Compounds containing sulfur and (meth)acrylate moieties suitable for bonding organic polymers to metals

Abstract

Articles are described that include an organic polymer layer containing a compound that includes at least one sulfur moiety and at least one (meth)acrylate moiety, the surface of which is bonded to a metal (e.g., a thin layer), such as gold or silver. Also described are various compounds that include at least one sulfur moiety and at least one (meth)acrylate moiety, methods for making such compounds, and polymerizable resins that include such compounds.

Description

Summary of the Invention

[0001] In one embodiment, an article is described that includes an organic polymer layer containing a compound comprising at least one sulfur moiety and at least one (meth)acrylate moiety, wherein the surface of the organic polymer layer is associated with a metal. In some embodiments, the metal comprises gold or silver. In some embodiments, the metal has a thickness of 5 microns, 1 micron, 500 nm, 250 nm, 100 nm, or 50 nm or less.

[0002] The compound comprising at least one sulfur moiety and at least one (meth)acrylate moiety may comprise one or more novel compounds.

[0003] In other embodiments, various compounds are described that include at least one sulfur moiety and at least one (meth)acrylate moiety.

[0004] In one embodiment, the compound is a Michael addition reaction product of a multifunctional thiol compound, one or more diacrylate compounds, and a base.

[0005] In one embodiment, the compound has the following formula I: [ka] [In the formula, R S is the residue of a multifunctional thiol, R A are, independently of each other, the residue of a diacrylate, and n is 2 to 6 (e.g., the number of thiol groups in a multifunctional thiol).

[0006] In another embodiment, the compound is the reaction product of a multifunctional thiol compound, one or more isocyanato(meth)acrylate compounds, and a base, wherein the reaction product contains a compound having at least one isocyanato(meth)acrylate group and one or more thiol groups.

[0007] In one embodiment, the compound has the following formula II: [ka] [In the formula, R1 is H or CH3; R is a linear or branched alkylene having 2 to 10 carbon atoms, optionally substituted with O; R S is the residue of a multifunctional thiol, q is 1 to 5; m is 1 to 5 (e.g., the number of unreacted thiol groups in a polyfunctional thiol), However, the sum of q+m is 2 to 6 (for example, the number of thiol groups in a multifunctional thiol).

[0008] In another embodiment, the compound is a Michael addition reaction product of a compound containing at least one isocyanato(meth)acrylate group and one or more thiol groups (as described immediately above) with a diacrylate compound.

[0009] In one embodiment, the compound has the following formula III: [ka] [In the formula, R1 is H or CH3, R is a linear or branched alkylene having 2 to 10 carbon atoms, optionally substituted with O; R S is the residue of a multifunctional thiol, q is 1 to 5; m is 0 to 4 (for example, the number of unreacted thiol groups in a polyfunctional thiol), s is 1 to 5, However, the sum of q+m+s is 2 to 6 (for example, the number of thiol groups in a multifunctional thiol).

[0010] In some embodiments, m is at least one.

[0011] Also described herein are polymerizable resin compositions comprising one or more (meth)acrylate monomers, and compounds comprising at least one sulfur moiety and at least one (meth)acrylate moiety.

[0012] Also described are methods for making compounds containing at least one sulfur moiety and at least one (meth)acrylate moiety. These compounds may be prepared in organic solvents, or solventless methods may be used, such as forming the compounds in a polymerizable resin. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic diagram of a two-layer article. [Figure 2] FIG. 1 is a schematic diagram of a three-layer article. [Figure 3] FIG. 1 is a schematic diagram of a multi-layer stack used to evaluate the adhesion strength of a metal layer to a cured resin. DETAILED DESCRIPTION OF THE INVENTION

[0014] Described herein are compounds containing sulfur moieties and (meth)acrylate moieties that are useful as coupling agents for bonding organic polymer layers, such as cured organic resins, to metals.

[0015] The compounds comprising sulfur moieties and acrylate moieties are prepared by the reaction of a polyfunctional thiol compound. In some embodiments, the polyfunctional thiol compound and its reaction product are aliphatic. In other embodiments, the polyfunctional thiol compound and its reaction product are aromatic polyfunctional thiols.

[0016] Examples of polyfunctional thiols include the following: aliphatic thiols, such as methanedithiol, propanedithiol, cyclohexanedithiol, 2-mercaptoethyl-2,3-dimercaptosuccinic acid ester, 2,3-dimercapto-1-propanol (2-mercaptoacetate), diethylene glycol bis(2-mercaptoacetate), 1,2-dimercaptopropyl methyl ether, bis(2-mercaptoethyl) ether, trimethylolpropane tris(thioglycolate), pentaerythritol tetra(mercaptopropionate), pentaerythritol tetra(thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris(β-thiopropionate), and propoxylated alkanes. tris-mercaptan derivatives of triglycidyl ethers of the above, dipentaerythritol poly(β-thiopropionate); halogen-substituted derivatives of these aliphatic thiols; aromatic thiols, such as di-, tri-, or tetra-mercaptobenzene, bis-, tris-, or tetra-(mercaptoalkyl)benzene, dimercaptobiphenyl, toluenedithiol, and naphthalenedithiol; halogen-substituted derivatives of these aromatic thiols; heterocyclic ring-containing thiols, such as amino-4,6-dithiol-shim-triazine, alkoxy-4,6-dithiol-shim-triazine, aryloxy-4,6-dithiol-shim-triazine, and 1,3,5-tris(3-mercaptopropyl)isocyanurate; halogen-substituted derivatives of these heterocyclic ring-containing thiols;Thiol compounds having at least two mercapto groups and containing a sulfur atom in addition to the mercapto groups, such as bis-, tris-, or tetra(mercaptoalkylthio)benzene, bis-, tris-, or tetra(mercaptoalkylthio)alkane, bis(mercaptoalkyl)disulfide, hydroxyalkyl sulfide bis(mercaptopropionate), hydroxyalkyl sulfide bis(mercaptoacetate), mercaptoethyl ether bis(mercaptopropionate), 1,4-dithiane-2,5-diol bis(mercaptoacetate), thiodiglycolic acid bis(mercaptoalkyl ester), thiodipropionic acid bis(2-mercaptoalkyl ester), 4,4-thiobutyric acid bis(2-mercaptoalkyl ester), 3,4-thiophenedithiol, bismuth thiol, 2,5-dimercapto-1,3,4-thiadiazole;

[0017] Various polyfunctional thiol compounds are commercially available. Representative examples of polyfunctional thiol compounds are shown below: [Table 1]

[0018] After reaction with an acrylate or (meth)acrylate group in the presence of a base, a residue of a multifunctional thiol remains. The residue of a multifunctional thiol is an organic group present between the sulfur atoms in the multifunctional thiol. For example, if the multifunctional thiol has the following structure: [ka] The residue of the polyfunctional thiol is: [ka]

[0019] The residue of the polyfunctional thiol is a linear or branched organic group. When the polyfunctional thiol has three or more thiol groups, there is usually a branch corresponding to each thiol group, as shown above. The organic group may contain various organic moieties, including alkylene, arylene, alkarylene, aralkylene; oxygen-containing moieties such as ethers or esters; and nitrogen-containing moieties such as isocyanurates. The organic group may also contain an alicyclic or heteroalicyclic moiety. In some embodiments, the organic group may contain a combination of these moieties.

[0020] In some embodiments, the polyfunctional thiol compound comprises an ester moiety. In some embodiments, the ratio of ester moieties to thiol moieties is 1:1. Therefore, such compounds can be characterized as thioesters. In some embodiments, the polyfunctional thiol compound further comprises a heterocyclic group, such as an isocyanurate group.

[0021] In some embodiments, the polyfunctional thiol compound contains at least three or four thiol groups. In some embodiments, the greater the number of thiol groups, the quicker the desired reaction product can be formed. For example, PETMP (described below) can form the desired reaction product within 2.5 hours. The number of thiol groups is typically six or fewer, five or fewer, or four or fewer.

[0022] The polyfunctional thiol compounds (and their residues) typically have a molecular weight of about 1200 or 1000 g / mol or less. Furthermore, the thiol equivalent weight, or in other words, the molecular weight divided by the number of thiol groups, is typically at least about 100 or 125 grams / thiol group. In some embodiments, the thiol equivalent weight is 250, 200, or 150 grams / thiol group or less.

[0023] The methods for producing the multifunctional thiol compounds described herein generally include reacting a multifunctional thiol with one or more diacrylate monomers or isocyanato(meth)acrylate compounds in the presence of a base. In some embodiments, the methods for producing the multifunctional thiol compounds include reacting the multifunctional thiol with an isocyanato(meth)acrylate to form an intermediate, and then reacting the intermediate with a diacrylate monomer.

[0024] A variety of bases can be used. In some embodiments, a phosphine-based base such as dimethylphenylphosphine is used. In other embodiments, the base is an amine compound. Amine compounds include primary amines, secondary amines, and tertiary amines. Representative amine compounds include alkylamines (e.g., triethylamine, diisopropylethylamine), alkylaminoacrylates (e.g., 2-(dimethylamino)ethyl acrylate), and hydroxyl-functional amines (e.g., N,N-dimethylaminoethanol). In some embodiments, a phosphine-based base such as dimethylphenylphosphine is used. The amount of base used is typically 0.025, 0.050, 0.10, 0.25, 0.50, or more parts by weight per 100 parts by weight of the diacrylate and multifunctional thiol combined. In some embodiments, the amount of base is typically 2.5, 2.0, 1.5, 1.0, or 0.50 parts by weight or less. When the base concentration is low, a longer reaction time may be required.

[0025] Tertiary amines (e.g., alkylamines), especially diisopropylethylamine, may be suitable for short reaction times. Other tertiary amines include methyldiethanolamine, triethanolamine, diethylaminopropylamine, benzyldimethylamine, m-xylylenedi(dimethylamine), N,N'-dimethylpiperazine, N-methylpyrrolidine, N-methylhydroxypiperidine, N,N,N',N'-tetramethyldiaminoethane, N,N,N',N',N'-pentamethyldiethylenetriamine, tributylamine, trimethylamine, diethyldecylamine, triethylenediamine, diisopropyl ... diamine, N-methylmorpholine, N,N,N',N'-tetramethylpropanediamine, N-methylpiperidine, N,N'-dimethyl-1,3-(4-piperidino)propane, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,8-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, and 4-(N-pyrrolidino)pyridine, triethylamine, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0026] The synthesis reaction may be carried out in an organic solvent or without solvent, including ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl amyl ketone, and N-methylpyrrolidone (NMP); ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and methyl tetrahydrofurfuryl ether; esters such as methyl acetate, ethyl acetate, and butyl acetate; and cyclic esters such as δ-valerolactone and γ-valerolactone.

[0027] Examples of diacrylate monomers include 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylates, alkoxylated cyclohexanedimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, cyclohexanedimethanol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, hydroxypivalaldehyde-modified trimethylolpropane triacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol diacrylate, and tripropylene glycol diacrylate.

[0028] In some embodiments, the diacrylate monomer has a molecular weight of 500, 400, or 300 g / mole or less. In other embodiments, the diacrylate monomer has a higher molecular weight, greater than 500, 750, 1000, 1250, or 1500 g / mole. In some embodiments, the molecular weight is 5000, 4500, 4000, 3500, 3000, 2500, or 2000 g / mole or less. These higher molecular weight monomers may be characterized as oligomers.

[0029] Oligomeric diacrylate monomers include, for example, urethane acrylates, polyester acrylates, and epoxy acrylates can also be used. In some embodiments, the oligomer can be derived from polycaprolactone diol and H12MDI (dicyclohexylmethane diisocyanate, sold by Covestro as Desmodur W).

[0030] In some embodiments, the diacrylate oligomer comprises an aliphatic urethane acrylate oligomer having a tensile strength of less than 10,000 kPa, an elongation of 30-50%, a modulus of elasticity of 50,000-10,000 kPa, and a glass transition temperature of 25-50°C.

[0031] The reaction mixture may optionally contain a multifunctional (meth)acrylate having more than two (meth)acrylate groups. Examples include tri(meth)acrylate-containing monomers such as glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated triacrylates (e.g., ethoxylated trimethylolpropane triacrylate), propoxylated triacrylates (e.g., propoxylated glyceryl triacrylate, propoxylated trimethylolpropane triacrylate), trimethylolpropane triacrylate, and tris(2-hydroxyethyl)isocyanurate triacrylate, as well as higher-functional (meth)acrylate-containing monomers such as ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, and caprolactone-modified dipentaerythritol hexaacrylate.

[0032] In one embodiment, a method of making a compound (e.g., via Michael addition) is described, which includes reacting a multifunctional thiol compound with one or more diacrylate compounds in the presence of a base. In this embodiment, the compound is a Michael addition reaction product of the multifunctional thiol compound, the one or more diacrylate compounds, and the base.

[0033] In this embodiment, such compounds may be formed under conditions in which a substantial excess of (meth)acrylate monomers, including diacrylate monomers, is used. In this embodiment, the compounds may be formed in the polymerizable (meth)acrylate resin composition, as opposed to being synthesized separately and then added to the polymerizable (meth)acrylate resin composition. Note that the methacrylate monomer may be included in the polymerizable (meth)acrylate resin composition, even though it does not react with the polyfunctional thiol compound in the base-catalyzed Michael reaction.

[0034] In this embodiment, the amount of diacrylate acrylate monomer is at least 80, 90, 95, 96, 97, 98, 99, or 99.9 wt. % based on the total solids content of the reaction mixture (i.e., excluding any organic solvents that may be present). When other (meth)acrylate monomers are present, the amount of diacrylate monomer may be less than 80 wt. % (e.g., at least 50, 60, or 70 wt. %).

[0035] In this embodiment, the amount of the multifunctional thiol is typically at least 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt. % of the total solids content of the reaction mixture (i.e., excluding any organic solvents and bases that may be present). The amount of the multifunctional thiol is typically less than 20 wt. In some embodiments, the amount of the multifunctional thiol is less than 15, 14, 13, 12, 11, or 10 wt. Similarly, polymerizable resins and organic polymer layers containing the cured multifunctional thiol acrylate compound may contain less than 15, 14, 13, 12, 11, or 10 wt. % of the polyfunctional thiol moiety (residue).

[0036] In this embodiment, the method and compound may have an equivalent ratio of acrylate groups to thiol groups ranging from 33:1 to 3:1. As shown in the examples below, a ratio that is too low can result in poor adhesion and delamination of the laminate at interface D (as further explained in the examples below). In some embodiments, the equivalent ratio of acrylate groups to thiol groups is at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, or at least 10:1. In other embodiments, the equivalent ratio is at least 15:1, at least 20:1, at least 25:1, or at least 30:1. In other embodiments, the equivalent ratio of acrylate groups to thiol groups is less than 30:1, less than 25:1, less than 20:1, less than 15:1, or less than 10:1. If a compound is synthesized using a small amount of diacrylate compound and then added to a polymerizable resin (which may contain other (meth)acrylate monomers), the equivalent ratio may be lower.

[0037] A representative reaction scheme is as follows: [ka]

[0038] "Residue of a diacrylate" refers to an organic group located between the oxygen atoms of an acrylate group. For example, the residue of hexanediol diacrylate is -CHCHCHCHCHCHCH-. In other embodiments, the diacrylate has the following structure: [ka]

[0039] Furthermore, some of the "residues of diacrylates" may be residues of multifunctional acrylates having three or more acrylate groups, as described above.

[0040] The residue of a multifunctional acrylate (e.g., diacrylate) is a linear or branched organic group. The organic group may contain various organic moieties, such as alkylene, arylene, alkarylene, or aralkylene, and may also contain oxygen-containing moieties, such as ethers and esters, or nitrogen-containing moieties, such as urethanes or isocyanurates. The organic group may also contain an alicyclic or heteroalicyclic moiety. In some embodiments, the organic group may contain a combination of these moieties.

[0041] When a mixture of diacrylates is reacted with a multifunctional thiol, the reaction product generally contains residues of each multifunctional acrylate in approximately the same equivalent ratio as was present in the initial reaction mixture. For example, consider a 100g multifunctional acrylate mixture containing 75 parts by weight (75g) of an aliphatic urethane (Photomer 6210) and 25 parts by weight (25g) of HDDA. The acrylate equivalent weight of Photomer 6210 is 475.2g / eq, meaning that 75g contains 75 / 475.2 = 0.1578 equivalents of acrylate. Similarly, the acrylate equivalent weight of HDDA is 226 / 2 = 113g / eq, meaning that 25g contains 25 / 113 = 0.221 equivalents of acrylate. The total equivalent weight of acrylates in this 100g sample is 0.1578 + 0.221 = 0.3788. In percentage terms, the proportion of acrylate groups coming from Photomer 6210 is (0.1578 / 0.3788) × 100 = 41.66%, and the proportion coming from HDDA is 100 - 41.66 = 58.343%. A typical formulation would have a 95:5 weight ratio of this acrylate mixture to PETMP (126.5 thiol equivalents). For ease of calculation, assume there is no photoinitiator or base present in 100 g of the acrylate mixture. A 95:5 acrylate mixture would proportionally contain 5.26 g of PETMP, which corresponds to 5.26 / 126.5 = 0.041 equivalents of thiol groups. Assuming the multi-thiol is fully capped with diacrylate and the reactivities of the acrylate components are equal, the resulting adduct is statistically predicted to contain approximately 41.66% diacrylate residues from Photomer 6210 and approximately 58.34% from HDDA. This capped material consumes 2 × 0.041 = 0.082 equivalents of acrylate groups, since both Photomer 6210 and HDDA are diacrylates. Therefore, 41.66% of the acrylate equivalents from Photomer 6210, or 0.082 × 0.4166 = 0.03416 equivalents, or 0.017 moles × 950.4 = 16.23 g (due to the bifunctional nature of Photomer 6210), are incorporated into the thiol-diacrylate adduct.This gives us 0.1578 - 0.03416 = 0.12364 unreacted acrylate equivalents of Photomer 6210, which corresponds to 0.06182 moles, or 0.06182 × 950.4 = 58.75 g by weight. Balancing the weights, we find that the amount of Photomer 6210 in the mixture is 16.23 + 58.75 = 74.98 g, or 75 g after rounding. Similarly, 58.34% of the acrylate equivalents from HDDA, or 0.082 × 0.5834 = 0.04784 equivalents, are incorporated into the thiol-diacrylate adduct, which corresponds to 0.02392 moles × 226 = 5.406 g. This gives an unreacted acrylate equivalent of 0.221 - 0.04784 = 0.1732 equivalents, or 0.08658 moles, which corresponds to 0.08658 x 226 = 19.567 g by weight. The weight balance of HDDA is 5.406 + 19.567 = 24.97 g, or 25 g after rounding.

[0042] It is understood that some of the individual compounds contain residues of the same diacrylate (e.g., HDDA), and it is also understood that some of the individual compounds contain unreacted thiol groups.

[0043] In one embodiment, the compound has the following formula I: [ka] [In the formula, R S is the residue of a multifunctional thiol, R A are independently the residue of a diacrylate, and n is 2 to 6 (e.g., the number of thiol groups in a multifunctional thiol).

[0044] In some embodiments, n is 3 or 4.

[0045] In another embodiment, a method for preparing a compound is described, which comprises reacting a multifunctional thiol compound with one or more isocyanato(meth)acrylate compounds in the presence of a base. The multifunctional thiol compound and base can be similar to those described above. The reaction can be carried out in an organic solvent or without a solvent, as described above.

[0046] The (meth)acrylate compound may be aliphatic or aromatic. Representative compounds include isocyanatoethyl methacrylate (commercially available under the trade name "KARENZ MOI"), isocyanatoethoxyethyl methacrylate (commercially available under the trade name "KARENZ MOI-EG"), isocyanatoethyl acrylate (commercially available under the trade name "KARENZ AOI"), and 1,1-(bisacryloyloxymethyl)ethyl isocyanate (commercially available under the trade name "KARENZ BEI"), which are commercially available from, for example, Showa Denko K.K. (Tokyo, Japan). Other examples include the (meth)acryloyl group-containing aromatic isocyanates described in U.S. Pat. No. 8,044,235. Examples include the following structural formula in which R2 is H or methyl: [ka]

[0047] In some embodiments, the amounts of reactants are selected so that there is an insufficient amount of isocyanato(meth)acrylate present to react with all of the thiol groups, In such embodiments, the compound contains at least one isocyanato(meth)acrylate group and one or more thiol groups.

[0048] In this embodiment, the amount of isocyanato(meth)acrylate is at least 10, 15, 20, 25, 30, 35, 40, 45 wt. % based on the total solids content of the reaction mixture (i.e., excluding organic solvents and base that may be present). The amount of isocyanato(meth)acrylate typically does not exceed 65, 60, 55, or 50 wt. %.

[0049] In this embodiment, the amount of multifunctional thiol is typically at least 30, 35, 40, 45, 50, 60, or 65 wt.% based on the total solids content of the reaction mixture (i.e., excluding organic solvents and bases that may be present). The amount of multifunctional thiol is typically less than 85, 80, 75, or 70 wt.%.

[0050] A representative reaction scheme is as follows: [ka]

[0051] In this reaction scheme, one of the thiol groups is reacted with an isocyanato(meth)acrylate compound. In other embodiments, more thiol groups are reacted. In a typical embodiment, more than one, but not all, of the thiol groups are reacted with an isocyanato(meth)acrylate compound.

[0052] In some embodiments, the resulting urethane compound has the following Formula II: [ka] [In the formula, R1 is H or CH3, R is a linear or branched alkylene having 2 to 10 carbon atoms, optionally substituted with O; R S is the residue of a multifunctional thiol, q is 1 to 5; m is 1 to 5 (e.g., the number of unreacted thiol groups in a polyfunctional thiol), However, the sum of q+m is 2 to 6 (for example, the number of thiol groups in a multifunctional thiol).

[0053] In some embodiments, q is 2 or 3. In some embodiments, m is 2 or 3. In some embodiments, the sum of q+m is 3 or 4.

[0054] In yet another embodiment, a method for preparing the compound is described, which includes reacting (e.g., Michael addition) a multifunctional thiol compound containing at least one isocyanato(meth)acrylate group and one or more thiol groups with a diacrylate.

[0055] A representative reaction scheme is as follows: [ka] [ka]

[0056] In one embodiment, the resulting compound has the following formula III: [ka] [In the formula, R1 is H or CH3, R is a linear or branched alkylene having 2 to 10 carbon atoms, optionally substituted with O; R S is the residue of a multifunctional thiol, q is 1 to 5; m is 0 to 4 (for example, the number of unreacted thiol groups in a polyfunctional thiol), s is 1 to 5, However, the sum of q+m+s is 2 to 6 (for example, the number of thiol groups in a multifunctional thiol).

[0057] In some embodiments, m is at least 1, 2, 3, or 4 (e.g., an example where m is 1 is shown in Scheme 4). In some embodiments, q is 2 or 3. In some embodiments, the sum of q+m+s is 3 or 4.

[0058] Also described are polymerizable resin compositions containing one or more (meth)acrylate monomers and a compound comprising at least one sulfur moiety and at least one (meth)acrylate moiety, as described herein. The polymerizable resin may contain the same one or more (meth)acrylate monomers as used in synthesis, or different (meth)acrylate monomers.

[0059] The polymerizable composition may contain optional additional components, such as organic solvents (e.g., those described above), stabilizers, colorants, photosensitizers, fillers, wetting agents, leveling agents, and the like.

[0060] Also described is a method for producing a cured composition, comprising providing a (e.g., photo)polymerizable composition comprising the coupling agent described herein and curing the polymerizable composition. The (meth)acrylic groups are subject to free radical curing by exposure to ultraviolet (UV) radiation, electron beam (e-beam), ionizing radiation (gamma radiation), plasma radiation, and thermal polymerization. In some embodiments, the method further comprises applying the polymerizable composition to a substrate before curing. In some embodiments, the polymerizable composition forms a film or film layer after radiation curing.

[0061] In some embodiments, the substrate may be a flexible substrate, e.g., a web of infinitely long polymeric material. The flexible substrate or web may be stretched (e.g., in the machine direction and / or cross direction) as it travels along the web path. The flexible substrate may comprise, for example, polyethylene terephthalate (PET), polycarbonate (PC), glycol-modified polyethylene terephthalate (PETG), polyethylene, polyimide, polystyrene, polyurethane, etc. The processes described herein may be carried out in a roll-to-roll apparatus including one or more rollers for transporting the web along the web path. The thickness of the substrate may be, for example, about 2 mm or less, about 1 mm or less, about 500 microns or less, or about 200 microns or less.

[0062] In some embodiments, radiation curing involves exposing the (eg, coated) composition to ultraviolet (UV) and visible light wavelengths.

[0063] Such compositions generally include, for example, an effective amount of an initiator for free radical polymerization (also known as a free radical initiator). The free radical initiator may be heat-activated (e.g., peroxides and certain azo compounds) and / or light-activated (e.g., Norrish Type I and Type II photoinitiators). Such photoinitiators are activated by exposure to actinic radiation (e.g., ultraviolet and / or visible electromagnetic radiation).

[0064] Free radical polymerization may be effected, for example, by heating or exposure to actinic radiation (e.g., ultraviolet and / or visible light, gamma radiation, electron beam), depending on the presence and / or selection of a free radical initiator. Of these, exposure to actinic radiation is often preferred due to ease of implementation.

[0065] When a photoinitiator is included, its amount is typically an effective amount. In some embodiments, the effective amount of free radical initiator is less than 10 wt. %, more typically less than 7 wt. %, and even more typically less than 3 wt. %, based on the weight of the total adhesive layer. It should be understood that curing may be considered complete even if polymerizable (meth)acrylate groups remain in the organic compound.

[0066] Representative photoinitiators include alpha-cleavage type photoinitiators such as benzoin and its derivatives.

[0067] Examples of suitable actinic radiation sources include lasers, arc lamps (e.g., medium pressure mercury arc lamps), LED lamps, xenon flash lamps, microwave-driven lamps (e.g., those equipped with H-type or D-type bulbs), etc. Selection of appropriate irradiation conditions will be within the ability of one skilled in the art.

[0068] The free-radically polymerizable (meth)acrylate composition may be disposed on the surface of a substrate (e.g., as a continuous or discontinuous, optionally patterned, film) and then polymerized (e.g., by exposure to an effective amount of actinic radiation).

[0069] In some embodiments, the substrate is metal or includes a metal surface layer, in which a free-radically polymerizable (meth)acrylate composition comprising sulfur moieties and (meth)acrylate moieties, as described herein, is applied to the metal substrate or metal surface layer and cured as described above.

[0070] In this embodiment, the article includes an organic polymer layer 7, which includes a compound comprising at least one sulfur moiety and at least one (meth)acrylate moiety. The surface of the organic polymer layer is bonded to a metal 6.

[0071] In some embodiments, the metal may include gold or silver. The thickness of the metal may be 5, 4, 3, 2, or 1 micron or less. In some embodiments, the thickness of the metal layer is less than 1 micron, 750 nm, 500 nm, 250 nm, 100 nm, 50 nm, 25 nm, or 10 nm. The thickness may be 10 nm or more, or 25 nm or more. The metal layer may be continuous or discontinuous.

[0072] In some embodiments, the thickness of the organic polymer layer is 50 nm or more and 500, 400, or 300 μm or less. In other embodiments, the thickness is 500 nm, 750 nm, 1 micron, 5 microns, or 10 microns or more. In some embodiments, the thickness is 50 or 25 microns or less.

[0073] In some embodiments, a relatively thin metal layer is bonded to a (eg, transparent) substrate 9 with an organic polymer layer 7, such as a cured (meth)acrylate resin.

[0074] The (e.g., transparent) substrate 9 may be a sheet, plate, or film comprising any of glass, metal, organic polymer (e.g., polyethylene terephthalate (PET), polycarbonate (PC), glycol-modified polyethylene terephthalate (PETG), polyethylene, polyimide, polystyrene, or polyurethane), inorganic metal oxides, and combinations thereof.

[0075] In some embodiments, the substrate is an organic polymer film with a surface roughness (Ra) of less than 1 micron, 750 nm, 500 nm, or 250 nm, such that the interface between the substrate 9 and the organic polymer layer 7 (e.g., a cured (meth)acrylate resin) may be difficult to bond.

[0076] The compounds described herein can be used as coupling agents for materials and methods for forming nanostructures on a substrate, such as those described in International Publication No. WO 2020 / 095258. In one embodiment, the coupling agent is present in a transfer layer comprising a cured (e.g., non-fluorinated) (meth)acrylate coating.

[0077] As described in International Publication No. WO 2020 / 095258, (meth)acrylate coatings suitable for use as transfer layers may be prepared by a process of vapor-depositing (meth)acrylate monomers, optionally with the addition of adhesion promoters and / or photoinitiators, and further cured by exposure to ultraviolet (UV), electron beam (e-beam), ionizing (gamma) or plasma radiation. This process and suitable photocurable monomer materials for use therein are described in U.S. Pat. No. 8,658,248 and the references incorporated therein.

[0078] Referring to Figure 2, an exemplary article is shown that includes a layer 6 of a metal, such as gold or silver, bonded to an organic polymer layer 7, such as a cured (meth)acrylate resin. The organic layer includes a compound containing sulfur moieties and (meth)acrylate moieties, as described herein. The illustrated metal layer 6 has patterned nanostructures. The organic polymer layer 7 (e.g., a cured (meth)acrylate resin) is bonded to a (e.g., transparent) substrate 9, as described above. The combination of the substrate, organic layer, and metal layer (i.e., 6, 7, and 9) can be described as a tooling film 8.

[0079] In use of the tooling film, a free-radically polymerizable (e.g., (meth)acrylate) resin 4 is applied to the metal surface of the tooling film, then a substrate 2 (e.g., roughened PET) is applied to the resin 4, after which the free-radically polymerizable (e.g., (meth)acrylate) resin is cured. As described herein, if the organic polymer layer 7 (e.g., the cured (meth)acrylate resin) contains a compound that includes a sulfur moiety and a (meth)acrylate moiety, a strong bond is formed, allowing the cured resin 4 to be peeled from the metal surface of the tooling film.

[0080] Referring to FIG. 1 , in some embodiments, the amount of metal transferred (exfoliation at interface "C") is at least 85, 90, 95, or 100%, as estimated visually without a microscope. When most of the metal is transferred, the transparency of the tooling film is also high. In some embodiments, the transparency of the tooling film is at least 85, 90, 95, or 100%. When most of the metal is transferred, the transparency of the roughened PET is low. In some embodiments, the transparency of the roughened PET is less than 20, 15, 10, or 5%.

[0081] Objects and advantages of the present disclosure are further illustrated by the following non-limiting examples, although the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit the present disclosure. [Example]

[0082] Unless otherwise stated or apparent from the context, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight. The following table lists the materials used in the examples and their sources. [Table 2-1] [Table 2-2]

[0083] [General Procedure] Nanostructured template films were prepared from nickel templates: Nanostructured template films were prepared by die-coating a 60 / 20 / 20 / 0.5 mixture of PHOTOMER 6210, SR238, SR351, and IRGACURE TPO (by weight) onto a 125-micron-thick polycarbonate film (Tekra, New Berlin, Wisconsin) with a double-sided gloss finish. The coated film was pressed against a nanostructured nickel surface mounted on a steel roller controlled at 60°C using a rubber-coated roller at a speed of 15.2 m / min. The structured nickel tool was patterned with tiles containing nanoscale pit features ranging in size from 100 to 300 nm and 50 to 150 nm deep, interspersed with random macroscopic roughness. This random macroscopic roughness was on the order of Ra of approximately 0.7 μm. The resin coating thickness on the film was sufficient to completely wet the nickel surface and form a rolling bead of resin when the coated film was pressed against the nanostructured nickel surface. The film, while in contact with the nanostructured nickel surface, was exposed to radiation from two Fusion UV lamp units (obtained under the trade designation "F600" from Fusion UV Systems, Inc., Gaithersburg, MD) equipped with D bulbs and operating at 142 W / cm. After peeling the film from the nanostructured nickel surface, the nanostructured side of the film was exposed to radiation from a Fusion UV lamp unit ("F600," Fusion UV Systems) equipped with D bulbs and operating at 142 W / cm.

[0084] The nanostructured template film was subjected to a release treatment: A silicon-containing release film layer (methods described in U.S. Pat. Nos. 6,696,157 (David), 8,664,323 (Iyer), and U.S. Patent Application Publication No. 2013 / 0229378 (Iyer)) was applied to the nanostructured template film in a parallel-plate capacitively coupled plasma reactor. The chamber had a central cylindrical powered electrode with a surface area of ​​18.3 square feet. After the nanostructured template film was placed on the powered electrode, the reactor chamber was evacuated to a base pressure of less than 2 mTorr (1.3 Pa). O2 gas was introduced into the chamber at a rate of 1,000 SCCM. The treatment was carried out by a plasma-assisted CVD method, in which RF power was supplied to the reactor at a frequency of 13.56 MHz and an applied power of 2,000 watts. The treatment time was controlled by moving the nanostructured template film through the reaction zone at a speed of 30 feet per minute, resulting in an exposure time of approximately 10 seconds. After the deposition process was completed, the RF power was shut off and the gas was vented from the reactor. A second plasma treatment was performed in the same reactor without returning to atmospheric pressure after the first treatment. HMDSO gas was introduced at approximately 1750 SCCM, achieving a pressure of 9 mTorr. Subsequently, 13.56 MHz RF power was supplied to the reactor at an applied power of 1000 W. The nanostructured template film was then passed through the reaction zone at a speed of 30 ft / min for an exposure time of approximately 10 seconds. At the end of this treatment period, the RF power and gas supply were shut off, and the chamber was returned to atmospheric pressure.

[0085] The exfoliated nanostructured template film was replicated: A PET film (Melinex 454) was pressed against the release-treated nanostructured template film by laminating it between a 90-durometer rubber roll and a steel roll controlled at 54°C (130°F). These rolls were pressed together using two Bimba air cylinders applying a pressure of 0.27 MPa. The film was laminated at a speed of 3 m / min (10 fpm). MAMA was delivered at 3–4 cc / min, resulting in a patterned area of ​​10–13 cm (4–5 in) wide. The film was exposed to radiation from a Fusion UV processor (Heraeus, Gaithersburg, MD) equipped with a D bulb. The PET film and cured MAMA were then separated from the release-treated nanostructured template film, yielding the nanostructured film.

[0086] Prior to metallization, the replicated nanostructured films were plasma treated: Oxygen plasma was applied to the nanostructured films in a parallel-plate capacitively coupled plasma reactor. The chamber had a surface area of ​​1.7 m. 2 The reactor chamber had a cylindrical central powered electrode measuring 18.3 square feet (200 sq ft). After the nanostructured film was placed on the powered electrode, the reactor chamber was evacuated to a base pressure of less than 0.5 Pa (0.8 mTorr). O2 gas was introduced into the chamber at a rate of 1000 SCCM (standard cubic centimeters per minute). The process was carried out using a plasma-assisted CVD method in which RF power was supplied to the reactor at a frequency of 13.56 MHz and an applied power of 6000 Watts. The process time was controlled by moving the nanostructured film through the reaction zone at a speed of 10.6 m / min (35 fpm), resulting in an exposure time of approximately 8 seconds. After the deposition process was completed, the RF power was shut off, the gases were vented from the reactor, and the chamber was returned to atmospheric pressure.

[0087] Metals were deposited on the plasma-treated replicated nanostructured films: A metal layer was deposited on the plasma-treated nanostructured film to produce the final nanostructured metallized film. The nanohole structures were vapor-coated with Ag / Au using a roll-to-roll DC sputtering system, with the target positioned parallel to the substrate film during deposition. The sputtering target was 85% Ag / 15% Au and measured 9.8 cm x 53.3 cm x 0.64 cm. Ag / Au was deposited at 3.8 kW of power under 0.4 Pa argon pressure. Film thicknesses of 50, 100, or 250 nm were achieved by varying the line speed and number of passes through the deposition zone. For the 50 nm film thickness, the line speed was 2.67 m / min. For the 100 nm film thickness, the line speed was 1.34 m / min. For the 250 nm film thickness, two passes through the deposition zone were performed at 1.07 m / min. After the sputtering process, the pressure was returned to atmospheric pressure and the metallized structural film was removed from the apparatus.

[0088] Roughened PET: PET (Melinex ST504) film substrates (Tekra) were roughened by simultaneously or sequentially depositing a discontinuous silicon-containing layer by PECVD and etching the surface with reactive species, as described in U.S. Patents 10,134,566 and 8,634,146. Reactive ion etching was performed on the PET film substrate in the same homemade reactor used to deposit the release layer. After the film was placed on a powered electrode, the reactor chamber was evacuated to a base pressure of less than 1.3 Pa (1 mTorr). HMDSO and O2 gases were introduced into the chamber at flow rates of 18 SCCM and 750 SCCM, respectively. Subsequently, 13.56 MHz RF power was supplied to the reactor at an applied power of 7500 W. The film was passed through the reaction zone at a speed of 15 ft / min for an exposure time of approximately 20 seconds. After processing, the RF power and gas supply were turned off, and the chamber was returned to atmospheric pressure.

[0089] Resin Adhesion Test: Multifunctional thiol and MAMA were mixed in a 20 cc cup in approximately 10 g batches in the proportions shown in the examples. The components were mixed in a Speedmixer at 3000 rpm for 30 seconds. The polymerizable resin mixture was allowed to stand at room temperature for the required time. The mixture was then coated onto the final nanostructured metallized film using a #40 Meyer rod. The film was placed in an Athena Blue oven (model M01420A) set at 70°C for 2 minutes. The film was manually laminated to roughened PET and then heated at 32 V, 2 A, and 28 mW / cm using a UV-LED unit with 385 nm UV-LEDs installed in a 16 x 4 array over a 16 cm x 4 cm area. 2 The film was placed on a table with the tooling underneath and the roughened PET on top, and the roughened PET was peeled off the tooling film at a peel rate of approximately 5 cm / sec.

[0090] Multifunctional thiol and isocyanato(meth)acrylate compounds were also prepared, the details of which are described below. The polymerizable resins were coated onto the final nanostructured metallized film, laminated to roughened PET, and cured in the same manner as described above.

[0091] Figure 1 shows the interfaces of the laminated layers. The adhesion between the resin and the roughened PET (interface "A") in Figure 1 was typically very good. The adhesion between layers within the tooling film (interface "D") was also typically very good. The Au / Ag layer either peeled off from the tooling film (interface "C") or did not adhere to the resin (interface "B"). The amount of metal transfer (peeling at interface "C") was assessed visually. When all the metal was transferred, the roughened PET was no longer reflective and transparent, and the tooling film was transparent. The transparency of the tooling film and the roughened PET was measured using a haze-gard (4775 "haze-gard i" by BYK Instruments). The samples were oriented so that light first passed through the haze-gard and the roughened PET. The measured transparency of the tooling film and the roughened PET provides a quantitative indicator for evaluating the adhesive strength of the resin / metal layer compared to the metal / tooling film layer.

[0092] The following comparative example (CE) shows that unreacted polyfunctional thiol and polyfunctional acrylate (without base) are ineffective as silver-gold coupling agents. A control sample of polyfunctional acrylate resin without coupling agent was also ineffective. The Ag / Au layer thickness was 100 nm. [Table 3]

[0093] In the following examples, 95 parts of MAMA, 5 parts of a given multifunctional thiol, and 0.5 parts of Hunig's base as a 10% solids solution in THF were added. These solutions were stored for the indicated times and evaluated (coating, curing, and stripping tests). The Ag / Au layer thickness was 50 nm. [Table 4]

[0094] During storage, the multifunctional thiol reacted with MAMA. This reaction was 13 C. 1 This was confirmed by H and heteronuclear single quantum correlation (HSQC) proton-carbon correlation nuclear magnetic resonance analysis. At time 0 and other time points where the percent peeling at interface C was zero, the solution had two peaks corresponding to unreacted multifunctional thiol and unreacted MAMA. At reaction times where the percent peeling at interface C was 100%, the peak corresponding to unreacted multifunctional thiol significantly decreased, and a new peak corresponding to the reaction product between the multifunctional thiol and MAMA appeared. At reaction times where the percent peeling at interface C was greater than 0% but less than 100%, peaks corresponding to both the multifunctional thiol and its reaction product with MAMA were present, and the peak for the reaction product was smaller than that at reaction times where the percent peeling at interface C was 100%.

[0095] Additional bases were evaluated in a formulation containing 95 parts MAMA and 5 parts PETMP. The bases were added as 10% solids solutions in THF. These solutions were allowed to react for a set period of time and evaluated (coating, curing, and stripping tests). The Ag / Au layer thickness was 50 nm. Comparative Example CE-7 was 100% MAMA with no coupling agent. [Table 5]

[0096] The acrylate equivalent weight of Photomer 6210 is 475 g / eq. The acrylate equivalent weight of HDDA is 226 / 2 = 113 g / eq. A 75:25 blend of Photomer 6210:HDDA has a weighted average acrylate equivalent weight of 0.75 x 475 + 0.25 x 113 = 384.53. Assuming a total resin weight of 100 g, the equivalent weight and equivalent ratio are calculated as follows: [Table 6]

[0097] In the following examples, 100 parts of MAMA and PETMP were used, with 0.5 parts of Hunig's base (10% solution in THF) added. The amount of PETMP used is listed. For example, for 1 part PETMP, 99 parts MAMA, and for 20 parts PETMP, 80 parts MAMA. After aging for 2 hours, coatings were applied and cured, with the results shown below. The Ag / Au layer thickness was 100 nm. [Table 7]

[0098] The table below shows Examples 44 to 47, which used compositions without adding a solvent. MAMA and multifunctional thiol were spin-mixed at 3000 rpm for 5 minutes before adding the base, and the resulting compositions were spin-mixed at 3000 rpm for 1 minute. In the case of DMAEA, the base has an acrylate functional group. Comparative examples performed at the same time are also shown. [Table 8]

[0099] In the following examples, 95 parts of the indicated diacrylate and 5 parts of PETMP were used for a total of 100 parts, with 0.5 parts of Hunig's base (10% solution in THF) added. Photomer 6210 and Photomer 4039 each contained 0.5 parts of 4265. Comparative examples using Photomer 6210 and Photomer 4039 contained only the diacrylate, 0.5 parts of 4265, and no added base or PETMP. The Ag / Au layer thickness was 250 nm. [Table 9]

[0100] Reaction of polyfunctional thiols with isocyanato(meth)acrylates All reactions were adjusted to 40% solids based on the multifunctional thiol and isocyanato(meth)acrylate. In Example PE-1 below, 17.18 g of solids was diluted with 25.78 g of solvent for a total weight of 42.96 g. The 10% solution of Hunig's base and acetic acid are calculated as part of the added solvent (0.63 + 0.58 + 24.57 = 25.78). The multifunctional thiol was always diluted with an equal weight of THF. The isocyanatoalkyl(meth)acrylate was diluted in the remaining solvent before being added to the multifunctional thiol (25.78 - (0.63 + 0.58 + 12.5) = 12.07 g). All THF was dried through 4 Å sieves.

[0101] Preparation example 1 (PE-1) TMMP:IEM=3:1 To a solution of 12.50 g (0.0905 eq, 138 thiol eq) of TMMP and 0.625 g (0.000483 eq) of a 10% solution of Hunig's base in 12.50 g of THF, cooled to -11.7 °C under dry air, 4.68 g (0.0302 eq) of IEM in 12.07 g of THF was added dropwise over 1 hour using a pressure-balanced addition funnel. At this point, an aliquot was taken and subjected to FTIR analysis, which showed a peak at 2265 cm -1 No NCO peak was detected. The reaction was treated with 0.581 g (0.000967 equivalents) of a 10% solution of acetic acid in THF. The reaction was bottled and stored in a freezer at -30°C. An aliquot of the reaction was diluted with an equal volume of CDCl3 and 1 HNMR was consistent with the desired structure. [Table 10]

[0102] In the following examples, the solution consisted of 95 parts MAMA and 5 parts of the specified PE. After aging for the specified time, the aged solution was evaluated (coating, curing, and stripping tests). The Ag / Au layer thickness was 100 nm. [Table 11]

[0103] Dithiols and secondary thiols may be less preferred. However, higher concentrations of multifunctional thiol isocyanatoacrylate adducts may improve the % release at interface C.

[0104] In the following examples, a total of 100 parts of MAMA and PE-5 were used. The amount of PE-5 used is listed in the table. For example, 1 part PE-5 = 99 parts MAMA, and 20 parts PE-5 = 80 parts MAMA. After aging the solution for a specified time, the aged solution was evaluated (coated, cured, and stripped). The thickness of the Ag / Au layer was 100 nm. After aging for 2 days, the coating peeled the silver-gold from the roughened PET when coated and cured. [Table 12]

[0105] The following examples consisted of 95 parts MAMA and 5 parts of the indicated PE or composition described. The solutions were aged for the indicated time and then evaluated (coating, curing, and stripping tests) as aged solutions. The Ag / Au layer thickness was 250 nm. [Table 13]

[0106] The following tests were performed using 95 parts MAMA and 5 parts PE-15. Identical coating solution samples were evaluated (coated, cured, and stripped) for 0, 2, 4, 6, 8, and 28 hour aged samples, and simultaneously, coating solutions (diluted with an equal volume of CDCl3) were evaluated by NMR at as close to the same time intervals as possible. The Ag / Au layer thickness was 100 nm. The % stripping increased with time, 1 In HNMR, peaks of Michael adducts were observed at 2.83-2.78 ppm and 2.67-2.64 ppm, and the peaks increased with time. [Table 14]

[0107] Additional bases were evaluated in compositions containing 95 parts MAMA and 5 parts PE-15. All bases were added as 10% solids solutions in THF. The solutions were allowed to react for the specified time and evaluated (coating, curing, stripping test). The Ag / Au layer thickness was 50 nm. The control, CE-7, was 100% MAMA with no coupling agent. [Table 15]

[0108] Hunig's base was tested in compositions containing 95 parts MAMA and 5 parts PETMP at various solids levels and solution aging times to evaluate its effect on improving percent release. Hunig's base was added as a 10% solids solution in THF unless otherwise noted. These solutions were evaluated (coated, cured, and stripped) after aging for the specified time. The Ag / Au layer thickness was 100 nm. [Table 16]

Claims

1. 1. An article comprising an organic polymer layer containing a compound comprising at least one sulfur moiety and at least one (meth)acrylate moiety, The article wherein the surface of the organic polymer layer is bonded to a metal.

2. The article of claim 1 , wherein the metal comprises gold or silver.

3. 3. The article of claim 1 or 2, wherein the metal has a thickness of 5 microns or less, 1 micron or less, 500 nm or less, 250 nm or less, 100 nm or less, or 50 nm or less.

4. The article of any one of claims 1 to 3, wherein the metal is a continuous layer.

5. The article of any one of claims 1 to 4, wherein the metal facing surface is a microstructured or nanostructured surface.

6. The article of claim 1 , wherein the organic polymer layer comprises a cured multifunctional (meth)acrylate monomer and less than 15% by weight of a multifunctional thiol moiety.

7. The article of any one of claims 1 to 6, wherein the opposite surface of the organic polymer layer is disposed on a substrate.

8. 8. The article of claim 7, wherein the surface of the organic polymer layer has a surface roughness of less than 1 micron, less than 750 nm, less than 500 nm, or less than 250 nm.

9. 9. The article of claim 7 or 8, wherein the substrate is a transparent film.

10. An article according to any one of claims 1 to 9, wherein the cured compound is a compound according to one or more of claims 11 to 18 below.

11. a polyfunctional thiol compound; one or more diacrylate compounds; base The compound is a Michael addition product of

12. The compound of claim 11, wherein the equivalent ratio of acrylate groups to thiol groups is from 33:1 to 3:

1.

13. Formula I: 【Chemistry 1】 [In the formula, R Ｓ is the residue of a multifunctional thiol, R Ａ are independently the residue of a diacrylate, n is 2 to 6. Compound.

14. a polyfunctional thiol compound; one or more isocyanato(meth)acrylate compounds; base wherein the reaction product comprises a compound having at least one isocyanato(meth)acrylate group and one or more thiol groups.

15. Formula II: 【Chemistry 2】 [In the formula, R1 is H or CH ３ and R is a linear or branched alkylene having 2 to 10 carbon atoms and optionally substituted by O; R Ｓ is the residue of a multifunctional thiol, q is 1 to 5; m is 1 to 5; provided that the sum of q and m is 2 to 6. Compound.

16. A compound which is a Michael addition reaction product of the reaction product of claim 14 or 15 with a diacrylate compound.

17. Formula III: 【Transformation 3】 [In the formula, R1 is H or CH ３ and R is a linear or branched alkylene having 2 to 10 carbon atoms and optionally substituted by O; R Ｓ is the residue of a multifunctional thiol, q is 1 to 5; m is 0 to 4; s is 1 to 5; provided that the sum of q, m, and s is 2 to 6. Compound.

18. 18. The compound of claim 17, wherein m is at least 1.

19. one or more (meth)acrylate monomers; At least one compound comprising at least one sulfur moiety and at least one (meth)acrylate moiety according to any one of claims 11 to 18; A polymerizable resin composition comprising:

20. 20. The polymerizable resin composition of claim 19, wherein the composition is cured.

21. A method for preparing compounds via Michael addition, comprising reacting a multifunctional thiol compound with one or more diacrylate compounds in the presence of a base.

22. 1. A method for producing a compound comprising reacting a multifunctional thiol compound with one or more isocyanato(meth)acrylate compounds in the presence of a base, wherein the compound comprises at least one isocyanato(meth)acrylate group and at least one thiol group.

23. 23. A method for preparing a compound comprising reacting the compound of claim 22 with a diacrylate compound.

24. 24. The compound, polymerizable resin, or method of any one of claims 1 to 23, wherein the base is a tertiary amine.

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