Active energy ray curable composition, laminate, and method for manufacturing laminate

Abstract

An objective of the present invention is to provide an active energy ray curable composition capable of forming a cured coating or cured layer having weather resistance and chemical resistance and with an outstanding appearance, as well as a laminate having the cured layer and a method for manufacturing the laminate.　The present invention relates to the active energy ray curable composition characterized by containing a compound (A) comprising a chain hydrocarbon group having 2 to 12 carbon atoms and two (meth)acryloyloxy groups, and a compound having an isocyanurate bond or an allophanate bond.

Description

Active energy ray curable composition, laminate, and method for producing laminate

[0001] The present invention relates to an active energy ray-curable composition, a laminate, and a method for producing the laminate.

[0002] Resin materials, particularly transparent resin materials such as polycarbonate, are widely used in a variety of applications, taking advantage of their low specific gravity, light weight, ease of processing, and impact resistance compared to inorganic glass. Furthermore, resin primers are often applied to glass and metal steel sheets for the purposes of coloring, rust prevention, and adhesion to other materials. However, resin materials and resin primers have drawbacks, such as surface scratches that easily cause loss of gloss and transparency, susceptibility to organic solvents, poor weather resistance (e.g., light stability against ultraviolet rays), and poor heat resistance. Therefore, resin materials are often coated with various protective films to improve their surface properties. Examples of such protective films include hard coat layers formed by curing active energy ray-curable compositions.

[0003] Resin materials used outdoors require excellent weather resistance. Patent Document 1 discloses an active energy ray-curable composition that combines adhesion, abrasion resistance, and weather resistance, which contains inorganic oxide fine particles, a poly[(meth)acryloyloxyalkyl]isocyanurate having at least two (meth)acryloyl groups in the molecule, a urethane poly(meth)acrylate having at least two (meth)acryloyl groups in one molecule and an alicyclic skeleton, an alkyl di(meth)acrylate having 4 to 12 carbon atoms, and a photopolymerization initiator in specific ratios.

[0004] JP 2013-10921 A

[0005] In recent years, resin materials, resin primers, and active energy ray-curable compositions that can be used in harsh environments such as outdoors or around automobiles have come to require not only weather resistance and abrasion resistance, but also resistance to acid rain and automobile battery fluid, i.e., excellent chemical resistance. However, the invention described in Patent Document 1 does not address chemical resistance. Furthermore, the composition described in Patent Document 1 contains organic monomers that are highly corrosive to substrates, such as alkyl di(meth)acrylates having 4 to 12 carbon atoms. Therefore, when using resin substrates such as polycarbonates, which are susceptible to corrosion, or various resin primers, these can be excessively corroded, resulting in poor appearance and poor weather resistance of the coating film. Therefore, the invention described in Patent Document 1 did not address both the issues of chemical resistance and weather resistance and could not form coatings or cured films with good appearance.

[0006] The present invention has been made in view of the above problems, and an object of the present invention is to provide an active energy ray-curable composition capable of forming a cured coating film or cured layer that has weather resistance and chemical resistance and excellent appearance, as well as a laminate having the cured layer, and a method for producing the laminate.

[0007] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by using an alkane di(meth)acrylate compound, which is effective in improving adhesion and weather resistance, in combination with a compound having an isocyanurate bond or an allophanate bond, which can suppress the corrosion of the alkane di(meth)acrylate against resin substrates and resin primers, and have thus completed the present invention.

[0008] That is, the present invention provides the following inventions. (1) An active energy ray-curable composition characterized by containing a compound (A) consisting of a chain hydrocarbon group having 2 to 12 carbon atoms and two (meth)acryloyloxy groups, and a compound having an isocyanurate bond or an allophanate bond. (2) The active energy ray-curable composition of (1), in which the compound having an isocyanurate bond or an allophanate bond is a urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond. (3) The active energy ray-curable composition of (2), further containing a (meth)acrylate compound (C) having an isocyanurate bond. (4) The active energy ray-curable composition of (2), in which the urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond contains, in the structure, a —O—C(═O)—(CH ２ ) ｎＡ (nA represents an integer of 1 to 6), and a compound (B1) having, in the structure, —O—C(═O)—(CH ２ ) ｎＡ (nA represents an integer of 1 to 6). (5) The active energy ray-curable composition of any of (1) to (4), further containing a compound (D) containing four or more (meth)acryloyl groups in one molecule. (6) The active energy ray-curable composition of any of (1) to (5), wherein the active energy ray-curable composition does not contain an organic solvent or contains an organic solvent in an amount of 30 mass% or less of the total amount of the composition. (7) A laminate having a cured layer of the active energy ray-curable composition of any of (1) to (6). (8) A method for producing a laminate, comprising: Step 1: applying the active energy ray-curable composition of any of (1) to (6) onto a substrate to obtain a coating film; and Step 2: irradiating the coating film with active energy rays to cure part or all of the coating film. (9) The method for producing a laminate according to (8), wherein after step 2, steps 1 and 2 are repeated in this order at least once.

[0009] The active energy ray-curable composition of the present invention can form a cured coating having excellent chemical resistance and weather resistance and an excellent appearance while satisfying the properties required of a cured coating, such as adhesion and abrasion resistance. This cured coating has excellent adhesion to resin substrates such as polycarbonate and resin primers, and has excellent durability even in high-temperature, high-humidity environments and environments where it may come into contact with chemicals. Therefore, the active energy ray-curable composition of the present invention can be suitably used as a hard coat for resin materials in automotive and building material applications, and is particularly suitable for automotive exterior applications and automotive glazing applications.

[0010] <Active Energy Ray-Curable Composition> The active energy ray-curable composition of the present invention (hereinafter may be simply referred to as the "composition" or "composition") contains a compound (A) (hereinafter may be referred to as the "component (A)") consisting of a chain hydrocarbon group having 2 to 12 carbon atoms and two (meth)acryloyloxy groups, and a compound having an isocyanurate bond or an allophanate bond. In this specification, the compound represented by formula (1) is referred to as "compound (1)", and the same applies to compounds represented by other formulas. Furthermore, "acrylate" and "methacrylate" are collectively referred to as "(meth)acrylate". "Acrylic acid" and "methacrylic acid", "acryloyl group" and "methacryloyl group", "acryloyloxy group (CH ２ =CH—CO—O—) and “methacryloyloxy group” (CH ２ =C(CH ３ Similarly, the expressions "(meth)acrylic acid" and "(meth)acryloyloxy group" will be explained as concepts that include both of them.

[0011] [Component (A)] Component (A) is a compound comprising a chain hydrocarbon group having 2 to 12 carbon atoms and two (meth)acryloyloxy groups, and the inclusion of component (A) in the composition improves the substrate adhesion and weather resistance of the cured coating. The chain hydrocarbon group having 2 to 12 carbon atoms may be linear or branched, but linear is preferred. The number of carbon atoms is preferably 4 to 10, and more preferably 6 to 10. In particular, from the viewpoint of reducing skin irritation to workers during production work, 8 to 10 is preferred. Specific examples of the component (A) include (meth)acrylates having a linear hydrocarbon group, such as 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate; and (meth)acrylates having a branched hydrocarbon group, such as neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, and 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate.

[0012] The component (A) may be a single compound or a combination of two or more compounds. The content of the component (A) is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, and even more preferably 20 to 50% by mass, based on a total of 100% by mass of the component (A), the compound having an isocyanurate bond or an allophanate bond (specifically, one or more compounds selected from the group consisting of a urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond and a (meth)acrylate compound (C) having an isocyanurate bond), and the optionally contained component (D) (hereinafter referred to as "100% by mass of the total of components (A) to (D)"). By setting the content at or above the lower limit, substrate adhesion and weather resistance are further improved, and by setting the content at or below the upper limit, weather resistance is further improved.

[0013] [Compound Having an Isocyanurate or Allophanate Bond] The composition of the present invention contains a compound having an isocyanurate or allophanate bond. The isocyanurate and allophanate bonds are represented by the following formulas (i) and (ii), respectively. By using a compound having an isocyanurate or allophanate bond in combination with component (A), excessive corrosion of the resin substrate or resin primer by component (A) can be prevented, thereby preventing poor appearance of the coating film and deterioration of the weather resistance of the cured coating. The structure of this compound is not particularly limited as long as it has an isocyanurate or allophanate bond, but it preferably has a polymerizable group, and more preferably has a (meth)acryloyl group ((meth)acryloyloxy group) similar to component (A).

[0014]

[0015] Among these, the compound having an isocyanurate bond or an allophanate bond is preferably at least one selected from the group consisting of a urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond and a (meth)acrylate compound (C) having an isocyanurate bond. Each of these compounds will be described below.

[0016] [Component (B)] The urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond (hereinafter sometimes referred to as "component (B)") is a component that contributes to the weather resistance and adhesion of the cured coating. Component (B) is not particularly limited as long as it is a compound having an isocyanurate bond or an allophanate bond, a urethane bond, and a (meth)acrylate structure ((meth)acryloyl group). However, component (B) may be a compound having a -O-C(=O)-(CH ２ ) ｎＡ (nA represents an integer of 1 to 6), and a compound represented by the following formula (2) is preferred.

[0017]

[0018] In formula (2), R ２１ ~R ２５ are each independently a group having a polymerizable group. ２１ ~R ２５ The polymerizable group contained in the (meth)acryloyl group (CH ２ =CR ４ -CO-(R ４ is the same as above.) is preferred, and R ２１ ~R ２５ R is preferably a combination of a (meth)acryloyl group and a divalent linking group. ２１ ~R ２５ Examples of the divalent linking group 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. The hydrogen atoms of the groups listed as divalent linking groups may be substituted with an alkyl group, an alkoxy group, an acyl group, or the like.

[0019] n1 and n2 each independently represent 0 or 1. ２１ ~L ２２ are each independently a divalent linking group. ２１ ~L ２２The divalent linking group preferably has a structure in which hydroxyl groups have been removed from both ends of an alkylene diol, a caprolactone-modified diol, or polytetramethylene glycol. The alkylene diol is preferably an alkylene diol having 2 to 10 carbon atoms, and the number of repeating tetramethylene groups in the polytetramethylene glycol is preferably 8 to 30. Examples of caprolactone-modified diols include "PLACCEL 205," a polycaprolactone diol having a mass average molecular weight of 530, "PLACCEL 205BA," a polycaprolactone diol having a mass average molecular weight of 530 and having a carboxyl group in the side chain, "PLACCEL L205AL," a polycaprolactone diol having a mass average molecular weight of 500 as a liquid at room temperature, and "PLACCEL L205AL," a polycaprolactone diol having a mass average molecular weight of 530 and improved water resistance compared to PLACCEL 205. "PLACCEL 205H" is a polycaprolactone diol; "PLACCEL 205U" is a polycaprolactone diol with a mass average molecular weight of 530 that has lower viscosity and acid value than PLACCEL 205; "PLACCEL 208" is a polycaprolactone diol with a mass average molecular weight of 830; "PLACCEL L208AL" is a polycaprolactone diol that is liquid at room temperature and has a mass average molecular weight of 830; and "PLACCEL L208AL" is a polycaprolactone diol with a mass average molecular weight of 1000. "PLACCEL 210" is a polycaprolactone diol with a mass average molecular weight of 1000 and a carboxyl group in the side chain, "PLACCEL 210BA" is a polycaprolactone diol with a mass average molecular weight of 1000 that has a lower acid value and improved water resistance compared to PLACCEL 210, and "PLACCEL 210CP" is a polycaprolactone diol with a mass average molecular weight of 1000 that has a narrower molecular weight distribution compared to PLACCEL 210. "PLACCEL 210N", "PLACCEL 212", a polycaprolactone diol having a mass average molecular weight of 1250, "PLACCEL L212AL", a polycaprolactone diol having a mass average molecular weight of 1250 when liquid at room temperature, "PLACCEL 220", a polycaprolactone diol having a mass average molecular weight of 2000, "PLACCEL 220BA", a polycaprolactone diol having a carboxyl group in the side chain and a mass average molecular weight of 2000,"PLACCEL 220CPB" is a polycaprolactone diol with a mass average molecular weight of 2000 that has a lower acid value and improved water resistance compared to PLACCEL 220; "PLACCEL 220N" is a polycaprolactone diol with a mass average molecular weight of 2000 that has a narrower molecular weight distribution compared to PLACCEL 220; "PLACCEL 220NP1" is a polycaprolactone diol with a mass average molecular weight of 2000 that has lower crystallinity compared to PLACCEL 220; "PLACCEL L220AL" is a polycaprolactone diol with a mass average molecular weight of 2000 as a liquid at room temperature; "PLACCEL 230" is a polycaprolactone diol with a mass average molecular weight of 3000; "PLACCEL L230AL" is a polycaprolactone diol with a mass average molecular weight of 3000 as a liquid at room temperature; Examples of such polycaprolactone diols include "PLACCEL 230CP," a polycaprolactone diol with a mass average molecular weight of 3,000 that has a lower acid value and improved water resistance compared to PLACCEL 230; "PLACCEL 240," a polycaprolactone diol with a mass average molecular weight of 4,000; "PLACCEL 240CP," a polycaprolactone diol with a mass average molecular weight of 4,000 that has a lower acid value and improved water resistance compared to PLACCEL 240; "PLACCEL 220EB," a polycaprolactone diol with a mass average molecular weight of 2,000 that has improved hydrolysis resistance compared to PLACCEL 220; and "PLACCEL 220EC," a polycaprolactone diol with a mass average molecular weight of 2,000 that has better elastic recovery compared to PLACCEL 220EB (all trade names, manufactured by Daicel Chemical Industries, Ltd.). Among these, polycaprolactone diols having a mass average molecular weight in the range of 500 to 1500 are preferred, and those in the range of 500 to 1000 are more preferred, from the viewpoint of the weather resistance and abrasion resistance of the resulting cured coating. ２１ ~L ２２ It is preferable that R has another linking group in addition to any one of the structures obtained by removing a hydroxyl group from the terminal of an alkylene diol, a caprolactone-modified diol, or a polytetramethylene glycol. ２１ ~R ２５ The divalent linking group represented by the formula "has" is preferred.

[0020] Z ２１ ~Z ２３are each independently a structure represented by the following formula (2z).

[0021]

[0022] 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.

[0023] * in formula (2z) represents a bond, and formula (2z) corresponds to Z in formula (2). ２１ When 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 formula (2z) is Z in formula (2). ２２ When B1 is L ２２ , the bond represented by B2 is R ２４ , the bond represented by B3 is R ２３ and formula (2z) is Z in formula (2). ２３ When B1 is L ２１ , the bond represented by B2 is R ２２ , the bond represented by B3 is R ２５ directly bonded to

[0024] Z １ is an oxygen atom or a nitrogen atom, and Z ２ is a hydrogen atom or —C(═O)—, provided that Z １ When is an oxygen atom (—O—), Z ２ becomes a hydrogen atom (-H). １ When is a nitrogen atom, Z ２ becomes -C(=O)-, and Z １ Nitrogen atom and Z ２ and -C(=O)- to form a ring. １ When is an oxygen atom, formula (2z) has an allophanate bond, and Z １When is a nitrogen atom, the formula (2z) has a structure having an isocyanurate bond. As the component (B), the formula (2z) has a structure having an isocyanurate bond.

[0025] Among these, compounds represented by the following formulae (2-1) to (2-4) are preferred as compound (2).

[0026]

[0027]

[0028]

[0029]

[0030] In formulas (2-1) to (2-4), R ２６ are each independently a hydrogen atom or a methyl group. ２７ are each independently an alkylene group having 2 to 10 carbon atoms (preferably having 2 to 4 carbon atoms), R Ａ -(O-CO-(CH ２ ) ５ ) ｎ - or R Ａ -(O-(CH ２ ) ４ ) ｎ - is. R Ａ represents an alkylene group, preferably an alkylene group having 2 to 4 carbon atoms. Each n independently represents an integer of 1 to 10, preferably an integer of 1 to 5.

[0031] In formulas (2-1) to (2-4), X ２２ are each 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. １ is a structure in which a hydroxyl group is removed from the end of any of alkylene diol, caprolactone-modified diol, or polytetramethylene glycol, and L ２１ ~L ２２ The same as that explained in the above. ２６ , R ２７ , X２２ may be the same or different from each other.

[0032] The component (B) may be a single compound or a combination of two or more compounds. In particular, it is preferable to use a combination of two or more compounds (B) because this can achieve a good balance of various properties.

[0033] When two or more types are used, in addition to the isocyanurate bond, allophanate bond, and (meth)acryloyl group, ２ ) ｎＡ (nA represents an integer of 1 to 6), and a compound (B1) having, in the structure, —O—C(═O)—(CH ２ ) ｎＡ (nA represents an integer of 1 to 6) is preferably used in combination with a compound (B2) that does not have the formula (nA).

[0034] When two or more types are used, the component (B) preferably contains the component (B11) and the component (B22). ２７ At least one of the following is R Ａ -(O-CO-(CH ２ ) ５ ) ｎ - or R Ａ -(O-(CH ２ ) ４ ) ｎ -, or a compound represented by the formula (2-2) or the formula (2-4), １ Examples of the component (B22) include compounds in which a hydroxyl group has been removed from the end of polytetramethylene glycol or polycaprolactone diol. ２７ is an alkylene group, or a compound represented by the formula (2-2) or the formula (2-4), １Among these, a combination of a component (B11) represented by formula (2-1) and a component (B22) represented by formula (2-1), or a combination of a component (B11) represented by formula (2-2) in which A1 has a polycaprolactone structure and a component (B22) represented by formula (2-1) is preferred.

[0035] When component (B) includes components (B1) and (B2) or components (B11) and (B22), the content of component (B1) or component (B11) is preferably 9 to 90 mass%, more preferably 20 to 70 mass%, even more preferably 30 to 60 mass%, and particularly preferably 45 to 60 mass%, based on 100 mass% of the total solids content of components (A) to (C). The content of component (B2) or component (B22) is preferably 5 to 60 mass%, more preferably 10 to 50 mass%, even more preferably 15 to 40 mass%, and particularly preferably 20 to 30 mass%, based on 100 mass% of the total solids content of components (A) to (C).

[0036] When the composition of the present invention contains component (B), the total content of component (B) is preferably 10 to 80 mass%, more preferably 15 to 70 mass%, and even more preferably 25 to 60 mass%, based on 100 mass% of the total of components (A) to (D). By ensuring that the content is equal to or greater than the lower limit, weather resistance is improved, and by ensuring that the content is equal to or less than the upper limit, abrasion resistance is improved.

[0037] [Component (C)] The (meth)acrylate compound (C) having an isocyanurate bond (hereinafter sometimes referred to as "component (C)") is a component that contributes to the abrasion resistance and adhesion of the cured coating. Component (C) is a compound that does not fall under the category of component (B) described above, and is a compound that does not have a urethane bond and has an isocyanurate bond and a (meth)acrylate structure ((meth)acryloyl group). Specifically, component (C) is preferably a compound represented by the following formula (1):

[0038]

[0039] In formula (1), R １ , R ２ and R ３are each independently an oxyalkylene group or a polyoxyalkylene group. The number of carbon atoms in the oxyalkylene group is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. The number of carbon atoms in the polyoxyalkylene group per repeating unit is also preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. The number of repeating oxyalkylene groups in the polyoxyalkylene group is preferably in the range of 1 to 10. The oxygen atom in the oxyalkylene group and the terminal oxygen atom in the polyoxyalkylene group are preferably X in the formula １ , X ２ or X ３ and combine.

[0040] X １ , X ２ and X ３ are each independently CH ２ =CR ４ -CO-, CH ２ =CR ４ -CO(O(CH ２ ) ５ -CO) ａ１ represents -, a hydrogen atom or an alkyl group, and X １ ~X ３ At least two of them are CH ２ =CR ４ -CO- or CH ２ =CR ４ -CO(O(CH ２ ) ５ -CO) ａ１ That is, the compound (1) is a difunctional or trifunctional (meth)acrylate. ４ represents a hydrogen atom or a methyl group, and a plurality of R ４ may be the same or different, but is preferably a hydrogen atom. 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 these, X １ , X ２ and X ３ is CH ２ =CR ４ -CO-, CH ２ =CR ４ -CO(O(CH ２ ) ５ -CO)ａ１ - or a hydrogen atom is preferred, and X １ ~X ３ At least two of them are CH ２ =CR ４ More preferably, all three are —CO—, and ２ =CR ４ It is particularly preferably —CO—.

[0041] Particularly preferred compounds (1) include compounds represented by the following formula (1-1): ４ is the same as above, and R １’ ~R ３’ is an alkylene group having 1 to 5 carbon atoms (preferably 1 to 3).

[0042]

[0043] Specific examples of the structure of component (C) include bis(2-acryloyloxyethyl)hydroxylethyl isocyanurate, tris(2-acryloyloxyethyl)isocyanurate (manufactured by Toagosei Co., Ltd. under the trade names Aronix M-313 and Aronix M-315, manufactured by Shin-Nakamura Chemical Co., Ltd. under the trade names NK Ester A9300 and A9300S, and Arkema SR368 and SR368NS), and bis(2-acryloyloxypropyl)hydroxylethyl 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), and tris(2-acryloyloxyethyl)isocyanurate modified with three caprolactones per molecule (manufactured by Toagosei Co., Ltd., trade name: Aronix M-327).

[0044] The component (C) may be a single compound or a combination of two or more compounds. When the composition of the present invention contains the component (C), the content of the component (C) is preferably 1 to 79 mass%, more preferably 3 to 67.5 mass%, and even more preferably 5 to 50 mass%, based on 100 mass% of the total of the components (A) to (D). By ensuring that the content is equal to or greater than the lower limit, the abrasion resistance and adhesion are further improved, and by ensuring that the content is equal to or less than the upper limit, the weather resistance and chemical resistance are further improved.

[0045] The compound having an isocyanurate bond or an allophanate bond may be component (B), component (C), or component (B) and component (C). Among these, the combined use of component (B) and component (C) is preferred because the combined use of these makes it easier to achieve improvements in weather resistance, chemical resistance, and adhesion and to reduce appearance defects.

[0046] [Component (D)] Component (D) is a compound containing four or more (meth)acryloyl groups in one molecule, and does not fall under any of the aforementioned components (A) to (C). The inclusion of component (D) in the composition improves the abrasion resistance and chemical resistance of the cured coating. The component (D) is not particularly limited as long as it has four or more (meth)acryloyl groups in one molecule, and examples thereof include polyfunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, polypentaerythritol poly(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; and urethane (meth)acrylates obtained by reacting an isocyanate compound with a (meth)acrylate compound.

[0047] The polyfunctional (meth)acrylate as component (D) is preferably a compound represented by the following formula (3-0).

[0048]

[0049] In formula (3-0), a plurality of R ３０ At least four of them are CH ２ =CR Ｂ -COO- or a (meth)acryloyloxy group CH modified with caprolactone ２ =CR Ｂ -CO(O(CH ２ ) ５ C=O) ｙ -O-, and the remaining R ３０ is a hydroxyl group, or CH ２ =CR Ｂ -COO-, CH2=CR 8 -CO(O(CH ２ ) ５ C=O) ｙ represents —O—. Ｂ represents a hydrogen atom or a methyl group, R Ｂ When R is a hydrogen atom, it becomes an acryloyl group, and R Ｂ is a methyl group, the compound becomes a methacryloyl group, and y is an integer of 1 or more. That is, compound (3-0) is a polymerizable compound having a pentaerythritol skeleton and having four or more (meth)acryloyloxy groups in its structure. By having four or more (meth)acryloyloxy groups, the crosslink density upon curing increases, resulting in improved abrasion resistance and chemical resistance. n30 represents an integer of 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and it is particularly preferable that n30 = 1 and compound (3-0) becomes a dipentaerythritol skeleton. As compound (3-0), one compound may be used alone, or two or more compounds may be used in combination.

[0050] The urethane (meth)acrylate as the component (D) can be obtained by reacting a (meth)acrylate compound having a hydroxyl group with an isocyanate compound.

[0051] The (meth)acrylate compound having a hydroxyl group used in the production of urethane (meth)acrylate is preferably a compound represented by the following formula (3-1) or (3-2): ３１ ~R ３２each independently represents a hydrogen atom or a methyl group, and ３１ , R ３２ may be the same or different from each other.

[0052]

[0053] The isocyanate compound used in the production of the urethane (meth)acrylate is preferably an aliphatic polyisocyanate or alicyclic polyisocyanate having two or more isocyanate groups. Specific examples thereof include aliphatic polyisocyanates such as 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate, or dimers or trimers thereof; and alicyclic polyisocyanates such as norbornane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, hydrogenated xylylene diisocyanate, 2-methyl-1,3-diisocyanatocyclohexane, and 2-methyl-1,5-diisocyanatocyclohexane, or dimers or trimers thereof.

[0054] 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 also preferred.

[0055]

[0056] In the formula, X ３１ ~X ３２ Each of X independently represents an alkylene group having 2 to 17 carbon atoms, and preferably an alkylene group having 2 to 6 carbon atoms. ３１ , X ３２ may be the same or different. ３３ is -R Ｃ -O-CO-CH=CH ２ or a structure obtained by removing a hydroxyl group from a compound represented by formula (3-1) or (3-2), R Ｃrepresents an alkylene group, and the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.

[0057] When the composition of the present invention contains component (D), the total content of component (D) is preferably 1.0 to 40 mass%, more preferably 2.5 to 20 mass%, and even more preferably 5.0 to 10 mass%, based on 100 mass% of the total of components (A) to (D). By ensuring that the content is equal to or greater than the lower limit, chemical resistance is improved, and by ensuring that the content is equal to or less than the upper limit, weather resistance is improved.

[0058] [Other Components] The composition of the present invention may optionally contain other components in addition to the above components (A) to (D), as long as the effects of the present invention are achieved. Examples of other components include organic solvents, reactive compounds, various resins, fillers, polymerization initiators, stabilizers, UV absorbers, and leveling agents. Furthermore, the composition may further contain inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, catalysts, surfactants, flow adjusters, coupling agents, dyes, rheology control agents, antioxidants, plasticizers, etc.

[0059] The composition of the present invention may contain an organic solvent, or may not contain an organic solvent. Among these, a solvent-free composition containing no organic solvent or a high-solids composition containing a relatively low amount of organic solvent is preferred. By using a solvent-free or low-solvent / high-solids composition, the amount of volatile organic compounds (VOCs) can be reduced, thereby reducing the environmental impact. When an organic solvent is contained, its content is preferably 30% by mass or less of the total amount of the composition, more preferably 25% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less. Examples of organic solvents include ester-based solvents, ketone-based solvents, ether-based solvents, aliphatic solvents, aromatic solvents, and alcohol-based solvents. Specific examples of ester solvents include ethyl acetate, propyl acetate, and butyl acetate; ketone solvents include acetone, 2-butanone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents include tetrahydrofuran and dioxolane; aliphatic solvents include hexane and cyclohexane; aromatic solvents include toluene and xylene; and alcohol solvents include ethanol, methanol, propanol, butanol, and propylene glycol monomethyl ether.

[0060] As the reactive compound, a (meth)acrylate compound other than components (A) to (D) 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)acrylates and di- or trifunctional (meth)acrylates that do not fall under components (A) to (D).

[0061] Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates having an alkyl group having 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, and lauryl (meth)acrylate; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; and ω-alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate. Examples of such an acrylate include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy(meth)acrylate (for example, 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, and (meth)acrylic acid adducts of various epoxy esters.

[0062] Examples of difunctional or trifunctional (meth)acrylates include dihydric alcohol di(meth)acrylates such as 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, and 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 or more moles 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 1 mole of tris(2-hydroxyethyl)isocyanurate with 2 to 3 moles of acrylic acid, trimethylolpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate modified with ethylene oxide, polypropylene glycol di(meth)acrylate modified with propylene oxide, tetra Examples of the polytetramethylene glycol di(meth)acrylate modified with methylene oxide, glycerol tri(meth)acrylate modified with ethylene oxide, glycerol tri(meth)acrylate modified with propylene oxide, trimethylolpropane tri(meth)acrylate, 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, phosphate tri(meth)acrylate modified with ethylene oxide, polyester(meth)acrylate compounds synthesized by the condensation reaction of a polyhydric alcohol with (meth)acrylic acid and a polyfunctional carboxylic acid, epoxy(meth)acrylate compounds synthesized by the addition reaction of a novolac epoxy resin with a glycidyl group-containing acrylic polymer and (meth)acrylic acid, and acrylic acrylate compounds.

[0063] The reactive compounds 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, relative to 100% by mass of the total solid content of components (A) to (D).

[0064] The various resins may include thermosetting resins and thermoplastic resins. Thermosetting resins are resins that become substantially insoluble and infusible when cured by means of heat, radiation, catalysts, or the like. Specific examples of thermosetting resins include phenolic 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, and styrene-maleic anhydride (SMA) resins. These thermosetting resins may be used alone or in combination of two or more.

[0065] 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, and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

[0066] A liquid organic polymer may also be used to adjust the viscosity. The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples thereof include modified carboxyl group-containing polymers (FLOWLEN G-900, NC-500: Kyoeisha), acrylic polymers (FLOWLEN WK-20: Kyoeisha), amine salts of special modified phosphate esters (HIPLAAD ED-251: Kusumoto Chemicals), and modified acrylic block copolymers (DISPERBYK2000: BYK-Chemie).

[0067] As a filler, for example, silica can be blended for the purpose of improving abrasion resistance. There are no limitations on the silica, and known silica microparticles such as powdered silica, colloidal silica, and nanosilica can be used. Examples of commercially available powdered silica microparticles include Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., E220A and E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Ltd., and SG Flake manufactured by Nippon Sheet Glass Co., Ltd. Furthermore, 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, and ST-OL, all of which are manufactured by Nissan Chemical Industries, Ltd.

[0068] Reactive silica may be used as the silica. Examples of reactive silica include silica modified with a reactive compound. Examples of reactive compounds 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 and R711 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, and MEK-AC-2140Z manufactured by Nissan Chemical Industries, Ltd. Other examples of reactive silica include silica modified with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane and then subjected to an addition reaction with acrylic acid, and silica modified with a compound having 3-isocyanatepropyltriethoxysilane and a hydroxyl group and a (meth)acryloyl group subjected to a urethane reaction.

[0069] The shape of the silica microparticles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous microparticles can be used. For example, commercially available hollow silica microparticles such as Silinax manufactured by Nittetsu Mining Co., Ltd. can be used. The primary particle diameter is preferably in the range of 5 to 200 nm. If the diameter is 5 nm or more, the inorganic microparticles in the composition are sufficiently dispersed, and if the diameter is 200 nm or less, sufficient strength of the cured product can be maintained. The amount of silica blended is preferably 3 to 60 mass% based on 100 mass% of the composition.

[0070] Fillers other than silica include inorganic fillers and organic fillers. There is no limitation on the shape of the filler, and examples thereof include particulate, plate-like, and fibrous fillers. Fillers with excellent heat resistance include alumina, magnesia, titania, zirconia, etc.; fillers with excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc.; fillers with excellent electrical conductivity include metal fillers and / or metal-coated fillers using metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); and fillers with excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, and smectite, as well as potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, and titanium oxide. Inorganic particles include barium sulfate, zinc oxide, and magnesium hydroxide; those with a high refractive index include barium titanate, zirconia oxide, and titanium oxide; those exhibiting photocatalytic properties include photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, cerium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, and lead, as well as composites of these metals and oxides thereof; those with excellent wear resistance include metals such as alumina, zirconia, and magnesium oxide, as well as composites and oxides thereof; those with excellent conductivity include metals such as silver and copper, tin oxide, and indium oxide; and those with excellent ultraviolet shielding properties include titanium oxide and zinc oxide. These inorganic particles can be selected appropriately depending on the application, and can be used alone or in combination. Furthermore, the inorganic particles have various properties in addition to those listed as examples, so they can be selected appropriately depending on the application.

[0071] Examples of inorganic fibers include inorganic fibers such as carbon fiber, glass fiber, boron fiber, alumina fiber, and silicon carbide fiber, as well as carbon fiber, activated carbon fiber, graphite fiber, glass fiber, tungsten carbide fiber, silicon carbide fiber (silicon carbide fiber), ceramic fiber, alumina fiber, natural fiber, mineral fiber such as basalt, boron fiber, boron nitride fiber, boron carbide fiber, and metal fiber. Examples of the metal fiber include aluminum fiber, copper fiber, brass fiber, stainless steel fiber, and steel fiber.

[0072] Examples of organic fibers 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.

[0073] The amount of the filler to be blended is preferably 3 to 60% by mass relative to 100% by mass of the composition.

[0074] 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. As the photopolymerization initiator, any known initiator may be used, and for example, one or more selected from the group consisting of acetophenones, benzil ketals, and benzophenones can be preferably used.

[0075] Specific examples of the photoinitiated polymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-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, dienes, acetophenone compounds such as acetophenone, 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; methylbenzoyl formate, oxypheny α-ketoester compounds such as 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester of phenylacetic 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, benzoin methyl ether ... benzoin-based compounds such as benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; titanocene-based compounds; acetophenone / benzophenone hybrid photopolymerization initiators such as 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfinyl)propan-1-one; oxime ester photopolymerization initiators such as 2-(O-benzoyloxime)-1-[4-(phenylthio)]-1,2-octanedione; and camphorquinone.

[0076] The photopolymerization initiator may be used alone or in combination of two or more. The amount of the photopolymerization initiator used is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, based on 100% by mass of the composition.

[0077] The composition of the present invention may contain an ultraviolet absorber for the purpose of improving weather resistance. Various compounds or substances can be used as the ultraviolet absorber. Specific examples of the ultraviolet absorber include 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-ethylhexyloxy) ... benzotriazine-based ultraviolet absorbers such as 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; Examples of suitable ultraviolet absorbers include 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, and 2-[2-hydroxy-5-(2-(meth)acryloyloxyethyl)phenyl]-2H-benzotriazole; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate and octyl-2-cyano-3,3-diphenylacrylate; and inorganic particles that absorb ultraviolet light, such as titanium oxide fine particles, zinc oxide fine particles, and tin oxide fine particles. The ultraviolet absorbers listed above may be used alone or in combination of two or more.

[0078] Commercially available ultraviolet absorbers may also be used, including TINUVIN PS, TINUVIN 99-2, TINUVIN 234, TINUVIN 326, TINUVIN 329, TINUVIN 900, TINUVIN 928, TINUVIN 360, TINUVIN 384-2, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (all manufactured by BASF), Adeka STAB LA-46, Adeka STAB LA-F70, Adeka STAB LA-29, Adeka STAB LA-31G, Adeka STAB LA-32, and Adeka STAB LA-36 (all manufactured by ADEKA Corporation), and RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0079] From the viewpoint of improving weather resistance, benzotriazine-type ultraviolet absorbers or ultraviolet absorbers having a (meth)acryloyl group are preferred, and preferred are TINUVIN 400, TINUVIN 405, and TINUVIN 479 (all manufactured by BASF), Adekastab LA-46 (manufactured by ADEKA), and RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0080] 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.

[0081] The composition of the present invention may contain a hindered amine light stabilizer (HALS) for the purpose of improving weather resistance. Known hindered amine light stabilizers can be used as the hindered amine light stabilizer, and specific examples thereof include 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, and bis(1 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-octoxy-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(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 tetracarboxylate, a 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, and a 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.

[0082] Commercially available hindered amine light stabilizers may also be used, including TINUVIN 123, TINUVIN 292, TINUVIN 152, TINUVIN 144, TINUVIN 622SF, TINUVIN 111FDL, TINUVIN 249, and Adeka STAB LA-52 (all manufactured by BASF Corporation); and Adeka STAB LA-57, Adeka STAB LA-63P, Adeka STAB LA-68, Adeka STAB LA-72, Adeka STAB LA-81, Adeka STAB LA-82, and Adeka STAB LA-87 (all manufactured by ADEKA Corporation).

[0083] From the viewpoint of improving weather resistance, TINUVIN 123, TINUVIN 152, TINUVIN 144 (all manufactured by BASF Corporation); 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 Corporation), Adeka STAB LA-82 (manufactured by ADEKA Corporation), and Adeka STAB LA-87 (manufactured by ADEKA Corporation) are preferred. More preferred are TINUVIN 123 and TINUVIN 152 (all manufactured by BASF Corporation); Adeka STAB LA-63P, Adeka STAB LA-82 (manufactured by ADEKA Corporation), and Adeka STAB LA-87 (manufactured by ADEKA Corporation).

[0084] The amount of the hindered amine light stabilizer used is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass, based on 100% by mass of the composition.

[0085] Various surface modifiers may be added to the composition of the present invention for the purposes of improving leveling during application, increasing the slipperiness of the cured film, and improving scratch resistance. As surface modifiers, various additives that modify surface properties, commercially available under names such as surface conditioners, leveling agents, slipperiness-imparting agents, and antifouling agents, can be used. Among these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include 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, and fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain. One or more of these may be used. For purposes such as improving the durability of slipperiness, a compound containing a (meth)acryloyl group in the molecule may also be used.Specific surface modifiers include EBECRYL350 (Daicel Allnex Co., Ltd.), BYK-333 (BYK Japan Co., Ltd.), BYK-377 (BYK Japan Co., Ltd.), BYK-378 (BYK Japan Co., Ltd.), BYK-UV3500 (BYK Japan Co., Ltd.), BYK-UV3505 (BYK Japan Co., Ltd.), BYK-UV3576 (BYK 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 Corporation), TOKA), ZX-201 (T & K TOKA Corporation), ZX-202 (T & K TOKA Corporation), ZX-212 (T & K TOKA Corporation), ZX-214-A (T & K TOKA Corporation), 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.), and the like.

[0086] The active energy ray-curable composition of the present invention can be suitably used as a cured coating for protecting a substrate by applying it to at least one surface of various materials and then irradiating it with active energy rays. The cured coating formed from the composition of the present invention has weather resistance and abrasion resistance, as well as high chemical resistance, and exhibits excellent adhesion to various materials even in harsh environments such as high temperature and humidity. Therefore, it exhibits excellent effects when used as a protective coating for materials used for long periods in harsh environments such as outdoors or around automobiles. Furthermore, the active energy ray-curable composition of the present invention has moderate substrate erosion properties and therefore particularly excellent adhesion to the substrate. Therefore, a highly adhesive coating can be formed on a coating formed by partially or completely curing the active energy ray-curable composition. Therefore, even if the thickness of the cured coating is insufficient after a single application and curing, repeated application and curing can form a thick cured coating with excellent durability.

[0087] <Laminate> The laminate of the present invention has a cured layer of the above-mentioned active energy ray-curable composition. The laminate may have one or more other layers in addition to the cured layer, and the other layers may include, for example, a substrate layer. Methods for producing the substrate and the laminate will be described later.

[0088] <Method for producing laminate> The method for producing a laminate of the present invention includes step 1 of applying the above-described active energy ray-curable composition onto a substrate to obtain a coating film, and step 2 of irradiating the coating film with active energy rays to cure a part or all of the coating film.

[0089] (Step 1) In step 1, the active energy ray-curable composition described above is applied to a substrate to obtain a coating film. The substrate is not particularly limited and may be selected appropriately depending on the application. Specific examples include plastic, wood, metal (steel, stainless steel, aluminum, etc.), metal oxide, paper, silicon, modified silicon, etc., and may be a substrate obtained by joining different materials, or a substrate on which the active energy ray-curable composition of the present invention or another composition is laminated as a primer. In particular, the active energy ray-curable composition of the present invention has excellent adhesion to plastic substrates (resin substrates) and resin primers. As described above, resin materials have drawbacks such as low abrasion resistance, which easily leads to loss of gloss and transparency, and poor weather resistance. However, these drawbacks can be improved by coating a plastic substrate or resin primer with the composition of the present invention. Therefore, a plastic substrate or a resin primer is preferred as the substrate for the laminate.

[0090] The plastic substrate is not particularly limited as long as it is made of resin and can be selected according to the purpose. Specifically, the above-mentioned thermosetting resins and thermoplastic resins can be used. When a transparent laminate is to be obtained, polycarbonate resins (e.g., aliphatic polycarbonates, aromatic polycarbonates, alicyclic polycarbonates, etc.), polymethyl methacrylate resins, polystyrene resins, etc. are preferably used. Furthermore, the plastic substrate may be made of a single resin or a blend of multiple resins, and may have a single layer or a laminate structure of two or more layers. Furthermore, the plastic substrate may contain known additives such as known antistatic agents, antifogging agents, antiblocking agents, ultraviolet absorbers, antioxidants, pigments, organic fillers, inorganic fillers, light stabilizers, crystal nucleating agents, and lubricants, and may be fiber-reinforced plastic (FRP).

[0091] The resin primer may be a known water-soluble or water-dispersed paint, an organic solvent-based or organic solvent-dispersed paint, or a powder paint. Specifically, various types of primers may be used, such as acrylic resin-based paints, polyester resin-based paints, alkyd resin-based paints, epoxy resin-based paints, fatty acid-modified epoxy resin-based paints, silicone resin-based paints, polyurethane resin-based paints, fluoroolefin-based paints, or amine-modified epoxy resin paints. The undercoat paint may be a clear paint that does not contain a pigment, an enamel-based paint that contains the pigment, or a metallic paint that contains aluminum flakes or the like. It may also be a paint used for electrodeposition paints, intermediate paints, topcoats, or precoats of metals used on automobile bodies.

[0092] The shape of the substrate is not particularly limited, and may be any shape depending on the purpose, such as a flat plate, a sheet, or a three-dimensional shape having a curvature (bending) over the entire surface or in part, etc. Furthermore, the hardness, thickness, etc. of the substrate are not particularly limited, and can be determined arbitrarily.

[0093] The method for applying the composition is not particularly limited, and examples thereof include inkjet coating, spray coating, spin coating, dipping, roll coating, blade coating, doctor roll coating, doctor blade coating, curtain coating, slit coating, and screen printing. A coating film can be obtained by applying the composition to a substrate using these methods. Furthermore, when the composition is to be recoated after curing, inkjet coating and spray coating are preferred from the viewpoint of coating technique.

[0094] (Step 2) In step 2, the coating film obtained in step 1 is irradiated with active energy rays to partially or completely cure the coating film. Since the composition of the present invention contains a compound having a polymerizable unsaturated group, it can be cured by irradiating with active energy rays to form a cured coating (cured layer). The entire coating film may be cured by a single irradiation to form a cured coating, or it may be cured by irradiating only a portion of the coating film, and then irradiating multiple times to gradually increase the degree of curing to finally form a cured coating. Furthermore, between multiple irradiations, an active energy ray-curable composition may be further applied from above.

[0095] Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. Among these, ultraviolet rays (UV) are preferred from the standpoints of curability and convenience. When ultraviolet rays are used as active energy rays, examples of devices 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, and LED lamps. By using these, a cured coating or cured product can be obtained by irradiating a coated or molded composition with ultraviolet rays having a wavelength of approximately 180 to 400 nm. The amount of ultraviolet radiation is appropriately selected depending on the type and amount of the photopolymerization initiator used.

[0096] After completion of step 2, steps 1 and 2 may be repeated in this order at least once. Repeating step 1 (application) and step 2 (curing) can thicken the cured coating. This method is useful when the thickness of the cured coating is insufficient after a single application and curing, due to the balance between the application method and the required coating thickness. Because the composition of the present invention has moderate substrate erosion properties, adhesion is not impaired even when a cured coating is formed on a coating made of the cured composition. Furthermore, to improve adhesion, the coating film can be left partially cured (semi-cured) rather than completely cured in step 2 during the intermediate stage. Leaving a portion uncured improves adhesion to the underlying layer. When only a portion of the coating film is cured, the degree of curing can be adjusted by adjusting the amount of active energy radiation irradiated.

[0097] The laminate of the present invention may further include a second substrate on the substrate and the cured layer. The material of the second substrate is not particularly limited, and examples thereof include wood, metal, metal oxide, plastic, paper, silicon, or modified silicon. It may also be a substrate obtained by bonding different materials. The shape of the substrate is not particularly limited, and it may be any shape depending on the purpose, such as a flat plate, a sheet, or a three-dimensional shape having curvature on the entire surface or in part. Furthermore, there are no limitations on the hardness, thickness, etc. of the substrate.

[0098] The laminate of the present invention can be preferably used as an interlayer material between different materials because the cured layer has high adhesion to both plastics and inorganic materials. It is particularly preferred that the substrate is plastic and the second substrate is an inorganic layer. Examples of inorganic layers include quartz, sapphire, glass, optical films, ceramic materials, inorganic oxides, vapor-deposited films (CVD, PVD, sputtering), magnetic films, reflective films, metals such as Ni, Cu, Cr, Fe, and stainless steel, paper, SOG (Spin On Glass), SOC (Spin On Carbon), plastic layers such as polyester, polycarbonate, and polyimide, TFT array substrates, PDP electrode plates, conductive substrates such as ITO and metals, insulating substrates, silicon substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon.

[0099] Furthermore, the cured layer of the present invention has excellent processability even after the active energy ray-curable composition has cured to form a cured layer, and therefore can be bent together with the substrate. For example, the composition can be directly applied to a flat substrate to obtain a coated substrate, and then the coating film can be irradiated with active energy rays to form a cured film-coated substrate (i.e., a laminate), and the cured film can still be bent. This eliminates the need for consideration when applying the composition to a curved substrate, significantly improving the productivity of bendable materials. Furthermore, the molded product of the present invention not only has excellent flexibility under heat, but also excellent hard coat properties after thermal bending. When bending is performed, the thickness of the coating film obtained by applying the composition of the present invention is preferably 0.5 to 40 μm, more preferably 3 to 35 μm, even more preferably 5 to 30 μm, and particularly preferably 10 to 25 μm. A thickness of at least the above lower limit ensures sufficient abrasion resistance and weather resistance, while a thickness of at most the above upper limit ensures good flexibility.

[0100] The bending method is not particularly limited, and examples thereof include bending the laminate directly, as well as press molding, free blow molding, vacuum molding, pressure molding, twin composite molding, etc. The temperature for the hot bending is preferably 80°C or higher, more preferably 150°C or higher. The upper limit temperature can be appropriately set below the melting temperature of the substrate.

[0101] The laminate of the present application is excellent in weather resistance, abrasion resistance, chemical resistance, adhesion, and appearance, and therefore can be particularly suitably 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, and resin glass protection, and is particularly suitable for use in automobile headlamp lenses, automobile glazing, automobile body exteriors, plastic building materials, and steel sheet building materials.

[0102] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following aspects. In the examples, "parts" and "%" are by mass unless otherwise specified.

[0103] (Synthesis Example 1: Synthesis of UA-1) In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, BASF "Basonat (registered trademark) HA 3000" (NCO equivalent 19.5% by mass, 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, and the temperature was raised to 70°C. 2-hydroxyethyl acrylate (116.1 parts by mass) was added in portions over 1 hour. After the addition, 2250 cm3 indicating an isocyanate group was obtained. －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, yielding a urethane (meth)acrylate compound UA-1 having an allophanate bond.

[0104] (Synthesis Example 2: Synthesis of UA-2) In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, BASF's "Basonat (registered trademark) HA 3000" (NCO equivalent 19.5% by mass, 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, and the temperature was raised to 70°C. 4-hydroxybutyl acrylate (144.2 parts by mass) was added in portions over 1 hour. After the addition, 2250 cm3 indicating an isocyanate group was obtained. －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, yielding a urethane (meth)acrylate compound UA-2 having an allophanate bond.

[0105] (Synthesis Example 3: Synthesis of UA-3) A 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer was charged with BASF's "Basonat (registered trademark) HA 3000" (NCO equivalent 19.5% by mass, 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), and the temperature was raised to 70°C. 2-hydroxyethyl acrylate (77.4 parts by mass) and Daicel's "Placcel-210" (hydroxyl value: 113.4, 164.90 parts by mass) were charged in portions over 1 hour. After charging, the 2250 cm3 indicating the isocyanate group was －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, yielding a urethane (meth)acrylate compound UA-3 having an allophanate bond.

[0106] Synthesis Example 4 Synthesis of UA-4 A 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer was charged with BASF's "Basonat (registered trademark) HA 3000" (NCO equivalent 19.5% by mass, 213.39 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.12 parts by mass), methoxyhydroquinone (0.11 parts by mass), and dibutyltin diacetate (0.11 parts by mass), and the temperature was raised to 70°C. Plaxel FA-2D (344.0 parts by mass) was added in portions over 1 hour. After the addition, a 2250 cm3 (indicating an isocyanate group) was obtained. －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, yielding a urethane (meth)acrylate compound UA-4 having an allophanate bond.

[0107] Synthesis Example 5 Synthesis of UA-5 A 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer was charged with DIC Corporation's "Burnoc DN-902S" (NCO equivalent 23.5% by mass, 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), and the temperature was raised to 70°C. 2-hydroxyethyl acrylate (116.1 parts by mass) was added in portions over 1 hour. After the addition, a 2250 cm3 (indicating an isocyanate group) was obtained. －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, yielding a urethane (meth)acrylate compound UA-5 having an isocyanurate bond.

[0108] Synthesis Example 6 Synthesis of UA-6 A 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer was charged with DIC Corporation's "Burnoc DN-902S" (NCO equivalent 23.5% by mass, 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), and the temperature was raised to 70°C. 4-hydroxybutyl acrylate (144.2 parts by mass) was added in portions over 1 hour. After the addition, the 2250 cm3 (indicating the isocyanate group) －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, thereby obtaining a urethane (meth)acrylate compound UA-6 having an isocyanurate bond.

[0109] Synthesis Example 7: Synthesis of UA-7 A 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer was charged with DIC Corporation's "Burnoc DN-902S" (NCO equivalent 23.5% by mass, 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), and the temperature was raised to 70°C. 2-hydroxyethyl acrylate (77.4 parts by mass) and Daicel Corporation's "Placcel-210" (hydroxyl value: 113.4, 164.90 parts by mass) were added in portions over 1 hour. After the addition, 2250 cm －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, yielding a urethane (meth)acrylate compound UA-7 having an isocyanurate bond.

[0110] Synthesis Example 8 Synthesis of UA-8 A 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer was charged with DIC Corporation's "Burnoc DN-902S" (NCO equivalent 23.5% by mass, 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), and the temperature was raised to 70°C. Plaxel FA-2D (344.0 parts by mass) was added in portions over 1 hour. After the addition, the 2250 cm －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, yielding a urethane (meth)acrylate compound UA-8 having an isocyanurate bond.

[0111] (Synthesis Example 9: Synthesis of UA-9) In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Desmodur I" (NCO equivalent 37.8% by mass, 111.15 parts by mass) manufactured by Sumika Covestro Urethane Co., Ltd., 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 (116.1 parts by mass) was added in portions over 1 hour. After the addition, 2250 cm3 indicating an isocyanate group was obtained. －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, yielding a urethane (meth)acrylate compound UA-9 having an isocyanurate bond.

[0112] (Synthesis Example 10: Synthesis of UA-10) In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Desmodur I" manufactured by Sumika Covestro Urethane Co., Ltd. (NCO equivalent 37.8% by mass, 111.15 parts), 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 (116.1 parts by mass) and "Placcel-210" manufactured by Daicel Corporation (hydroxyl value: 113.4, 247.35 parts by mass) were added in portions over 1 hour. After the addition, 2250 cm3 indicating an isocyanate group was obtained. －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, yielding a urethane (meth)acrylate compound UA-10 having an isocyanurate bond.

[0113] (Synthesis Example 11: Synthesis of UA-11) A 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer was charged with Covestro's "Desmodur H" (84.10 parts by mass), 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), and the mixture was heated to 70 ° C., and Toagosei's "Aronix M-403 (hydroxyl value 92)" (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 an isocyanate group disappeared, to obtain a tetrafunctional or higher (meth)acrylate compound UA-11.

[0114] Synthesis Example 12 Synthesis of UA-12 A 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer was charged with DIC Corporation's "Burnoc DN-902S" (178.72 parts by mass), 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), and the temperature was raised to 70°C. To the flask, Toagosei Co., Ltd.'s "Aronix M-306 (hydroxyl value 157.2)" (356.87 parts by mass) was added in portions over 1 hour. After the addition, a 2250 cm3 (indicating an isocyanate group) was obtained. －１ The reaction was continued at 80° C. until the infrared absorption spectrum of the compound disappeared, yielding a tetrafunctional or higher (meth)acrylate compound UA-12.

[0115] Example 1 An active energy ray-curable composition of Example 1 was prepared by uniformly mixing 10 parts by mass of 1,4-butanediol diacrylate as the component (A), 10 parts by mass of UA-1 as the component (B2), 80 parts by mass of tris-(2-acryloxyethyl)isocyanurate as the component (C), 1.5 parts by mass of Omunirad 754 (manufactured by IGM) and 1.5 parts by mass of Omunirad 819 (manufactured by IGM) as photopolymerization initiators, 0.25 parts by mass of Tinuvin 123 (manufactured by BASF) as a HALS, and 4 parts by mass of RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorber with a 50 / 50 mass% mixed organic solvent of propylene glycol monomethyl ether / butyl acetate to a solids content of 70 mass%.

[0116] (Examples 2 to 44, Comparative Examples 1 to 5) Active energy ray-curable compositions of each example were obtained in the same manner as in Example 1, except that the compositions and solid content ratios were changed as shown in Tables 1 to 6. Note that, although the photopolymerization initiator and organic solvent type are not shown in the tables, they were used in all examples in the same manner as in Example 1.

[0117] [Preparation of Evaluation Samples] The active energy ray-curable composition of each example was applied to a substrate shown in Tables 1 to 6 using a bar coater, dried at 80°C for 4 minutes, and then exposed to an ultraviolet ray irradiation device (GS-YUASA Corporation, high-pressure mercury lamp) in the atmosphere at an illuminance of 200 mW / cm. ２ , irradiation light amount 1000mJ / cm ２ A laminate having a cured coating film with a thickness of 20 μm was obtained.

[0118] [Appearance Evaluation] The appearance of the evaluation sample of each example after curing was visually observed and evaluated according to the following criteria, with a grade of B or higher being considered acceptable. The results are shown in Tables 1 to 6 as "appearance." A: No poor appearance B: Irregularities in the base or scratches on the base during painting are slightly visible C: Partial whitening D: Complete whitening

[0119] [Chemical Resistance Evaluation] A spot test was performed on each evaluation sample using a drop test method using a 40% by weight aqueous solution of sulfuric acid in accordance with JIS K 5600-6. The maximum time during which no appearance defects were observed in the cured coating was recorded as the evaluation result. A time of 15 minutes or more was considered pass, and a score of "50" was recorded when no appearance defects were observed for more than 50 minutes after the end of the test. The resulting time (unit: minutes) is recorded as "chemical resistance" in Tables 1 to 6.

[0120] [Weather Resistance Evaluation A] An accelerated weather resistance test (SUV test) was performed on the evaluation samples of each example under the following conditions: Conditions: Irradiation (63°C, 90% RH, 100 mW / cm ２The test was repeated under the following conditions: darkness (70°C, 90% RH, 4 hours) → darkness (70°C, 90% RH, 4 hours) → condensation (30°C, 98% RH, 4 hours), with showers before and after irradiation. The appearance was visually checked after each cycle (96 hours), and the maximum number of cycles in which cracks were not observed in the cured coating was used as the evaluation result. 3 cycles (288 hours) or more was considered a pass. If no cracks were observed after 15 cycles or more, the result was rated as "15." The maximum number of cycles for each example is shown in Tables 1 to 6 as the result for "Weather Resistance A."

[0121] [Weather Resistance Evaluation B] An SUV test was conducted under the same conditions as in Weather Resistance Evaluation A, and a cellophane tape adhesion test was conducted on the surface of the evaluation sample every 96 hours. In the cellophane tape adhesion test, the surface condition after the peel test was visually observed, and if peeling was observed, the number of cycles that had elapsed at that point was used as the evaluation result, with 3 cycles (288 hours) or more being considered a pass. If no peeling was observed even after 15 cycles, the result was rated as "15." The maximum number of cycles for each example is listed in Tables 1 to 6 as the result for "Weather Resistance B."

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128] The abbreviations shown in Tables 1 to 6 respectively represent the following compounds or the compounds obtained in the above-mentioned synthesis examples: 1,4-BDA: 1,4-butanediol diacrylate 1,6-HDA: 1,6-hexanediol diacrylate 1,9-NDA: 1,9-nonanediol diacrylate 1,10-DDA: 1,10-decanediol diacrylate DPGDA: dipropylene glycol diacrylate (manufactured by Daicel Allnex Corporation) A-200: polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) A-DCP: tricyclodecane dimethane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) A9300: tris(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd.) A9300-CL: caprolactone-modified tris(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd.) TEMPTA: Trimethylolpropane triacrylate (manufactured by Daicel Allnex Corporation) DPHA: Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) DPCA-20: Caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) DPCA-60: Caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.) Tinuvin 123: HALS "Tinuvin 123" (trade name, manufactured by BASF Corporation) Tinuvin 152: HALS "Tinuvin 152" (trade name, manufactured by BASF Corporation) LA-82: HALS "ADK STAB LA-82" (trade name, manufactured by ADEKA Corporation) LA-46: UV absorber "ADK STAB LA-46" (trade name, manufactured by ADEKA Corporation) Tinuvin 479: UV absorber "Tinuvin 479" (trade name, manufactured by BASF Corporation) Ruva-93: UV absorber "Ruv a-93" (trade name, manufactured by Otsuka Chemical Co., Ltd.) PE: Polyester resin-coated steel sheet (a substrate obtained by applying a white polyester-isocyanate paint with a pigment mass concentration (PWC) of 60% to the surface of a 2 mm-thick zinc-treated steel sheet to a dry film thickness of 30 to 40 μm and heat-curing the paint for 30 minutes at 80°C, substrate thickness 2 mm) PC: Polycarbonate resin substrate (Teijin Limited, Panlite L-1225ZL, thickness 3 mm)ABS: ABS resin substrate (Nippon A&L "Clarastic GA-701 JH22", thickness 3 mm) AU: Acrylic urethane resin-coated steel plate (a substrate obtained by applying a white acrylic urethane paint with a PWC of 60% to the surface of a 2 mm-thick zinc-treated steel plate to a dry film thickness of 30-40 μm and heat-curing the paint for 30 minutes at 80°C, substrate thickness 2 mm) EP: Epoxy resin-coated steel plate (a substrate obtained by applying a white acid-epoxy curing paint with a PWC of 60% to the surface of a 2 mm-thick zinc-treated steel plate to a dry film thickness of 30-40 μm and heat-curing the paint for 30 minutes at 80°C, substrate thickness 2 mm)

[0129] The results of Examples 1 to 44 confirmed that the cured coatings of the active energy ray-curable compositions of the present invention were excellent in appearance, chemical resistance, weather resistance, and adhesion, whereas Comparative Examples 1 to 5, which did not contain any of the components, were inferior in at least one of the properties.

[0130] Example 45 The active energy ray-curable composition of Example 2 was applied to the same polyester resin-coated steel sheet substrate as above using a bar coater, dried at 80°C for 4 minutes, and then irradiated with ultraviolet light in the atmosphere using an ultraviolet ray irradiation device (GS-YUASA Corporation, high-pressure mercury lamp) at an illuminance of 200 mW / cm. ２ , the irradiation light amount 1 (unit: mJ / cm ２ The same active energy ray-curable composition was applied onto the resulting coating using a bar coater, dried at 80°C for 4 minutes, and then irradiated with a similar ultraviolet ray irradiation device at an illuminance of 200 mW / cm under atmospheric pressure. ２ , the irradiation light amount 2 (unit: mJ / cm ２ ) to obtain a laminate having a cured coating with a total thickness of 20 μm.

[0131] (Examples 46 to 50, Comparative Examples 6 to 9) Using the active energy ray-curable compositions of the Examples or Comparative Examples shown in Tables 7 to 8, laminates of each example were obtained in the same manner as in Example 45, except that the irradiation light amount in Tables 7 to 8 was changed to 1 or 2.

[0132] The obtained laminates of each example were used as evaluation samples and were subjected to appearance evaluation, chemical resistance evaluation, and weather resistance evaluations A and B in the same manner as in Example 1. The results are shown in Tables 7 and 8. Note that in the weather resistance evaluation B of Comparative Example 8, peeling was observed before the start of the test, so the result was set to "0."

[0133]

[0134]

[0135] The results of Examples 45 to 50 confirmed that the cured coatings of the active energy ray-curable compositions of the present invention were excellent in appearance, chemical resistance, weather resistance, and adhesion, whereas Comparative Examples 6 to 9 were inferior in at least one of the properties.

Claims

1. An active energy ray-curable composition comprising: a compound (A) having a chain hydrocarbon group having 2 to 12 carbon atoms and two (meth)acryloyloxy groups; a urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond; and a (meth)acrylate compound (C) having an isocyanurate bond.

2. The urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond has, in addition to the isocyanurate bond, the allophanate bond and the (meth)acryloyl group, —O—C(═O)—(CH ２ ) ｎＡ (nA represents an integer of 1 to 6), and a compound (B1) having, in addition to an isocyanurate bond, an allophanate bond, and a (meth)acryloyl group, —O—C(═O)—(CH ２ ) ｎＡ (nA represents an integer of 1 to 6).

3. The active energy ray-curable composition according to claim 1 , further comprising a compound (D) containing four or more (meth)acryloyl groups in one molecule.

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

5. A laminate having a cured layer of the active energy ray-curable composition according to any one of claims 1 to 4.

6. A step 1 of applying the active energy ray-curable composition according to any one of claims 1 to 4 onto a substrate to obtain a coating film; and A method for producing a laminate, comprising the step 2 of irradiating the coating film with active energy rays to partially or entirely cure the coating film.

7. The method for producing a laminate according to claim 6 , further comprising repeating steps 1 and 2 in this order at least once after step 2.