzoyl-4'-methyl-diphenyl sulfide; α-ketoester compounds such as methyl benzoylformate, 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester of oxyphenylacetic acid, and 2-(2-hydroxyethoxy)ethyl ester of oxyphenylacetic acid; phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; titanocene compounds; acetophenone / benzophenone hybrid photoinitiators such as 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfinyl)propan-1-one; oxime ester photoinitiators such as 2-(O-benzoyloxime)-1-[4-(phenylthio)]-1,2-octanedione; and camphorquinone and the like.

[0082] The photoinitiator may be used alone or in combination of two or more. The amount of the photoinitiator used is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, based on 100% by mass of the composition.

[0083] For the purpose of improving the weather resistance, the composition of the present invention may contain an ultraviolet absorber. Various compounds or substances can be used as the ultraviolet absorber. Specific examples of the ultraviolet absorber include benzotriazine-based ultraviolet absorbers such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl-hexyloxy)propyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyryloxyphenyl)-6-(2,4-bis-butyryloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; Benzotriazole-based ultraviolet absorbers such as 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; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, cyanoacrylate-based ultraviolet absorbers such as ethyl 2-cyano-3,3-diphenylacrylate, octyl 2-cyano-3,3-diphenylacrylate, inorganic fine particles that absorb ultraviolet rays such as titanium oxide fine particles, zinc oxide fine particles, and tin oxide fine particles, etc. are mentioned. The above-listed ultraviolet absorbers may be used alone or in combination of two or more.

[0084] Commercially available products can also be used as the ultraviolet absorber. Commercially available products include TINUVIN PS, TINUVIN 99-2, TINUVIN234, TINUVIN326, TINUVIN329, TINUVIN900, TINUVIN928, TINUVIN360, TINUVIN384-2, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (manufactured by BASF above); AdekaStab LA-46, AdekaStab LA-F70, AdekaStab LA-29, AdekaStab LA-31G, AdekaStab LA-32, AdekaStab LA-36 (manufactured by ADEKA above); RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) can be used.

[0085] From the viewpoint of improving weather resistance, a benzotriazine-type ultraviolet absorber or an ultraviolet absorber having a (meth)acryloyl group is preferred. Preferably, TINUVIN400, TINUVIN405, TINUVIN479 (manufactured by BASF above); AdekaStab LA-46 (manufactured by ADEKA), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) are preferred.

[0086] The amount of the ultraviolet absorber used is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the composition.

[0087] For the purpose of improving the weather resistance, the composition of the present invention may be blended with a hindered amine light stabilizer (HALS). As the hindered amine light stabilizer, known hindered amine light stabilizers can be used. Specifically, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-pentyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-heptyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-nonyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(4-methoxybenzylidene) malonate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, the condensate of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol, the condensate of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-pentamethyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol, etc. can be mentioned.

[0088] Hindered amine light stabilizers can also be commercially available products. Commercially available products include TINUVIN 123, TINUVIN 292, TINUVIN 152, TINUVIN 144, TINUVIN 622SF, TINUVIN 111FDL, TINUVIN 249 (manufactured by BASF); Adeka Stab LA-52, Adeka Stab LA-57, Adeka Stab LA-63P, Adeka Stab LA-68, Adeka Stab LA-72, Adeka Stab LA-81, Adeka Stab LA-82, Adeka Stab LA-87 (manufactured by ADEKA) can be used.

[0089] From the viewpoint of improving weather resistance, hindered amine light stabilizers having no (meth)acryloyl group are preferred. Preferably, TINUVIN 123, TINUVIN 152, TINUVIN 144 (manufactured by BASF); Adeka Stab LA-52, Adeka Stab LA-57, Adeka Stab LA-63P, Adeka Stab LA-68, Adeka Stab LA-72, Adeka Stab LA-81 (manufactured by ADEKA) are preferred. More preferably, TINUVIN 123, TINUVIN 152 (manufactured by BASF); Adeka Stab LA-63P, Adeka Stab LA-68, Adeka Stab LA-72, Adeka Stab LA-81 (manufactured by ADEKA).

[0090] The amount of the hindered amine light stabilizer used is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the composition.

[0091] For the purpose of enhancing the leveling property during coating or enhancing the slidability of the cured film to improve scratch resistance, various surface modifiers may be added to the composition of the present invention. As the surface modifier, various additives for modifying surface physical properties, which are commercially available under names such as surface conditioner, leveling agent, slip property imparting agent, antifouling property imparting agent, etc., can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specifically, silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain, etc. may be mentioned. One or more of these may be used. For the purpose of enhancing the durability of slipperiness, etc., those containing a (meth)acryloyl group in the molecule may be used. Specific surface modifiers include EBECRYL350 (Daicel Ornex Co., Ltd.), BYK-333 (BYK-Chemie Japan Co., Ltd.), BYK-377 (BYK-Chemie Japan Co., Ltd.), BYK-378 (BYK-Chemie Japan Co., Ltd.), BYK-UV3500 (BYK-Chemie Japan Co., Ltd.), BYK-UV3505 (BYK-Chemie Japan Co., Ltd.), BYK-UV3576 (BYK-Chemie Japan Co., Ltd.), Megafac RS-75 (DIC Corporation), Megafac RS-76-E (DIC Corporation), Megafac RS-72-K (DIC Corporation), Megafac RS-76-NS (DIC Corporation), Megafac RS-90 (DIC Corporation), Megafac RS-91 (DIC Corporation), Megafac RS-55 (DIC Corporation), Optool DAC-HP (Daikin Industries, Ltd.), ZX-058-A (T&K TOKA Co., Ltd.), ZX-201 (T&K TOKA Co., Ltd.), ZX-202 (T&K TOKA Co., Ltd.), ZX-212 (T&K TOKA Co., Ltd.), ZX-214-A (T&K TOKA Co., Ltd.), X-22-164AS (Shin-Etsu Chemical Co., Ltd.), X-22-164A (Shin-Etsu Chemical Co., Ltd.), X-22-164B (Shin-Etsu Chemical Co., Ltd.), X-22-164C (Shin-Etsu Chemical Co., Ltd.), X-22-164E (Shin-Etsu Chemical Co., Ltd.), X-22-174DX (Shin-Etsu Chemical Co., Ltd.), etc.

[0092] The active energy ray-curable coating composition of the present invention can be suitably used as a cured film for protecting a substrate by irradiating active energy rays after coating at least one surface of various materials. The cured film formed from the composition of the present invention has high chemical resistance while having weather resistance and abrasion resistance, and excellent adhesion to various materials even under harsh environments such as high temperature and high humidity. Therefore, when used as a protective film for materials that are used for a long time in harsh environments such as outdoors and around automobiles, it exhibits excellent effects.

[0093] <Molded article>

[0094] (Structure and materials) The molded article of the present invention has a cured film of the active energy ray-curable coating composition of the present invention and a substrate. The substrate is not particularly limited and may be appropriately selected according to the application. Examples include plastics, wood, metals (such as steel, stainless steel, and aluminum), metal oxides, paper, silicon, or modified silicon. A substrate obtained by joining different materials, or a substrate on which this composition or another composition is laminated as a primer may also be used. The shape of the substrate is also not particularly limited and may be any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape having curvature (bending) on the entire surface or a part thereof. Also, there are no restrictions on the hardness, thickness, etc. of the substrate.

[0095] The active energy ray-curable coating composition of the present invention has excellent adhesion to plastic substrates (resin substrates). As described above, since resin materials have disadvantages such as low abrasion resistance, easy loss of gloss and transparency, and poor weather resistance, these disadvantages can be improved by coating with the composition of the present invention. The plastic substrate is not particularly limited as long as it is made of resin. For example, the above-mentioned thermosetting resins or thermoplastic resins may be used. The substrate may be a single resin or a substrate containing a plurality of types of resins, and may have a single-layer or multi-layer laminated structure. Also, these plastic substrates may be fiber-reinforced (FRP). When obtaining a transparent molded article, it is preferable to use a plastic substrate such as a polycarbonate resin (e.g., aliphatic polycarbonate, aromatic polycarbonate, alicyclic polycarbonate, etc.), polymethyl methacrylate resin, polystyrene resin, etc.

[0096] In addition, the substrate may contain known additives such as antistatic agents, antifogging agents, antiblocking agents, ultraviolet absorbers, antioxidants, pigments, organic fillers, inorganic fillers, light stabilizers, crystal nucleating agents, lubricants, etc., as long as the effects of the present invention are not inhibited.

[0097] The molded article of the present invention may further have a second substrate on the substrate and the cured film. The second substrate is not particularly limited in terms of material, and examples include wood, metal, metal oxide, plastic, paper, silicon or modified silicon, etc., and a substrate obtained by joining different materials may also be used. The shape of the substrate is not particularly limited, and it may be any shape according to the purpose, such as a flat plate, sheet-like, or having a curvature on the entire or part of the three-dimensional shape. Also, there are no restrictions on the hardness, thickness, etc. of the substrate.

[0098] Since the molded article of the present invention has high adhesion to both plastics and inorganic substances, it can also be preferably used as an interlayer material for different materials. Particularly preferably, the substrate is plastic and the second substrate is an inorganic layer. Examples of the inorganic layer include quartz, sapphire, glass, optical film, ceramic material, inorganic oxide, vapor deposition film (CVD, PVD, sputtering), magnetic film, reflective film, metals such as Ni, Cu, Cr, Fe, stainless steel, paper, SOG (Spin On Glass), SOC (Spin On Carbon), plastic layers such as polyester, polycarbonate, polyimide, TFT array substrate, electrode plate of PDP, conductive substrates such as ITO and metal, insulating substrates, silicon-based substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc.

[0099] (Manufacturing method) The molded article of the present invention is obtained by coating the surface of the substrate with the composition of the present invention. The coating of the substrate may be carried out by a method of directly applying or directly molding the composition onto the substrate and then curing it, or it may also be a method of laminating the cured product of the composition. In the case of direct coating, the coating method is not particularly limited, and examples include spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, screen printing method, inkjet method, etc. In the case of direct molding, examples include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding, etc. When laminating the cured product of the composition, a semi-cured product may be laminated on the substrate and then fully cured, or a fully cured product may be laminated on the substrate.

[0100] Since the composition of the present invention contains a compound having a polymerizable unsaturated group, it can be cured by irradiating active energy rays. Active energy rays include ionizing radiations such as ultraviolet rays, electron beams, α-rays, β-rays, γ-rays, etc. Among these, ultraviolet rays (UV) are particularly preferable from the viewpoints of curability and convenience. Here, when using ultraviolet rays as the active energy rays, examples of the apparatus for irradiating the ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, black light lamps, mercury-xenon lamps, short arc lamps, helium-cadmium lasers, argon lasers, sunlight, LED lamps, etc. By irradiating the applied or molded composition with ultraviolet rays having a wavelength of about 180 to 400 nm using these, it is possible to obtain a cured film or a cured product. The irradiation amount of ultraviolet rays is appropriately selected according to the type and amount of the photoinitiator used.

[0101] In addition, since the molded article of the present invention is excellent in workability even after the active energy ray-curable coating composition has cured to form a cured film, it can be bent together with the substrate. For example, after directly applying the coating composition to a flat substrate to obtain a coated substrate, and then irradiating the coating film with active energy rays to obtain a substrate with a cured film (i.e., a molded article which is a laminate), bending can still be performed. Therefore, there is no need to take special consideration when applying the coating composition to a curved substrate, and the productivity of the bent processed material can be significantly improved. Further, the molded article of the present invention is not only extremely excellent in flexibility under heating, but also excellent in hard coat properties after thermoforming. When performing bending, the thickness of the coating film formed by applying the composition of the present invention is preferably 0.5 to 40 μm, more preferably 3 to 35 μm, still more preferably 5 to 30 μm, and particularly preferably 10 to 25 μm. By setting the thickness to be equal to or greater than the above lower limit value, abrasion resistance and weather resistance can be sufficiently exhibited, and by setting the thickness to be equal to or less than the above upper limit value, flexibility can be improved.

[0102] The method of bending is not particularly limited, and in addition to the bending process of directly bending the laminate, processing methods such as press molding, free blow molding, vacuum molding, pressure air molding, and twin composite molding can be mentioned. For thermoforming, 80°C or higher is preferable, and 150°C or higher is more preferable. Also, the upper limit temperature can be appropriately set to be less than the melting temperature of the substrate.

[0103] (Use) Since the molded article of the present application is excellent in weather resistance, abrasion resistance, chemical resistance, and adhesion, it can be particularly preferably used as various protective materials. For example, it can be used for building materials, housing equipment, transportation equipment such as automobiles, ships, aircraft, and railways, electronic materials, recording materials, optical materials, lighting, packaging materials, protection of outdoor installations, optical fiber coating, resin glass protection, etc., and is particularly suitable for use in automotive headlamp lens applications, automotive glazing applications, automotive body exterior applications, plastic applications for building materials, and steel plate applications for building materials.

Examples

[0104] Hereinafter, the present invention will be described more specifically using Examples and Comparative Examples, but the present invention is not limited to the following aspects. In addition, in this Example, "parts" and "%" are based on mass unless otherwise specified.

[0105] (Synthesis Example 1: Synthesis of UA-1) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Burnock DN-902S" manufactured by DIC (NCO equivalent: 23.5 wt%, 178.72 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.84 parts by mass), methoxyhydroquinone (0.084 parts by mass), and dibutyltin diacetate (0.084 parts by mass) were added, and the temperature was raised to 70 °C. 2-Hydroxyethyl acrylate (77.4 parts by mass) and "PTMG-1000" manufactured by Mitsubishi Chemical Corporation (hydroxyl value: 113.95, 164.11 parts by mass) were charged in portions over 1 hour. After the charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappeared. represented by the following structural formula A urethane resin UA-1 having a (meth)acryloyl group was obtained. presumed to be . [Chemical formula]

[0106] (Synthesis Example 2: Synthesis of UA-2) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Burnock DN-902S" manufactured by DIC (NCO equivalent: 23.5 wt%, 178.72 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.84 parts by mass), methoxyhydroquinone (0.084 parts by mass), and dibutyltin diacetate (0.084 parts by mass) were added, and the temperature was raised to 70 °C. 2-Hydroxyethyl acrylate (77.4 parts by mass) and "Placcel-210" manufactured by Daicel Corporation (hydroxyl value: 113.4, 164.90 parts by mass) were charged in portions over 1 hour. After the charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappeared. represented by the following structural formula A urethane resin UA-2 having a (meth)acryloyl group was obtained.presumed to be .

Chem.

[0107] (Synthesis Example 3: Synthesis of UA-3) To a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Barnock DN-902S" manufactured by DIC (NCO equivalent: 23.5 wt%, 178.72 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.05 parts by mass), methoxyhydroquinone (0.11 parts by mass), and dibutyltin diacetate (0.11 parts by mass) were added. The temperature was raised to 70 °C, and Placcel FA-2D (344.0 parts by mass) was charged in portions over 1 hour. After the charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm-1 indicating isocyanate groups disappeared, represented by the following structural formula to obtain a urethane resin UA-3 having a (meth)acryloyl group presumed to be .

Chem.

[0108] (Synthesis Example 4: Synthesis of UA-4) To a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Basonat® HA 3000" manufactured by BASF (NCO equivalent: 19.5 wt%, 213.39 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.91 parts by mass), methoxyhydroquinone (0.09 parts by mass), and dibutyltin diacetate (0.09 parts by mass) were added. The temperature was raised to 70 °C, and 2-hydroxyethyl acrylate (77.4 parts by mass) and "PTMG-1000" manufactured by Mitsubishi Chemical Corporation (hydroxyl value: 113.95 〇〇 parts by mass) were charged in portions over 1 hour. After the charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm-1 indicating isocyanate groups disappeared, represented by the following structural formula to obtain a urethane resin UA-4 having a (meth)acryloyl group presumed to be .

Chem.

[0109] (Synthesis Example 5: Synthesis of UA-5) To a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, add "Basonat® HA 3000" manufactured by BASF (NCO equivalent 19.5 wt%, 213.39 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.91 part by mass), methoxyhydroquinone (0.09 part by mass), and dibutyltin diacetate (0.09 part by mass). Heat the temperature to 70°C, and add 2-hydroxyethyl acrylate (77.4 parts by mass) and "Placcel-210" manufactured by Daicel Corporation (hydroxyl value: 113.4, 164.90 parts by mass) in portions over 1 hour. After the addition, carry out the reaction at 80°C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappears, represented by the following structural formula A urethane resin UA-5 having a (meth)acryloyl group was obtained presumed to be . [Chemical formula]

[0110] (Synthesis Example 6: Synthesis of UA-6) To a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, add "Basonat® HA 3000" manufactured by BASF (NCO equivalent 19.5 wt%, 213.39 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.12 parts by mass), methoxyhydroquinone (0.11 part by mass), and dibutyltin diacetate (0.11 part by mass). Heat the temperature to 70°C, and add Placcel FA-2D (344.0 parts by mass) in portions over 1 hour. After the addition, carry out the reaction at 80°C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappears, represented by the following structural formula A urethane resin UA-6 having a (meth)acryloyl group was obtained presumed to be . [Chemical formula]

[0111] (Synthesis Example 7: Synthesis of UA-7) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Barnock DN-902S" manufactured by DIC (NCO equivalent 23.5 wt%, 178.72 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.59 parts by mass), methoxyhydroquinone (0.06 parts by mass), and dibutyltin diacetate (0.06 parts by mass) were added. The temperature was raised to 70°C, and 2-hydroxyethyl acrylate (116.2 parts by mass) was charged in portions over 1 hour. After the charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappeared, represented by the following structural formula and a urethane resin UA-7 having a (meth)acryloyl group was obtained presumed to be . [Chemical formula]

[0112] (Synthesis Example 8: Synthesis of UA-8) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Barnock DN-902S" manufactured by DIC (NCO equivalent 23.5 wt%, 178.72 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.51 parts by mass), methoxyhydroquinone (0.05 parts by mass), and dibutyltin diacetate (0.05 parts by mass) were added. The temperature was raised to 70°C, and 2-hydroxyethyl acrylate (77.4 parts by mass) and "MPD (3-methyl-1,5-pentanediol)" manufactured by Kuraray Co., Ltd. (19.70 parts by mass) were charged in portions over 1 hour. After the charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappeared, represented by the following structural formula and a urethane resin UA-8 having a (meth)acryloyl group was obtained presumed to be . [Chemical formula]

[0113] (Synthesis Example 9: Synthesis of UA-9) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Barnock DN-902S" manufactured by DIC (NCO equivalent 23.5 wt%, 178.72 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.65 parts by mass), methoxyhydroquinone (0.07 parts by mass), and dibutyltin diacetate (0.07 parts by mass) were added, the temperature was raised to 70 °C, and 4-hydroxybutyl acrylate (144.2 parts by mass) was charged in portions over 1 hour. After charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappeared, represented by the following structural formula a urethane resin UA-9 having a (meth)acryloyl group was obtained presumed to be .

Chemical formula

[0114] (Synthesis Example 10: Synthesis of UA-10) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Basonat® HA 3000" manufactured by BASF (NCO equivalent 19.5 wt%, 213.39 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.66 parts by mass), methoxyhydroquinone (0.07 parts by mass), and dibutyltin diacetate (0.07 parts by mass) were added, the temperature was raised to 70 °C, and 2-hydroxyethyl acrylate (116.2 parts by mass) was charged in portions over 1 hour. After charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappeared, represented by the following structural formula a urethane resin UA-10 having a (meth)acryloyl group was obtained presumed to be .

Chemical formula

[0115] (Synthesis Example 11: Synthesis of UA-11) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Basonat® HA 3000" manufactured by BASF (NCO equivalent 19.5 wt%, 213.39 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.72 parts by mass), methoxyhydroquinone (0.07 parts by mass), and dibutyltin diacetate (0.07 parts by mass) were added. The temperature was raised to 70°C, and 4-hydroxybutyl acrylate (144.2 parts by mass) was charged in portions over 1 hour. After the charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappeared, represented by the following structural formula urethane resin UA-11 having a (meth)acryloyl group was obtained presumed to be . [Chemical formula]

[0116] (Synthesis Example 12: UA-12) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Desmodur I" manufactured by Covestro (111.15 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.94 parts by mass), methoxyhydroquinone (0.09 parts by mass), and dibutyltin diacetate (0.09 parts by mass) were added. The temperature was raised to 70°C, and "Aronix M-306 (hydroxyl value 157.2)" manufactured by Toagosei Co., Ltd. (356.87 parts by mass) was charged in portions over 1 hour. After the charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappeared, represented by the following structural formula urethane resin UA-12 having a (meth)acryloyl group was obtained presumed to be . [Chemical formula]

[0117] (Synthesis Example 13: UA-13) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Desmodul H" (84.10 parts by mass) manufactured by Covestro, 2,6-di-tert-butyl-4-methylphenol (1.39 parts by mass), methoxyhydroquinone (0.14 parts by mass), and dibutyltin diacetate (0.14 parts by mass) were added, and the temperature was raised to 70 °C. "Aronix M-403 (hydroxyl value 92)" manufactured by Toagosei Co., Ltd. (609.78 parts by mass) was charged in portions over 1 hour. After charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm-1 indicating isocyanate groups disappeared, represented by the following structural formula UA-13 having a (meth)acryloyl group was obtained presumed to be 。

Chemical formula

[0118] (Synthesis Example 14: UA-14) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Desmodul I" (111.15 parts by mass) manufactured by Covestro, 2,6-di-tert-butyl-4-methylphenol (1.44 parts by mass), methoxyhydroquinone (0.14 parts by mass), and dibutyltin diacetate (0.14 parts by mass) were added, and the temperature was raised to 70 °C. "Aronix M-403 (hydroxyl value 92)" manufactured by Toagosei Co., Ltd. (609.78 parts by mass) was charged in portions over 1 hour. After charging, the reaction was carried out at 80 °C until the infrared absorption spectrum at 2250 cm-1 indicating isocyanate groups disappeared, represented by the following structural formula UA-14 having a (meth)acryloyl group was obtained presumed to be 。

Chemical formula

[0119] (Synthesis Example 15: UA-15) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, add "Barnock DN-902S" (178.72 parts by mass) manufactured by DIC, 2,6-di-tert-butyl-4-methylphenol (1.01 parts by mass), methoxyhydroquinone (0.10 parts by mass), and dibutyltin diacetate (0.10 parts by mass). Heat the mixture to 70 °C, and gradually add "Aronix M-306 (hydroxyl value 157.2)" (356.87 parts by mass) manufactured by Toagosei Co., Ltd. over 1 hour. After the addition, carry out the reaction at 80 °C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappears, represented by the following structural formula to obtain a urethane resin UA-15 having a (meth)acryloyl group presumed to be . [Chemical formula]

[0120] (Synthesis Example 16: UA-16) Into a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, add "Barnock DN-902S" (178.72 parts by mass) manufactured by DIC, 2,6-di-tert-butyl-4-methylphenol (1.57 parts by mass), methoxyhydroquinone (0.16 parts by mass), and dibutyltin diacetate (0.16 parts by mass). Heat the mixture to 70 °C, and gradually add "Aronix M-403 (hydroxyl value 92)" (203.26 parts by mass) manufactured by Toagosei Co., Ltd. over 1 hour. After the addition, carry out the reaction at 80 °C until the infrared absorption spectrum at 2250 cm-1 indicating the isocyanate group disappears, represented by the following structural formula to obtain UA-16 having a (meth)acryloyl group presumed to be . [Chemical formula]

[0121] (Example 1) As component (A), 1 part by mass of 2-hydroxyethyltriacrylate isocyanurate; as component (B-1), 90 parts by mass of UA-4; as component (B-2), 8 parts by mass of UA-10; as component (C), 1 part by mass of UA-12; as a photoinitiator, 3 parts by mass of Omunirad819 (manufactured by IGM); as a HALS, 0.5 parts by mass of Tinuvin123; as an ultraviolet absorber, 4 parts by mass of Tinuvin479; and as an organic solvent, propylene glycol monomethyl ether were uniformly mixed so that the solid content was 50% by mass to prepare the active energy ray-curable coating composition of Example 1.

[0122] (Examples 2 to 46, Comparative Examples 1 to 4) Except for changing to the compositions shown in Tables 1 to 7, the active energy ray-curable coating compositions of each example were obtained in the same manner as in Example 1.

[0123] [Preparation of Evaluation Samples] The active energy ray-curable coating composition of each example was coated on a polycarbonate substrate (Panlite L-1225ZL manufactured by Teijin Limited) with a thickness of 3 mm using a bar coater, dried at 80°C for 4 minutes, and then irradiated with ultraviolet rays in the atmosphere using an ultraviolet irradiation device (manufactured by GS-YUASA, high-pressure mercury lamp) at an illuminance of 200 mW·cm 2 , and an irradiation light amount of 1000 mJ / m 2 to obtain a polycarbonate laminate having a cured film with a film thickness of 20 μm.

[0124] [Chemical Resistance Evaluation] For the evaluation samples of each example, a spot test was carried out by the dropping method in accordance with JIS K 5600-6 using a 40 wt% sulfuric acid aqueous solution. The maximum time when no appearance defect was observed in the coating film was taken as the evaluation result. Pass was defined as 15 minutes or more, and when no appearance defect was observed for more than 60 minutes, it was recorded as "60". The resulting time (unit: minute) is described in Tables 1 to 7 as "chemical resistance".

[0125] [Wear Resistance Evaluation] The Taber abrasion test was carried out by rubbing the cured film surface of the evaluation sample surface of each example by a method compliant with ANSI 2007 (abrasion wheel CS-10F, 500 g, 500 times). The abrasion resistance was evaluated by measuring the difference in haze value between the initial state and after the Taber abrasion test, that is, the change in haze value ΔHaze (%). The change in haze value before and after the test was calculated from the haze value obtained by measuring the light transmission value using a haze meter according to the following formula Th = Td / Tt × 100 (Th: haze value (%), Td: scattered light transmittance, Tt: total light transmittance) ΔHaze less than 20 was considered qualified. ΔHaze is described in Tables 1 to 7 as "abrasion resistance".

[0126] [Weather resistance evaluation A] Using the following conditions, an accelerated weathering test (SUV test) was carried out on the evaluation samples of each example. Conditions: Irradiation (63 °C · 70% RH · 4 hours) → Darkness (70 °C · 90% RH · 4 hours) → Dew condensation (30 °C, 98% RH · 4 hours) were repeated, with shower before and after irradiation The maximum time when no crack was observed in the cured film was taken as the evaluation result, and 650 hours or more was considered qualified. If no crack was observed beyond 1296 hours, it was recorded as "1296". The results (unit: hours) are described in Tables 1 to 7 as "weather resistance A".

[0127] [Weather resistance evaluation B] An SUV test was carried out under the same conditions as the above weather resistance evaluation A. After the cellophane tape adhesion test was carried out on the sample surface every 12 hours up to 1296 hours, the surface state was observed and evaluated. The evaluation of the cellophane tape adhesion test was based on the observation of the surface state after the peeling test. If peeling occurred, the elapsed time at that point was taken as the evaluation result, and 650 hours or more was considered qualified. If no peeling was observed even after 1296 hours, it was recorded as "1296". The results (unit: hours) are described in Tables 1 to 7 as "weather resistance B".

[0128]

Table 1

[0129]

Table 2

[0130]

Table 3

[0131]

Table 4

[0132]

Table 5

[0133]

Table 6

[0134]

Table 7

[0135] The abbreviations shown in Tables 1 to 7 respectively indicate the following compounds or the compounds obtained in the above synthesis examples. A-1: 2-Hydroxyethyl isocyanurate triacrylate UA-1 to UA-16: Compounds obtained in Synthesis Examples 1 to 16 DPHA: Dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) S-1: Modified silica fine particles (“MEK-AC2140Z” manufactured by Nissan Chemical Industries, Ltd.) I-1: Photoinitiator “Omnirad 819” (trade name, manufactured by IGM) H-1: Non-reactive HALS “Tinuvin 123” (trade name, manufactured by BASF) H-2: Non-reactive HALS “Tinuvin 152” (trade name, manufactured by BASF) H-3: Reactive HALS “Adekastab LA-82” (trade name, manufactured by ADEKA) UVA1: Triazine-type ultraviolet absorber “Tinuvin400” (trade name, manufactured by BASF) UVA2: Triazine-type ultraviolet absorber “Adekastab LA-46” (trade name, manufactured by ADEKA) UVA3: Triazine-type ultraviolet absorber “Tinuvin479” (trade name, manufactured by BASF) UVA4: Reactive ultraviolet absorber “RUVA-93” (trade name, manufactured by Otsuka Chemical Co., Ltd.)

[0136] From the results of Examples 1 to 46, it was confirmed that the cured film of the active energy ray-curable coating composition of the present invention is excellent in chemical resistance, abrasion resistance, weather resistance, and adhesion. On the other hand, it was confirmed that Comparative Example 1 not containing the component (C) was inferior in chemical resistance; Comparative Examples 2 or 4 not containing the component (A) were inferior in abrasion resistance or weather resistance; and Comparative Example 3 not containing the component (B) was inferior in chemical resistance and weather resistance.

[0137] (Examples 47 to 60, Comparative Examples 5 to 7) [Preparation of Evaluation Samples and Bending Process Test] The active energy ray-curable coating composition of Example 2 was applied onto a polycarbonate substrate (manufactured by Asahi Glass Co., Ltd., "CarboGlass Polish Clear") with a thickness of 2 mm using a bar coater, dried at 80°C for 4 minutes, and then irradiated with ultraviolet rays under the atmosphere using an ultraviolet irradiation apparatus (manufactured by GS-YUASA Co., Ltd., high-pressure mercury lamp) at an illuminance of 200 mW·cm 2 , an irradiation light amount of 1000 mJ / m 2 to obtain a laminate for bending processing of Example 47 having a cured film with a film thickness of 20 μm. Except that the active energy ray-curable coating composition of the example or comparative example shown as "composition" in Tables 8 to 10 was used instead of the active energy ray-curable coating composition of Example 2, laminates for bending processing of Examples 48 to 60 and Comparative Examples 5 to 7 were obtained in the same manner as in Example 47.

[0138] [Appearance Evaluation] After heating each laminate for bending processing in a thermostatic chamber at 170°C for 5 minutes, those in which no wrinkles were observed in the cured film were rated as acceptable (〇), and those in which wrinkles were observed were rated as unacceptable (×). The results are described in Tables 8 to 10 as "Appearance".

[0139] [Adhesion Evaluation] After heating each laminate for bending processing in a thermostatic chamber at 170°C for 5 minutes, with the cured film on the outside, the laminate for bending processing was wound around the outer circumference of a cylinder with a diameter of 10.5 to 3 cm to evaluate the flexibility (bendability). Those in which no peeling occurred at the maximum diameter at which no cracks were observed in the cured film were rated as acceptable (〇), and those in which peeling occurred were rated as unacceptable (×). The results are described in Tables 8 to 10 as "Adhesion".

[0140] [Heat Resistance Flexibility Evaluation] After heating each laminate for bending processing in a thermostatic chamber at 170°C for 5 minutes, with the cured film on the outside, the laminate for bending processing was wound around the outer circumference of a cylinder with a diameter of 10.5 to 3 cm to evaluate the flexibility (bendability). The maximum diameter at which no cracks were observed in the cured film was taken as the evaluation result, and those with a diameter of 10 cm or less were rated as acceptable. The results (unit: cm) are described in Tables 8 to 10 as "Flexural Resistance".

[0141]

Table 8

[0142]

Table 9

[0143]

Table 10

[0144] As a result, it was confirmed that the cured films of the active energy ray-curable coating compositions according to the present invention of Examples 47 to 60 are excellent in bend processability. On the other hand, it was confirmed that the cured films of Comparative Examples 5 to 7 are inferior in any of appearance, adhesion, and flex resistance.

Claims

1. An active energy ray-curable coating composition containing the following components (A) to (C), containing, as component (A), a compound represented by the following formula (1), containing, as component (B), any one of the compounds represented by the following formulas (2-1) to (2-4), as component (C), a polyfunctional urethane acrylate which is a reaction product of an isocyanate compound represented by the following formula (3-3) or (3-4) and a compound represented by the following formula (3-1) or (3-2), the isocyanate compound containing 6 or more (meth)acryloyl groups in one molecule, or dipentaerythritol hexa(meth)acrylate (however, component (C) excludes compounds corresponding to component (A) or component (B)), in the total solid content of the above components (A) to (C), the content of component (A) is 1% by mass or more and 85% by mass or less, the content of component (B) is 14% by mass or more and 98% by mass or less, and when component (C) is a polyfunctional urethane acrylate which is a reaction product of an isocyanate compound represented by the following formula (3-3) or (3-4) and a compound represented by the following formula (3-1) or (3-2), its content is 1% by mass or more and 20% by mass or less, and when component (C) contains dipentaerythritol hexa(meth)acrylate, its content is 1% by mass or more and 9% by mass or less. An active energy ray-curable coating composition characterized by the above. 【Chemical Formula 1】 (wherein, R １ , R ２ and R ３ each independently represents an oxyalkylene group or a polyoxyalkylene group, X １ , X ２ and X ３ each independently represents CH ２ =CR ４ -CO-, CH ２ =CR ４ -CO(O(CH ２ )) ５ -CO) ａ１ -, a hydrogen atom or an alkyl group, R ４ represents a hydrogen atom or a methyl group, and a plurality of R ４ may be the same or different, and a1 is an integer of 1 or more. However, at least two of X １ to X ３ are CH ２ =CR ４ -CO- or CH ２ =CR ４ -CO(O(CH ２ )) ５ -CO) ａ１ -. ) 【Chemical 2】 (wherein R ２６ each independently represents a hydrogen atom or a methyl group, R ２７ each independently represents an alkylene group, R Ａ -(O-CO-(CH ２ ) ５ ) ｎ - or R Ａ -(O-(CH ２ ) ４ ) ｎ - and represents R Ａ represents an alkylene group, n each independently represents an integer of 1 to 10, X ２２ each independently represents an alkylene group having 2 to 17 carbon atoms. A plurality of Rs in the formula ２６ , R ２７ , X ２２ may be the same as or different from each other. ) [Chemical Formula 3] (wherein, R ２６ , R ２７ , X ２２ are the same as described above, A １ represents a structure in which a hydroxyl group is removed from either end of an alkylene diol, a caprolactone-modified diol, or polytetramethylene glycol. A plurality of Rs ２６ , R ２７ , X ２２ , A １ may be the same as or different from each other. ) [Chemical Formula 4] (wherein, R ２６ , R ２７ , X ２２ are the same as described above, and a plurality of R ２６ , R ２７ , X ２２ may be the same as or different from each other. ) 【Chemical Formula 5】 (wherein, R ２６ , R ２７ , X ２２ , A １ are the same as described above, and a plurality of R ２６ , R ２７ , X ２２ may be the same as or different from each other. ) [Chemical Formula 6] (wherein, R ３１ ~R ３２ each independently represents a hydrogen atom or a methyl group, and a plurality of R ３１ , R ３２ may be the same as or different from each other. ) [Chemical Formula 7] (wherein, X ３１ ~X ３２ each independently represents an alkylene group having 2 to 17 carbon atoms, and R ３３ represents -RC-O-CO-CH=CH ２ , or represents a structure obtained by removing a hydroxyl group from the compound represented by the formula (3-1) or (3-2), and R Ｃ represents an alkylene group. A plurality of X ３１ , X ３２ in the formula may be the same as or different from each other.)

2. An active energy ray-curable coating composition containing the following components (A) to (C), containing, as component (A), a compound represented by the following formula (1), containing, as component (B), any one of the compounds represented by the following formulas (2-1) to (2-4), component (B) includes component (B-1) and component (B-2), The component (B-1) is R in the formula (2-1) or (2-3). ２７ At least one or more of Ａ is R ２ -(O-CO-(CH ５ )) ｎ -, or R Ａ -(O-(CH ２ )) ４ ), or a compound in which A in the formula (2-2) or (2-4) is a compound obtained by removing a hydroxyl group from the end of polytetramethylene glycol or polycaprolactone diol, ｎ and １ contains The component (B-2) is R in the formula (2-1) or (2-3) ２７ which is a compound having an alkylene group, or A in the formula (2-2) or (2-4) １ which is a compound having a structure obtained by removing a hydroxyl group from the terminal of an alkylenediol, and includes in the total solid content of the above components (A) to (C), the content of component (B-1) is 9% by mass or more and 90% by mass or less, and the content of component (B-2) is 5% by mass or more and 60% by mass or less, characterized in that it contains, as component (C), a compound containing 6 or more (meth)acryloyl groups in one molecule. An active energy ray-curable coating composition characterized by the above. 【Chemical Formula 4】 (wherein R １ , R ２ and R ３ each independently represents an oxyalkylene group or a polyoxyalkylene group, and X １ , X ２ and X ３ each independently represents CH ２ = CR ４ - CO-, CH ２ = CR ４ - CO(O(CH ２ ) ５ - CO) ａ１ -, a hydrogen atom or an alkyl group, R ４ represents a hydrogen atom or a methyl group, a plurality of R4s may be the same or different, and a1 is an integer of 1 or more. However, at least two of X １ to X ３ are CH ２ = CR ４ - CO- or CH ２ = CR ４ - CO(O(CH ２ ) ５ - CO) ａ１ -. ) 【Chemical Formula 5】 (wherein R ２６ each independently represents a hydrogen atom or a methyl group, R ２７ each independently represents an alkylene group, R Ａ -(O-CO-(CH ２ ) ５ ) ｎ - or R Ａ -(O-(CH ２ ) ４ ) ｎ - and represents, R Ａ represents an alkylene group, n each independently represents an integer of 1 to 10, X ２２ each independently represents an alkylene group having 2 to 17 carbon atoms. A plurality of Rs in the formula ２６ , R ２７ , X ２２ may be the same as or different from each other. ) 【Chemical Formula 6】 (wherein, R ２６ , R ２７ , X ２２ are the same as described above, A １ represents a structure obtained by removing a hydroxyl group from either end of an alkylene diol, a caprolactone-modified diol, or polytetramethylene glycol. A plurality of Rs ２６ , R ２７ , X ２２ , A １ may be the same as or different from each other. ) 【Chemical Formula 7】 (wherein, R ２６ , R ２７ , X ２２ are the same as described above, and a plurality of R ２６ , R ２７ , X ２２ may be the same as or different from each other. ) 【Chemical Formula 8】 (wherein, R ２６ , R ２７ , X ２２ , A １ are the same as described above, and a plurality of R ２６ , R ２７ , X ２２ may be the same as or different from each other. )

3. In the total solid content of the components (A) to (C), the content of the component (A) is 1% by mass or more and 85% by mass or less, the content of the component (B) is 14% by mass or more and 98% by mass or less, and the content of the component (C) is 1% by mass or more and 20% by mass or less. The active energy ray-curable coating composition according to claim 2.

4. The component (B) includes a component (B-1) and a component (B-2), The component (B-1) is such that at least one of Rs in the formula (2-1) or (2-3) is R ２７ -(O-CO-(CH Ａ )) ２ ) ５ ) ｎ -, or R Ａ -(O-(CH ２ )) ４ ) ｎ -, or the component (B-1) contains a compound obtained by removing a hydroxyl group from the terminal of polytetramethylene glycol or polycaprolactone diol where A in the formula (2-2) or (2-4) is １ such a compound, The component (B-2) is R in the formula (2-1) or (2-3) ２７ which is a compound having an alkylene group, or A in the formula (2-2) or (2-4) １ which is a compound having a structure obtained by removing a hydroxyl group from the terminal of an alkylenediol In the total solid content of the components (A) to (C), the content of the component (B-1) is 9% by mass or more and 90% by mass or less, and the content of the component (B-2) is 5% by mass or more and 60% by mass or less. The active energy ray-curable coating composition according to claim 1.

5. The active energy ray-curable coating composition according to claim 1 or 2, which does not contain an organic solvent or contains an organic solvent in an amount of 30% by mass or less based on the total amount of the composition.

6. A molded article having a cured film of the active energy ray-curable coating composition according to any one of claims 1 to 4 and a substrate.

7. The molded article according to claim 6, wherein the substrate is a polycarbonate resin.

8. The molded article according to claim 6, which is used for automotive headlamp lenses, automotive glazing, automotive body exterior, plastics for building materials, and steel sheets for building materials.

9. A molded article obtained by bending the molded article according to claim 7 by thermoforming.

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