Photocurable composition

Abstract

To provide a photocurable composition which can form a cured article having good adhesion to an inorganic base material, low warpage, and excellent ion migration resistance.SOLUTION: A photocurable composition contains a monofunctional acrylic monomer (A), a multi-functional acrylic monomer (B), and a compound (D) having a structural unit derived from a dimer acid, and (meth)acryloyl at the terminal. In the photocurable composition, the structural unit derived from a dimer acid in the compound (D) may be a dimer diol structural unit or a dimer diamine structural unit, and a content of each component based on the composition is such that: the monofunctional acrylic monomer (A): 10-80 wt.% based on 100 wt.% of the composition; the multi-functional acrylic monomer (B): 5-50 wt.% based on 100 wt.% of the composition; and the compound (D): 10-80 wt.% based on 100 wt.% of the composition. An active energy ray- curable ink composition or the like containing the photocurable composition is also provided.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photocurable composition that is suitable for use in producing display elements, printed wiring boards, flexible wiring boards, semiconductor package substrates, solar cell substrates, and other electronic circuit boards. [Background technology]

[0002] A wide range of research has been conducted on coating agents that form films on the surfaces of various substrates, such as resin plates, glass plates, and metal plates used in construction materials and electrical and electronic fields, with the aim of protecting the substrate from scratches and contamination. Thermosetting resins and photocurable resins are commonly used as coating agents. Photocurable resins are often used to protect the surfaces of organic substrates because they often produce cured products with high surface hardness and cure instantly upon light irradiation, resulting in high productivity. However, cured products made with photocurable resins generally lack sufficient adhesion to inorganic substrates. Therefore, various efforts have been made to improve adhesion to inorganic substrates.

[0003] For example, Patent Document 1 describes a photocurable inkjet ink containing a specific monofunctional polymerizable monomer component (A), a polyfunctional polymerizable monomer (B), and a polymerization initiator (C) in predetermined amounts, respectively. By using this photocurable inkjet ink, it is possible to form a cured product that has good adhesion to inorganic substrates.

[0004] However, as electronic components become thinner and smaller, the cured film formed using the photocurable inkjet ink described in Patent Document 1 is no longer sufficient in some cases. For example, when a cured film with a thickness of approximately 10 μm that insulates EMI shielding from metal wiring is formed using the photocurable inkjet ink described in Patent Document 1, ion migration was found to occur during reliability testing. Here, ion migration is a phenomenon in which metals used as wiring or electrodes ionize, migrate, and grow, causing short circuits in electronic components. For this reason, preventing ion migration is important from the perspective of the reliability of electronic components.

[0005] In general, in printed wiring boards used in electronic devices, etc., solder resist is formed in areas other than connection holes on the board on which the circuit pattern is formed, in order to prevent solder from adhering to unnecessary areas and to prevent the circuit conductors from being exposed and corroded by oxidation or moisture.

[0006] One method for forming a solder resist of a desired pattern on a substrate is a formation method using photolithography technology. For example, a photosensitive solder resist made of an alkali-developable photocurable resin composition is exposed through a pattern mask and then alkali-developed, thereby utilizing the difference in solubility in an alkali developer between the exposed and unexposed areas to form a pattern.

[0007] When forming a solder resist, shrinkage and dimensional changes due to at least one of light and heat curing can impair adhesion between the solder resist and the substrate, making it prone to cracking and peeling, and therefore low cure shrinkage is required of the material resin composition. To improve this property, conventional solder resists have been filled with fillers such as silica to achieve low cure shrinkage and reduce the thermal expansion coefficient of the cured product (e.g., Patent Documents 2 and 3).

[0008] However, when a high amount of filler is added to obtain a higher effect, the flexibility of the cured product and its adhesion to the substrate may decrease. Therefore, there has been a demand for a means for improving the low cure shrinkage of a material resin composition other than by adding a filler. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Patent Publication No. 2013 / 015125 [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-053448 [Patent Document 3] Japanese Patent Application Laid-Open No. 2002-236363 Summary of the Invention [Problem to be solved by the invention]

[0010] An object of the present invention is to provide a photocurable composition that can form a cured product that has good adhesion to inorganic substrates, low warpage, and good resistance to ion migration. [Means for solving the problem]

[0011] The present inventors have conducted research to solve the above problems and have found that a combination of specific components results in a composition that can form a cured product that has good adhesion to inorganic substrates, low warpage, and good resistance to ion migration. The present invention is based on this finding and has the following features.

[0012] [1] monofunctional acrylic monomer (A), a polyfunctional acrylic monomer (B), and A photocurable composition containing a compound (D) having a structural unit derived from a dimer acid and having a (meth)acryloyl group at its terminal, The structural unit derived from a dimer acid in the compound (D) may be a dimer diol structural unit or a dimer diamine structural unit, The content of each component in the composition is: Monofunctional acrylic monomer (A): 10 to 80% by weight based on 100% by weight of the composition Polyfunctional acrylic monomer (B): 5 to 50% by weight based on 100% by weight of the composition Compound (D): 10 to 80% by weight based on 100% by weight of the composition The photocurable composition according to claim 1,

[0013] [2] The compound (D) The photocurable composition according to item [1] above, which has a dimer diol structural unit, and the dimer diol includes at least one compound selected from the group consisting of formulas (1) and (2).

[0014] TIFF0007725835000001.tif3374

[0015] (In the formula, R 1 and R 2 are each alkyl having 1 or more carbon atoms, a and b are each independently an integer of 1 or more, and R 1 and R 2 The total number of carbon atoms contained in the formula (a) and the formula (b) is 38 or less, and any bond between C and C in the formula may be replaced with a double bond.

[0016] TIFF0007725835000002.tif2357

[0017] (In the formula, R 3 and R 4 are each alkyl having 1 or more carbon atoms, c and d are each independently an integer of 1 or more, and R 3 and R 4 The total number of carbon atoms contained in the formula (I) and c and d is 42 or less, and any bond between C and C in the formula may be replaced with a double bond.

[0018] [3] The compound (D) The photocurable composition according to the above item [1], characterized in that the compound (D-1) is a urethane di(meth)acrylate compound that is a reaction product of the dimer diol and an isocyanate having a (meth)acryloyl group.

[0019] [4] The compound (D) The photocurable composition according to item [1] above, which has a dimer diamine structural unit, and the dimer diamine includes at least one compound selected from the group consisting of formulas (3) and (4).

[0020] TIFF0007725835000003.tif3375

[0021] (In the formula, R 5 and R 6 are each alkyl having 1 or more carbon atoms, e and f are each independently an integer of 1 or more, and R 5 and R 6 The total number of carbon atoms contained in the formula (I) and the groups e and f is 38 or less, and any bond between C—C in the formula may be replaced with a double bond.

[0022] TIFF0007725835000004.tif2360

[0023] (In the formula, R 7 and R 8 are each alkyl having 1 or more carbon atoms, g and h are each independently an integer of 1 or more, and R 7 and R 8 The total number of carbon atoms contained in g and h is 42 or less, and any bond between C—C in the formula may be replaced with a double bond.

[0024] [5] The compound (D) The photocurable composition according to the above item [1], characterized in that it is a urea di(meth)acrylate compound (D-3) which is a reaction product of the dimer diamine and an isocyanate having a (meth)acryloyl group.

[0025] [6] The photocurable composition according to the present invention, Further, the composition contains 0.1 to 30% by weight of a hydroxyl value adjuster (C) relative to 100% by weight of the composition, The photocurable composition according to any one of the above items [1] to [5], wherein the photocurable composition has a hydroxyl value of 1 to 100 mgKOH / g.

[0026] [7] The photocurable composition according to any one of the above items [1] to [6], wherein the monofunctional acrylic monomer (A) contains a (meth)acrylate having one or more groups selected from the group consisting of a fused cyclic hydrocarbon group, a polycyclic hydrocarbon group, and a monocyclic hydrocarbon group.

[0027] [8] The photocurable composition according to item [7], wherein the monofunctional acrylic monomer (A) is a monofunctional acrylic monomer represented by the following formula (7):

[0028] TIFF0007725835000005.tif3281

[0029] (In formula (7), R 11 is hydrogen or methyl, and R 12 is a monovalent organic group having 4 to 30 carbon atoms and having a fused cyclic hydrocarbon group, a monovalent organic group having 6 to 30 carbon atoms and having a polycyclic hydrocarbon group, or a monovalent organic group having 4 to 30 carbon atoms and having a monocyclic hydrocarbon group, and n A is an integer between 0 and 10.)

[0030] [9] R in the formula (7) 12 is a group represented by any one of the following formulas (8) to (11):

[0031] TIFF0007725835000006.tif72140

[0032] (In formulas (8) to (11), R 13 are each independently hydrogen or alkyl having 1 to 6 carbon atoms, and * is a bond.

[0033]

[10] The photocurable composition according to any one of the above items [1] to [6], wherein the polyfunctional acrylic monomer (B) is a bifunctional acrylic monomer represented by the following formula (12):

[0034] TIFF0007725835000007.tif33149

[0035] (In formula (12), R 14 are each independently hydrogen or methyl, and R 15 is a monovalent organic group having 4 to 30 carbon atoms and having a fused cyclic hydrocarbon group, a monovalent organic group having 6 to 30 carbon atoms and having a polycyclic hydrocarbon group, or a monovalent organic group having 4 to 30 carbon atoms and having a monocyclic hydrocarbon group and n B are each independently an integer from 0 to 10.

[0036]

[11] R in the formula (12) 15 is a group represented by any one of the following formulas (13) to (16):

[0037] TIFF0007725835000008.tif73140

[0038] (In formulas (13) to (16), * represents a bond.)

[0039]

[12] The hydroxyl value adjuster (C) is The hydroxyl value is 100 to 300 mg KOH / g, The photocurable composition according to item [6] above, which has a weight average molecular weight of 100 to 5,000.

[0040]

[13] The photocurable composition according to any one of the above items [1] to

[12] , further comprising a photopolymerization initiator (E) in an amount of 5 to 15% by weight relative to 100% by weight of the composition.

[0041]

[14] The photocurable composition according to any one of the above items [1] to

[12] , wherein the composition has a hydroxyl value of 5 to 40 mgKOH / g.

[0042]

[15] An actinic ray-curable ink composition containing the photocurable composition according to any one of the above items [1] to

[14] .

[0043]

[16] An inkjet ink composition containing the photocurable composition according to any one of the above items [1] to

[14] .

[0044]

[17] A cured product obtained by photocuring the photocurable composition according to any one of the above items [1] to

[16] .

[0045]

[18] A cured product obtained by photocuring the photocurable composition according to any one of the above items [1] to

[16] , and then thermally curing the cured product.

[0046]

[19] An electronic component comprising the cured product according to the above item

[17] or

[18] .

[0047] The present invention further includes the following two items.

[0048] [3-2] Compound (D) is The photocurable composition according to the above item [1], characterized in that the alkyl di(meth)acrylate compound (D-2) is a reaction product of the dimer diol and a compound having a (meth)acryloyl group.

[0049] [5-2] The compound (D) The photocurable composition according to the above item [1], characterized in that the compound (D-4) is represented by formula (5):

[0050] TIFF0007725835000009.tif22161

[0051] (In the formula, Z is independently a structural unit represented by the following formula (6) (a structural unit derived from a dimer acid), Y is independently a substituted or unsubstituted aliphatic, aryl, or heteroaryl, and X is independently an acrylate or methacrylate. n is 0 to 10.)

[0052] TIFF0007725835000010.tif3361

[0053] (In the formula, R 9 and R 10 are each independently an alkyl having one or more carbon atoms, i and j are each independently an integer of 1 or more, and R 9 and R 10 The total number of carbon atoms in i and j is 38 or less.

[0054] In this specification, the term "(meth)acryloyl" refers to either an acryloyl or methacryloyl group. The same applies to "(meth)acrylate," which refers to either an acrylate or methacrylate compound. The (meth)acryloyl in compound (D) of the present invention may be either acryloyl or methacryloyl, but when acryloyl is selected, the curing rate of the photocurable composition of the present invention tends to be faster, while when methacryloyl is selected, the curing rate tends to be slower. Therefore, the curing rate of the photocurable composition of the present invention can be adjusted by this selection. [Effects of the Invention]

[0055] The photocurable composition of the present invention contains a monofunctional acrylic monomer (A), a polyfunctional acrylic monomer (B), and a compound (D) having a structural unit derived from a dimer acid and having a (meth)acryloyl group at the end. As a result, a cured product formed from the photocurable composition exhibits good adhesion to inorganic substrates, low warpage, and good resistance to ion migration. DETAILED DESCRIPTION OF THE INVENTION

[0056] The photocurable composition of the present invention (hereinafter also referred to as "composition") contains a monofunctional acrylic monomer (A), a polyfunctional acrylic monomer (B), and a compound (D) having a structural unit derived from a dimer acid and having a (meth)acryloyl group at the end. Each of these components will be described below.

[0057] 1. Compound (D): A compound having a structural unit derived from a dimer acid and having a (meth)acryloyl group at the terminal. The composition of the present invention contains a compound (D) having a structural unit derived from a dimer acid and a (meth)acryloyl group at the end (hereinafter also referred to simply as "compound (D)").

[0058] (1-1) Structural units derived from dimer acids The term "structural unit derived from a dimer acid" used herein refers to a structure obtained by removing at least one terminal carboxylic acid group from a dimer acid. Specific examples of the structural unit derived from a dimer acid include a dimer acid structural unit, a dimer diol structural unit (obtained by reducing a dimer acid), and a dimer diamine structural unit (obtained by reductively amminating a dimer acid or its ester).

[0059] Generally, "dimer acid" refers to a dibasic acid obtained by the intermolecular polymerization reaction of unsaturated fatty acids. For example, it is a dibasic acid obtained by dimerizing an unsaturated fatty acid having 11 to 22 carbon atoms using a clay catalyst or the like, and dimer acids containing a dibasic acid having 36 carbon atoms as the main component are well known. Industrially obtained dimer acids contain not only dibasic acids having about 36 carbon atoms, but also any amount of trimer acid and monomer acid depending on the degree of purification. Commercially available dimer acids include Pripol (registered trademark) 1009, 1025, and 1004 (all manufactured by Croda) and EMPOL (registered trademark) 1008 (BASF).

[0060] (1-2) Dimer diol structural unit Compound (D) may have a dimer diol structural unit. Note that the term "dimer diol structural unit" used herein refers to a structure in which at least one terminal hydroxyl group of a dimer diol has been removed.

[0061] Generally, "dimer diol" refers to a diol primarily composed of a diol obtained by reducing dimer acid and / or its lower alcohol ester in the presence of a catalyst, whereby the carboxylic acid moiety of the dimer acid is converted to an alcohol. Commercially available products include those primarily composed of a diol having 36 carbon atoms. Here, dimer acid refers to a dibasic acid obtained by the intermolecular polymerization reaction of unsaturated fatty acids, such as by dimerizing an unsaturated fatty acid having 11 to 22 carbon atoms using a clay catalyst. Industrially produced dimer acids contain not only dibasic acids having approximately 36 carbon atoms, but also arbitrary amounts of trimer acid and monomer acid depending on the degree of purification. Here, "major component" refers to a component present at 50% by mass or more. It is known that, in addition to the diol having 36 carbon atoms, diols having 22 to 44 carbon atoms but not 36 carbon atoms are also present. In this specification, "dimer diol" is defined to include not only a diol primarily composed of a 36-carbon dimer acid in which the carboxylic acid moiety of the dimer acid is converted to an alcohol, but also hydrogenated dimer diols obtained by hydrogenating the carbon-carbon double bonds derived from dimer acid. The dimer diol in the present invention is particularly preferably a hydrogenated dimer diol obtained by hydrogenating the carbon-carbon double bond derived from a dimer acid. Examples of commercially available dimer diols include Pripol (registered trademark) 2033 (manufactured by Croda) and Sovermol (registered trademark) 908 (manufactured by Cognis).

[0062] Representative structures of dimer diol compounds include, for example, the following formulas (1) and (2).

[0063] TIFF0007725835000011.tif3374

[0064] (In the formula, R 1 and R 2 are each alkyl having 1 or more carbon atoms, a and b are each independently an integer of 1 or more, and R 1 and R 2 The total number of carbon atoms contained in the formula (a) and the formula (b) is 38 or less, and any bond between C and C in the formula may be replaced with a double bond.

[0065] TIFF0007725835000012.tif2357

[0066] (In the formula, R 3 and R 4 are each alkyl having 1 or more carbon atoms, c and d are each independently an integer of 1 or more, and R 3 and R 4 The total number of carbon atoms contained in the formula (I) and c and d is 42 or less, and any bond between C and C in the formula may be replaced with a double bond.

[0067] (1-3) Compound (D-1): Urethane di(meth)acrylate compound The compound (D) described in the present invention may be a reaction product of the dimer diol and an isocyanate having a (meth)acryloyl group, i.e., a urethane di(meth)acrylate compound (D-1). A urethane bond is generated by the reaction of the hydroxyl group of the dimer diol with the isocyanate. This reaction can be carried out using a known urethane reaction. In this way, a urethane di(meth)acrylate compound (D-1) can be generated in which acryloyl groups are added to both ends of the dimer diol via urethane bonds.

[0068] The (meth)acryloyl-containing isocyanate used in the present invention includes, for example, a compound represented by formula (17). Commercially available (meth)acryloyl-containing isocyanates include, for example, 2-acryloyloxyethyl isocyanate (Karenz (registered trademark) AOI manufactured by Showa Denko K.K.), 2-methacryloyloxyethyl isocyanate (Karenz (registered trademark) MOI manufactured by Showa Denko K.K.), and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate (Karenz (registered trademark) MOI-EG manufactured by Showa Denko K.K.).

[0069] TIFF0007725835000013.tif3367

[0070] (In the formula, R 16 represents H or CH3, and R 17 represents a hydrocarbon group having 2 to 12 carbon atoms.

[0071] In formula (17), R 16 When R =H, it means that the compound (D) of the present invention has acryloyl at the molecular terminal. 16 When R =CH3, it means that the molecule has methacryloyl at the end. 17 From the viewpoint of increasing the curing rate of the photocurable composition of the present invention, is preferably a hydrocarbon group having 2 to 8 carbon atoms, and more preferably a hydrocarbon group having 2 to 6 carbon atoms.

[0072] By using the urethane dimethacrylate as the compound (D) of the present invention, the reactivity of the photocurable composition of the present invention can be increased. For example, it is possible to obtain a cured product in a short time with a small amount of exposure. Furthermore, unreacted acryloyl after the photocuring reaction can be reduced, thereby increasing the ion migration resistance of the cured product. This is thought to be because aggregation due to hydrogen bonding in the urethane structure makes it easier for acryloyl to gather, thereby increasing the reactivity of radical polymerization.

[0073] (1-4) Compound (D-2): Alkyl di(meth)acrylate compound The compound (D) of the present invention may be an alkyl di(meth)acrylate compound (D-2), which is a reaction product of the dimer diol and a compound having a (meth)acryloyl group.

[0074] The alkyl di(meth)acrylate compound (D-2) can be obtained by a general ester synthesis method such as a dehydration condensation method, an acid chloride method, or an ester exchange method using the dimer diol, a carboxylic acid having a (meth)acryloyl group, or an acid chloride or ester thereof as raw materials.

[0075] By using the alkyl di(meth)acrylate compound (D-2) as the compound (D), the elastic modulus of the cured product obtained by photocuring the photocurable composition of the present invention can be increased. Furthermore, the presence of an ester structure can impart acid resistance.

[0076] (1-5) Dimer diamine structural unit The compound (D) of the present invention may have a dimer diamine structural unit. Note that the term "dimer diamine structural unit" used herein refers to a structure obtained by removing at least one terminal amino group from a dimer diamine.

[0077] Generally, "dimer diamine" refers to a diamine obtained by reductive amination of the dimer acid and / or its lower alcohol ester to amine the carboxylic acid moiety of the dimer acid, and the diamine having a carbon number of 36 as the main component is well known commercially. This reaction can be carried out by known methods (e.g., JP-A-9-12712), such as a reduction method using ammonia and a catalyst. Here, "main component" means that it is present in an amount of 50% by mass or more. In addition to the diamine having a carbon number of 36, diamines having 22 to 44 carbon atoms but not 36 carbon atoms are known to exist. In this specification, "dimer diamine" is defined to include not only diamines having a carbon number of 36 as the main component obtained by amminating the carboxylic acid moiety of dimer acid, but also hydrogenated dimer diamines in which the carbon-carbon double bonds derived from dimer acid are hydrogenated. Hydrogenated dimer diamines in which the carbon-carbon double bonds derived from dimer acid are hydrogenated are particularly preferred as the dimer diamine of the present invention. Commercially available dimer diamine products include, for example, Priamine (registered trademark) 1074 (manufactured by Croda), Versamine 551 (trade name, BASF Japan Ltd.), and Versamine 552 (trade name, BASF Japan Ltd.).

[0078] Representative structures of dimer diamine compounds include compounds represented by the following formulas (3) and (4).

[0079] TIFF0007725835000014.tif3375

[0080] (In the formula, R 5 and R 6are each alkyl having 1 or more carbon atoms, e and f are each independently an integer of 1 or more, and R 5 and R 6 The total number of carbon atoms in e and f is 38 or less.)

[0081] TIFF0007725835000015.tif2360

[0082] (In the formula, R 7 and R 8 are each alkyl having 1 or more carbon atoms, g and h are each independently an integer of 1 or more, and R 7 and R 8 The total number of carbon atoms in g and h is 42 or less.

[0083] (1-6) Compound (D-3): Urea di(meth)acrylate The compound (D) of the present invention may be a reaction product of the dimer diamine and an isocyanate having a (meth)acryloyl group, i.e., a urea di(meth)acrylate compound (D-3). A urea bond is generated by reacting the amino group of the dimer diamine with the isocyanate group of the isocyanate having a (meth)acryloyl group. This reaction can be carried out using a known urea reaction. In this way, a urea di(meth)acrylate compound (D-3) can be generated in which acryloyl groups are added to both ends of the dimer diamine via urea bonds.

[0084] The isocyanate having (meth)acryloyl group used in the present invention includes, for example, the compound represented by the above formula (17). Examples of commercially available isocyanates having (meth)acryloyl group are also as described above.

[0085] By using the urea di(meth)acrylate compound (D-3) as compound (D), the reactivity of the photocurable composition of the present invention can be increased. For example, it is possible to obtain a cured product in a short time with a small amount of exposure. Furthermore, it is possible to reduce the amount of unreacted acryloyl in the cured product, thereby increasing the ion migration resistance of the cured product. This is thought to be because aggregation due to hydrogen bonding in the urea structure makes it easier for acryloyl to gather, thereby increasing the reactivity of radical polymerization.

[0086] Furthermore, by using the urea di(meth)acrylate as compound (D), the viscosity of the composition of the present invention can be increased. When applying the composition, it is possible to adjust the viscosity to a level suitable for the application method, such as die coating or jetting. This is thought to be because aggregation due to hydrogen bonding in the urea structure makes it easier for acryloyl to gather, thereby increasing the viscosity of the composition.

[0087] (1-7) Compound (D-4) The compound (D) of the present invention may be a compound (D-4) represented by formula (5).

[0088] TIFF0007725835000016.tif22161

[0089] (In the formula, Z is independently a structural unit represented by the following formula (6) (corresponding to a dimer acid structural unit), Y is independently a substituted or unsubstituted aliphatic, aryl, or heteroaryl, and X is independently an acrylate or methacrylate. n is 0 to 10.)

[0090] TIFF0007725835000017.tif3361

[0091] (In the formula, R 9 and R 10 are each alkyl having 1 or more carbon atoms, i and j are each independently an integer of 1 or more, and R 9 and R 10The total number of carbon atoms contained in each of i and j is 38 or less, and any bond between C—C in the formula may be replaced with a double bond.

[0092] Examples of commercially available products of compound (D-4) include PEAM-104; polyester acrylate methacrylate oligomer (trade name: PEAM-1044, Designer Molecules, hydroxyl value: 0 mg KOH / g, viscosity: 4,850 mPa·s).

[0093] By using the compound (D-4) represented by formula (5) as the compound (D), the viscosity of the composition of the present invention can be reduced. When applying the composition, it is possible to adjust the viscosity to a level suitable for application methods such as inkjet coating and spray coating. Furthermore, the presence of an ester structure can impart acid resistance.

[0094] (1-8) Content of Compound (D) The composition of the present invention contains 10 to 80 wt% of compound (D) relative to 100 wt% of the total weight of the components of the composition. From the viewpoints of improving the coatability when the composition of the present invention is used as an ink and forming a cured product with excellent low warpage, the content of compound (D) is preferably 10 to 80 wt%, and more preferably 10 to 60 wt%, relative to 100 wt% of the composition.

[0095] 2. Monofunctional acrylic monomer (A) The composition of the present invention contains 10 to 80% by weight of the monofunctional acrylic monomer (A) relative to 100% by weight of the sum of the weights of the components of the composition.

[0096] From the viewpoint of improving the coatability when the composition of the present invention is used as an ink and forming a cured product that is excellent in balance between heat resistance, adhesion to substrates, and ion migration resistance, the content of component (A) is preferably 20 to 80 wt %, and more preferably 30 to 80 wt %, relative to 100 wt % of the composition.

[0097] From the viewpoints of improving heat resistance, adhesion to substrates, particularly glass substrates, silicon substrates, and substrates on which conductors such as metal wiring and electrodes are formed, and ion migration resistance, the monofunctional acrylic monomer (A) preferably contains a (meth)acrylate having one or more groups selected from the group consisting of a fused cyclic hydrocarbon group, a polycyclic hydrocarbon group, and a monocyclic hydrocarbon group.

[0098] (2-1) Monofunctional acrylic monomer having a fused cyclic hydrocarbon group or a polycyclic hydrocarbon group (a-1) The monofunctional acrylic monomer (a-1) having a fused cyclic hydrocarbon group or a polycyclic hydrocarbon group is not particularly limited, but is preferably a monofunctional acrylic monomer containing an organic group having 7 to 50 carbon atoms and having a fused cyclic hydrocarbon group or a polycyclic hydrocarbon group, and more preferably a monofunctional acrylic monomer containing an organic group having 7 to 30 carbon atoms and having a fused cyclic hydrocarbon group or a polycyclic hydrocarbon group. The term "monofunctional acrylic monomer" refers to a monomer having one (meth)acryloyl group in one molecule.

[0099] Furthermore, a "fused cyclic hydrocarbon group" refers to a hydrocarbon group (composed of carbon atoms and hydrogen atoms) having two or more rings, which has at least one carbon atom that constitutes one ring and also constitutes another ring, and a "polycyclic hydrocarbon group" refers to a hydrocarbon group having two or more rings, in which one ring and another ring are bonded together by a single bond or an alkylene having 1 to 10 carbon atoms.

[0100] Furthermore, the "organic group having 7 to 50 carbon atoms and having a fused cyclic hydrocarbon group or a polycyclic hydrocarbon group" refers to, for example, n other than (meth)acryloyl in the compound represented by formula (7). A repeating units and R 12 It refers to a group containing

[0101] TIFF0007725835000018.tif3281

[0102] (In formula (7), R 11is hydrogen or methyl, and R 12 is a monovalent organic group having 4 to 30 carbon atoms and having a fused cyclic hydrocarbon group, a monovalent organic group having 6 to 30 carbon atoms and having a polycyclic hydrocarbon group, or a monovalent organic group having 4 to 30 carbon atoms and having a monocyclic hydrocarbon group, and n A is an integer between 0 and 10.)

[0103] As the monomer (a-1), it is preferable to use a compound represented by formula (7) from the viewpoint of obtaining a cured product that is excellent in heat resistance, adhesion to a substrate, and resistance to ion migration.

[0104] In formula (7), R 12 is preferably non-polar, and (in formula (7), R 11 is hydrogen or methyl, and R 12 is a monovalent organic group having 4 to 30 carbon atoms and having a fused cyclic hydrocarbon group, a monovalent organic group having 6 to 30 carbon atoms and having a polycyclic hydrocarbon group, or a monovalent organic group having 4 to 30 carbon atoms and having a monocyclic hydrocarbon group, and more preferably a group represented by any one of formulas (8) to (11). A is preferably 0 or 1.

[0105] TIFF0007725835000019.tif72140

[0106] (In formulas (8) to (11), R 13 are each independently hydrogen or alkyl having 1 to 6 carbon atoms, and * is a bond.

[0107] In the formulas (8) to (11), R 13 is preferably hydrogen. Note that * is a bond, which bonds to O- at the right end of the formula (7).

[0108] Further examples of the monomer (a-1) include at least one compound selected from the following compound group (I) (some of these compounds contain structures other than those of the above formulas (8) to (11)).

[0109] TIFF0007725835000020.tif224129

[0110] Among these, in consideration of the adhesion to the substrate, heat resistance, and ion migration resistance of the resulting cured product, the following compounds (101) to (110) are more preferred, with compounds (101) and (107) being even more preferred.

[0111] TIFF0007725835000021.tif34164

[0112] TIFF0007725835000022.tif34169

[0113] TIFF0007725835000023.tif36109

[0114] TIFF0007725835000024.tif36111

[0115] TIFF0007725835000025.tif46160

[0116] TIFF0007725835000026.tif39154

[0117] The monomer (a-1) may be a single compound selected from the above-mentioned compounds, or a mixture of two or more of these. A mixture of the compounds (101) and (107) is preferred. When both are used in combination, the weight ratio of the compound (101) to the compound (107) is preferably 5:10 to 10:5, more preferably 7:10 to 10:7, and even more preferably 9:10 to 10:9.

[0118] The monomer (a-1) may be a compound produced by a known method, or may be dicyclopentanyl acrylate (trade name: Fancryl FA-513AS, Hitachi Chemical Co., Ltd.), dicyclopentanyl methacrylate (trade name: Fancryl FA-513M, Hitachi Chemical Co., Ltd.), dicyclopentenyl acrylate (trade name: Fancryl FA-511AS, Hitachi Chemical Co., Ltd.), dicyclopentenyl methacrylate (trade name: Fancryl FA-51 ... Commercially available products such as cyclopentenyloxyethyl acrylate (trade name: Fancryl FA-512AS, Hitachi Chemical Co., Ltd.), dicyclopentenyloxyethyl methacrylate (trade name: Fancryl FA-512M, Hitachi Chemical Co., Ltd.), isobornyl acrylate (trade name: IB-XA, Kyoeisha Chemical Co., Ltd.), isobornyl methacrylate (trade name: IBXMA, Kyoeisha Chemical Co., Ltd.), and 1-adamantyl methacrylate (trade name: Adamantate M-104, Idemitsu Kosan Co., Ltd.) may also be used.

[0119] (2-2) Monofunctional polymerizable monomer having a monocyclic hydrocarbon group (a-2) The term "monocyclic hydrocarbon group" refers to a hydrocarbon group having one ring (including an aromatic ring). The monomer (a-2) may be a compound produced by a known method, or may be a commercially available product such as benzyl acrylate, cyclohexyl acrylate (trade name: V#155, Osaka Organic Chemical Industry Co., Ltd.), or cyclohexyl methacrylate (trade name: Light Ester CH, Kyoeisha Chemical Co., Ltd.).

[0120] 3. Polyfunctional acrylic monomer (B) The composition of the present invention contains 10 to 30% by weight of a polyfunctional acrylic monomer (B) relative to 100% by weight of the composition. The "polyfunctional acrylic monomer" refers to a monomer having two or more (meth)acryloyl groups in one molecule.

[0121] Specific examples of the monomer (B) include tricyclodecane dimethanol di(meth)acrylate, bisphenol F ethylene oxide modified di(meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, and pentaerythritol di(meth)acrylate monomer. Benzyl alcohol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol Dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, epichlorohydrin-modified trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, ethylene oxide-modified glycerin tri(meth)acrylate, propylene oxide oxide-modified glycerin tri(meth)acrylate, epichlorohydrin-modified glycerin tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, diglycerin tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified phosphate tri(meth)acrylate, tris[(meth)acryloxyethyl]isocyanurate, caprolactone-modified tris[(meth)acryloxyethyl]isocyanurate, and the compound represented by formula (12).

[0122] TIFF0007725835000027.tif33149

[0123] (In formula (12), R 14 are each independently hydrogen or methyl, and R 15 is a monovalent organic group having 4 to 30 carbon atoms and having a fused cyclic hydrocarbon group, a monovalent organic group having 6 to 30 carbon atoms and having a polycyclic hydrocarbon group, or a monovalent organic group having 4 to 30 carbon atoms and having a monocyclic hydrocarbon group, and n B are each independently an integer from 0 to 10.

[0124] From the viewpoint of improving the ion migration resistance of the cured product formed from the composition, R 15 is preferably a group represented by any one of the formulas (13) to (16), and more preferably a group represented by the formula (12). B is preferably 0 or 1.

[0125] TIFF0007725835000028.tif73140

[0126] (In formulas (13) to (16), * represents a bond.)

[0127] The monomer (B) may be one compound selected from the above-mentioned compounds, or may be a mixture of two or more of these compounds.

[0128] In the composition of the present invention, the content of the monomer (B) is preferably 5 to 50% by weight, more preferably 5 to 30% by weight, and even more preferably 8 to 25% by weight, relative to 100% by weight of the composition, since a composition with excellent photocurability can be obtained and a cured product with a good balance of heat resistance, adhesion to substrates, and ion migration resistance can be obtained.

[0129] 4. Hydroxyl value adjuster (C) The composition of the present invention may contain a hydroxyl value adjuster (C). Here, the hydroxyl value adjuster (C) is a compound having a hydroxyl value different from that of the components (A) and (B), and is preferably a compound having a hydroxyl value higher than that of the components (A) and (B). The difference between the hydroxyl value of the component (C) and the hydroxyl value of the component (A) is preferably 100 mgKOH / g or more and 300 mgKOH / g or less, more preferably 150 mgKOH / g or more and 280 mgKOH / g or less. The difference between the hydroxyl value of the component (C) and the hydroxyl value of the component (B) is preferably 150 mgKOH / g or more and 250 mgKOH / g or less, more preferably 100 mgKOH / g or more and 200 mgKOH / g or less. The hydroxyl value adjuster (C) may be used alone or as a mixture of two or more kinds.

[0130] The composition of the present invention may be prepared by, for example, blending a hydroxyl value adjuster (C) having a hydroxyl group with the monofunctional acrylic monomer (A) having no hydroxyl groups and the polyfunctional acrylic monomer (B) having no hydroxyl groups to adjust the hydroxyl value of the entire composition. In this case, from the viewpoint of forming a cured product having good ion migration resistance, the content of the hydroxyl value adjuster (C) is preferably 0.1 to 30 wt%, more preferably 0.3 to 25 wt%, and even more preferably 0.5 to 20 wt%, based on 100 wt% of the composition.

[0131] Since the hydroxyl value of the composition can be easily adjusted to a predetermined range with the above-mentioned preferred blending amount, the hydroxyl value of the hydroxyl value adjuster (C) is preferably 100 to 300 mgKOH / g, more preferably 150 to 250 mgKOH / g. Specific examples of the hydroxyl group regulator (C) include OT-2503, an acrylic oligomer (Aronix OT-2503, trade name, manufactured by Toagosei Co., Ltd., weight-average molecular weight 1000, hydroxyl value 172 mg KOH / g, Tg 94°C), M305, pentaerythritol triacrylate and pentaerythritol tetraacrylate (Aronix M305, trade name, manufactured by Toagosei Co., Ltd., weight-average molecular weight 323, hydroxyl value 116 mg KOH / g, Tg 107°C), and EA-5422LC, a dicyclopentadiene dimethanol glycidyl ether acrylic acid adduct (NK Oligo EA-5422LC, manufactured by Shin-Nakamura Chemical Co., Ltd., hydroxyl value 248 mg KOH / g).

[0132] In the present invention, the hydroxyl value of the composition containing the components (A), (B), and (D) is adjusted to 1 to 100 mgKOH / g using the hydroxyl value adjuster (C), which allows the composition to form a cured product that has excellent dischargeability and photocurability when used as an inkjet ink, as well as excellent heat resistance, adhesion to substrates (particularly silicon substrates, glass substrates, and substrates having conductors such as metal wiring and electrodes formed thereon), and ion migration resistance. From the viewpoint of obtaining a cured product with excellent ion migration resistance, the hydroxyl value of the composition is more preferably 2 to 40 mgKOH / g, and even more preferably 5 to 40 mgKOH / g.

[0133] From the viewpoint of adjusting the hydroxyl value of the composition with the hydroxyl value adjuster (C) and forming a cured product having excellent ion migration resistance, the hydroxyl value of each of the components (A), (B) and (D) is preferably 100 mgKOH / g or less, more preferably 10 mgKOH / g or less, and even more preferably 0 mgKOH / g.

[0134] 5. Photopolymerization initiator (E) The composition of the present invention may further contain a photopolymerization initiator (E). The photopolymerization initiator may be any compound that generates radicals when irradiated with ultraviolet light, visible light, electromagnetic waves, etc., and can initiate polymerization of the monomer components contained in the composition of the present invention, and commonly used compounds can be used. Specific examples of the photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoate, and the like. Zoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1'-(methylene-di-4,1-phenylene)bis(2-hydroxy-2-methyl-1-propanone), camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-dimethylamino Ethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate, Isoamyl 4-dimethylaminobenzoate, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4' -dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[pN,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-Bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5' -tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-biimidazole Bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4, 4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'-di(tert-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(tert-butylperoxycarbonyl)benzophenone, etc. Commercially available products include, for example, BASF's product names: Irgacure 379EG, Irgacure 127, Irgacure 184, and IGM Resins B.V.'s product names: Omnirad 379EG, Omnirad 127, Omnirad 184. Among these, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one is preferred.

[0135] From the viewpoint of forming a cured product with good ion migration resistance, the photopolymerization initiator (E) is preferably contained in an amount of 5 to 15% by weight, more preferably 7 to 12% by weight, relative to 100% by weight of the composition. The photopolymerization initiator (D) may be a single compound or a mixture of two or more compounds.

[0136] 6. Active energy ray-curable ink composition, inkjet composition The present invention can also be embodied as an actinic radiation-curable ink composition containing the composition of the present invention. Here, actinic radiation refers to energy radiation capable of generating active species by decomposing a compound that generates active species. Examples of such actinic radiation include light energy radiation such as visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, γ-rays, and electron beams.

[0137] When the composition of the present invention is used as a composition for inkjet recording, the viscosity at 25° C. is preferably from 1 to 100 mPa·s, and more preferably from 3 to 70 mPa·s, from the viewpoint of improving the ejection properties.

[0138] In order to improve various properties, the composition of the present invention may contain other components such as a flame retardant, a resin containing a phenolic hydroxyl group, a melamine resin, an epoxy compound, an oxetane compound, a curing agent, a surfactant, a colorant, a polymerization inhibitor, and a solvent, within a range that does not impair the effects of the present invention.

[0139] 7.Cured product The cured product of the present invention can be obtained by photocuring the composition of the present invention.

[0140] The cured product can be formed, for example, by applying the composition to a substrate. The application method is not particularly limited, and may be an inkjet method, jetting method, spin coating method, roll coating method, slit coating method, dipping method, spray coating method, gravure coating method, reverse coating method, rod coating method, bar coating method, die coating method, kiss coating method, reverse kiss coating method, air knife coating method, curtain coating method, or the like.

[0141] Furthermore, the substrate is not particularly limited, but examples thereof include polyester resin substrates made of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc.; polyolefin resin substrates made of polyethylene and polypropylene, etc.; organic polymer films made of polyvinyl chloride, fluororesin, acrylic resin, polyamide, polycarbonate, polyimide, etc.; cellophane; metal foil; laminated films of polyimide and metal foil; paper sealed with glassine paper, parchment paper, polyethylene, clay binder, polyvinyl alcohol, starch, carboxymethyl cellulose (CMC), etc.; silicon substrates; and glass substrates.

[0142] The present invention can also be embodied as an ink-jet ink composition containing the composition of the present invention, or an actinic energy ray-curable ink composition containing the ink-jet ink composition.

[0143] When the composition of the present invention is used as an inkjet ink, a cured product can be produced by a method including the following steps 1 and 2. (Step 1) A step of applying the composition of the present invention onto a substrate by an inkjet method to form a coating film. (Step 2) A step of irradiating the coating film obtained in Step 1 with light to harden the coating film and form a hardened product on the substrate.

[0144] The inkjet method is not particularly limited, and any known inkjet method can be used. The substrate is not particularly limited as long as it can be used to apply the ink of the present invention, and the shape of the substrate is not limited to a flat plate, and may be curved, etc.

[0145] By using the inkjet method, the ink of the present invention can be easily applied in a predetermined pattern, and a uniform pattern can be formed on a large substrate.

[0146] The temperature when ejected from the inkjet coating device is preferably 10 to 120° C. The viscosity of the ink of the present invention at this temperature is preferably 1 to 100 mPa·s, and more preferably 3 to 70 mPa·s.

[0147] When using ink with a viscosity of more than 30 mPa·s at 25°C, more stable ejection can be achieved by heating the inkjet head to reduce the viscosity of the ink during ejection. When jetting by heating the inkjet head, the heating temperature is preferably 40 to 120°C. When heating the inkjet head, it is preferable to use ink that does not contain solvent.

[0148] The thickness of the resulting coating film may be appropriately selected depending on the desired application, but is preferably 1 to 50 μm, more preferably 5 to 30 μm.

[0149] When irradiating with ultraviolet light or visible light, the exposure dose may be adjusted appropriately depending on the composition of the composition of the present invention. When measured using a UV monitor manufactured by Opsytec ("UV-Pad", wavelength: UV-A (315-400 nm)), the exposure dose is 100 to 10,000 mJ / cm. 2 The preferred range is 150 to 5000 mJ / cm 2 The preferred range is 180 to 3000 mJ / cm 2 More preferably, the range is 200 to 2000 mJ / cm 2The wavelength of the ultraviolet light or visible light to be irradiated is preferably 200 to 500 nm, more preferably 300 to 450 nm.

[0150] When irradiating light, an exposure machine may be used. The exposure machine is preferably equipped with a UV-LED lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a halogen lamp, a black light lamp, or the like, and is a device that irradiates ultraviolet rays, visible light, or the like in the range of 200 to 500 nm.

[0151] If necessary, the cured product cured by irradiation with light may be further heated and baked. Typically, heating and baking at 80 to 250°C for 10 to 60 minutes will result in a stronger cured product.

[0152] The thickness of the cured product of the present invention may be appropriately selected depending on the desired application, but is preferably 1 to 50 μm, more preferably 5 to 30 μm.

[0153] The cured product of the present invention is a cured product that has excellent heat resistance, adhesion to substrates, and ion migration resistance, and is therefore suitable for use as a protective film or insulating film in display elements such as liquid crystal display elements or EL display elements, and in electronic circuit boards such as printed wiring boards, flexible wiring boards, semiconductor package substrates, and solar cell substrates.Furthermore, the cured product of the present invention is suitable for use as a coverlay film or solder resist that protects conductors such as metal wiring and electrodes that form a predetermined circuit pattern.

[0154] 8. Electronic Components The electronic component of the present invention preferably includes the cured product of the present invention and is produced by a method including the steps 1 and 2. The cured product of the present invention has excellent heat resistance, adhesion to a substrate, and resistance to ion migration, and therefore the electronic component of the present invention has excellent electrical properties and long-term reliability. [Example]

[0155] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0156] The following components were used in the Examples and Comparative Examples. The following abbreviations are used to indicate the respective components as appropriate. [Monofunctional acrylic monomer (A)] FA-513AS: Dicyclopentanyl acrylate (trade name: Fancryl FA-513AS, Hitachi Chemical Co., Ltd., hydroxyl value: 0 mg KOH / g, glass transition temperature (Tg) of homopolymer: 120°C) IB-XA: Isobornyl acrylate (trade name: IB-XA; Kyoeisha Chemical Co., Ltd., hydroxyl value 0 mg KOH / g, Tg 97°C)

[0157] [Polyfunctional acrylic monomer (B)] IRR214-K: Tricyclodecane dimethanol diacrylate (hydroxyl value 0 mg KOH / g, Tg 190°C)

[0158] [Hydroxyl value adjuster (C)] EA-5422LC: Dicyclopentadiene dimethanol glycidyl ether acrylic acid adduct (trade name: NK Oligo EA-5422LC, Shin-Nakamura Chemical Co., Ltd., hydroxyl value 248 mg KOH / g)

[0159] [Compound (D-4)] PEAM-104: Polyester acrylate methacrylate oligomer (trade name: PEAM-1044, Designer Molecules, hydroxyl value: 0 mg KOH / g, viscosity: 4,850 mPa·s)

[0160] [Photopolymerization initiator (E)] Irg379; 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (IRGACURE379; trade name, BASF Japan Ltd.)

[0161] [Synthesis Example 1] [Urethane di(meth)acrylate compound (D-1)] The urethane di(meth)acrylate compound (D-1) derived from dimer diol was synthesized by the following method. Under a nitrogen atmosphere, in a three-necked flask (100 mL) equipped with a reflux condenser, a thermometer, and a dropping funnel, dimer diol (Croda Japan Co., Ltd.; Pripol 2033, 23, 7 g, 48 mmol) was heated to 80 ° C., and then AOI (2-isocyanatoethyl acrylate, Showa Denko K.K.; Karenz AOI, 16.3 g, 105 mmol) was introduced into the dropping funnel and quickly added dropwise to start the reaction. The mixture was stirred at the same temperature for 3 hours. Then, MEOH (3.1 g, 96 mmol, Kanto Chemical Co., Ltd.) was added and stirred for 30 minutes. The flask was then cooled to room temperature by placing it in a bath to obtain a urethane di(meth)acrylate compound (D-1). The resulting reaction liquid was transparent, and the weight molecular weight determined by GPC analysis was 1,200, the molecular weight distribution was 1.0, and the viscosity at 25°C determined using an E-type viscometer (Toki Sangyo Co., Ltd. TV-22, the same applies hereinafter) was 540 mPa·s.

[0162] [Synthesis Example 2] [Alkyl di(meth)acrylate compound (D-2)] The alkyl di(meth)acrylate compound (D-2) derived from dimer diol was synthesized by the following method. Dimer diol (Croda Japan; Pripol 2033, 284.4 g, 500 mmol) was dissolved in dry acetone (450 mL) under nitrogen in a 1-liter, three-neck flask equipped with a mechanical stirrer and a dropping funnel. Triethylamine (101.2 g, 1 mol) was added to the solution, and the solution was cooled to 4°C in an ice bath. Acryloyl chloride (90.5 g, 1 mol) solvated in dry acetone (100 mL) was charged to the dropping funnel and added dropwise to the stirred reaction solution over the course of 60 minutes, maintaining an internal temperature of T<10°C. The solution was stirred on ice for an additional 2 hours, then allowed to return to room temperature and stirred for 4 hours. Most of the solvent was removed by evaporation, and the remaining residue was solvated in CHCl (1 L). This solution was then washed with 5% aqueous HCl (800 ml) and HO (1200 ml). The isolated organic material was dried over anhydrous MgSO, filtered, and the solvent was removed using an evaporator to obtain alkyl di(meth)acrylate compound (D-2). The viscosity at 25°C measured using an E-type viscometer (Toki Sangyo Co., Ltd. TV-22, hereinafter the same) was 126 mPa·s.

[0163] [Synthesis Example 3] [Urea di(meth)acrylate compound (D-3)] The urea di(meth)acrylate compound (D-3) derived from dimer diamine was synthesized by the following method. Under a nitrogen atmosphere, dimer diamine (Croda Japan; Priamine 1074, 21, 3 g, 43 mmol), IBXA (24 g, 108 mmol), and phenothiazine (Kanto Chemical, 0.3 g, 1.5 mmol) were charged into a three-neck flask (100 mL) equipped with a reflux condenser, a thermometer, and a dropping funnel. After cooling to 5°C in an ice bath, AOI (2-isocyanatoethyl acrylate, Showa Denko; Karenz AOI, 14.7 g, 95 mmol) was introduced into the dropping funnel and added dropwise to the stirred reaction solution over the course of 30 minutes, maintaining an internal temperature T<20°C. The ice bath was then removed, the mixture was allowed to return to room temperature, and the mixture was then heated to 50°C and stirred for 1 hour. Morpholine (1.5 g, 17 mmol, manufactured by Kanto Chemical Co., Inc.) was then added and stirred for 30 minutes. The flask was then cooled to room temperature by placing it in a bath, yielding a solution containing 60 wt% of urea di(meth)acrylate compound (D-3). The resulting solution was transparent, and GPC analysis determined that the weight-average molecular weight of the urea di(meth)acrylate compound was 1,200, with a molecular weight distribution of 1.1. The viscosity of the resulting solution at 25°C, determined using an E-type viscometer (Toki Sangyo Co., Ltd. TV-22, the same applies hereinafter), was 8,930 mPa·s.

[0164] [Example 1] <Preparation of Photocurable Composition> A mixture of 35 g of FA-513AS and 35 g of IB-XA (monofunctional acrylic monomers A), 20 g of IRR214-K (multifunctional (bifunctional) acrylic monomer B), 10 g of EA-5422LC (hydroxyl value adjuster C), 20 g of the urethane di(meth)acrylate (D-1) obtained in Synthesis Example (1) (compound D), and 12 g of Irg379 (photopolymerization initiator E) was used to obtain a solution. The resulting solution was then filtered through a 0.2 μm pore size ultra-high molecular weight polyethylene (hydrophobic) membrane filter (Nihon Entegris Co., Ltd.) to obtain the filtrate (hereinafter referred to as "Photocurable Composition 1"). The viscosity of the photocurable composition at 25°C was measured using an E-type viscometer (Toki Sangyo Co., Ltd. TV-22, the same applies hereinafter) and found to be 29.2 mPa·s.

[0165] [Examples 2 to 6] Photocurable compositions 2 to 6 were prepared in the same manner as in Example 1, except that the materials shown in Table 1 were used. The viscosity of the photocurable compositions was measured at 25°C using an E-type viscometer (TV-22, manufactured by Toki Sangyo Co., Ltd.; the same applies hereinafter), and the results are shown in Table 2. Note that the values in the table representing the contents of components (A), (B), (C), and (D) are all in weight percent.

[0166] [Comparative Example 1] Photocurable composition 7 was prepared in the same manner as in Example 1, except that the materials shown in Table 1 were used. The viscosity of the photocurable composition at 25°C was measured using an E-type viscometer (TV-22, manufactured by Toki Sangyo Co., Ltd.; the same applies hereinafter), and the results are shown in Table 2. Note that the values in the table representing the contents of components (A), (B), (C), and (D) are all in weight percent.

[0167] <Formation of cured product> 2.5 mL of each of the obtained photocurable compositions 1 to 7 was dropped onto a 10 cm square piece of aluminum foil, and a coating film with a uniform thickness was formed using a bar coater (rod No. 75). The obtained coating film was irradiated with 2000 mJ / cm of ultraviolet light with a wavelength of 365 nm using a UV-LED lamp "LSS-08aAUV" light source: UV-LED (manufactured by CCS Corporation, lamp wavelength: 365 nm). 2 The coating was photocured by irradiating it with UV exposure (measured with a UV monitor ("UV-Pad") manufactured by Opsytec, wavelength: UV-A (315-400 nm)) and then heated and baked for 60 minutes at 200°C in a clean oven DT-610 (manufactured by Yamato Scientific Co., Ltd.) to obtain cured films 1 to 7 with a thickness of approximately 50 μm.

[0168] <Evaluation of the cured film alone> The obtained cured films 1 to 7 were peeled off from the aluminum foil to obtain the cured films 1 to 7. The breaking elongation and glass transition temperature of the obtained cured films were evaluated. The test methods and evaluation criteria are as follows, and the evaluation results are shown in Table 2.

[0169] (Tensile test) The cured film alone was cut into strips with a width of 5 mm and a length of 50 mm. Using a tensile testing machine (manufactured by Shimadzu Corporation), both ends of the sample were gripped with a pair of chucks, and measurements were carried out under the conditions of a temperature of 25°C - 50% RH and a tensile speed of 50 mm / min. The length at the time when the sample broke was determined, and the elongation at break was determined from the following formula. The initial length was 15 mm (the distance between the pair of chucks at the start of the test). (Elongation at break) = ((Length at break) - (Initial length)) / (Initial length)

[0170] (Measurement of glass transition temperature) The cured film alone was cut into strips with a width of 5 mm and a length of 50 mm. Using a viscoelasticity measuring device, both ends of the sample were gripped with a pair of chucks, and dynamic viscoelasticity measurements were carried out under the conditions of a temperature increase speed of 10°C / min and a frequency of 1 Hz. The glass transition temperature is the value read from the temperature of tanδ with the largest peak intensity among the peak positions of tanδ represented by the ratio of the storage modulus E' and the loss modulus E'' obtained from the viscoelasticity measurement. Note that tanδ can be obtained from the following formula. (tanδ) = ((Storage modulus E') / (Loss modulus E''))

[0171] <Fabrication of IMG evaluation substrate> The obtained photocurable compositions 1 to 7 were applied onto a substrate with a comb-shaped electrode pattern (manufactured by Raytech Corporation, L / S = 18 μm / 18 μm), and spin-coated at a rotational speed of 1,000 - 3,000 rpm to obtain a coating film covering the overlap margin of the comb-shaped electrodes. The obtained substrate was irradiated with ultraviolet light having a wavelength of 365 nm at a UV exposure dose of 2000 mJ / cm 2 (measured with a UV monitor (「UV-Pad」) manufactured by Opsytec, wavelength: UV-A (315 - 400 nm)) to photocure the coating film, and then heated and baked at 200°C for 60 minutes using a clean oven DT-610 (manufactured by Yamato Scientific Co., Ltd.) to obtain IMG evaluation substrates 1 to 7 with a coating film thickness of approximately 10 μm on the copper electrodes.

[0172] <Fabrication of adhesion evaluation substrate> The obtained photocurable compositions 1 to 7 were applied to a flexible copper-clad laminate (manufactured by Connectec Japan Co., Ltd., hereinafter referred to as copper substrate) and spin-coated at a rotation speed of 1,000 to 3,000 rpm to obtain a coating film. The obtained copper substrate was irradiated with ultraviolet light of 365 nm wavelength at 2,000 mJ / cm using a UV-LED lamp "LSS-08aAUV" (manufactured by CCS Inc., lamp wavelength: 365 nm). 2 The coating was photocured by irradiating it with UV exposure (measured using a UV monitor ("UV-Pad") manufactured by Opsytec, wavelength: UV-A (315-400 nm)) and then baked in a clean oven DT-610 (manufactured by Yamato Scientific Co., Ltd.) at 200°C for 60 minutes to obtain adhesion evaluation substrates 1 to 7 with coating thicknesses of approximately 10 μm.

[0173] <Preparation of film stress evaluation substrate> The obtained photocurable compositions 1 to 7 were applied to a 4 cm x 4 cm glass (EagleXG) and spin-coated at a rotation speed of 1,000 to 3,000 rpm to obtain a coating film. The obtained substrate was irradiated with ultraviolet light at a wavelength of 365 nm at 2,000 mJ / cm using a UV-LED lamp "LSS-08aAUV" (manufactured by CCS Corporation, lamp wavelength: 365 nm). 2 The coating was photocured by irradiating it with UV exposure (measured with an Opsytec UV monitor ("UV-Pad"), wavelength: UV-A (315-400 nm)) and then heated and baked for 60 minutes at 200°C in a clean oven DT-610 (Yamato Scientific Co., Ltd.) to obtain film stress evaluation substrates 1 to 7 with a cured film thickness of approximately 10 μm.

[0174] <Evaluation of cured substrate> Using the IMG evaluation substrates 1 to 7, adhesion evaluation substrates 1 to 7, and film stress evaluation substrates 1 to 7 obtained above, ion migration resistance, adhesion to a copper substrate, and film stress were evaluated, respectively. The test methods and evaluation criteria are as follows, and the evaluation results are shown in Table 2.

[0175] (Ion migration resistance test) The ion migration resistance of the IMG evaluation substrates 1 to 7 obtained above was evaluated by the following method. The obtained MG evaluation substrate was connected to an ion migration tester MIG-87 (IMV Corporation) with wiring and placed in a HAST chamber EHS-411M (Espec Corporation). A DC voltage of 30 V was then applied for 100 hours in an environment of 130°C and 85% humidity.

[0176] (Evaluation criteria) The above test was carried out on four IMG evaluation boards, and after 100 hours of application, the resistance value was 1×10 6 The samples that exhibited the above were deemed to have passed the test. The ion migration resistance was evaluated based on the number of samples that passed the test. X / 4: Of the four IMG samples, X passed the test.

[0177] (Adhesion: Cross-cut peel test) The cured product obtained on the substrate for evaluating adhesion was cross-cut into 1 mm x 1 mm squares (checkerboard pattern) to create 100 areas surrounded by the cuts. An adhesive peeling tape was applied over the areas, and the number of peeled areas was counted when the tape was peeled off. The results were evaluated according to the following criteria. The peeling tape used was Scotch #610 (product name, manufactured by 3M), 402 N / 100 mm (vertical direction). (Evaluation criteria) ◎: Not a single area peeled off out of 100 ○: Missing area (peeled area) is 5% or less △: Missing area is over 5% and less than 50% ×: Missing area exceeds 51%

[0178] (membrane stress measurement) Film stress evaluation: The profile of the diagonal (4 cm) of the substrate was measured using a step gauge (P-16+; KLA-Tencor Corporation) for the glass before the coating film was formed on the substrate and for the substrate surface after the cured film was formed. From the obtained profile, the radius of curvature before and after the cured film was formed was calculated, and the film stress was calculated using the following formula (X1), and the change in glass warpage was calculated using the following formula (X2).

[0179] TIFF0007725835000029.tif1898

[0180] (σ in the formula f is the membrane stress (MPa), E s is the elastic modulus of the glass substrate, ts is the thickness of the cured film, t f is the thickness of the cured film, ν s represents the Poisson's ratio of the glass, R1 represents the radius of curvature of the substrate after the cured film is formed, and R0 represents the radius of curvature of the glass substrate.)

[0181] (Warpage change amount) = (Warpage amount of substrate after coating) - (Warpage amount of substrate before coating) Formula (X2)

[0182] (Ink ejection test) The dischargeability of photocurable compositions 1 to 7 obtained in each example and comparative example was evaluated. Photocurable compositions 1 to 7 were poured into an inkjet cartridge DMC-11610 (manufactured by FUJIFILM Corporation), which was then attached to an inkjet device (FUJIFILM Corporation DMP-2831). The discharge conditions were a discharge voltage (piezoelectric voltage) of 17 to 25 V, a head temperature of 32 to 70°C, a drive frequency of 5 kHz, and one application, and the evaluation criteria were as follows. The evaluation results are shown in Table 2. Good: Good discharge from 12 or more consecutive nozzles △: Good discharge from consecutive nozzles 4 to 11 ×: Good discharge from 4 or fewer consecutive nozzles

[0183] (Photocuring test) The obtained photocurable compositions 1 to 7 were applied to a 4 cm x 4 cm glass (Eagle XG) and spin-coated at a rotation speed of 1,000 to 3,000 rpm to prepare photocurable test coatings 1 to 7. The obtained coatings were irradiated with 2,000 mJ / cm2 of ultraviolet light at a wavelength of 365 nm using a UV-LED lamp "LSS-08aAUV" (manufactured by CCS Corporation, lamp wavelength: 365 nm). 2 The coating film was irradiated with a UV exposure of 1000 kJ / h (measured with a UV monitor ("UV-Pad") manufactured by Opsytec, wavelength: UV-A (315-400 nm)). The coating film surface was touched with a finger to evaluate whether or not it had tackiness. (Evaluation criteria) ◎: No tackiness 〇: Tacky ×: Liquid (uncured)

[0184] [Table 1]

[0185] [Table 2]

[0186] As shown in Tables 1 and 2, by using a composition containing compound (D), the film stress and warpage were reduced while maintaining the ion migration resistance (hereinafter referred to as "IMG resistance") and adhesion of the cured product. From these results, it is believed that the structure of the dimer acid alleviates the stress caused by cure shrinkage, reducing the film stress and warpage of the cured film.

[0187] Furthermore, the viscosity of the photocurable composition can be adjusted depending on the structure of the compound (D) having a structural unit derived from a dimer acid and a (meth)acryloyl group at the terminal. For example, in Example 1, which contains a compound (D) having a urethane structure, and in Examples containing a compound (D) having an imide skeleton, the viscosity of the composition can be kept low, making it suitable for use as an inkjet ink. On the other hand, Example 5, which contains a compound (D) having a urea structure, can increase the viscosity, making it suitable for use as an ink intended for application methods using an applicator or jet dispenser. [Industrial Applicability]

[0188] The photocurable composition of the present invention can be used to form a cured product that exhibits excellent adhesion to silicon substrates, glass substrates, polyimide substrates, and substrates having conductors such as metal wiring and electrodes formed thereon, as well as excellent resistance to ion migration and low warpage.

Claims

1. A monofunctional acrylic monomer (A) represented by the following formula (7): A polyfunctional acrylic monomer (B) represented by the following formula (12), and A photocurable composition containing a compound (D) having a structural unit derived from a dimer acid and having a (meth)acryloyl group at its terminal, The structural unit derived from a dimer acid in the compound (D) is a dimer diamine structural unit, The content of each component in the composition is: Monofunctional acrylic monomer (A): 10 to 80% by weight based on 100% by weight of the composition Polyfunctional acrylic monomer (B): 5 to 50% by weight based on 100% by weight of the composition Compound (D): 10 to 80% by weight based on 100% by weight of the composition The photocurable composition according to claim 1, (In formula (7), R １１ is hydrogen or methyl, and R １２ is a group represented by any one of the following formulas (8) to (11), and n Ａ is an integer of 0 to 10, and in formulas (8) to (11), R １３ are each independently hydrogen or alkyl having 1 to 6 carbon atoms, * is a bond, and in formula (12), R １４ are each independently hydrogen or methyl, and R １５ is a group represented by any one of the following formulas (13) to (16), and n Ｂ are each independently an integer of 0 to 10, and in formulas (13) to (16), * represents a bond.

2. The compound (D) is The photocurable composition according to claim 1, having a dimer diamine structural unit, wherein the dimer diamine comprises at least one compound selected from the group consisting of formulas (3) and (4). (In the formula, R ５ and R ６ are each alkyl having 1 or more carbon atoms, e and f are each independently an integer of 1 or more, and R ５ and R ６ The total number of carbon atoms contained in e and f is 38 or less, and any C-C bond in the formula may be replaced with a double bond. (In the formula, R ７ and R ８ are each alkyl having 1 or more carbon atoms, g and h are each independently an integer of 1 or more, and R ７ and R ８ The total number of carbon atoms contained in g and h is 42 or less, and any C-C bond in the formula may be replaced with a double bond.

3. The compound (D) is 2. The photocurable composition according to claim 1, wherein the photocurable composition is a urea di(meth)acrylate compound (D-3), which is a reaction product of the dimer diamine and an isocyanate having a (meth)acryloyl group.

4. Further, the composition contains 0.1 to 30% by weight of a hydroxyl value adjuster (C) relative to 100% by weight of the composition, The photocurable composition according to any one of claims 1 to 3, wherein the photocurable composition has a hydroxyl value of 1 to 100 mgKOH / g.

5. 5. The photocurable composition according to claim 1, wherein the monofunctional acrylic monomer (A) contains a (meth)acrylate having one or more selected from the group consisting of a fused cyclic hydrocarbon group, a polycyclic hydrocarbon group, and a monocyclic hydrocarbon group.

6. The hydroxyl value adjuster (C) is a hydroxyl value of 100 to 300 mgKOH / g; 5. The photocurable composition according to claim 4, which has a weight average molecular weight of 100 to 5,000.

7. 7. The photocurable composition according to claim 1, further comprising a photopolymerization initiator (E) in an amount of 5 to 15% by weight relative to 100% by weight of the composition.

8. 7. The photocurable composition according to claim 1, wherein the hydroxyl value is from 5 to 40 mgKOH / g.

9. An actinic ray-curable ink composition comprising the photocurable composition according to any one of claims 1 to 8.

10. An ink-jet ink composition comprising the photocurable composition according to any one of claims 1 to 8.

11. A cured product obtained by photocuring the photocurable composition according to any one of claims 1 to 10.

12. A cured product obtained by photocuring the photocurable composition according to any one of claims 1 to 10 and then thermally curing it.

13. An electronic part comprising the cured product according to claim 11 or 12.

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