Electron beam curable composition and method for producing the same

Abstract

An electron beam curable composition comprising (meth)acrylic (meth)acrylate, The cured film has excellent weather resistance, flexibility, toughness, and a smooth surface finish. To provide an electron beam curable composition. [Solution] An electron beam curable composition containing the following component (A). • Component (A): A (meth)acrylate polymer having (meth)acryloyl groups in its side chains. It has a (meth)acrylic equivalent of 500-2,000 (g / eq), and the weight average is The particle count is 10,000 or less, and the glass transition temperature in the uncured state is -15 to 80°C. A polymer.

Description

Technical Field

[0001] The present invention relates to an electron beam curable composition whose cured film is excellent in weather resistance, flexibility, toughness, and finish, and can be suitably used as a coating agent.

Background Art

[0002] (Meth)acrylate polymers having a (meth)acryloyl group in the side chain, so-called (meth)acrylic (meth)acrylate, have an excellent feature of weather resistance when used in coating agents and the like because the main chain skeleton is composed of a (meth)acrylic structure.

[0003] On the other hand, as a coating agent, an active energy ray curable composition is known. The active energy ray curable composition has advantages such as a short curing time and a small required energy amount compared with a thermosetting curable composition. In particular, the electron beam curable composition has an advantage that it is not necessary to blend a photoinitiator compared with an ultraviolet ray curable composition, so that curing is possible even when the pigment content is high, and the cured film has excellent weather resistance.

[0004] As an electron beam curable coating agent composition using (meth)acrylic (meth)acrylate, the compositions described in Patent Documents 1 to 4 are known. Patent Document 1 describes an electron beam curable composition containing an acrylic poly(meth)acrylate having a coating film glass transition point of 150°C or higher, and a polyhydric alcohol (meth)acrylate containing two or more (meth)acryloyl groups and having a (meth)acryloyl group equivalent of 150 or less. Patent Document 2 describes an electron beam curable paint containing A: colored particles, B: an acrylic poly(meth)acrylate containing 1.5 mol or more of (meth)acryloyl groups per 1,000 molecular weight, and C: a polyhydric alcohol (meth)acrylate containing two or more (meth)acryloyl groups and having a (meth)acryloyl equivalent of 150 or less. Patent Document 3 describes an electron beam curable composition containing a polymerizable acrylic polymer that includes ultraviolet-stable monomer units and polymerizable double bonds in its side chains. Patent Document 4 describes an electron beam curable coating composition comprising inorganic fine particles (A) having a specific Knoop hardness, and a poly(meth)acrylate (B) having a glass transition temperature (Tg) of 20 to 200°C and two or more (meth)acryloyl groups. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 08-047671 [Patent Document 2] Japanese Patent Application Publication No. 08-257498 [Patent Document 3] Japanese Patent Publication No. 2000-109523 [Patent Document 4] Japanese Patent Publication No. 2005-075835 [Patent Document 5] Japanese Patent Publication No. 2021-105170 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, the electron beam curable compositions containing the aforementioned (meth)acrylic (meth)acrylate had the following problems. The compositions described in Patent Documents 1 and 4 had problems such as the cured film lacking flexibility, not stretching, and being prone to cracking, because the double bond equivalent of (meth)acrylic (meth)acrylate was low, that is, the double bond concentration was too high. The compositions described in Patent Documents 1, 2, and 3 had problems such as insufficient flexibility and brittleness of the cured film due to the glass transition temperature of (meth)acrylic (meth)acrylate being too high. Furthermore, the compositions described in Patent Documents 1 to 4 had the problem of insufficient curing film finish, specifically, the problem of high surface roughness.

[0007] On the other hand, the present inventors have proposed an active energy ray curable product containing (meth)acrylic (meth)acrylate, which includes an active energy ray curable product containing (meth)acrylate, and a (meth)acrylate-based polymer modified with an unsaturated double bond-containing oligomer having a glass transition temperature (Tg) of -30 to -90°C (Patent Document 5). The cured film of the composition exhibited excellent mechanical properties, weather resistance, and heat resistance, but its weather resistance under more severe conditions was sometimes insufficient.

[0008] The inventors of the present invention have diligently conducted research to find an electron beam curable composition containing (meth)acrylic (meth)acrylate in which the cured film exhibits excellent weather resistance, flexibility, toughness, and a smooth surface finish. [Means for solving the problem]

[0009] As a result of diligent research to solve the aforementioned problems, the present inventors have found that an electron beam curable composition containing a (meth)acrylate polymer having a (meth)acryloyl group in its side chain, having a specific (meth)acrylic equivalent, a specific weight-average molecular weight, and a specific glass transition temperature in the uncured state, can solve the aforementioned problems and can be suitably used as a coating agent, thus completing the present invention.

[0010] In other words, the present invention relates to an electron beam curable composition comprising the following component (A). • Component (A): A (meth)acrylate polymer having (meth)acryloyl groups in its side chains, having a (meth)acrylic equivalent of 500 to 2,000 (g / eq), a weight-average molecular weight of 10,000 or less, and a glass transition temperature of -15 to 80°C in the uncured state. [Effects of the Invention]

[0011] The electron beam curable composition of the present invention has a cured film that exhibits excellent weather resistance, flexibility, toughness, and a smooth surface finish, making it suitable for use as a coating agent. [Modes for carrying out the invention]

[0012] The present invention relates to an electron beam curable composition comprising the following component (A). • Component (A): A (meth)acrylate polymer having (meth)acryloyl groups in its side chains, having a (meth)acrylic equivalent of 500 to 2,000 (g / eq), a weight-average molecular weight (hereinafter referred to as "Mw") of 10,000 or less, and a glass transition temperature (hereinafter referred to as "Tg") in the uncured state of -15 to 80°C. As component (A), a reaction product of a copolymer (a1) [hereinafter referred to as "polymer (a1)"] containing constituent units derived from a (meth)acrylate monomer (a1-1) that does not have a reactive group and constituent units derived from a (meth)acrylate monomer (a1-2) that has a reactive group, and a compound (a2) [hereinafter referred to as "unsaturated compound (a2)"] having a group that reacts with the reactive group and a (meth)acryloyl group via the reactive group is preferred. The following describes component (A), the electron beam curable composition, and the method of use in detail. In this invention, "(meth)acrylate polymer" means a polymer containing (meth)acrylate as the main component of its constituent units, "(meth)acrylate" means acrylate and / or methacrylate, "(meth)acrylic" means acrylic and / or methacrylic, and "(meth)acryloyl" means acryloyl and / or methacryloyl.

[0013] 1. Ingredient (A) Component (A) is a (meth)acrylate polymer having (meth)acryloyl groups in its side chains, with a (meth)acrylic equivalent of 500 to 2,000 g / eq, a Mw of 10,000 or less, and an uncured Tg of -15 to 80°C.

[0014] The (meth)acrylic equivalent weight of component (A) is 500 to 2,000 g / eq. When the (meth)acrylic equivalent weight is less than 500 g / eq, the flexibility (elongation) of the cured film decreases. When it exceeds 2,000 g / eq, the weather resistance of the cured film decreases. As the (meth)acrylic equivalent weight of component (A), preferably it is 600 to 1,500 g / eq, and more preferably 700 to 1,200 g / eq.

[0015] In the present invention, the (meth)acrylic equivalent weight (g / eq) represents the weight (g) per 1 equivalent (eq) of the (meth)acryloyl group. The higher the numerical value, the lower the concentration of the (meth)acryloyl group, and the lower the numerical value, the higher the concentration of the (meth)acryloyl group.

[0016] The acrylic equivalent weight is determined by the following formula. In the following formula, the number of moles of the (meth)acryloyl group in component (A) is the number of moles of the (meth)acryloyl group added to the copolymer (a1) in the subsequent modification reaction, and the (meth)acryloyl groups derived from the unreacted unsaturated compound (a2) mixed after the subsequent modification reaction are excluded.

[0017]

Number

[0018] The Mw of component (A) is 10,000 or less. When Mw exceeds 10,000, the finish (smoothness) of the cured film decreases. As the Mw of component (A), preferably it is 3,000 to 10,000, more preferably 3,500 to 9,000, and even more preferably 4,000 to 8,000. When the Mw of component (A) is 3,000 or more, sagging during uncured state is suppressed and the weather resistance of the cured film becomes good.

[0019] In this invention, Mw refers to the value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as GPC) to polystyrene equivalent.

[0020] The Tg of component (A) in its uncured state is -15 to 80°C. If the Tg is below -15°C, sagging occurs in the uncured state, tack occurs, contaminants such as dust adhere to it, contamination of the surrounding area by unirradiated material occurs, making it difficult to handle, and the strength of the cured film decreases. If the Tg exceeds 80°C, the flexibility (elongation) of the cured film decreases. The Tg of component (A) in its uncured state is preferably -10 to 70°C, and more preferably 0 to 50°C.

[0021] In this invention, Tg refers to the value determined from the intersection of the baseline and the tangent at the inflection point of the heat flux curve obtained using a differential scanning calorimeter such as TA Instrument (Q-100). The heat flux curve is obtained by cooling approximately 10 mg of the sample to -100°C in a nitrogen atmosphere, holding for 5 minutes, then raising the temperature to 120°C at 10°C / min, continuing to cool to -100°C, holding for 5 minutes, and then raising the temperature to 350°C at 10°C / min.

[0022] As component (A), various polymers can be used as long as they are (meth)acrylate polymers having (meth)acryloyl groups in the side chains that satisfy the (meth)acrylic equivalent, Mw, and Tg in the uncured state described above. As component (A), a (meth)acrylate polymer modified with an unsaturated compound (a2) is preferred. As stated above, a (meth)acrylate polymer refers to a polymer that contains (meth)acrylate as the main component of its constituent units, and specifically refers to a polymer that contains 80 to 100% by weight of (meth)acrylate in all constituent monomer units.

[0023] A typical example of component (A) is a compound in which an unsaturated compound (a2) is bonded to the terminal or side chain of a (meth)acrylate polymer. Component (A) is preferably a copolymer (a1) consisting of constituent units derived from a (meth)acrylate monomer (a1-1) without reactive groups (hereinafter referred to as "monomer (a1-1)") and constituent units derived from a (meth)acrylate monomer (a1-2) having reactive groups (hereinafter referred to as "monomer (a1-2)"), and a reaction product of a group that reacts with the reactive group and an unsaturated compound (a2). Specifically, as component (A), a copolymer (a1) is used as the core polymer, and a polymer obtained by reacting the reactive groups of the core polymer with the reactive groups of the unsaturated compound (a2) is bonded with ethylenically unsaturated groups as side chains. Furthermore, in monomers (a1-1) and (a1-2), "reactive group" refers to a functional group other than the (meth)acryloyl group. The following describes the copolymer (a1), the unsaturated compound (a2), the method for producing component (A), and the physical properties of component (A).

[0024] (1) Copolymer (a1) The copolymer (a1), which is the raw material copolymer of component (A), is a copolymer consisting of constituent units derived from monomer (a1-1) and constituent units derived from monomer (a1-2). The monomers (a1-1) and (a1-2) will be described below.

[0025] (1-1) Monomer (a1-1) Monomer (a1-1) is a (meth)acrylate monomer (a1-1) that does not have a reactive group. Specific examples of monomer (a1-1) are not particularly limited as long as they are (meth)acrylate monomers that do not possess the above-mentioned reactive group, but include, for example, alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, and stearyl (meth)acrylate; Alicyclic (meth)acrylates such as isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate; N-(meth)acryloylmorpholine; Acrylamides such as (meth)acrylamide, N-methylolacrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide; and Examples include acrylonitrile and methacronitrile (meth)acrylonitrile.

[0026] As monomer (a1-1), among the compounds mentioned above, methyl (meth)acrylate and (meth)acrylates having saturated alicyclic groups such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate are preferred. The copolymerization ratio of these monomers is preferably such that, when the monomers used in the polymerization of copolymer (a1) are 100 parts by mass, these monomers are present in an amount of 55% by mass or more. By including 55% by mass or more, the strength and weather resistance of the cured film are excellent.

[0027] (1-2) Monomers (a1-2) Monomers (a1-2) are (meth)acrylate monomers that have a reactive group. As monomers (a1-2), (meth)acrylate monomers having a reactive group selected from the group consisting of epoxy groups, carboxyl groups, hydroxyl groups, and isocyanate groups are preferred.

[0028] Examples of monomers (a1-2) having an epoxy group as a reactive group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether.

[0029] Examples of monomers (a1-2) having a hydroxyl group as a reactive group include hydroxyalkyl (meth)acrylates and unsaturated oligomers having a hydroxyl group. Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0030] Examples of unsaturated oligomers having a hydroxyl group include ε-caprolactone adducts of hydroxyalkyl (meth)acrylates such as ε-caprolactone adducts of 2-hydroxyethyl (meth)acrylate, polypropylene glycol adducts of (meth)acrylic acid, polyethylene glycol adducts of (meth)acrylic acid, poly(3-hydroxybutyrate) adducts of 2-hydroxyethyl (meth)acrylate, and polytetramethylene glycol adducts of (meth)acrylic acid. ε-caprolactone adducts of 2-hydroxyethyl (meth)acrylate are commercially available, including Praxel FA2D (ε-caprolactone adduct of 2-hydroxyethyl acrylate, trade name of Daicel Corporation, hereinafter the same; molecular weight 344, Tg=-78℃), FA5 (ε-caprolactone adduct of 2-hydroxyethyl acrylate; molecular weight 689), FM2D (ε-caprolactone adduct of 2-hydroxyethyl methacrylate; molecular weight 358), FM3 (ε-caprolactone adduct of 2-hydroxyethyl methacrylate; molecular weight 473), and FM5 (ε-caprolactone adduct of 2-hydroxyethyl methacrylate; molecular weight 701). Examples of polypropylene glycol adducts of acrylic acid include compounds with a Tg of -75°C, examples of polyethylene glycol adducts of acrylic acid include compounds with a Tg of -41°C, examples of poly(3-hydroxybutyrate) adducts of 2-hydroxyethyl acrylate include compounds with a Tg of -40°C, and examples of polytetramethylene glycol adducts of acrylic acid include compounds with a Tg of -84°C.

[0031] Examples of monomers (a1-2) having an isocyanate group as a reactive group include (meth)acryloxyethyl isocyanate, and specific products include "Kalenz MOI" and "Kalenz AOI" (both trade names, manufactured by Showa Denko K.K.).

[0032] Examples of monomers (a1-2) having a carboxyl group as a reactive group include (meth)acrylic acid, itaconic acid, maleic acid, half-esters of maleic acid and monohydric alcohols (1:1 reaction product), monohydroxyethyl acrylate phthalate, ω-carboxy-polycaprolactone (n ≈ 2) monoacrylate, (meth)acryloyloxyethyl succinate, (meth)acryloyloxyethyl hexahydrophthalate, (meth)acryloyloxyethyl phthalate, (meth)acryloyloxyethyl-2-hydroxyethyl phthalate, β-carboxyethyl acrylate, phthalic anhydride adduct of pentaerythritol triacrylate, succinic anhydride adduct of pentaerythritol triacrylate, succinic anhydride adduct of dipentaerythritol triacrylate, and phthalic anhydride adduct of dipentaerythritol triacrylate.

[0033] (1-3) Polymerization method of copolymer (a1) There are no particular restrictions on the method for producing the copolymer (a1) before modification with the unsaturated compound (a2), but known methods such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization can be used. Among these methods, bulk polymerization and solution polymerization are preferred because they are easy to manufacture and do not contain impurities such as emulsifiers.

[0034] (1-3-1) Solution polymerization Solution polymerization methods include dissolving the raw material monomers in an organic solvent, adding a thermal polymerization initiator, and heating and stirring. When synthesis is performed by radical polymerization in solution polymerization, the raw material monomers are dissolved in an organic solvent, a thermal radical polymerization initiator is added, and the polymer is obtained by heating and stirring. In addition, a chain transfer agent can be used to adjust the molecular weight of the polymer as needed.

[0035] Organic solvents used in solution polymerization include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; ethers such as propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene and xylene; and aliphatic hydrocarbons such as hexane, heptane, and mineral spirits.

[0036] Examples of thermal polymerization initiators include azo-based initiators such as azobisisobutyronitrile, azobisisovaleronitrile, azobiscyclohexanecarbonnitrile, and azobiscyanovaleric acid; organic peroxides such as t-butyl peroxypivalate, t-hexyl peroxypivalate, dilauroyl peroxide, di(2-ethylhexyl)peroxydicarbonate, di-t-butyl peroxide, and dicumyl peroxide; and hydrogen peroxide-iron(II) salts, peroxodisulfate-sodium bisulfite, cumenehydroperoxide-iron(II) salts, etc. The proportion of thermal polymerization initiator used should be set appropriately according to the target molecular weight. The proportion of thermal radical polymerization initiator used is preferably 0.1 to 10 parts by weight per 100 parts by weight of the total monomers used.

[0037] (1-3-2) Bulk polymerization Examples of bulk polymerization methods are described in Japanese Patent Publication No. 57-502171 and Japanese Patent Publication No. 59-6207. Examples include publicly known methods disclosed in Japanese Patent Publication No. 60-215007, etc. For example, fill a pressurized reactor with a solvent, set it to a predetermined temperature under pressure, and then each monomer A monomer mixture consisting of a polymerization solvent, and optionally a polymerization solvent, is supplied to the reactor at a constant supply rate. One method involves extracting an amount of polymerization solution that corresponds to the amount of monomer mixture supplied. Furthermore, polymerization initiators may be added to the monomer mixture as needed. In this case, the mixing ratio is 0.001 to 2 parts by weight per 100 parts by weight of the monomer mixture. It is preferable to do so. The pressure depends on the reaction temperature and the boiling points of the monomer mixture and solvent used, and may have an impact on the reaction. The pressure should not have any effect, but should be sufficient to maintain the specified reaction temperature. The residence time of the monomer mixture is preferably 1 to 60 minutes. If not present, the monomers may not react sufficiently, and if the residence time exceeds 60 minutes, Productivity may be reduced. The preferred residence time is 2 to 40 minutes.

[0038] An example of a polymerization initiator used to obtain copolymer (a1) is a radiating agent at a predetermined reaction temperature. Any initiator that generates CAL will do. Specifically, di-t-butyl peroxide, Di-t-hexyl peroxide, t-hexyl peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, cumene hydroperoxide, t- Organic peroxides such as butyl hydroperoxide, 2,2'-azobis(isobutyronitrile) (L), 2,2'-azobis(2-methylbutyronitrile), azobiscyclohexacarb Nitriles, azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-A Midinopropane dihydrochloride, 4,4'-azobis(4-cyanovaleric acid) Examples include azo compounds such as (D). Polymerization initiators may be used individually or in combination of two or more.

[0039] The amount of polymerization initiator used depends on the type of polymerization initiator and monomer, the desired molecular weight, polymerization conditions, etc. It can be adjusted as needed, but generally, 0 for every 100 parts by weight of the monomer used. It is 0.001 to 10 parts by weight.

[0040] When organic solvents are used in the production of copolymer (a1), organic hydrocarbon compounds are suitable. tetrahydrofuran and cyclic ethers such as dioxane, benzene, toluene and xyl Aromatic hydrocarbon compounds such as lene, esters such as ethyl acetate and butyl acetate, acetone, Ketones such as methyl ethyl ketone and cyclohexanone, methanol, ethanol, etc. Examples of alcohols such as sopropanol are given, and the use of one or more of these is permitted. Yes, it is possible. In organic solvents that do not dissolve (meth)acrylate copolymers well, scum can form on the walls of the reactor. Kale grows easily, which can lead to production problems during the washing process and other stages.

[0041] The amount of organic solvent used should be 80 parts by weight or less per 100 parts by weight of total vinyl monomer. This is preferable. By using 80 parts by weight or less, a high conversion rate can be obtained in a short time. Preferably, the amount is 1 to 50 parts by weight. Also, trimethyl orthoacetate and trimethyl orthoformate. Dehydrating agents such as the above can also be added. Known chain transfer agents may be used in the production of copolymer (a1).

[0042] The reaction liquid, once removed from the reactor, can proceed directly to the next step, or it can be processed by distillation or other means. By distilling off unreacted monomers, organic solvents, and volatile components such as low molecular weight oligomers... The polymer can be isolated by distillation. Unreacted monomers, solvent, and low molecular weight polymers are removed from the reaction solution. Some of the volatile components, such as oligomers, are returned to the raw material tank or directly to the reactor, and then re-processed. It can also be used in compound reactions. This method of recycling unreacted monomers and solvents is preferable from an economic standpoint. Therefore, when recycling, maintain the desired monomer ratio and desired solvent amount in the reactor. Therefore, it is necessary to determine the mixing ratio of the newly supplied monomer mixture.

[0043] (1-3-3) Properties of copolymer (a1) The Mw of copolymer (a1) is typically 1,500 to 50,000, and 1,500 to 4, 0000 is preferred, more preferably 2,000 to 30,000, even more preferably The range is 2,500 to 25,000, and particularly preferably 3,000 to 15,000. Because w is 50,000 or less, the resulting component (A) has low viscosity even at relatively high concentrations. Because it can be cured, it has good coating properties, and when mixed with other curable compounds, it has good compatibility. Therefore, because Mw is 1,500 or more, the cured film of the obtained component (A) has weather resistance. This results in superior tensile properties.

[0044] There are no particular restrictions on the Tg (glass transition temperature) of copolymer (a1), but it is usually -40. The temperature is between 0°C and 90°C, and preferably between 0°C and 90°C. As a result, the hardened film has excellent strength, and because the temperature is below 90°C, the hardened film is flexible. This results in excellent flexibility. More preferably, the temperature is 30 to 80°C. Furthermore, the Tg of copolymer (a1) is determined by appropriately selecting the type of monomers that constitute it and the copolymerization ratio. This can be adjusted.

[0045] In the case of a typical solution polymerization method, such as the one disclosed in Japanese Patent Publication No. 2014-115538, Because the polymerization temperature is relatively low, the number of functional groups in the polymer is affected by the copolymerization reactivity ratio. This results in a bias for each molecule. On the other hand, in the case of high-temperature polymerization, the effect of the copolymerization reactivity ratio is low. Furthermore, if continuous polymerization occurs, a constant polymer is continuously produced, so the individual functional groups of each molecule The bias in numbers becomes extremely small. Furthermore, when comparing conventional solution polymerization and high-temperature polymerization, when synthesizing polymers of the same molecular weight, high Warm polymerization requires less polymerization initiator and less initiator residue, thus reducing the amount of polymerization initiator needed. Weatherability improves. In particular, in the case of electron beam curing, polymerization catalysts such as photoinitiators are used in the curing reaction. Since no initiator is used, the amount of initiator residue contained in the polymer significantly affects its weather resistance. Therefore, the copolymer (a1) used in the present invention generally has a terminal double bond concentration of 0 A concentration of 0.5 meq / g or less is preferred, and a concentration of 0.4 meq / g or less is more preferred. When the terminal double bond concentration is 0.5 meq / g or less, the decrease in curing rate can be suppressed. In addition, in the present invention, the copolymer (a1) obtained by high-temperature continuous polymerization is used. In this case, the terminal double bond concentration of copolymer (a1) is 0.02 meq / g or more, or 0.5 meq / g. It is preferable to have a concentration of 0.02 meq / g or less. A concentration of 0.02 meq / g or more allows for rapid curing during the curing process. Because the stress is suppressed and less residual stress remains, the mechanical properties of the material improve.

[0046] (2) Unsaturated compound (a2) The unsaturated compound (a2) has a group that reacts with the reactive group of copolymer (a1) and (meth)acrylic. It is a compound having a royl group. Here, as the (meth)acryloyl group, acryloyl is chosen because of its excellent curability by electron beam. A yl group is preferred. As described above, component (A) is in the copolymer (a1) obtained by the polymerization method described above. It is obtained by reacting the reactive group with the reactive group of the unsaturated compound (a2). Specifically, the copolymer (a1) having the above-mentioned reactive group is subjected to unsaturation via the above-mentioned reactive group. It is obtained by chemically bonding and adding compound (a2).

[0047] The unsaturated compound (a2) may be either a low molecular weight compound or an oligomer. In this invention, "oligomer" refers to a compound with a molecular weight of 250 or more and 2,000 or less. do. As for oligomers, (meth)acrylate oligomers with a Tg of -30 to -90°C are preferred. It seems so.

[0048] Copolymer (a1) is a copolymer having an epoxy polymer or a hydroxyl group as a reactive group. In this case, the unsaturated compound (a2) is a functional group that reacts with the above reactive group, such as a carboxyl group. Compounds having a cyanate group or an isocyanate group can be used.

[0049] As an unsaturated compound (a2) having a carboxyl group, the reactive group is carboxyl Examples of monomers (a1-2) containing a cy group include the compounds exemplified above. Furthermore, as an unsaturated compound (a2) having a carboxyl group, (meth)acrylic acid ε- Examples include caprolactone adducts. ε-caprolactone adducts of acrylic acid are commercially available, such as Arronix M-5300. Examples include [product name manufactured by Toagosei Co., Ltd., Tg=-78℃, polycaprolactone chain length≈2]. It can be done.

[0050] As an unsaturated compound (a2) having an isocyanate group, (meth)acryloyl ox C-alkyl isocyanates, and urethane (meth)acrylates having an isocyanate group at one end. Examples include relation. (meth)acryloyloxyalkyl isocyanates include (meth)acryloyl Examples include oxyethyl isocyanate.

[0051] Urethane acrylates with an isocyanate group at one end are diols and diisocyanates. A compound having isocyanate groups at both ends is produced by reacting it with a hydroxyl group-containing Examples include compounds obtained by reacting with acrylates. In this case, the diisocyanate is: Examples include sophorone diisocyanate and hexamethylene diisoanate, and diols and Examples include polytetramethylene glycol, etc., as hydroxyl group-containing acrylates. Examples include 2-hydroxyethyl acrylate. For example, the compound is produced in the presence of a tin-based catalyst such as dioctyltin, and organic Diisocyanates and diols are reacted in a solvent to produce compounds with isocyanate groups at both ends. After obtaining a urethane oligomer, hydroxyl group-containing (meth)acrylates are used in the presence of a polymerization inhibitor. Methods for causing a reaction include the following.

[0052] Copolymer (a1) having an isocyanate group or a carboxyl group as a reactive group. In the case of the isomer, the unsaturated compound (a2) is a functional group that reacts with the above reactive group, such as hydr Unsaturated compounds containing a roxy group can be used. Examples of unsaturated compounds containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate. 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate acrylates, mono(meth)acrylates of glycerin, and cyclohexanedimethanol Examples include mono(meth)acrylates. Examples of unsaturated compounds containing a hydroxyl group include unsaturated oligomers containing a hydroxyl group. The following are examples, and the monomer (a1-2) having a hydroxyl group as the reactive group is hydroxy Examples of unsaturated oligomers containing a c group include compounds similar to those listed above.

[0053] (3) Method for producing component (A) Component (A) consists of the reactive group of copolymer (a1) and the aforementioned reaction in unsaturated compound (a2). It is preferable to produce it by reacting a reactive group with a reactive group. This is sometimes referred to as a "denaturation reaction" below. In other words, the reaction of adding an unsaturated compound (a2) to a copolymer (a1) is as follows: A copolymer (a1) having an epoxy group or a hydroxyl group as a base, and having a carboxyl group A method for reacting an unsaturated compound (a2), and a reactive group consisting of an isocyanate group or A copolymer (a1) having a carboxyl group, and an unsaturated compound (a2) having a hydroxyl group. A method for reacting the two, and a copolymer (a1) having a carboxyl group as a reactive group, and epoxy One method involves reacting an unsaturated compound (a2) having a xy group.

[0054] The reaction ratio of copolymer (a1) and unsaturated compound (a2) is as follows: You can set it appropriately depending on the type, etc. For every mole of reactive groups in copolymer (a1), the amount of reactive groups in unsaturated compound (a2) The reactive group is preferably 0.5 to 1.5 moles, more preferably 0.8 to 1.2 moles, and further Preferably, it is 0.9 to 1.1 moles.

[0055] A copolymer (a1) having an epoxy group, and an unsaturated compound (a2) having a carboxyl group. A method of adding by reaction involves a copolymer having an epoxy group (a1), and a carboxyl group. An unsaturated compound (a2) having a group, a catalyst, and an organic solvent are mixed together at 60-120°C. One method involves heating to a certain temperature (°C) and heating for approximately 5 to 30 hours.

[0056] A copolymer having an epoxy group (a1) and an unsaturated compound having a carboxyl group (a2) The reaction ratio is as follows: 1 mole of epoxy group in the epoxy group copolymer (a1) The unsaturated compound (a2) having a carboxyl group is preferably in an amount of 0.5 to 1.5 moles of carboxyl groups. More preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1.

[0057] As catalysts, tetrabutylammonium bromide and tetrabutylammonium chloride Tetramethylammonium bromide, tetramethylammonium chloride, triphe Nylphosphine, tributylphosphine, 1,8-diazabicyclo[5,4,0]-7- Examples include undecene and 1,4-diazabicyclo[2,2,2]octane. Furthermore, triphenylphosphine is used because it exhibits minimal discoloration after heat resistance testing of the cured film. It is preferable to do so.

[0058] The amount of catalyst added is the copolymer having epoxy groups (a1) and the unsaturated copolymer having carboxyl groups. The amount is preferably about 0.5 to 5% by weight relative to the total amount of the combined compound (a2).

[0059] Examples of organic solvents include ethyl acetate, butyl acetate, acetone, and methyl ethyl ketone. It can be done. Furthermore, if the copolymer (a1) having an epoxy group is in liquid form, it can be done without adding a solvent. It can also be used to perform denaturation reactions.

[0060] A copolymer having a hydroxyl group (a1) is mixed with an unsaturated compound having a carboxyl group (a2 A common method for reacting hydroxy is the dehydration esterification method. Copolymer having a group (a1), unsaturated compound having a carboxyl group (a2), catalyst, and The organic solvent is mixed and heated at 100-120°C, and the organic solvent and the resulting water are heated in an azeotrope. One method involves allowing the reaction to proceed by dehydrating the product.

[0061] As catalysts, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid are used. Examples include hydroxyl acid and sulfuric acid, and the amount of catalyst used is in proportion to the number of moles of hydroxyl groups to be reacted. It is used in concentrations of 0.05 to 5 mol.

[0062] As an organic solvent, it has low solubility with water produced in the dehydration esterification reaction, and it can form an azeotrope with water. It is preferable to use an organic solvent that allows the reaction to proceed while being removed by distillation. Preferred organic solvent Examples include aromatic hydrocarbons such as toluene, benzene, and xylene, hexane, and xylene. Aliphatic hydrocarbons such as chlorohexane and heptane, as well as methyl ethyl ketone and cyclohexane. Examples include ketones such as xanone. The proportion of the organic solvent is 30 to 70 times the total volume of the reaction mixture. Amount in percent is preferred.

[0063] After the reaction, the acid is generally removed with water or an alkaline aqueous solution.

[0064] A copolymer (a1) having an isocyanate group, and an unsaturated compound having a hydroxyl group ( A method of adding by reacting a2) is a copolymer having an isocyanate group (a1) And after mixing with an unsaturated compound (a2) having a hydroxyl group, dibutyl is added as needed. One possible method involves adding a curing catalyst such as tin dilaurate and heating it to 60-100°C. .

[0065] A copolymer having a carboxyl group (a1) and an unsaturated compound having a hydroxyl group (a2 As a method of adding by reacting ) a copolymer having a carboxyl group (a1) and hydro After mixing an unsaturated compound (a2) containing a xyl group, sulfuric acid, methanesulfonic acid, and p-toluene were added. Add sulfonic acid, sulfonated polystyrene, and catalysts such as Nafion-H, and if necessary Then, the esterification reaction is carried out by heating to 80-120°C in the presence of an organic solvent such as toluene. Methods include removing the water generated during the process by distillation. Furthermore, the catalyst remaining after the reaction is used for washing with water, alkali neutralization, ion exchange resin, and catalyst removal. Removed by using one or more methods such as chemical filters and filtration. can.

[0066] A copolymer (a1) having a carboxyl group, and an unsaturated compound (a2) having an epoxy group. Methods of adding by reaction include a copolymer having a carboxyl group (a1), epoxy An unsaturated compound (a2) having a group, a catalyst, and an organic solvent are mixed together at 60-120°C. One method involves heating to a certain temperature (°C) and heating for approximately 5 to 30 hours.

[0067] A copolymer having a carboxyl group (a1) and an unsaturated compound having an epoxy group (a2) The reaction ratio is as follows: 1 mole of epoxy group of copolymer (a1) having a carboxyl group The unsaturated compound (a2) having an epoxy group is preferably composed of 0.5 to 1.5 moles of carboxyl groups. More preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1.

[0068] As catalysts, tetrabutylammonium bromide and tetrabutylammonium chloride Tetramethylammonium bromide, tetramethylammonium chloride, triphe Nylphosphine, tributylphosphine, 1,8-diazabicyclo[5,4,0]-7- Examples include undecene and 1,4-diazabicyclo[2,2,2]octane. Furthermore, triphenylphosphine is used because it exhibits minimal discoloration after heat resistance testing of the cured film. It is preferable to do so.

[0069] The amount of catalyst added is the copolymer having a carboxyl group (a1) and the unsaturated copolymer having an epoxy group. The amount is preferably about 0.5 to 5% by weight relative to the total amount of the combined compound (a2).

[0070] Examples of organic solvents include ethyl acetate, butyl acetate, acetone, and methyl ethyl ketone. It can be done. Furthermore, if the copolymer (a1) having a carboxyl group is in liquid form, no solvent is added. Denaturation reactions can also be carried out using this method.

[0071] Furthermore, in any of the above denaturation reactions, the purpose is to suppress gelation or to improve the storage stability of the denatured product. To improve this, it is preferable to add a polymerization inhibitor. Polymerization inhibitors include methoxyphenol, hydroquinone, and dibutylhydroxytoxyl Examples include ene. From the viewpoint of suppressing discoloration of the cured film, dibutylhydroxytoluene is used. It is especially preferable to do so.

[0072] (4) Physical properties of component (A) As mentioned above, component (A) has a (meth)acrylic equivalent of 500-2,000 g / eq The Mw is 10,000 or less, and the Tg in the uncured state is -15 to 80°C. It is a polymer.

[0073] Component (A) should have an average of 1.5 to 20 double bonds per molecule. This is preferable. Having 1.5 or more improves the strength and weather resistance of the cured film, and 20 Having fewer than 100 double bonds results in good flexibility of the cured film. The average number of double bonds is: More preferably, it is 2 to 15, and even more preferably, 4 to 12.

[0074] 2.Electron beam curable composition The present invention relates to an electron beam curable composition comprising component (A). The method for manufacturing the composition involves using component (A) and, if necessary, other components as described below. Methods include stirring and mixing.

[0075] The viscosity of the composition can be set appropriately depending on the intended use and purpose. The viscosity is 100 to 20,000 mPa·s, more preferably 200 to 8. It is 000 mPa·s. In this invention, viscosity is measured at 25°C using an E-type viscometer (cone plate viscometer). It means the value obtained.

[0076] The composition of the present invention is essential for component (A), but may contain other components as needed. Various ingredients can be incorporated. Other preferred components include compounds having ethylenically unsaturated groups other than component (A). (B) [hereinafter referred to as "component (B)"], and organic solvent (C) [hereinafter referred to as "component (C)" and [Examples include:] Furthermore, the present invention is an electron beam curable composition, and the composition contains a photoradical polymerization initiator. Although it hardens without any issues, conventionally known photoradicals may be used as needed to improve the hardening properties. A small amount of the initiator can also be included. The following will explain component (B), component (C), and other components. I will reveal it. In the following, components (A) and (B) are referred to as "curing components."

[0077] (1) Component (B) The composition of the present invention is intended to reduce the overall viscosity of the composition and to adjust other physical properties. And, if necessary, component (B) is an ethylenically unsaturated compound other than component (A) mentioned above. It may contain.

[0078] Specific examples of component (B) include monomer (a1-1), monomer (a1-2), monomer (a1-1), and (a1-2) Other (meth)acrylates [hereinafter referred to as "other (meth)acrylates"] Examples include N-vinyl-2-pyrrolidone, etc.

[0079] Other (meth)acrylates include compounds having one (meth)acryloyl group. [Hereinafter referred to as "monofunctional (meth)acrylate"] or two or more (meth)acryloyl groups Examples include compounds having the characteristic [hereinafter referred to as "polyfunctional (meth)acrylate"].

[0080] A specific example of a monofunctional (meth)acrylate is trimethylcyclohexyl(meth)acrylate. acrylate, 1-adamantyl (meth)acrylate, tetrahydrofurfuryl (meth) Acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate )Acrylate, benzyl(meth)acrylate, allyl(meth)acrylate, 2- Ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-f Phenylphenol EO-modified (n=1~4) (meth)acrylate, p-cumylphenol EO-modified (n=1~4) (meth)acrylate, phenyl (meth)acrylate, o-f Phenylphenyl (meth)acrylate, p-Cumylphenyl (meth)acrylate, N- (meth)acryloylmorpholine, N-vinylformamide, N-(meth)acryloyl Oxyethylhexahydrophthalimide, N-(meth)acryloyloxyethyl tetra Examples include hydrophthalimide.

[0081] A specific example of a polyfunctional (meth)acrylate is a urethane with a polyester backbone. Urethane (meth)acrylate such as acrylate and urethane having a polycarbonate skeleton Urethane (meth)acrylates such as acrylate; Bisphenol A EO-modified (n=1~2) di(meth)acrylate, and bisphenol Di(meth)acrylates having a bisphenol skeleton, such as A di(meth)acrylate; Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate , triethylene glycol di(meth)acrylate, tetraethylene glycol di( Meth)acrylate, polyethylene glycol (n=5~14) di(meth)acrylate , propylene glycol di(meth)acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol Glycol di(meth)acrylate, polypropylene glycol (n=5~14) di(meth) Acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanedi All di(meth)acrylate, polybutylene glycol (n=3~16) di(meth) Crylate and poly(1-methylbutylene glycol) (n=5~20) di(meth) (Poly)alkylene glycol di(meth)acrylates such as acrylates 1,6-Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth) Aliphatic diols such as acrylates, neopentyl glycol di(meth)acrylates (meth)acrylate; Neopentyl glycol di(meth)acrylate hydroxypivalate; Di(meth)acrylates and other di(meth)acrylates having an alicyclic skeleton ) Acrylate; Isocyanuric acid EO-modified diacrylate, and ε-caprolactone-modified tris((meth) (meth)acrylic having an isocyanurate skeleton such as acrooxyethyl isocyanurate. rate Glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate Pentaerythritol tri or tetra(meth)acrylate, ditrimethylol Ropan tri or tetra(meth)acrylate, diglycerin tri or tetra(meth) Acrylates and dipentaerythritol tri, tetra, penta or hexa(meth) Polyols such as acrylates, and poly(meth)acrylates; Tri(meth)acrylates of glycerin alkylene oxide adducts, pentaerythritol Tri- or tetra(meth)acrylates of alkylene oxide adducts, ditrimethyl Tri or tetra(meth)acrylate adducts of chloropropane alkylene oxide, jig Tri or tetra(meth)acrylates of ricerine alkylene oxide adducts, dipenta Tri, tetra, penta, or hexa(meth) erythritol alkylene oxide adducts Polyol alkylene oxide adducts such as acrylates, poly(meth)acrylates, etc. These are some examples. In the above, EO modification refers to ethylene oxide modification, where n is alkylene oxide. This refers to the number of repetitions in the phosphate unit. Among these compounds, urethane (meth)acrylates are considered to be polyfunctional (meth)acrylates. (Meth)acrylates having a relate and isocyalate skeleton are preferred. Component (B) Compositions containing urethane (meth)acrylate exhibit excellent tensile properties of the cured film, particularly elongation. It can be considered as such.

[0082] As for component (B), whether you use only one of the aforementioned compounds or two or more in combination good.

[0083] The mixing ratio of component (A) and component (B) can be set appropriately according to the purpose. The ratio of (B) should be such that it does not reduce the flexibility of the resulting cured film, but the components (A) and component (B) together make up 100% by weight of component (A) to 5-95% by weight of component ( It is preferable that component (A) contains 95-5% by weight of B), and more preferably 40-90% by weight of component (A). The amount and component (B) are 60-10% by weight. By setting the proportion of component (A) to 5% by weight or more, the weather resistance of the cured film is improved. This allows for the cured film to maintain flexibility by setting the proportion of component (A) to 95% by weight or less. It can be made to be superior.

[0084] Furthermore, the total double bond equivalent of component (A) and component (B) is 500-2500 g / It is preferably eq, and more preferably 700 to 1200 g / eq. By setting the equivalent amount of the double bond to 500 g / eq or more, the tensile properties (breaking strength) of the cured film can be improved. The degree of curing and the physical properties (hardness) of the cured film can be made excellent, and the equivalent of the double bond is 250 By setting the concentration to 0g / eq or less, excellent weather resistance can be achieved.

[0085] Furthermore, the total double bond equivalent of components (A) and (B) can be calculated using the following formula. In the formula, the number of moles of (meth)acryloyl groups in component (A) is the number of moles of copolymer (a) in the modification reaction described below. 1) This is the number of moles of (meth)acryloyl groups added to the above, and represents the number of moles of unmixed groups present after the modification reaction described below. The (meth)acryloyl group derived from the unsaturated compound (a2) in the reaction is excluded.

[0086]

number

[0087] In the above formula, "the total number of moles of unsaturated groups in component (A) and component (B)" means "component (A) Total moles of (A) (meth)acryloyl groups and component (B) ethylenically unsaturated groups It means number.

[0088] If the (meth)acryloyl group in component (A) is a methacryloyl group, then component In (B), acryloy is used as the ethylenically unsaturated group because it exhibits excellent curability. It is preferable that it contains an ethylenically unsaturated group. The sum of the ethylenically unsaturated groups of component (A) and component (B) is Preferably, 30 mol% or more are acryloyl groups. More preferably, 50 It is 30 mol% or more. By making the proportion of acryloyl groups 30 mol% or more, the composition hardens. The film can be made to have excellent physical properties, and in particular, it can be made to have excellent tensile properties. ru.

[0089] (2) Component (C) The composition of the present invention, for the purpose of improving the coating properties on a substrate, uses an organic solvent as component (C). It can contain. Even if it is the same compound, when used in a reaction system, it is labeled as an "organic solvent." Furthermore, when used in compositions such as paints, it is labeled as an "organic solvent," and this invention In the Meiji era, these were collectively referred to as "organic solvents."

[0090] Specific examples of component (C) include n-hexane, benzene, toluene, xylene, and ethyl hydrocarbon solvents such as benzene and cyclohexane; Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- Butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol , 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol, 2-butoxy Ethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2- Phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetra Hydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl Ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and pro Alcohol-based solvents such as pyrene glycol monomethyl ether; Tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol cellulose diethyl ether, ethylene glycol dibutyl ether, bis(2-methoxy ether) 2-ethyl ether, bis(2-ethoxyethyl) ether and bis(2-butoxyethyl) ether Ether-based solvents such as tel; Acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, butyl Methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, di-n-propyl ketone Diisobutyl ketone, phorone, isophorone, cyclopentanone, cyclohexanone and Ketone solvents such as methylcyclohexanone; Ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol Ester solvents such as recall monomethyl ether acetate and cellosolve acetate; N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide Examples include aprotic polar solvents such as N-methyl-2-pyrrolidone and γ-butyrolactone. It can be done.

[0091] As component (C), one or more of the aforementioned compounds can be used. Component (C) may be added separately to dilute component (A), and also in the manufacturing of component (A) The organic solvents used may be used as is without separation.

[0092] The proportion of component (C) should be set appropriately, taking into consideration the viscosity of the composition and its intended use. Preferably, with respect to 100 parts by weight of component (A), if component (B) is included, For a total of 100 parts by weight of component (A) and component (B), component (C) is 150 parts by weight or less. Preferably, 100 parts by weight or less, more preferably 67 parts by weight or less, 2 5 to 67 parts by weight is particularly preferred.

[0093] (3) Other components not mentioned above In addition to the aforementioned components, various other components can be blended depending on the purpose. When the composition of the present invention is used as a coating agent, for example, a polymerization inhibitor may be used. or / and antioxidants, lightfastness improvers, inorganic particles, surface modifiers, pigments, dyes, and tackiness Examples include fertilizers and the like. The following are other ingredients, including polymerization inhibitors and / or antioxidants, and lightfastness enhancers: I will explain about this.

[0094] <Polymerization inhibitors and / or antioxidants> The composition of the present invention contains a polymerization inhibitor and / or antioxidant to improve storage stability. It can contain. Polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, and 2,6-di-t ert-butyl-4-methylphenol and various phenolic antioxidants are preferred. However, sulfur-based secondary antioxidants, phosphorus-based secondary antioxidants, etc., may also be used. The total amount of these polymerization inhibitors and / or antioxidants is, per 100 parts by weight of component (A) And, if it contains component (B), then for every 100 parts by weight of the total amount of component (A) and component (B) Preferably, the amount is 0.001 to 3 parts by weight, and more preferably 0.01 to 0.5 parts by weight. It is a department.

[0095] <Lightfastness improver> The composition of the present invention may contain lightfastness enhancers such as ultraviolet absorbers and light stabilizers. As a UV absorber, 2-(2'-hydroxy-5-methylphenyl)benzotrione is used. Zole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotria Zol, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)benzo Benzotriazole compounds such as riazole; 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octane Triazine compounds such as (xyxyphenyl)-s-triazine; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone n, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydro Xy-4-methoxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2 ,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydro Xybenzophenone, 2,3',4,4'-tetrahydroxybenzophenone, or 2, Benzophenone compounds such as 2'-dihydroxy-4,4'-dimethoxybenzophenone, etc. We can list some examples. As a light stabilizer, N,N'-bis(2,2,6,6-tetramethyl-4-piperidi (Lu)-N,N'-diformylhexamethylenediamine, bis(1,2,6,6-)penta Methyl-4-piperidyl)-2-(3,5-diter-butyl-4-hydroxyben Zyl)-2-n-butylmalonate, bis(1,2,2,6,6-pentamethyl-4-butylmalonate) Low molecular weight hindered amine compounds such as peridinyl sebacate; N,N'-bis(2, 2,6,6-Tetramethyl-4-piperidyl)-N,N'-Diformylhexamethylenedi Amines, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, etc. Examples of hindered amine-based light stabilizers include high molecular weight hindered amine compounds. . The amount of lightfastness improver to be added is when component (B) is included in 100 parts by weight of component (A). The amount is 0 to 5 parts by weight per 100 parts by weight of the total amount of component (A) and component (B). Preferably, it is 0 to 1 part by weight.

[0096] 3.How to use The composition of the present invention can be used in various ways depending on the purpose. For example, when using the composition of the present invention as a coating agent, the composition is applied to the substrate. Furthermore, if the composition contains an organic solvent, the organic solvent in the composition is evaporated by heating, and then irradiated with an electron beam. One method involves injecting and hardening the material. Furthermore, when using the composition of the present invention as an adhesive, the composition is applied to a substrate, and an organic solvent is used. If it contains, after evaporating the organic solvent in the composition by heating, and then bonding it to another substrate, Another method involves curing the material by irradiating it with an electron beam.

[0097] The composition of the present invention can be applied to a variety of substrates, including inorganic materials and plastics. Examples include tics and paper. Examples of inorganic materials include glass, metal, mortar, concrete, and stone. Examples of metals include steel plates, aluminum and chromium, zinc oxide (ZnO) and indioxide. Examples include metal oxides such as tin umbus (ITO). Specific examples of plastics include polyolefins such as polyethylene and polypropylene. ABS resin, polyvinyl alcohol, triacetylcellulose and diacetylcellulose Cellulose acetate resin, acrylic resin, polyethylene terephthalate (hereinafter, "PET resin", polycarbonate, polyarylate, polyethersulfone, Cyclic polyolefin resins using cyclic olefins such as norbornene as monomers, polychlorinated vinyl Examples include vinyl, epoxy resins, and polyurethane resins. Thermoplastics are also used as plastics. Plastics are preferred, and specific examples include PET resin, acrylic resin, and ABS resin. Examples include lipids, polycarbonate, polypropylene, and polyethylene, with PET resin being preferred. It seems so. Among these materials, metals and plastics are preferred as the base material. The shape of the substrate is not particularly limited and may be in the form of a sheet, film, or plate. stomach.

[0098] The coating method for the composition can be appropriately selected depending on the purpose, such as conventionally known bar coating. Applicator, doctor blade, knife coater, comma coater, reverse throw Diacoaters, lip coaters, gravure coaters, and microgravure coaters. One method is to apply the coating using a painter or similar device.

[0099] The thickness of the cured film of the composition relative to the substrate can be set appropriately according to the purpose. In that case, the choice should be made according to the substrate used and the application of the substrate with the manufactured cured film. The particle size is preferably 1 to 100 μm, and more preferably 2 to 40 μm.

[0100] The present invention is an electron beam curable composition, which is cured by an electron beam. Electron beam curable compositions do not necessarily require a photopolymerization initiator, unlike visible light / ultraviolet curable compositions. It is preferable because it does not require any additives and the cured film has excellent heat resistance and weather resistance.

[0101] Regarding irradiation conditions such as dose, irradiation intensity, etc. in electron beam irradiation, the composition used The appropriate material should be selected according to the type of material, base material, and purpose. When using electron beams, the acceleration voltage is 50-300kV, and the absorbed dose is 10-1. It is preferable to irradiate to a value of 000 kGy.

[0102] The composition of the present invention can be used for a variety of purposes. Specific examples include coating agents, adhesives, inks, and films. It can be preferably used as a coating agent. Specific uses of the coating agent include various paints, decorative films, topcoat agents, etc. Examples thereof include. More specific uses of the coating agent include hard coat applications. In this case, substrates include plastic films used for polarizer protection films and anti-reflection films, as well as resin molded products used for home appliances and interior and exterior automotive parts, etc. Examples thereof include. Other uses of the coating agent can be preferably used as a coating agent for metal substrates, such as an electrode protection material for PDP (Plasma Display Panel), a circuit protection material for an electric bicycle substrate, an electrode protection coating agent used for lithium ion batteries, etc., and a coating agent for interior and exterior automotive members. Since the cured film of the composition of the present invention is excellent in weather resistance, it can be particularly preferably used as an outdoor coating agent for building exterior decoration, outdoor signs, and automotive exterior, etc.

Examples

[0103] Hereinafter, examples and comparative examples will be given to more specifically explain the present invention. In the following, "parts" means parts by weight. Also, the molecular weight, Tg, acid value, solid content, and (meth)acrylic equivalent amount in the production examples and examples were measured according to the following methods.

[0104] <Molecular weight measurement> Using a gel permeation chromatograph device (model name "HLC-8320", manufactured by Tosoh Corporation), Mw (weight average molecular weight) and number average molecular weight ( hereinafter referred to as "Mn") in terms of polystyrene conversion were obtained under the following conditions. ○Measurement conditions Column: 4 TSKgel SuperMultipore HZ-M manufactured by Tosoh Corporation Column temperature: 40 °C Eluent: Tetrahydrofuran Detector: RI

[0105] <Measurement of Tg> The Tg of the copolymer (a1) and component (A) was measured under the following conditions using a differential scanning calorimeter (DSC). ○ Pretreatment of the copolymer (a1) The measurement was carried out after removing the solvent at 100 °C under vacuum. ○ Pretreatment of component (A) 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, which is a polymerization inhibitor, was added to the (A) solution at 1000 ppm with respect to component (A), dissolved, and the solvent was removed at 80 °C under vacuum before carrying out the measurement. ○ Measurement conditions DSC: Q-100 manufactured by TA Instrument Temperature increase rate: 10 °C / min Measurement atmosphere: Nitrogen

[0106] <Measurement of acid value> The measurement was carried out in accordance with JIS K0070 for acid value measurement. That is, the sample was weighed so that the titration volume would be approximately 10 mL, diluted with approximately 50 mL of tetrahydrofuran, and then titrated with a 0.1 N KOH / ethanol solution using an automatic titrator COM-1600ST (manufactured by Hiranuma Sangyo Co., Ltd.).

[0107] <Solid content>[[ID=At 150 °C for 1 hour, the solid content was determined from the weight loss by drying with a ventilation dryer. Note that the solid content was adjusted so that the viscosity would be easy to apply (1,000 to 4,000 mPa·s). Therefore, it can be seen that a high solid content is excellent in that the amount of organic solvent used is small.[[ID=P]] ]>

[0108] ​​​​​​​​<(meth)acrylic equivalent (g / eq)> Component (A) is calculated from the monomer, the weight of the denaturing agent, and the acid value, or from IR. The amount of (meth)acrylic equivalent contained in component (A) was determined using the reaction rate. The composition was calculated using the weighted average of the (meth)acrylic equivalents of each component.

[0109] 1. Manufacturing example (1) Manufacturing example 1 The temperature of the 1000 mL pressurized stirred-tank reactor with an oil jacket is set to 206°C. It was kept constant. Next, while maintaining a constant pressure in the reactor, methyl methacrylate (hereinafter, 70 copies of MMA (hereinafter referred to as "EA"), 10 copies of ethyl acrylate (hereinafter referred to as "EA"), 20 parts of lysidyl methacrylate (hereinafter referred to as "GMA"), with methyl as the organic solvent. 12 parts of ethyl ketone (hereinafter referred to as "MEK"), trimethyl orthoacetate (manufactured by Nippo Chemical Co., Ltd.) , 3 parts of the product name "MOA" (hereinafter referred to as "MOA"), and di-t-hex as a polymerization initiator Silperoxide (manufactured by NOF Corporation, trade name "Perhexyl D", hereinafter referred to as "DTHP") A monomer mixture consisting of 1 part of the original material is supplied at a constant rate (48 g / min, residence time: 12 min) Start continuous supply from the material tank to the reactor, and discharge a reaction solution equivalent to the amount of monomer mixture supplied. These were extracted sequentially. Immediately after the reaction started, the reaction temperature decreased, and then a temperature increase due to the heat of polymerization was observed. By controlling the temperature of the oil jacket, the reaction temperature was maintained at 202-204°C. .

[0110] The point at which the temperature stabilizes after the start of supplying the monomer mixture is defined as the starting point for sampling the reaction solution. After continuing the reaction for 37 minutes, 1.78 kg of monomer mixture was supplied, and 1.78 kg The reaction solution was collected. The reaction solution was then introduced into a thin-film evaporator to remove unreacted monomers and other volatile components. Separating the epoxy group into an epoxy group-containing (meth)acrylate polymer (hereinafter referred to as "polymer a1-1") 1.08 kg of (this substance) was obtained. Table 1 shows the Mw and Tg of copolymer a1-1.

[0111] Next, copolymer a1-1 (100 parts), and dibutylhydroxytoluene as a polymerization inhibitor. 0.15 parts of methyl phosphate (hereinafter referred to as "BHT"), 1 part of acrylic acid (hereinafter referred to as "AA") 0.1 parts (corresponding to the acid value of 1.0 equivalent of the epoxy group of copolymer a1-1) and an organic solvent Then, butyl acetate (47.2 parts) is added to a 1 L flask, and a 5% oxygen-nitrogen mixture gas is bubbled into it. While stirring, the liquid temperature was raised to 95°C to dissolve copolymer a1-1. After homogeneous dissolution, triphenylphosphine (hereinafter referred to as "TPP") is used as a reaction catalyst. (0.55 parts) was added and stirred for 12 hours while maintaining an internal temperature of 95°C. Furthermore, TPP (0.55 parts) was added and the mixture was allowed to react for 12 hours. Afterwards, the acid value was measured and found to be 0.2 mgK. The reaction was terminated after confirming that the OH / g ratio was correct. As a result, polymer A-1, which is an acrylic acid adduct of copolymer a1-1, was obtained.

[0112] Solid content, acid value, Mn, Mw, (meth)acrylic equivalent, and per molecule of polymer A-1 The number of double bonds and Tg are shown in Table 2.

[0113] (2) Manufacturing examples 2-11, 14-16 Except for the changes shown in Tables 1 and 2, Polymer A-2~ was produced using the same procedure as in Manufacturing Example 1. I obtained 11, 14-16.

[0114] Solids content, acid value, Mn, Mw, and (meth)acrylic equivalent of polymers A-2 to A-11 and A-14 to A-16 The number of double bonds per molecule and Tg are shown in Table 2.

[0115] (3) Production Example 12 A copolymer a1-12 was obtained by the same operation as in Production Example 1, except for the changes shown in Table 1. obtained. The Mw, Tg, and terminal double bond concentration of the polymer a1-12 are shown in Table 1.

[0116] Next, 100 parts of the copolymer a1-12, 0.13 parts of BHT, 2-acryloyl oxyethyl isocyanate [trade name Karenz AOI, manufactured by Showa Denko Materials Co., Ltd.] ( 28.5 parts, corresponding to 1.0 equivalent of isocyanate equivalent to the hydroxyl groups of the polymer a1-12), dibutyltin dilaurate (0.025 parts) as a catalyst, and butyl acetate (55.1 parts) were charged into a 1 L flask, and while bubbling a 5% oxygen-nitrogen mixed gas, the liquid temperature was raised to 80 °C to dissolve the polymer a1-12. subsequently, the mixture was stirred for 6 hours while maintaining the temperature at 80 °C, and using an ATR method infrared spectrophotometer (Spectrum100 manufactured by Perkin Elmer), it was confirmed that the absorption due to isocyanate at 2200 cm-1 had disappeared, and the reaction was terminated. As a result, polymer A -12, which is an AOI adduct (acrylate-modified product) of the copolymer a1-12, was obtained. obtained.

[0117] The solid content, Mn, Mw, (meth)acrylic equivalent, number of double bond combinations per molecule, and Tg of polymer A-12 are shown in Table 2.

[0118] (4) Production Example 13 Polymer A-1 3 was produced by the same method as in Production Example 12, except for the changes as shown in Tables 1 and 2. Solid content, Mn, Mw, (meth)acrylic equivalent, and double bond per molecule of polymer A-13 The total number of cells and Tg are shown in Table 1.

[0119] (5) Comparative manufacturing examples 1-5 Polymer A'-1 was produced by the same procedure as in Production Example 1, except for the changes shown in Tables 3 and 4. I got a score of ~5. Solid content, acid value, Mn, Mw, (meth)acrylic equivalent, per molecule of polymer A'-1 to 5 The number of double bonds and Tg of each compound are shown in Table 4.

[0120] [Table 1]

[0121] [Table 2]

[0122] [Table 3]

[0123] [Table 4]

[0124] The abbreviations in Tables 1 and 3 have the following meanings. Note that in the following contexts, the meanings are as already defined above. Some of the items listed are duplicates. MMA: Methyl methacrylate • EA: Ethyl acrylate • BA: n-butyl acrylate CHMA: Cyclohexyl methacrylate IBX: Isobornyl methacrylate IBXA: Isobornyl acrylate • FA-513M: Dicyclopentanyl methacrylate [Manufactured by Showa Denko Materials Co., Ltd.] 、Product Name: Funcril FA-513M) ·BMA: 2-Butyl methacrylate ·GMA: Glycidyl methacrylate ·AA: Acrylic acid ·MOI: 2-Methacryloyloxyethyl isocyanate [Karenz MOI (Product Name) 、manufactured by Showa Denko K.K.) ·HEMA: 2-Hydroxyethyl methacrylate ·MEK: Methyl ethyl ketone ·MOA: Trimethyl orthoacetate [MOA (Product Name), manufactured by Nippon Petrochemical Co., Ltd.] ·DTHP: Di-t-hexyl peroxide [Perhexyne D (Product Name), manufactured by NOF Corporation manufactured)

[0125] The abbreviations in Table 2 and Table 4 mean the following, except those defined above. ·HBA: 4-Hydroxybutyl acrylate ·AOI: 2-Acryloyloxyethyl isocyanate [manufactured by Showa Denko K.K., Product Name Karenz AOI] ·HBAGE: 4-Hydroxybutyl acrylate glycidyl ether ​​​​​​​​​​​​​​​​​​​​​​The obtained composition was used to evaluate its tensile properties, weather resistance, and cured film properties according to the following procedure. The results are shown in Tables 5-7.

[0127] a) Tensile properties <Preparation of samples for tensile testing> The base film is Lumirror T-60 (product name, PET film manufactured by Toray Industries, Inc., film thickness; Prepare a 100μm sheet, attach tape to both ends of it, and apply a bar coat to the surface of the base film. Using #0, the above examples and comparative examples were obtained such that the film thickness after drying was 80-100 μm. The electron beam-curable composition was applied. Then, it was dried in a forced-air dryer at 90°C for 10 minutes. A coated film having a dried coating of the composition was obtained. Next, using an electron beam irradiation device manufactured by NHV Corporation, at an acceleration voltage of 150k V, dose 150 kGy (adjusted by beam current and transport speed), oxygen concentration 300 ppm or less A cured film was obtained by irradiating with an electron beam under certain conditions.

[0128] <Tensile Test> Using a tensile testing machine (Autograph AGS-J, manufactured by Shimadzu Corporation), this cured film was subjected to a tensile test. The elongation at break (%) and breaking strength (unit: MPa) were measured under a tensile speed of 5 mm / min. The breaking strength is preferably 10 MPa or higher, and the breaking elongation is preferably 2% or higher.

[0129] b) Weather resistance <Preparation of weather resistance test samples> Zeonor (product name, manufactured by Nippon Zeon Co., Ltd., 50 μm) was prepared as the base film, Tape is attached to both ends, and the surface of the base film is coated with bar coater #0, and the film after drying is formed. The electron beam curable compositions obtained in the above examples and comparative examples were prepared to have a thickness of 50-60 μm. The coating was applied. Then, it was dried in a ventilated dryer at 90°C for 10 minutes to obtain a dried coating of the composition. A coated film was obtained. Next, electron beam irradiation is performed using the same electron beam irradiation apparatus as described above, under the same conditions as described above. A cured film was obtained.

[0130] <Weather resistance test> The resulting hardened film is used in a metal weather meter (Dypra Wintes Co., Ltd.) Manufactured by "DAIPLA METAL WEATHER KU-R5NCI-A" (product name) The device was placed in a container and accelerated weathering tests were conducted. The conditions were irradiation at 63°C, 70% RH, and illuminance of 80 mW / cm². The experiment involved showering for two minutes every two hours, for a total of 500 hours. Using films with cured coatings before and after weather resistance testing, the following method was used to determine color difference and haze. The size was measured.

[0131] (Measurement of color difference) Using the SE-2000 spectrophotometer (product name) manufactured by Nippon Denshoku Industries Co., Ltd., the yellowness (YI) was measured. The following was measured (YI is as shown in the formula below). ΔYI is preferably 4 or less. YI = 100(1.28X-1.06Z) / Y (X, Y, Z are color coordinate systems) ΔYI = YI - YI0 (where YI0 represents YI before the heating test)

[0132] (Haze measurement) Measurements were taken using the NDH2000 (product name) manufactured by Nippon Denshoku Industries Co., Ltd., and the haze before and after heating was measured. The difference (Δ-haze) was evaluated. A Δ-haze of 3 or less is preferable.

[0133] c) Physical properties of cured film <Preparation of samples for evaluation of hardened films> On a chromate-treated aluminum plate, a bar coater #20 was used to create a film thickness of approximately 10 μm after drying. The electron beam curable compositions of the examples and comparative examples obtained above were applied in such manner. Then, the film is dried in a forced-air dryer at 90°C for 10 minutes to obtain a coated film having a dried coating of the composition. Ta. Next, electron beam irradiation is performed using the same electron beam irradiation apparatus as described above, under the same conditions as described above. A cured film was obtained.

[0134] <Pencil hardness> The hardened film surface was scratched with a pencil under a 750g load, and the hardest pencil that did not leave any damage was selected. The hardness was defined as pencil hardness. A hardness of F or higher is preferred.

[0135] <Impact resistance (DuPont impact test)> At 23°C, using a DuPont impact tester, the tip diameter of the impact core was 1 / 2 inch, and the load was 500. The test was conducted under condition g. The maximum height (cm) at which no coating damage occurred is shown. A height of 30 cm or more is preferable.

[0136] <Surface roughness Ra> The surface roughness Ra was measured using a laser microscope "VK-9710" manufactured by Keyence Corporation. Measurements were taken in accordance with JIS B0601:2000. A surface roughness of 2 μm or less is preferred.

[0137] [Table 5]

[0138] [Table 6]

[0139] [Table 7]

[0140] The results in Tables 5-7 show the following: The compositions of Examples 1 to 20 have cured films that exhibit excellent tensile properties and weather resistance, and have a surface roughness. It excelled at producing small finished products. In contrast, the composition of a comparative example containing a polymer that differs from component (A) of the present invention in the following respects The items were as follows: A'-1 contains a polymer whose (meth)acrylic equivalent is less than the lower limit of 500 g / eq of the present invention. In the case of Comparative Example 1, the cured film exhibited a decrease in tensile elongation. A'- The composition of Comparative Example 2, which includes 2, has a cured film in which the tensile strength of the material is reduced and the weather resistance is reduced. And, in particular, the haze level has decreased. A'-3 contains polymers whose uncured state Tg is less than the lower limit of -15°C specified in the present invention. The composition of Comparative Example 3 shows that the cured film has reduced tensile strength and, in terms of weather resistance, particularly The haze level has decreased. A ratio containing A'-4 in which the Tg of the uncured polymer exceeds the upper limit of 80°C of the present invention. The composition in Comparative Example 4 exhibits reduced elongation in its cured film and a large surface roughness. The finish was poor. Composition of Comparative Example 5, which includes A'-5 in which the polymer Mw exceeds the upper limit of 10,000 of the present invention. The cured film of the material had a very rough surface and a poor finish. The composition of Comparative Example 6, which contains no polymer and only a polyfunctional acrylate, has a cured film that In terms of weather resistance, both YI and haze have decreased. [Industrial applicability]

[0141] The electron beam curable composition of the present invention has excellent weather resistance, flexibility, toughness, and surface roughness. It excels at producing a small finish and can be used for various applications, including coating. It can be preferably used as an agent, and more preferably as an outdoor coating agent. It is possible.

Claims

1. An electron beam curable composition containing the following component (A). • Component (A): A (meth)acrylate polymer having (meth)acryloyl groups in its side chains. The (meth)acrylic equivalent is 500 to 2,000 (g / eq), and the weight average is The particle count is 10,000 or less, and the glass transition temperature in the uncured state is -15 to 80°C. A polymer.

2. The aforementioned component (A) is derived from a (meth)acrylate monomer (a1-1) that does not have a reactive group. The constituent units and the (meth)acrylate monomers (a1-2) having reactive groups A copolymer (a1) containing the constituent units [hereinafter referred to as "polymer (a1)"] A compound having a group that reacts with the reaction group via a group and a (meth)acryloyl group (a 2) The electron according to claim 1, which is a reaction product with [hereinafter referred to as "unsaturated compound (a2)"] Line curable composition.

3. The copolymer (a1) is composed of a (meth)acrylate monomer having a reactive group (a1 -2) From the group consisting of epoxy groups, carboxyl groups, hydroxyl groups and isocyanate groups The electron beam according to claim 2, which is a (meth)acrylate monomer having selected reactive groups. Curable composition.

4. The claim 2 or 3 is that the unsaturated compound (a2) is (meth)acrylic acid. Electron beam curable composition.

5. Furthermore, compound (B) having an ethylenically unsaturated group other than component (A) (hereinafter referred to as "component ( An electron beam curable composition according to any one of claims 1 to 4, comprising (B)).

6. In a total of 100% by weight of components (A) and (B), component (A) is present in an amount of 5 to 95% by weight and The electron beam curable composition according to claim 5, comprising 95 to 5% by weight of component (B).

7. The total of component (A) and component (B) is such that the double bond equivalent is 500 to 2500 g / eq. An electron beam curable composition according to claim 5 or claim 6.

8. Furthermore, it contains an organic solvent (C) (hereinafter referred to as "component (C)"), and the mixture of component (A) If the total amount of 100 parts by weight includes component (B), then component (A) and component (B) Claims 1 to Claims 1 to 100 parts by weight of the total, wherein the above component (C) is included in a quantity of 150 parts by weight or less. An electron beam curable composition according to any one of item 7.

9. Coating comprising the electron beam curable composition according to any one of claims 1 to 8 Electron beam curable composition for pharmaceutical use.

10. Electron beam curable composition for outdoor coating agent comprising the electron beam curable composition according to claim 9 thing.

11. A constituent unit (a1-1) derived from a (meth)acrylate monomer that does not have a reactive group, and Co-components consisting of constituent units derived from (meth)acrylate monomers (a1-2) having an responsive group The polymer (a1) is reacted with the unsaturated compound (a2) to form the copolymer (a1), Electron beam curing type including the step of adding the unsaturated compound (a2) via the reactive group. A method for producing a composition.

12. The copolymer (a1) is composed of a (meth)acrylate monomer having a reactive group (a1 -2) From the group consisting of epoxy groups, carboxyl groups, hydroxyl groups and isocyanate groups The electron according to claim 11, which is a (meth)acrylate monomer having a selected reactive group. A method for producing a linearly curing composition.

13. The electron beam curing according to claim 12, wherein the unsaturated compound (a2) is (meth)acrylic acid. A method for producing a molded composition.

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