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

Abstract

The purpose of the present invention is to provide: an active energy ray-curable composition capable of forming a cured coating film and a cured layer having weather resistance and chemical resistance and excellent appearance; a laminate having the cured layer; and a method for producing the laminate. The present invention relates to an active energy ray-curable composition characterized by containing a compound (A) containing a chain hydrocarbon group having 2-12 carbon atoms and two (meth) acryloyloxy groups, and a compound having an isocyanurate bond or an urea formate bond.

Description

Technical Field

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

[0002] Resin materials, particularly transparent resin materials such as polycarbonate, are widely used in a variety of applications due to their low specific gravity, light weight, ease of processing, and impact resistance compared to inorganic glass. Resin primers are also applied to glass and metal steel sheets to prevent discoloration and rust, and to provide adhesion to other materials.

[0003] However, resin materials and resin primers have the following disadvantages: susceptibility to surface damage, loss of gloss, poor transparency, susceptibility to corrosion by organic solvents, poor weather resistance (e.g., light stability to ultraviolet rays, etc.), 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 coats formed by curing active energy ray-curable compositions.

[0004] Resin materials used outdoors require excellent weather resistance.

[0005] As an active energy ray-curable composition having both adhesion, abrasion resistance, and weather resistance, Patent Document 1 discloses a composition containing the following substances in specific proportions: 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; and an alkyl di(meth)acrylate having 4 to 12 carbon atoms; and a photopolymerization initiator.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2013-10921 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] In recent years, resin materials, resin primers, and active energy ray-curable compositions suitable for use outdoors in harsh environments, such as those around cars, have been required to exhibit not only weather resistance and abrasion resistance, but also resistance to acid rain and automotive battery fluid, that is, excellent chemical resistance. However, the invention described in Patent Document 1 does not include research related to chemical resistance.

[0011] Furthermore, the composition described in Patent Document 1 contains organic monomers with high substrate-eroding properties, such as alkyl di(meth)acrylates having 4 to 12 carbon atoms. Therefore, when using resin substrates such as polycarbonate or various resin primers that are susceptible to corrosion, the composition may excessively erode these substrates, resulting in poor appearance of the coating film and deterioration of weather resistance.

[0012] Therefore, the invention described in Patent Document 1 cannot simultaneously solve the problems of chemical resistance and weather resistance, and cannot form a coating film or cured film with good appearance.

[0013] The present invention has been made in view of the above problems and provides an active energy ray-curable composition capable of forming a cured coating film and a cured layer having weather resistance and chemical resistance and excellent appearance, a laminate having the cured layer, and a method for producing the laminate.

[0014] Solutions for solving problems

[0015] The present inventors have diligently studied and, as a result, have discovered that the aforementioned problems can be solved by using, in combination, an alkyl di(meth)acrylate compound that is effective for improving adhesion and weather resistance and a compound having an isocyanurate bond or an allophanate bond that can inhibit the alkyl di(meth)acrylate from corroding the resin substrate / resin primer, thereby completing the present invention.

[0016] That is, the present invention provides the following inventions.

[0017] (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; and a compound having an isocyanurate bond or an allophanate bond.

[0018] (2) The active energy ray-curable composition according to (1), wherein 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.

[0019] (3) The active energy ray-curable composition according to (2), further comprising a (meth)acrylate compound (C) having an isocyanurate bond.

[0020] (4) The active energy ray-curable composition according to (2) or (3), wherein the urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond contains: in addition to the isocyanurate bond, the allophanate bond and the (meth)acryloyl group, a -OC(=O)-(CH2) nA(nA represents an integer of 1 to 6) compound (B1); and does not have -OC(=O)-(CH2) in the structure except for the isocyanurate bond, the allophanate bond and the (meth)acryloyl group nA (nA represents an integer of 1 to 6) is a compound (B2).

[0021] (5) The active energy ray-curable composition according to any one of (1) to (4), further comprising a compound (D) having four or more (meth)acryloyl groups in one molecule.

[0022] (6) The active energy ray-curable composition according to any one 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% by mass or less based on the total amount of the composition.

[0023] (7) A laminate having a cured layer of the active energy ray-curable composition according to any one of (1) to (6).

[0024] (8) A method for producing a laminate, characterized in that it comprises: step 1, applying the active energy ray-curable composition described in any one of (1) to (6) on a substrate to obtain a coating film; and step 2, irradiating the coating film with active energy rays to cure a portion or all of the coating film.

[0025] (9) The method for producing a laminate according to (8), wherein after the step 2, the steps 1 and 2 are repeated in this order at least once.

[0026] Effects of the Invention

[0027] The active energy ray-curable composition of the present invention can form a cured film that fully meets the required properties for a cured film, such as adhesion and abrasion resistance, while also exhibiting excellent chemical resistance, high weather resistance, and a superior appearance. This cured film exhibits excellent adhesion to resin substrates such as polycarbonate and resin primers, and exhibits excellent durability even in high-temperature, high-humidity environments and environments exposed to 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 applications, and is particularly suitable for automotive exterior applications and automotive glazing. DETAILED DESCRIPTION

[0028] <Active Energy Ray-Curable Composition>

[0029] The active energy ray-curable composition of the present invention (hereinafter sometimes simply referred to as "composition" or "composition") contains: a compound (A) (hereinafter sometimes referred to as "component (A)") containing 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.

[0030] 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. In addition, "acrylate" and "methacrylate" are collectively referred to as "(meth)acrylate". Regarding "acrylic acid" and "methacrylic acid", "acryloyl" and "methacryloyl", "acryloyloxy" (CH2=CH-CO-O-) and "methacryloyloxy" (CH2=C(CH3)-CO-O-), the expressions "(meth)acrylic acid" and "(meth)acryloyloxy" are also explained as including both concepts.

[0031] [(A) ingredient]

[0032] The component (A) is a compound containing a chain hydrocarbon group having 2 to 12 carbon atoms and two (meth)acryloyloxy groups. When the composition contains the component (A), the substrate adhesion and weather resistance of the cured film are improved.

[0033] The chain hydrocarbon group having 2 to 12 carbon atoms may be linear or branched, but is preferably linear. The number of carbon atoms is preferably 4 to 10, more preferably 6 to 10. In particular, from the perspective of reducing skin irritation to workers during production operations, the number of carbon atoms is preferably 8 to 10.

[0034] Specific examples of the component (A) include (meth)acrylates having a linear hydrocarbon group such as 1,3-propylene glycol di(meth)acrylate, 1,4-butylene glycol 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-propylene glycol di(meth)acrylate.

[0035] As the component (A), one compound may be used alone, or two or more compounds may be used in combination.

[0036] The content of component (A) in the total of 100% by mass of the component (A), the compound having an isocyanurate bond or an allophanate bond (specifically, one or more 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 "the total of 100% by mass of components (A) to (D)") is preferably 10% to 60% by mass, more preferably 15% to 55% by mass, and even more preferably 20% to 50% by mass. By setting the content to be greater than or equal to the lower limit, substrate adhesion and weather resistance are further improved, and by setting the content to be less than or equal to the upper limit, weather resistance is further improved.

[0037] [Compound having an isocyanurate bond or an allophanate bond]

[0038] The composition of the present invention contains a compound having an isocyanurate bond or an allophanate bond. The isocyanurate bond and the allophanate bond are represented by the following formula (i) and formula (ii), respectively. By combining the compound having an isocyanurate bond or an allophanate bond with component (A), excessive erosion of the resin substrate and the 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 film.

[0039] The compound has no particular limitation on other structures as long as it has an isocyanurate bond or an allophanate bond, but preferably has a polymerizable group, and more preferably has a (meth)acryloyl group ((meth)acryloyloxy group) as in the component (A).

[0040]

[0041] Among them, 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.

[0042] [(B) ingredient]

[0043] The urethane (meth)acrylate compound (B) (hereinafter, sometimes referred to as “component (B)”) having an isocyanurate bond or an allophanate bond is a component that contributes to the weather resistance and adhesion of the cured film.

[0044] The 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, it is preferred that the component (B) further has -OC(=O)-(CH2) in its structure in addition to the isocyanurate bond, the allophanate bond, and the (meth)acryloyl group. nA (nA represents an integer of 1 to 6), preferably a compound represented by the following formula (2).

[0045]

[0046] In formula (2), R 21 ~R 25 Each independently is a group having a polymerizable group.

[0047] As R 21 ~R 25 The polymerizable group is preferably a (meth)acryloyl group (CH2=CR 4 -CO-(R 4 Same as above)), R 21 ~R 25 A combination of a (meth)acryloyl group and a divalent linking group is preferred.

[0048] As R 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-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-, -C(=NH)-NH-, and -NH-C(=NH)-, and combinations thereof. It should be noted that the hydrogen atoms of the groups listed as the divalent linking groups may be substituted with an alkyl group, an alkoxy group, an acyl group, or the like.

[0049] n1 to n2 are each independently 0 or 1.

[0050] L 21 ~L 22 are each independently a divalent linking group.

[0051] L 21 ~L 22 The divalent linking group preferably has a structure in which hydroxyl groups are removed from both ends of an alkylene glycol, a caprolactone-modified diol, or a polytetramethylene glycol. The alkylene glycol is preferably an alkylene glycol having 2 to 10 carbon atoms, and the number of repeating tetramethylene groups in the polytetramethylene glycol is preferably 8 to 30.

[0052] Examples of the caprolactone-modified diol 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 a side chain; "Placcel L205AL," a polycaprolactone diol having a mass average molecular weight of 500 and being liquid at room temperature; "Placcel 205H," a polycaprolactone diol having a mass average molecular weight of 530 and having improved water resistance compared to Placcel 205; "Placcel 205U," a polycaprolactone diol having a mass average molecular weight of 530 and having a lower viscosity and acid value than Placcel 205; and "Placcel L205L," a polycaprolactone diol having a mass average molecular weight of 830. 208", a polycaprolactone diol with a mass average molecular weight of 830 that is liquid at room temperature, namely "Placcel L208AL", a polycaprolactone diol with a mass average molecular weight of 1000, namely "Placcel 210BA", a polycaprolactone diol with a mass average molecular weight of 1000 having a carboxyl group in the side chain, namely "Placcel 210CP", a polycaprolactone diol with a mass average molecular weight of 1000 that has a lower acid value and improved water resistance than Placcel 210, namely "Placcel 210N", a polycaprolactone diol with a mass average molecular weight of 1000 that has a narrower molecular weight distribution than Placcel 210, and a polycaprolactone diol with a mass average molecular weight of 1250, namely "Placcel 210CP". 212", "Placcel L212AL", a polycaprolactone diol with a mass average molecular weight of 1250 that is 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 having carboxyl groups in the side chains, "Placcel 220CPB", a polycaprolactone diol with a mass average molecular weight of 2000 that has a lower acid value and improved water resistance than Placcel 220, "Placcel 220N", a polycaprolactone diol with a mass average molecular weight of 2000 that has a narrower molecular weight distribution than Placcel 220, and "Placcel 220N", a polycaprolactone diol with a mass average molecular weight of 2000 that has lower crystallinity than Placcel 220. 220NP1", a polycaprolactone diol with a mass average molecular weight of 2000 that is liquid at room temperature, namely "Placcel L220AL", a polycaprolactone diol with a mass average molecular weight of 3000 that is liquid at room temperature, namely "Placcel 230", a polycaprolactone diol with a mass average molecular weight of 3000 that is liquid at room temperature, namely "Placcel L230AL", a polycaprolactone diol with a mass average molecular weight of 3000 that has a lower acid value and improved water resistance than Placcel 230, namely "PlaccelPlacel 230CP", a polycaprolactone diol with a mass average molecular weight of 4000, Placel 240CP, a polycaprolactone diol with a mass average molecular weight of 4000 having a lower acid value and improved water resistance than Placel 240, Placel 220EB, a polycaprolactone diol with a mass average molecular weight of 2000 having improved hydrolysis resistance compared to Placel 220, and Placel 220EC, a polycaprolactone diol with a mass average molecular weight of 2000 having excellent elastic recovery compared to Placel 220EB (all trade names, manufactured by Daicel Chemical Industries, Ltd.).

[0053] Among these, from the viewpoint of weather resistance and abrasion resistance of the obtained cured film, polycaprolactone diol having a mass average molecular weight within the range of 500 to 1500 is preferred, and polycaprolactone diol having a mass average molecular weight within the range of 500 to 1000 is more preferred.

[0054] Furthermore, L 21 ~L 22 It is preferred that the other linking groups be present in addition to any one of the structures obtained by removing a hydroxyl group from the terminal of any one of alkylene glycol, caprolactone-modified glycol, or polytetramethylene glycol. 21 ~R 25 The groups listed as "divalent connecting groups possessed by

[0055] Z 21 ~Z 23 Each independently represents a structure represented by the following formula (2z).

[0056]

[0057] In formula (2z), X 21 It 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.

[0058] The * shown in formula (2z) is a connecting bond, and the Z in formula (2) is 21 In this case, the connecting bond represented by B1* and R 21 Direct bonding, the connecting bond represented by B2* and L 21 or R 22 Direct bonding, the connecting bond represented by B3* and L 22 or R 23 Direct bonding; in formula (2z), Z in formula (2) 22 In this case, the connection bond represented by B1* and L 22Direct bonding, the connecting bond represented by B2* and R 24 Direct bonding, the connecting bond represented by B3* and R 23 Direct bonding; in formula (2z), Z in formula (2) 23 In this case, the connection bond represented by B1* and L 21 Direct bonding, the connecting bond represented by B2* and R 22 Direct bonding, the connecting bond represented by B3* and R 25 Direct bonding.

[0059] Z 1 is an oxygen atom or a nitrogen atom, Z 2 is a hydrogen atom or -C(=O)-. 1 When Z is an oxygen atom (-O-), 2 is a hydrogen atom (-H). On the other hand, in Z 1 When Z is a nitrogen atom, 2 is -C(=O)-, Z 1 The nitrogen atom and Z 2 The -C(=O)- of the alkylene group is bonded to form a ring.

[0060] That is, in Z 1 When Z is an oxygen atom, the formula (2z) is a structure having an allophanate bond. 1 When it is a nitrogen atom, the formula (2z) is a structure having an isocyanurate bond. As for the (B) component, the formula (2z) is preferably a structure having an isocyanurate bond.

[0061] Among them, the compound (2) is preferably a compound represented by the following formula (2-1) to formula (2-4).

[0062]

[0063]

[0064] In formulas (2-1) to (2-4), R 26 are each independently a hydrogen atom or a methyl group.

[0065] In formulas (2-1) to (2-4), R 27 are each 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 -.

[0066] R A represents an alkylene group, and is preferably an alkylene group having 2 to 4 carbon atoms.

[0067] n each independently represents an integer of 1-10, and is preferably an integer of 1-5.

[0068] In formulas (2-1) to (2-4), X 22 Each independently represents 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.

[0069] In formula (2-2) and formula (2-4), A1 is a structure obtained by removing a hydroxyl group from the terminal of any one of alkylene glycol, caprolactone-modified diol, or polytetramethylene glycol, and is 21 ~L 22 The same as described in the text.

[0070] Multiple R in formula (2-1) to formula (2-4) 26 、R 27 、X 22 They may be the same as or different from each other.

[0071] As the component (B), one compound may be used alone or two or more compounds may be used in combination. In particular, it is preferred to use two or more components (B) in combination in order to achieve a good balance of various properties.

[0072] When two or more types are used, it is preferred to use in combination a compound having -OC(=O)-(CH2) in the structure in addition to the isocyanurate bond, the allophanate bond and the (meth)acryloyl group. nA (nA represents an integer of 1 to 6) and a compound (B1) having no -OC(=O)-(CH2) in its structure except for an isocyanurate bond, an allophanate bond and a (meth)acryloyl group. nA (nA represents an integer of 1 to 6) is a compound (B2).

[0073] When two or more components are used, the component (B) preferably includes a component (B11) and a component (B22). Component (B11) includes R in formula (2-1) or formula (2-3). 27 At least one of the above is R A -(O-CO-(CH2)5) n - or R A -(O-(CH2)4) n -, or A1 in formula (2-2) or formula (2-4) is a compound obtained by removing a hydroxyl group from the terminal of polytetramethylene glycol or polycaprolactone diol. As component (B22), R of formula (2-1) or formula (2-3) can be listed. 27The compound being an alkylene group, or A1 in the formula (2-2) or the formula (2-4) is a compound obtained by removing a hydroxyl group from the terminal of an alkylene glycol.

[0074] Among them, a combination of the component (B11) represented by formula (2-1) and the component (B22) represented by formula (2-1), or a combination of the component (B11) represented by formula (2-2) in which A1 has a polycaprolactone structure and the component (B22) represented by formula (2-1) is preferred.

[0075] When component (B) includes components (B1) and (B2), or when component (B) includes components (B11) and (B22), the content of component (B1) or (B11) is preferably 9% to 90% by mass, more preferably 20% to 70% by mass, further preferably 30% to 60% by mass, and particularly preferably 45% to 60% by mass, based on 100% by mass of the total solid content of components (A) to (C). Furthermore, the content of component (B2) or (B22) is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, further preferably 15% to 40% by mass, and particularly preferably 20% to 30% by mass, based on 100% by mass of the total solid content of components (A) to (C).

[0076] When the composition of the present invention contains component (B), the content of the entire component (B) is preferably 10% to 80% by mass, more preferably 15% to 70% by mass, and even more preferably 25% to 60% by mass, based on 100% by mass of the total of components (A) to (D). When the content is equal to or greater than the lower limit, weather resistance is improved, and when the content is equal to or less than the upper limit, wear resistance is improved.

[0077] [(C) ingredient]

[0078] The (meth)acrylate compound (C) (hereinafter, sometimes referred to as “component (C)”) having an isocyanurate bond is a component that contributes to the abrasion resistance and adhesion of the cured film.

[0079] The component (C) is a compound that does not belong to the component (B) and has an isocyanurate bond and a (meth)acrylate structure ((meth)acryloyl group) instead of a urethane bond. Specifically, the component (C) is preferably a compound represented by the following formula (1).

[0080]

[0081] In formula (1), R 1 、R 2 and R 3are each independently an oxyalkylene group or a polyoxyalkylene group.

[0082] The carbon number of the oxyalkylene group is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3.

[0083] The number of carbon atoms in the polyoxyalkylene group per repeating unit is 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 within the range of 1 to 10.

[0084] It should be noted that the oxygen atom of the oxyalkylene group and the terminal oxygen atom in the polyoxyalkylene group are the same as X in the formula. 1 、X 2 or X 3 bonding.

[0085] X 1 、X 2 and X 3 Each independently represents CH2=CR 4 -CO-、CH2=CR 4 -CO(O(CH2)5-CO) a1 -, hydrogen atom or alkyl group, but 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 difunctional or trifunctional (meth)acrylate.

[0086] R 4 Represents a hydrogen atom or a methyl group, multiple R 4 They may be the same or different, and are preferably hydrogen atoms.

[0087] a1 is an integer of 1 or greater, preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

[0088] Among them, X 1 、X 2 and X 3 Preferably CH2=CR 4 -CO-、CH2=CR 4 -CO(O(CH2)5-CO) a1 - or a hydrogen atom, more preferably X 1 ~X 3 At least two of them are CH2=CR 4 -CO-, particularly preferably all three are CH2=CR 4 -CO-.

[0089] Particularly preferred examples of the compound (1) include compounds represented by the following formula (1-1).

[0090] In the following formula, R 4 Same as above, R 1' ~R 3' It is an alkylene group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms).

[0091]

[0092] Specific structures of the component (C) include bis(2-acryloyloxyethyl)hydroxyethyl isocyanurate, tris(2-acryloyloxyethyl)isocyanurate (trade names: Aronix M-313 and Aronix M-315, manufactured by Toagosei Co., Ltd., trade names: NK Ester A9300 and A9300S, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and SR368 and SR368NS, manufactured by Arkema), bis(2-acryloyloxypropyl)hydroxyethyl isocyanurate, tris(2-acryloyloxypropyl)isocyanurate, tris(2-acryloyloxyethyl)isocyanurate modified with one caprolactone per molecule (trade name: Aronix M-325, manufactured by Toagosei Co., Ltd.), and tris(2-acryloyloxyethyl)isocyanurate modified with three caprolactones per molecule (trade name: Aronix M-327, manufactured by Toagosei Co., Ltd.).

[0093] As the component (C), one compound may be used alone, or two or more compounds may be used in combination.

[0094] When the composition of the present invention contains component (C), the content of component (C) is preferably 1% to 79% by mass, more preferably 3% to 67.5% by mass, and even more preferably 5% to 50% by mass, based on 100% by mass of the total of components (A) to (D). By setting the content to be equal to or greater than the lower limit, wear resistance and adhesion are further improved, while by setting the content to be equal to or less than the upper limit, weather resistance and chemical resistance are further improved.

[0095] The compound having an isocyanurate bond or an allophanate bond may be component (B), component (C), or both component (B) and component (C). The combined use of components (B) and (C) is preferred because it is easier to achieve improvements in weather resistance, chemical resistance, and adhesion, and reduce appearance defects.

[0096] [(D) ingredient]

[0097] Component (D) is a component not included in components (A) to (C) and is a compound containing four or more (meth)acryloyl groups in one molecule. The inclusion of component (D) in the composition improves the abrasion resistance and chemical resistance of the cured film.

[0098] The component (D) is not particularly limited as long as it has four or more (meth)acryloyl groups in one molecule. 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.

[0099] (D) The polyfunctional (meth)acrylate as the component is preferably a compound represented by the following formula (3-0).

[0100]

[0101] In formula (3-0), multiple R 30 At least 4 of them represent CH2=CR B -COO- or caprolactone-modified (meth)acryloyloxy CH2=CR B -CO(O(CH2)5C=O) y -O-, remaining R 30 Represents hydroxyl or CH2=CR B -COO-, CH2=CR 8 -CO(O(CH2)5C=O) y -O-.

[0102] R B Represents a hydrogen atom or a methyl group, in R B When it is a hydrogen atom, it becomes an acryloyl group. B When it is a methyl group, it becomes a methacryloyl group, and y is an integer of 1 or greater.

[0103] That is, compound (3-0) is a polymerizable compound having a pentaerythritol skeleton and four or more (meth)acryloyloxy groups in its structure. The presence of four or more (meth)acryloyloxy groups increases the crosslinking density during curing, resulting in improved abrasion resistance and chemical resistance.

[0104] n30 represents an integer of 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably n30=1 and compound (3-0) has a dipentaerythritol skeleton.

[0105] As the compound (3-0), one compound may be used alone, or two or more compounds may be used in combination.

[0106] (D) Urethane (meth)acrylate as the component can be obtained by reacting a (meth)acrylate compound having a hydroxyl group with an isocyanate compound.

[0107] As the (meth)acrylate compound having a hydroxyl group used for production of the urethane (meth)acrylate, a compound represented by the following formula (3-1) or formula (3-2) is preferable.

[0108] In the following formula, R 31 ~R 32 Each independently represents a hydrogen atom or a methyl group, and the multiple R 31 、R 32 They may be the same as or different from each other.

[0109]

[0110] Furthermore, as the isocyanate compound used for the production of the urethane (meth)acrylate, an aliphatic polyisocyanate or an alicyclic polyisocyanate having two or more isocyanate groups is preferable.

[0111] Specific examples 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-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, hydrogenated xylylene diisocyanate, 2-methyl-1,3-diisocyanatocyclohexane, and 2-methyl-1,5-diisocyanatocyclohexane, or dimers or trimers thereof.

[0112] 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.

[0113]

[0114] Where, X 31 ~X 32Each independently represents an alkylene group having 2 to 17 carbon atoms, preferably an alkylene group having 2 to 6 carbon atoms. 31 、X 32 They may be the same as or different from each other.

[0115] R 33 Indicates -R C -O-CO-CH=CH2 or a structure obtained by removing a hydroxyl group from a compound represented by the formula (3-1) or (3-2), R C 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.

[0116] When the composition of the present invention contains component (D), the content of the entire component (D) is preferably 1.0% to 40% by mass, more preferably 2.5% to 20% by mass, and even more preferably 5.0% to 10% by mass, based on 100% by mass of the total of components (A) to (D). By setting the content to be greater than or equal to the lower limit, chemical resistance is improved, while by setting the content to be less than or equal to the upper limit, weather resistance is improved.

[0117] [Other ingredients]

[0118] The composition of the present invention may optionally contain other components other than the above-mentioned components (A) to (D) within a range in which the effects of the present invention are obtained.

[0119] Examples of other ingredients include organic solvents, reactive compounds, various resins, fillers, polymerization initiators, stabilizers, ultraviolet absorbers, and leveling agents. Furthermore, the composition may contain inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, catalysts, surfactants, flow modifiers, coupling agents, dyes, rheology control agents, antioxidants, and plasticizers.

[0120] The composition of the present invention may or may not contain an organic solvent. Preferred compositions are solvent-free compositions that do not contain an organic solvent or high-solid compositions that contain a relatively low amount of organic solvent. Solvent-free or low-solvent / high-solid compositions can reduce environmental impact by reducing the amount of volatile organic compounds (VOCs).

[0121] When an organic solvent is contained, the content is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less, based on the total amount of the composition.

[0122] Examples of the organic solvent include ester solvents, ketone solvents, ether solvents, aliphatic solvents, aromatic solvents, and alcohol solvents.

[0123] Specifically, examples of ester solvents include ethyl acetate, propyl acetate, and butyl acetate; examples of ketone solvents include acetone, 2-butanone, methyl ethyl ketone, and methyl isobutyl ketone; examples of ether solvents include tetrahydrofuran and dioxolane; examples of aliphatic solvents include hexane and cyclohexane; examples of aromatic solvents include toluene and xylene; and examples of alcohol solvents include ethanol, methanol, propanol, butanol, and propylene glycol monomethyl ether.

[0124] 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 added. Examples of the (meth)acryloyl compound include monofunctional (meth)acrylates and difunctional to trifunctional (meth)acrylates that are not components (A) to (D).

[0125] Examples of the monofunctional (meth)acrylate include: (meth)acrylic acid alkyl esters 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; (meth)acrylic acid cycloalkyl esters, such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; and (meth)acrylic acid ω-alkoxyalkyl esters, such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate.

[0126] Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate (for example, the 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.

[0127] Examples of the difunctional to trifunctional (meth)acrylates include diol 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;

[0128] 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 ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, di(meth)acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, di(meth)acrylate or tri(meth)acrylate obtained by reacting 1 mol of tris(2-hydroxyethyl)isocyanurate with 2 to 3 mol 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, tetramethylene oxide The present invention also includes polytetramethylene glycol di(meth)acrylate modified with ethylene oxide, glycerol tri(meth)acrylate modified with ethylene oxide, glycerol tri(meth)acrylate modified with propylene oxide, trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, hydroxypivalic acid-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-modified phosphoric acid tri(meth)acrylate, polyester (meth)acrylate compounds synthesized by a condensation reaction of a polyol with (meth)acrylic acid and a polyfunctional carboxylic acid, epoxy (meth)acrylate compounds synthesized by an addition reaction of a novolac-type epoxy resin with a glycidyl group-containing acrylic polymer and (meth)acrylic acid, and acrylic acrylate compounds.

[0129] The reactive compound may be used alone or in combination of two or more, and is preferably used in an amount of 0 to 300 mass % relative to 100 mass % of the total solid content of components (A) to (D).

[0130] As various resins, thermosetting resins and thermoplastic resins can be used.

[0131] So-called thermosetting resin is a resin having a characteristic that is substantially insoluble and can be changed into infusibility when being cured by means such as heating or radiation, catalysts. As its specific example, so-called thermosetting resin is a resin having a characteristic that is substantially insoluble and can be changed into infusibility when being cured by means such as heating or radiation, catalysts. As its specific example, it can be enumerated as: phenolic resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, epoxy resin, silicone resin, carbamate resin, furan resin, ketone resin, xylene resin, thermosetting polyimide resin, benzoxazine resin, active ester resin, aniline resin, cyanate ester resin, styrene-maleic anhydride (SMA) resin etc. These thermosetting resins can be used one or two or more.

[0132] The so-called 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, polyacrylate resin, thermoplastic polyimide resin, polyamideimide resin, polyetheretherketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndiotactic polystyrene resin, cyclic polyolefin resin, etc. These thermoplastic resins may be used alone or in combination of two or more.

[0133] Liquid organic polymers can also be used to adjust the viscosity. Liquid organic polymers are those that do not directly contribute to the curing reaction. Examples include modified carboxyl-containing polymers (Flowlen G-900, NC-500: Kyoei Co., Ltd.), acrylic polymers (Flowlen WK-20: Kyoei Co., Ltd.), specially modified phosphate amine salts (HIPLAAD ED-251: Kusumoto Chemicals), and modified acrylic block copolymers (DISPERBYK 2000; BYK-Chemie).

[0134] As a filler, for example, silica may be blended for the purpose of improving abrasion resistance.

[0135] As silica, there is no limitation, and known silica particles such as powdered silica, colloidal silica, and nano silica can be used. Examples of commercially available powdered silica particles include Aerosil 50 and 200 manufactured by Japan Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., E220A and E220 manufactured by Nippon Silica Industries Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Co., Ltd., and SG FLAKE manufactured by Nippon Sheet Glass Co., Ltd.

[0136] In addition, commercially available colloidal silica includes, for example, methanol silica sol manufactured by Nissan Chemical Industries, Ltd., 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.

[0137] Reactive silica can also be used as the silica. Examples of reactive silica include reactive compound-modified silica. 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.

[0138] Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50 and R711 manufactured by Japan 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. Furthermore, 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 a hydroxyl group and a (meth)acryloyl group through a urethanization reaction between 3-isocyanatepropyltriethoxysilane and a compound having a hydroxyl group and a (meth)acryloyl group.

[0139] The shape of the silica particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or irregularly shaped silica particles can be used. For example, commercially available hollow silica particles such as SiliNax manufactured by Nippon Steel Mining Co., Ltd. can be used.

[0140] The primary particle size is preferably in the range of 5 nm to 200 nm. If it is 5 nm or larger, the inorganic fine particles in the composition are sufficiently dispersed, and if it is 200 nm or smaller, sufficient strength of the cured product can be maintained.

[0141] The content of silica in 100% by mass of the composition is preferably 3% by mass to 60% by mass.

[0142] Examples of fillers other than silica include inorganic fillers and organic fillers. The shape of the filler is not limited, and examples thereof include granular, plate-like, and fibrous fillers.

[0143] Fillers with excellent heat resistance include aluminum oxide, magnesium oxide, titanium dioxide, zirconium oxide, etc.; fillers with excellent thermal conductivity include boron nitride, aluminum nitride, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc.; fillers with excellent electrical conductivity include metal fillers and / or metal-coated fillers using metal elements or alloys (such as iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); fillers with excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, etc. Fillers with high refractive index include barium titanate, zirconium oxide, titanium oxide, etc.; fillers showing 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, and lead, composites of the above metals, oxides of these metals, etc.; fillers with excellent wear resistance include metals such as aluminum oxide, zirconium oxide, and magnesium oxide, and composites and oxides of these metals, etc.; fillers with excellent electrical conductivity include metals such as silver and copper, tin oxide, indium oxide, etc.; fillers with excellent ultraviolet shielding properties include titanium oxide and zinc oxide, etc.

[0144] These inorganic particles can be selected as appropriate according to the application and can be used alone or in combination. In addition, the inorganic particles have various properties in addition to those listed in the examples, so they can be selected as appropriate according to the application.

[0145] Examples of inorganic fibers include carbon fibers, glass fibers, boron fibers, alumina fibers, and silicon carbide fibers, as well as carbon fibers, activated carbon fibers, graphite fibers, glass fibers, tungsten carbide fibers, silicon carbide fibers, ceramic fibers, alumina fibers, natural fibers, mineral fibers such as basalt, boron fibers, boron nitride fibers, boron carbide fibers, and metal fibers. Examples of the metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

[0146] Examples of organic fibers include synthetic fibers made of resin materials such as polybenzazole, polyaramid, 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 proteins, polypeptides, and alginic acid.

[0147] The content of the filler in 100% by mass of the composition is preferably 3% by mass to 60% by mass.

[0148] Since the composition of the present invention is cured by active energy rays, it is preferred to use a polymerization initiator, particularly a photopolymerization initiator. As the photopolymerization initiator, a known photopolymerization initiator can be used, for example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used.

[0149] Specific examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- Acetophenone compounds such as (4-morpholinylphenyl)-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; diphenyl ketones such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyl-diphenyl sulfide Ketone compounds; α-ketoester compounds such as methyl benzoylformate, 2-(2-oxo-2-phenylacetoxyethoxy)ethyl α-hydroxyphenylacetic acid, and 2-(2-hydroxyethoxy)ethyl α-hydroxyphenylacetic 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 mixed 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, etc.

[0150] 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, relative to 100% by mass of the composition.

[0151] The composition of the present invention may also contain an ultraviolet absorber for the purpose of improving weather resistance. Various compounds or substances can be used as the ultraviolet absorber.

[0152] 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 Benzotriazine-based UV absorbers such as benzotriazine, ...

[0153] Benzotriazole-based UV 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 UV absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; cyanoacrylate-based UV absorbers such as ethyl-2-cyano-3,3-diphenylacrylate and octyl-2-cyano-3,3-diphenylacrylate; and inorganic ultraviolet-absorbing fine particles such as titanium oxide fine particles, zinc oxide fine particles, and tin oxide fine particles. These UV absorbers may be used alone or in combination of two or more.

[0154] Commercially available UV absorbers may also be used. Examples of commercially available UV absorbers include 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); Adekastab LA-46, Adekastab LA-F70, Adekastab LA-29, Adekastab LA-31G, Adekastab LA-32, and Adekastab LA-36 (all manufactured by ADEKA Corporation); and RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0155] From the perspective of improving weather resistance, benzotriazine-type UV absorbers or UV absorbers having a (meth)acryloyl group are preferred. 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.).

[0156] The amount of the ultraviolet absorber used is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 10% by mass, relative to 100% by mass of the composition.

[0157] In order to improve weather resistance, the composition of the present invention may also be compounded with a hindered amine light stabilizer (HALS).

[0158] As the hindered amine light stabilizer, a known hindered amine light stabilizer can be used, 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, 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 methyl-4-piperidinyl) sebacate, bis(1-decyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-(4-methoxy-benzylidene) malonate, tetrakis(2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylic acid ester, condensation product of 1,2,3,4-butanetetracarboxylic acid with 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, condensation product of 1,2,3,4-butanetetracarboxylic acid with 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.

[0159] Commercially available hindered amine light stabilizers may also be used. Examples of commercially available hindered amine light stabilizers include TINUVIN 123, TINUVIN 292, TINUVIN 152, TINUVIN 144, TINUVIN 622SF, TINUVIN 111FDL, TINUVIN 249, and Adekastab LA-52 (all manufactured by BASF); and Adekastab LA-57, Adekastab LA-63P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-81, Adekastab LA-82, and Adekastab LA-87 (all manufactured by ADEKA).

[0160] From the viewpoint of improving weather resistance, preferred are TINUVIN 123, TINUVIN 152, and TINUVIN 144 (all manufactured by BASF); Adekastab LA-52, Adekastab LA-57, Adekastab LA-63P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-81 (manufactured by ADEKA), Adekastab LA-82 (manufactured by ADEKA), and Adekastab LA-87 (manufactured by ADEKA). More preferred are TINUVIN 123 and TINUVIN 152 (all manufactured by BASF); Adekastab LA-63P, Adekastab LA-82 (manufactured by ADEKA), and Adekastab LA-87 (manufactured by ADEKA).

[0161] The amount of the hindered amine light stabilizer used is preferably 0.01% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, relative to 100% by mass of the composition.

[0162] Various surface modifiers may be added to the composition of the present invention for purposes such as improving leveling during coating, improving the smoothness of the cured film, and thereby improving scratch resistance. Surface modifiers include various commercially available additives that modify surface properties, such as surface conditioners, leveling agents, smoothness-imparting agents, and antifouling agents. Silicone-based surface modifiers and fluorine-based surface modifiers are particularly suitable.

[0163] Specifically, silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, fluorine-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. can be listed. It is sufficient to use one or more of these. For the purpose of improving the lasting effect of the smoothness, substances containing a (meth)acryloyl group in the molecule can be used. Specific surface modifiers include: EBECRYL 350 (Daicel-Allnex 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 Co., Ltd.) Japan Co., Ltd.), BYK-UV3505 (BYK-Chemie Japan Co., Ltd.), BYK-UV3576 (BYK-Chemie Japan Co., Ltd.), MegafacRS-75 (DIC Co., Ltd.), Megafac RS-76-E (DIC Co., Ltd.), Megafac RS-72-K (DIC Co., Ltd.), Megafac RS-76-NS (DIC Co., Ltd.), 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.

[0164] The active energy ray-curable composition of the present invention can be suitably used as a cured film for protecting substrates by applying it to at least one surface of various materials and then irradiating them with active energy rays. Cured films comprising the composition of the present invention exhibit both weather resistance and abrasion resistance, as well as high chemical resistance. They also exhibit excellent adhesion to various materials even in harsh environments such as high temperature and high humidity. Therefore, they exhibit excellent effects when used as protective films for materials used for extended periods in harsh environments, such as those outdoors and in the automotive environment.

[0165] Furthermore, the active energy ray-curable composition of the present invention exhibits moderate substrate-eroding properties and therefore exhibits particularly excellent adhesion to substrates. This allows for the formation of a highly adhesive film on a film formed by partially or fully curing the active energy ray-curable composition. Therefore, even if a single application and curing process yields an insufficient cured film thickness, repeated application and curing can yield a durable, thick cured film.

[0166] <Laminate>

[0167] The laminate of the present invention comprises a cured layer of the active energy ray-curable composition. The laminate may also comprise one or more other layers in addition to the cured layer. Examples of such other layers include a substrate layer. Methods for manufacturing the substrate and laminate are described below.

[0168] <Method for Manufacturing Laminated Body>

[0169] The method for producing a laminate of the present invention comprises: step 1 of applying the active energy ray-curable composition on a substrate to obtain a coating film; and step 2 of irradiating the coating film with active energy rays to cure a portion or the entire coating film.

[0170] (Process 1)

[0171] In step 1, the active energy ray-curable composition is applied on a substrate to obtain a coating film.

[0172] The substrate is not particularly limited and can be appropriately selected depending on the intended use. Specifically, plastics, wood, metals (steel, stainless steel, aluminum, etc.), metal oxides, paper, silicon, or modified silicon may be mentioned. It may also be a substrate obtained by joining different raw materials, or a substrate obtained by laminating the active energy ray-curable composition of the present invention or another composition as a primer on a substrate.

[0173] The active energy ray-curable composition of the present invention exhibits excellent adhesion to plastic substrates (resin substrates) and resin primers. As mentioned above, resin materials have disadvantages such as easy loss of gloss, poor transparency, and poor weather resistance due to their low abrasion resistance. Coating plastic substrates and resin primers with the composition of the present invention can alleviate these shortcomings. Therefore, the substrate of the laminate is preferably a plastic substrate or a resin primer.

[0174] As the plastic substrate, as long as it contains a resin, there is no particular limitation and it can be selected according to the purpose. Specifically, the thermosetting resin or thermoplastic resin can be used. If it is the case of obtaining a transparent laminate, polycarbonate resins (for example, aliphatic polycarbonate, aromatic polycarbonate, alicyclic polycarbonate, etc.), polymethyl methacrylate resin, polystyrene resin, etc. can be suitably used.

[0175] The plastic substrate may include a single resin or a combination of multiple resins, and may be a single layer or have a laminated structure of two or more layers.

[0176] In addition, the plastic substrate may contain known additives such as antistatic agents, antifogging agents, antiblocking agents, UV absorbers, antioxidants, pigments, organic fillers, inorganic fillers, light stabilizers, crystallization nucleating agents, lubricants, etc., and may also be fiber reinforced (FRP).

[0177] As the resin primer, known water-soluble or water-dispersible paints, organic solvent-based or organic solvent-dispersible paints, powder paints, and the like can be used. Specifically, various types of paints can 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, and amine-modified epoxy resin-based paints. Furthermore, the primer can be a clear paint that does not contain a pigment, an enamel-based paint containing such a pigment, or a metallic paint containing aluminum flakes, or can be an electroplating paint, midcoat, topcoat, or pre-metallic paint used for automobile bodies.

[0178] The shape of the substrate is not particularly limited and may be any shape suitable for the purpose, such as a flat plate, a sheet, or a three-dimensional shape having curvature (curve) entirely or partially.

[0179] Furthermore, the hardness, thickness, etc. of the substrate are not particularly limited and can be arbitrarily determined.

[0180] The coating method of composition is not particularly limited, and can use inkjet method, spray method, spin coating method, dipping method, roller coating method, blade coating (blade coat) method, doctor roll (doctor roll) method, doctor blade (doctor blade) method, curtain coating method, slit coating method, screen printing method etc.By utilizing these methods, composition is coated on base material, film can be obtained.In addition, when reapplying this composition again after solidification, with regard to the viewpoint of coating method, preferably inkjet method, spray method.

[0181] (Process 2)

[0182] In step 2, the coating film obtained in step 1 is irradiated with active energy rays to cure a part or the entirety of the coating film.

[0183] Since the composition of the present invention contains a compound having a polymerizable unsaturated group, it can be cured by irradiation with active energy rays to form a cured film (cured layer). It should be noted that the entire coating can be cured by a single irradiation to form a cured film, or only a portion of the coating can be cured by irradiation, and then the degree of cure can be gradually increased by multiple irradiations to finally form a cured film. In addition, an active energy ray-curable composition can be further applied from above between multiple irradiations.

[0184] Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among them, ultraviolet rays (UV) are particularly preferred in terms of curability and convenience.

[0185] Here, when ultraviolet rays are used as active energy rays, the device for irradiating the ultraviolet rays includes, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium-cadmium laser, an argon laser, sunlight, a light-emitting diode (LED) lamp, etc. By using these to irradiate the applied or formed composition with ultraviolet rays having a wavelength of about 180nm to 400nm, a cured film or a cured product can be obtained. The amount of ultraviolet rays irradiated can be appropriately selected according to the type and amount of the photopolymerization initiator used.

[0186] After step 2 is completed, steps 1 and 2 can be repeated in sequence at least once. Repeating steps 1 (coating) and 2 (curing) can increase the thickness of the cured film. This method is useful in situations where a single coating and curing cycle is insufficient to achieve a desired film thickness, in order to balance the coating method with the desired film thickness.

[0187] Since the composition of the present invention has moderate substrate-eroding properties, even when a cured film is formed on a film composed of the composition after curing, the adhesiveness will not be deteriorated.

[0188] Furthermore, for the purpose of improving adhesion, the coating may be left in a partially cured state (semi-cured) without being completely cured in step 2. The adhesion to the underlying layer is improved by partially uncuring the coating. When only a portion of the coating is cured, the degree of cure can be adjusted by the amount of active energy ray irradiation.

[0189] The laminate of the present invention may further comprise 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, and may be a substrate obtained by joining different raw materials. The shape of the substrate is not particularly limited, and may be any shape suitable for the purpose, such as a flat plate, a sheet, or a three-dimensional shape having curvature throughout or in part. Furthermore, the hardness and thickness of the substrate are also not limited.

[0190] The cured layer of the laminate of the present invention is high in both plastics and inorganic adhesion, so it is also possible to preferably be used as the interlayer material of different materials.Particularly preferably, base material is plastic, and the second base material is an inorganic layer.As inorganic layer, for example, can be enumerated: the metals such as quartz, sapphire, glass, optical film, ceramic material, inorganic oxide, vapor-deposited film (CVD, PVD, sputtering), magnetic film, reflective film, Ni, Cu, Cr, Fe, stainless steel, paper, spin-on glass (Spin On Glass, SOG), spin-on carbon (Spin On Carbon, SOC), the plastic layers such as polyester-polycarbonate-polyimide, TFT array substrates, the electrode plates of PDP, ITO, metals, conductive substrates, insulating substrates, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon etc.

[0191] In addition, the cured layer of the present invention has excellent processability after the active energy ray-curable composition is cured to form a cured layer, and thus can be bent together with the substrate. For example, after directly applying the composition to a flat substrate to obtain a coated substrate, even after irradiating the coating with active energy rays to form a substrate with a cured film (i.e., a laminate), it can be bent. Therefore, there is no need to consider when applying the composition to a curved substrate, which can significantly improve the productivity of the curved material. In addition, the molded article of the present invention not only has excellent bendability under heating, but also has excellent hard coating properties after hot bending.

[0192] When bending is performed, the thickness of the coating film formed by applying the composition of the present invention is preferably 0.5 μm to 40 μm, more preferably 3 μm to 35 μm, even more preferably 5 μm to 30 μm, and particularly preferably 10 μm to 25 μm. A thickness of at least the lower limit allows for sufficient wear resistance and weather resistance, while a thickness below the upper limit allows for good bendability.

[0193] The bending method is not particularly limited, and examples thereof include bending methods in which the laminate is directly bent, press molding, free blow molding, vacuum molding, pressure molding, and dual composite molding.

[0194] The hot bending process is preferably performed at a temperature of 80° C. or higher, more preferably at a temperature of 150° C. or higher. The upper limit temperature can be appropriately set within a range lower than the melting temperature of the substrate.

[0195] The laminate of the present application is particularly suitable for use as various protective materials due to its excellent weather resistance, abrasion resistance, chemical resistance, adhesion, and appearance. For example, it can be used in building materials, residential equipment, transportation aircraft such as automobiles, ships, aircraft, and railways, electronic materials, recording materials, optical materials, lighting, packaging materials, protection of outdoor installations, optical fiber coatings, and resin glass protection. In particular, it can be suitably used in automobile headlamp lenses, automobile glass windows, automobile body exteriors, building plastics, and building steel sheets.

[0196] Example

[0197] Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited to the following embodiments. In the present examples, "parts" and "%" are based on mass unless otherwise specified.

[0198] (Synthesis Example 1: Synthesis of UA-1)

[0199] In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "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 placed. The temperature was raised to 70°C, and 2-hydroxyethyl acrylate (116.1 parts by mass) was added portionwise over 1 hour. After the addition, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was reached. -1 The reaction mixture was stirred for 2 hours until the infrared absorption spectrum of 100 Å disappeared, thereby obtaining a urethane (meth)acrylate compound UA-1 having an allophanate bond.

[0200] (Synthesis Example 2: Synthesis of UA-2)

[0201] In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Basonat (registered trademark) HA3000" (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 placed. The temperature was raised to 70°C, and 4-hydroxybutyl acrylate (144.2 parts by mass) was added portionwise over 1 hour. After the addition, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was detected. -1 The infrared absorption spectrum of 100 μg / ml was disappeared, thereby obtaining a urethane (meth)acrylate compound UA-2 having an allophanate bond.

[0202] (Synthesis Example 3: Synthesis of UA-3)

[0203] In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, BASF's "Basonat (registered trademark) HA3000" (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 placed. The temperature was raised to 70°C, and 2-hydroxyethyl acrylate (77.4 parts by mass) and Daicel's "Placcel 210" (hydroxyl value: 113.4, 164.90 parts by mass) were added in portions over 1 hour. After the additions, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was reached. -1 The infrared absorption spectrum of 100 μg / ml was disappeared, thereby obtaining a urethane (meth)acrylate compound UA-3 having an allophanate bond.

[0204] (Synthesis Example 4: Synthesis of UA-4)

[0205] In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Basonat (registered trademark) HA3000" manufactured by BASF (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) were placed. The temperature was raised to 70°C, and Placcel FA-2D (344.0 parts by mass) was added portionwise over 1 hour. After the addition, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was reached.-1 The infrared absorption spectrum of 100 μg / ml was disappeared, thereby obtaining a urethane (meth)acrylate compound UA-4 having an allophanate bond.

[0206] (Synthesis Example 5: Synthesis of UA-5)

[0207] In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, DIC Corporation's "Burnock 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) were placed. The temperature was raised to 70°C, and 2-hydroxyethyl acrylate (116.1 parts by mass) was added portionwise over 1 hour. After the addition, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was reached. -1 The reaction mixture was stirred for 2 hours until the infrared absorption spectrum of 100 Å disappeared, thereby obtaining a urethane (meth)acrylate compound UA-5 having an isocyanurate bond.

[0208] (Synthesis Example 6: Synthesis of UA-6)

[0209] In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, DIC Corporation's "Burnock 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) were placed. The temperature was raised to 70°C, and 4-hydroxybutyl acrylate (144.2 parts by mass) was added portionwise over 1 hour. After the addition, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was detected. -1 The reaction mixture was stirred for 2 hours until the infrared absorption spectrum of 100 Å disappeared, thereby obtaining a urethane (meth)acrylate compound UA-6 having an isocyanurate bond.

[0210] (Synthesis Example 7: Synthesis of UA-7)

[0211] In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, DIC Corporation's "Burnock 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) were placed. The temperature was raised to 70°C, and 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 additions, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was reached. -1 The reaction mixture was stirred for 2 hours until the infrared absorption spectrum of 100 Å disappeared, thereby obtaining a urethane (meth)acrylate compound UA-7 having an isocyanurate bond.

[0212] (Synthesis Example 8: Synthesis of UA-8)

[0213] In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, DIC Corporation's "Burnock 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) were placed. The temperature was raised to 70°C, and Placcel FA-2D (344.0 parts by mass) was added portionwise over 1 hour. After the addition, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was detected. -1 The reaction mixture was stirred for 2 hours until the infrared absorption spectrum of 100 Å disappeared, thereby obtaining a urethane (meth)acrylate compound UA-8 having an isocyanurate bond.

[0214] (Synthesis Example 9: Synthesis of UA-9)

[0215] 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 Company, Ltd. (NCO equivalent 37.8% by mass, 111.15 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 placed. The temperature was raised to 70°C, and 2-hydroxyethyl acrylate (116.1 parts by mass) was added portionwise over 1 hour. After the addition, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was reached. -1The reaction mixture was stirred for 2 hours until the infrared absorption spectrum of 100 Å disappeared, thereby obtaining a urethane (meth)acrylate compound UA-9 having an isocyanurate bond.

[0216] (Synthesis Example 10: Synthesis of UA-10)

[0217] 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 Company, Ltd. (NCO equivalent 37.8% by mass, 111.15 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 placed. The temperature was raised to 70°C, and 2-hydroxyethyl acrylate (116.1 parts by mass) and "Placcel 210" manufactured by Daicel (hydroxyl value: 113.4, 247.35 parts by mass) were added portionwise over 1 hour. After the addition, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was reached. -1 The reaction mixture was stirred for 2 hours until the infrared absorption spectrum of 100 Å disappeared, thereby obtaining a urethane (meth)acrylate compound UA-10 having an isocyanurate bond.

[0218] (Synthesis Example 11: Synthesis of UA-11)

[0219] In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "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) manufactured by Covestro were placed. The temperature was raised to 70°C, and "Aronix M-403 (hydroxyl value 92)" (609.78 parts by mass) manufactured by Toagosei Co., Ltd. was added in portions over 1 hour. After the addition, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was reached. -1 The reaction mixture was stirred for 2 hours until the infrared absorption spectrum of 100 Å disappeared, thereby obtaining a tetrafunctional or higher-functional (meth)acrylate compound UA-11.

[0220] (Synthesis Example 12: Synthesis of UA-12)

[0221] In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Burnock DN-902S" manufactured by DIC Corporation (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) were placed. 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 added in portions over 1 hour. After the addition, the reaction was allowed to proceed at 80°C until the 2250 cm-1 isocyanate group was reached. -1 The reaction mixture was stirred for 2 hours until the infrared absorption spectrum of 100 Å disappeared, thereby obtaining a tetrafunctional or higher-functional (meth)acrylate compound UA-12.

[0222] (Example 1)

[0223] 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-acryloyloxyethyl)isocyanurate as the component (C), 1.5 parts by mass of Omnirad 754 (manufactured by IGM) and 1.5 parts by mass of Omnirad 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 a UV absorber were uniformly mixed in a 50 / 50 mass % mixed organic solvent of propylene glycol monomethyl ether / butyl acetate to a solid content of 70 mass %, thereby preparing an active energy ray-curable composition of Example 1.

[0224] (Example 2 to Example 44, Comparative Example 1 to Comparative Example 5)

[0225] 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 to those shown in Tables 1 to 6. Although the description of the photopolymerization initiator and organic solvent species is omitted in the tables, they were used in the same manner as in Example 1 in all examples.

[0226] [Preparation of evaluation samples]

[0227] The active energy ray-curable composition of each example was applied to the substrates listed in Tables 1 to 6 using a bar coater, dried at 80°C for 4 minutes, and then irradiated with an ultraviolet irradiation device (manufactured by GS-YUASA Co., Ltd., high-pressure mercury lamp) at an illumination of 200 mW / cm 2 、Irradiation light dose 1000mJ / cm 2 Irradiation was performed to obtain a laminate having a cured film with a film thickness of 20 μm.

[0228] [Appearance evaluation]

[0229] The appearance of the evaluation sample of each example after curing was visually observed and evaluated according to the following criteria, with a score of B or higher being considered acceptable. The results are described in Tables 1 to 6 as "Appearance".

[0230] A: No appearance defects

[0231] B: The unevenness of the base or the scratches on the base during painting are slightly exposed

[0232] C: Local whitening

[0233] D: The entire face turns white

[0234] [Chemical resistance evaluation]

[0235] For the evaluation sample of each example, a spot test was carried out by a droplet method using a 40% by mass sulfuric acid aqueous solution in accordance with JIS K 5600-6.

[0236] The maximum time without any defective appearance on the cured film was used as the evaluation result. A score of 15 minutes or longer was considered a pass, and a score of "50" was given if no defective appearance was observed for more than 50 minutes after the end of the test. The resulting time (in minutes) is recorded as "Chemical Resistance" in Tables 1 to 6.

[0237] [Weather resistance evaluation A]

[0238] The evaluation sample of each example was subjected to an accelerated weather resistance test (SUV test) under the following conditions.

[0239] Conditions: Repeated irradiation (63°C / 90% RH / 100 mW / cm 2 / 4 hours) → dark (70℃ / 90%RH / 4 hours) → condensation (30℃, 98%RH / 4 hours), with spraying before and after irradiation

[0240] The appearance was visually inspected after each cycle (96 hours). The maximum number of cycles without cracks in the cured film was used as the evaluation result, with 3 cycles (288 hours) or more considered acceptable. It should be noted that if no cracks were observed after 15 cycles or more, the value was set as "15." The maximum number of cycles for each example is reported as the "Weather Resistance A" result in Tables 1 to 6.

[0241] [Weather resistance evaluation B]

[0242] The SUV test was conducted under the same conditions as those for the weather resistance evaluation A, and a cellophane tape adhesion test was performed on the surface of the evaluation sample every 96 hours.

[0243] For the cellophane tape adhesion test, the surface condition after the peel test was visually observed. If peeling occurred, the number of cycles at that time was used as the evaluation result, and 3 cycles (288 hours) or more were considered qualified. It should be noted that if no peeling was observed after 15 cycles, it was rated as "15." The maximum number of cycles for each example is recorded as the "Weather Resistance B" result in Tables 1 to 6.

[0244] [Table 1]

[0245]

[0246] [Table 2]

[0247]

[0248] [Table 3]

[0249]

[0250] [Table 4]

[0251]

[0252] [Table 5]

[0253]

[0254] [Table 6]

[0255]

[0256] The abbreviations shown in Tables 1 to 6 represent the following compounds or compounds obtained in the above-described synthesis examples, respectively.

[0257] 1,4-BDA: 1,4-Butanediol diacrylate

[0258] 1,6-HDA: 1,6-hexanediol diacrylate

[0259] 1,9-NDA: 1,9-nonanediol diacrylate

[0260] 1,10-DDA: 1,10-decanediol diacrylate

[0261] DPGDA: dipropylene glycol diacrylate (manufactured by DAICEL-ALLNEX LTD.)

[0262] A-200: Polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0263] A-DCP: tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0264] A9300: Tris(2-acryloyloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0265] A9300-CL: Caprolactone-modified tris(2-acryloyloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0266] TEMPTA: trimethylolpropane triacrylate (manufactured by DAICEL-ALLNEX LTD.)

[0267] DPHA: Dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku)

[0268] DPCA-20: Caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-20 manufactured by Nippon Kayaku)

[0269] DPCA-60: Caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-60 manufactured by Nippon Kayaku)

[0270] Tinuvin 123: HALS "Tinuvin 123" (trade name, manufactured by BASF)

[0271] Tinuvin 152: HALS "Tinuvin 152" (trade name, manufactured by BASF)

[0272] LA-82: HALS "Adekastab LA-82" (trade name, manufactured by ADEKA Corporation)

[0273] LA-46: UV absorber "Adekastab LA-46" (trade name, manufactured by ADEKA Corporation)

[0274] Tinuvin 479: UV absorber "Tinuvin 479" (trade name, manufactured by BASF)

[0275] Ruva-93: UV absorber "Ruva-93" (trade name, manufactured by Otsuka Chemical Co., Ltd.)

[0276] PE: Polyester resin-coated steel plate (a 2mm thick zinc-treated steel plate surface was coated with a white polyester / isocyanate coating having a pigment weight concentration (PWC) of 60% to a dry film thickness of 30 to 40 μm, and the coating was heat-cured at 80°C for 30 minutes. The substrate thickness is 2mm)

[0277] PC: Polycarbonate resin substrate (Panlite L-1225ZL manufactured by Teijin, thickness 3 mm)

[0278] ABS: ABS resin substrate ("KRALASTIC GA-701JH22" manufactured by Japan A&L Co., Ltd., thickness 3mm)

[0279] AU: Acrylic urethane resin-coated steel plate (a 2mm thick zinc-treated steel plate surface was coated with a white acrylic urethane paint having a PWC of 60% to a dry film thickness of 30 to 40 μm, and the paint was heat-cured at 80°C for 30 minutes. The substrate thickness was 2mm)

[0280] EP: Epoxy-coated steel plate (a 2mm thick zinc-treated steel plate surface was coated with a white acid-epoxy curing paint having a PWC of 60% to a dry film thickness of 30 to 40 μm, and the paint was heat-cured at 80°C for 30 minutes. The substrate thickness was 2mm)

[0281] The results of Examples 1 to 44 confirm that the cured films of the active energy ray-curable compositions of the present invention exhibit excellent appearance, chemical resistance, weather resistance, and adhesion. On the other hand, Comparative Examples 1 to 5, which do not contain any of the components, exhibit inferior properties in at least one of the following properties.

[0282] (Example 45)

[0283] The active energy ray curable composition of Example 2 was applied to the same polyester resin coated steel plate substrate as above using a bar coater, dried at 80°C for 4 minutes, and then irradiated with an ultraviolet irradiation device (GS-YUASA Co., Ltd., high pressure mercury lamp) at an illumination of 200 mW / cm 2 , the irradiation light amount shown in Table 7 1 (unit: mJ / cm 2 ) was irradiated to obtain a laminate having a film with a thickness of 10 μm.

[0284] Furthermore, the same active energy ray curable composition was applied to the obtained film using a bar coater, dried at 80°C for 4 minutes, and then irradiated with the same ultraviolet irradiation device in the atmosphere at an illumination of 200 mW / cm 2 , the irradiation light amount shown in Table 7 2 (unit: mJ / cm2 ) were irradiated to obtain a laminate having a cured film with a total film thickness of 20 μm.

[0285] (Examples 46 to 50, Comparative Examples 6 to 9)

[0286] The active energy ray-curable compositions of Examples or Comparative Examples shown in Tables 7 and 8 were used and the irradiation light intensity was changed to 1 or 2 in Tables 7 and 8. In the same manner as in Example 45, laminates of each example were obtained.

[0287] The obtained laminates of each example were used as evaluation samples, and appearance evaluation, chemical resistance evaluation, and weather resistance evaluations A to B were performed in the same manner as in Example 1. The results are shown in Tables 7 and 8. Note that in Weather Resistance Evaluation B of Comparative Example 8, since peeling was observed before the start of the test, the result was set to "0."

[0288] [Table 7]

[0289]

[0290] [Table 8]

[0291]

[0292] The results of Examples 45 to 50 confirm that the cured films of the active energy ray-curable compositions of the present invention are excellent in appearance, chemical resistance, weather resistance, and adhesion. On the other hand, Comparative Examples 6 to 9 are confirmed to be inferior in at least any one of the properties.

Claims

1. An active energy ray-curable composition, characterized in that: The present invention contains a compound (A) having 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 according to claim 1, wherein 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 according to claim 2 , further comprising a (meth)acrylate compound (C) having an isocyanurate bond.

4. The active energy ray-curable composition according to claim 2, wherein The urethane (meth)acrylate compound (B) having an isocyanurate bond or an allophanate bond contains: in addition to the isocyanurate bond, the allophanate bond and the (meth)acryloyl group, -OC(=O)-(CH2) in the structure nA and having no -OC(=O)-(CH2) in the structure except for the isocyanurate bond, the allophanate bond and the (meth)acryloyl group nA Compound (B2), wherein -OC(=O)-(CH2) nA In the formula (a), nA represents an integer from 1 to 6. The active energy ray-curable composition according to claim 1 , further comprising a compound (D) having four or more (meth)acryloyl groups in one molecule.

6. The active energy ray-curable composition according to claim 1, wherein The active energy ray-curable composition contains no organic solvent or contains an organic solvent in an amount of 30% by mass or less based on the total amount of the composition. 7 . A laminate comprising a cured layer of the active energy ray-curable composition according to claim 1 .

8. A method for producing a laminate, characterized in that: have: Step 1, applying the active energy ray-curable composition according to any one of claims 1 to 6 on a substrate to obtain a coating film; and In step 2, the coating film is irradiated with active energy rays to cure a part or the entirety of the coating film.

9. The method for producing a laminate according to claim 8, wherein: After the step 2, the steps 1 and 2 are repeated in sequence at least once.

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