Active energy ray-curable resin composition, coating agent using same, and sheet

Abstract

To provide an active energy ray-curable resin composition which has excellent adhesiveness to a substrate and spreadability when cured, has no surface tackiness feeling, and has excellent solvent resistance and excellent processability and productivity, and to provide a coating agent using the same and a sheet.SOLUTION: There is provided an active energy ray-curable resin composition which comprises a urethane (meth)acrylate-based compound (A) having a structural unit derived from a polyvalent isocyanate-based compound (a1), a structural unit derived from a polyol compound (a2) and a structural unit derived from a hydroxyl group-containing (meth)acrylate-based compound (a3), wherein the polyol compound (a2) contains a polyether polycarbonate diol (a2-1) represented by the following formula (1). (In formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer of 2 to 30 and m is an integer of 1 to 20. In addition, a plurality of R1 may be the same or different.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable resin composition, and more particularly to a cured coating film. When used in high temperatures, the coating film expands significantly, providing high abrasion resistance and solvent resistance. Excellent active energy ray-curable resin composition, coating agent using the same, and It concerns the seat. [Background technology]

[0002] Plastic substrates such as polycarbonate and polymethyl methacrylate are easy to process and have good impact resistance. It also has excellent optical properties such as impact resistance and transparency, making it suitable for use in home appliances, automotive products, and LCD displays. It is widely used in components such as aluminum.

[0003] However, these plastic substrates are prone to scratches on the surface, so they require scratch resistance. In order to impart this property, the surface of the plastic substrate is coated with a hard coating agent. The hard coating agent may be used for its adhesiveness to the plastic substrate. Active energy rays are used for reasons such as their excellent properties and fast curing speed, which contributes to improved productivity. Curable resin compositions are often used.

[0004] Furthermore, the active energy ray-curable resin composition can be used for decorative molding to impart design features. It may also be used when administering. Conventional decorative molding methods include kneading pigments into thermoplastic resins and molding them. In addition to the method of decorating the surface of the resin product by spraying paint, Insert molding, in-mold molding, and TOM molding (Three dimension) that does not require a mold Application of three-dimensional molding such as the sion overlay method (three-dimensional surface coating method) Use is also being considered.

[0005] The active energy ray-curable resin composition used in the decorative molding and the like is In particular, the material has excellent workability, such as no cracks occurring even when molded into complex shapes, and moldability. The material must have good conformability and elongation. In addition, when the active energy ray-curable resin composition is used as the outermost surface material of a molded product, In addition, when used in combination with other materials, it is necessary to use a solvent. Therefore, solvent resistance is required.

[0006] For example, in the following Patent Document 1, a polycarbonate-based polyurethane and a non-yellowing polyurethane are A decorative molded sheet having a surface layer made of a reaction-cured product of a resin composition containing isocyanate. Patent Document 1 discloses a molded product using the above decorative molded sheet. It is shown that the surface can be formed into a complex shape and has excellent scratch resistance. For example, Patent Document 2 below describes a method for producing a polycarbonate polyol, a polyether polyol, and a hydroxybenzoate. By using urethane acrylate containing phenol, the tensile strength and tensile elongation are uniform. It has been shown that the resulting cured product has excellent resistance and suitable hardness and flexibility. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-128922 [Patent Document 2] Patent No. 5384963 Summary of the Invention [Problem to be solved by the invention]

[0008] However, the resin composition disclosed in Patent Document 1 does not contain polyisocyanate as a heat curing agent. It contains acetone, and in order to complete the hardening of the coating film, heat or aging period is not required. This is inferior in productivity because it is necessary to provide a Furthermore, although the composition disclosed in Patent Document 2 is excellent in tensile strength and tensile elongation, the coating film The surface remains sticky and has poor abrasion resistance.

[0009] The present invention has been made in view of the above circumstances, and provides a composition which, when cured, has excellent adhesion to a substrate, It has excellent elongation, no tackiness on the surface, excellent solvent resistance, and excellent processability and productivity. Energy ray curable resin composition, coating agent using the same, and sheet - Patents.com provide. [Means for solving the problem]

[0010] The present inventors have conducted extensive research to solve the above problems. As the isocyanate used in the (meth)acrylate reaction, polyisocyanate The polyol used in the reaction of the urethane (meth)acrylate is The use of ether polycarbonate diol was investigated. It forms a coating film with good elongation properties, excellent abrasion resistance, and good solvent resistance. This has led to the present invention.

[0011] That is, the above problems are solved by the present inventions [1] to [7] below. [1] A structural unit derived from a polyisocyanate compound (a1), a polyol compound (a 2) and a structural unit derived from a hydroxyl group-containing (meth)acrylate compound (a3). The polymer contains a urethane (meth)acrylate compound (A) having a structural unit derived from the polymer. The diol compound (a2) is a polyether polycarbonate diol represented by the following formula (1): An active energy ray-curable composition comprising: a hydroxyl group (a2-1); [ka] (In the above formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and n is 2 to 3. 0, and m is an integer from 1 to 20. In addition, in formula (1), multiple R1's are the same. It may be the same or different.) [2] The polyol compound (a2) further comprises a polyol having a number average molecular weight of 300 or less. The active energy ray-curable composition according to [1], characterized by containing (a2-2). [3] The polyether polycarbonate diol (a2-1) and the polyol (a2- 2) The ratio (a2-1 / a2-2) of the weight ratio is 99 / 1 to 50 / 50. The active energy ray-curable resin composition according to [2]. [4] The polyether polycarbonate diol (a2-1) has a number average molecular weight of 50 The active element according to any one of [1] to [3], wherein the molecular weight of the active element is 0 to 20,000. Energy ray curable resin composition. [5] The hydroxyl group-containing (meth)acrylate (a3) ​​contains, in the molecule, a (meth)acryloyl group.

[0023] Any of [1] to [4], characterized in that the (meth)acrylate has one or more alkyl groups. The active energy ray-curable resin composition according to any one of claims 1 to 10. [6] A method for producing a resin composition comprising the active energy ray-curable resin composition according to any one of [1] to [5]. A coating agent characterized by having: [7] A curable resin composition according to any one of [1] to [5]. A sheet having a compound. [Effects of the Invention]

[0012] As described above, the active energy ray-curable resin composition of the present invention is a polyisocyanate-based compound. a structural unit derived from the polyol compound (a1), a structural unit derived from the polyol compound (a2), and and urethane having structural units derived from a hydroxyl group-containing (meth)acrylate compound (a3). The present invention is characterized in that it contains a poly(meth)acrylate compound (A), The ol compound (a2) is a polyether polycarbonate diol represented by the following formula (1): Lu (a2-1) [ka] (In the above formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and n is 2 to 3. 0, and m is an integer from 1 to 20. In addition, in formula (1), multiple R1's are the same. The number average molecular weight of the polymer may be 300 or less. Therefore, the active energy ray-curable polymer of the present invention can contain thiol (a2-2). A coating film formed from a resin composition, containing the active energy ray-curable resin composition of the present invention. A coating film formed by the coating agent and the active energy ray-curable resin of the present invention. The sheet made of the cured resin composition has good elongation properties and abrasion resistance under high temperature conditions, and further Furthermore, the active energy ray curable resin composition can be used to form a molded product. The resulting coating film has excellent conformability to the substrate and acts as a strong and stretchable substrate. These properties are also useful, and they can be used for a variety of purposes.

[0013] In particular, the polyether polycarbonate diol (a2-1) and the polyol (a2- 2) and the ratio (a2-1 / a2-2) of 99 / 1 to 50 / 50 by weight, It is easy to impart abrasion resistance and high elongation, and physical properties can be finely adjusted.

[0014] The polyether polycarbonate diol (a2-1) has a number average molecular weight of 5 When the molecular weight is 00 to 20,000, the elongation becomes better.

[0015] Furthermore, the hydroxyl group-containing (meth)acrylate (a3) ​​has a (meth)acryloyl group in the molecule. If the (meth)acrylate has one or more aryl groups, it is possible to impart an appropriate crosslinking structure to the cured coating film. This provides wear resistance. DETAILED DESCRIPTION OF THE INVENTION

[0016] Next, an embodiment of the present invention will be described in detail. It is not limited to the form.

[0017] The active energy ray-curable resin composition of the present invention (hereinafter sometimes abbreviated as "resin composition") is obtained by using a urethane (meth)acrylate (A). First, each component material constituting the active energy ray-curable resin composition will be described. .

[0018] Urethane (meth)acrylate (A) The urethane (meth)acrylate (A) used in the present invention is a polyisocyanate (a 1), polyol (a2), and hydroxyl group-containing (meth)acrylate (a3) ​​were used to react. The polyol (a2) is a reaction product obtained by reacting a polyol represented by the following formula (1): The polyether polycarbonate diol (a2-1) is also included. [ka] (In the above formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and n is 2 to 3. 0, and m is an integer from 1 to 20. In addition, in formula (1), multiple R1's are the same. It may be the same or different.) That is, the urethane (meth)acrylate (A) used in the present invention is a polyisocyanate. Structural units derived from ester (a1), and polyether polycarbonate diol (a2-1) a compound having a structural unit derived from a hydroxyl group-containing (meth)acrylate (a3) Furthermore, the urethane (meth)acrylate (A) has a number average It may contain a polyol (a2-2) having a molecular weight of 300 or less. From the viewpoint of the effect, 50% by weight or more, particularly 80% by weight or more of the total polyol (a2) is polyol. Consisting of ether polycarbonate diol (a2-1) and polyol (a2-2) It is preferable that all of the polyols (a2) are polyether polycarbonate diols ( It is more preferable that the polyol (a2-1) and the polyol (a2-2) are used.

[0019] In the present invention, (meth)acrylic refers to acrylic or methacrylic, and (meth)acrylic refers to acrylic or methacrylic. ) Acryloyl means acryloyl or methacryloyl, and (meth)acrylate means It means acrylate or methacrylate, respectively.

[0020] [Polyisocyanate (a1)] The polyisocyanate (a1) is a polyol (a2) and a hydroxyl group-containing (meth)acrylate. Specifically, for example, Tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane Polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate tetramethylxylylene diisocyanate, phenylene diisocyanate, naphtha Aromatic polyisocyanates such as diisocyanates; Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, aliphatic polyisocyanates such as toluene diisocyanate and lysine triisocyanate; Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, iso Norbornene diisocyanate, norbornene diisocyanate, 1,4-bis(isocyanate) alicyclic polyisocyanates such as methyl)cyclohexane; Alternatively, trimer compounds or polymer compounds of these polyisocyanates, allophanates type polyisocyanate, biuret type polyisocyanate, water-dispersible type polyisocyanate (For example, Tosoh Corporation's "Aquanate 100," "Aquanate 105," and "Aquanate Anate 120, Aquanate 210, etc.) These can be used alone or in combination of two or more.

[0021] Among these, alicyclic polyisocyanates and aromatic polyisocyanates are , which are preferred in terms of weather resistance and strength, and particularly preferred are isophorone diisocyanate, water-added Xylylene diisocyanate, xylylene diisocyanate, tolylene diisocyanate is.

[0022] [Polyol (a2)] As mentioned above, the polyol (a2) may be polyether polycarbonate diol. Polyol (a2-1) is used in combination with polyol (a2-2) having a number average molecular weight of 300 or less. It can also be used as such.

[0023] In particular, polyether polycarbonate diol (a2-1) and polyol (a2-2) The ratio of a2-1 to a2-2 (a2-1 / a2-2) is 99 / 1 to 50 / 50 by weight. This is preferable because it is easy to impart elongation and the physical properties can be finely adjusted. The ratio (weight ratio) is more preferably (a2-1 / a2-2)=98.5 / 15.5 or more. 51 / 49, particularly preferably in the range of (a2-1 / a2-2)=98 / 2 to 52 / 48 be.

[0024] In addition, the polyether polycarbonate diol (a2-1) has a number average molecular weight of 500 to 20,000, and the polyol (a2-2) is a polyol having a number average molecular weight of 60 to 300. It is preferable that the material is a polyester, since it is easy to impart high elongation and the physical properties can be finely adjusted. From the above viewpoints, the polyether polycarbonate diol (a2-1) has a number average molecular weight of 6 The polyol (a2-2) is a polyol having a number average molecular weight of 70 to 15,000. 250 polyol is more preferred, and polyether polycarbonate is particularly preferred. The carbonyl diol (a2-1) has a number average molecular weight of 700 to 10,000, and the polyol The number average molecular weight of the copolymer (a2-2) is 80 to 200.

[0025] The number average molecular weight is calculated based on the hydroxyl value measured in accordance with JIS K 1557. Specifically, the hydroxyl value is measured, and the terminal group determination method is used to calculate the number average molecular weight. 56.1 × 1000 × valence) / hydroxyl value [mgKOH / g]. In this case, the valency is the number of hydroxyl groups in one molecule.

[0026] <Polyether polycarbonate diol (a2-1)> The polyether polycarbonate diol (a2-1) is represented by the following formula (1): In the following formula (1), when m=1, "polyether polycarbonate diol" However, in the present invention, The term "polyether polycarbonate" includes the polyether carbonate diol represented by formula (1). It is called "carbonate diol (1)". [ka] (In the above formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and n is 2 to 3. 0, and m is an integer from 1 to 20. In addition, in formula (1), multiple R1's are the same. It may be the same or different.)

[0027] In the above formula (1), R1 preferably has 2 to 10 carbon atoms, more preferably has 3 to 10 carbon atoms. A linear or branched alkylene group having 6 carbon atoms is particularly preferred, and a butylene group having 4 carbon atoms or 5 is a 2-methylbutylene group, and particularly preferably an n-butylene group. That is, the formula (1) It has been found that R1-O- in the formula is derived from polytetramethylene ether glycol. It is preferred from the viewpoints of commercial availability and excellent physical properties of the resulting urethane (meth)acrylate. It's nice.

[0028] In the above formula (1), if n is less than 2, the flexibility of the resulting urethane (meth)acrylate is low. If the ratio exceeds 30, the resulting polyether polycarbonate diol tends to have poor properties. The viscosity and crystallinity increase, making handling difficult and also making the compatibility with other polyols poor. The transparency of the resulting urethane (meth)acrylate tends to decrease as a result of deterioration in the Therefore, n is 2 to 30, preferably 3 to 25, and more preferably 3 to 20.

[0029] In addition, in the above formula (1), when m is less than 1, the durability of the urethane (meth)acrylate is poor. If the value exceeds 20, the viscosity increases and handling may become difficult. Therefore, m is 1-20, preferably 2-10, and more preferably 2-6.

[0030] Polyether polycarbonate diol (a2-1) is a polyoxyalkylene glycol The copolymer is prepared by subjecting a carboxylic acid to a polymerization reaction with a carbonate compound in the presence of a catalyst according to a conventional method. It can be manufactured.

[0031] Polyoxyethylene used in the production of polyether polycarbonate diol (a2-1) Kylene glycol is a type of polyethylene glycol, polypropylene glycol, polytetrafluoroethylene glycol, Methylene ether glycol, 3-methyltetrahydrofuran and tetrahydrofuran Polymerized polytetramethylene ether glycol, neopentyl glycol and tetrahydrofuran Ran copolymer polyether polyol, copolymer of ethylene oxide and tetrahydrofuran Synthetic polyether polyol, copolymerized polyester of propylene oxide and tetrahydrofuran A methyl ether glycol is preferred from the viewpoint of the mechanical strength of the resulting urethane (meth)acrylate. Preferably, polytetramethylene ether glycol (PTMG) is more preferred. The polyoxyalkylene glycols may be used alone or in combination of two or more. They may be used in combination.

[0032] Polyoxyethylene used in the production of polyether polycarbonate diol (a2-1) The number average molecular weight (Mn) calculated from the hydroxyl value of polyethylene glycol is preferably 150 to 20 00, more preferably 200 to 1500, and even more preferably 250 to 1200. If the molecular weight is less than 300, the flexibility of the resulting urethane (meth)acrylate tends to be poor. When the viscosity exceeds 2000, the viscosity of the obtained polyether polycarbonate diol (a2-1) is The hardness and crystallinity become high, making it difficult to handle and also making it difficult to mix with other polyols. As a result, the transparency of the resulting urethane (meth)acrylate tends to decrease. The number average molecular weight (Mn) calculated from the hydroxyl value is specifically described in the Examples section below. It is measured by the method used.

[0033] Carbonates that can be used to produce polyether polycarbonate diol (a2-1) The compound is not limited as long as it does not impair the effects of the present invention, but may be a dialkyl carbonate. These include aryl carbonates, diaryl carbonates, and alkylene carbonates. Among these, dialkyl carbonate is preferred from the viewpoint of reactivity. and alkylene carbonates are preferred.

[0034] Specific examples of carbonate compounds include dimethyl carbonate and diethyl carbonate. , dibutyl carbonate, diphenyl carbonate, ethylene carbonate, etc. , dimethyl carbonate and ethylene carbonate are preferred.

[0035] When producing the polyether polycarbonate diol (a2-1), a polymerization promoter is used. For this purpose, an ester exchange catalyst can be used as needed. As a transesterification catalyst, any compound that is generally considered to have transesterification ability can be used. It can be used without restrictions.

[0036] Examples of transesterification catalysts include lithium, sodium, potassium, rubidium, and cerium. The long-form periodic table (hereinafter simply referred to as the "periodic table"), which includes Group 1 metals (excluding hydrogen), such as sodium Compounds of Group 2 of the periodic table, such as magnesium, calcium, strontium, and barium Compounds of metals; compounds of metals in Group 4 of the periodic table, such as titanium and zirconium; compounds of metals in Group 4 of the periodic table, such as hafnium Compounds of metals in Group 5 of the Periodic Table; compounds of metals in Group 9 of the Periodic Table, such as cobalt; compounds of metals in Group 1 of the Periodic Table, such as zinc Compounds of Group 2 metals; Compounds of Group 13 metals such as aluminum; Germanium, tin Compounds of metals in Group 14 of the Periodic Table, such as lead; compounds of metals in Group 15 of the Periodic Table, such as antimony and bismuth Compounds of lanthanide metals such as lanthanum, cerium, europium, and ytterbium Among these, from the viewpoint of increasing the transesterification reaction rate, Compounds of Group 1 metals (excluding hydrogen), compounds of Group 2 metals, compounds of Group 4 metals Compounds of metals in group 5 of the periodic table, compounds of metals in group 9 of the periodic table, compounds of metals in group 12 of the periodic table Compounds of metals of Group 13 of the periodic table and compounds of metals of Group 14 of the periodic table are preferred. Compounds of metals of Group 1 of the periodic table (excluding hydrogen), compounds of metals of Group 2 of the periodic table are more preferred, Compounds of metals of Group 2 of the Periodic Table are more preferred. Among compounds of metals of Group 1 of the Periodic Table (excluding hydrogen), However, lithium, potassium, and sodium compounds are preferred, and lithium and sodium compounds Compounds of Group 2 metals of the periodic table are more preferred, and compounds of sodium are even more preferred. Among these, magnesium, calcium and barium compounds are preferred, and calcium, magnesium and barium compounds are preferred. Compounds of cadmium are more preferred, and compounds of magnesium are even more preferred. Metal compounds are mainly used as hydroxides or salts. Examples of salts used as salts are: Examples include halide salts such as chlorides, bromides, and iodides; acetates, formates, and benzoates. Carboxylic acid salts; inorganic acid salts such as carbonates and nitrates; methanesulfonic acid and toluenesulfonic acid , sulfonates such as trifluoromethanesulfonic acid; phosphates, hydrogen phosphates, diphosphates Examples of the catalyst metal include phosphorus-containing salts such as hydrogen salts; acetylacetonate salts; etc. It can also be used as an alkoxide such as methoxide or ethoxide.

[0037] Among these, it is preferable to use at least one metal selected from Group 2 metals of the periodic table. Acid salts, nitrates, sulfates, carbonates, phosphates, hydroxides, halides, acetylacetonates Preferably, acetates and carbonates of metals in Group 2 of the periodic table are used. Hydroxides and acetylacetonates are used, and magnesium and calcium are more preferred. Acetates, carbonates, hydroxides and acetylacetonates of ammonium are used, and particularly preferred are Magnesium and calcium acetate and acetylacetonate salts are used, most preferably Magnesium acetylacetonate is used.

[0038] In the production of polyether polycarbonate diol (a2-1), carbonation The amount of the mixture used is not particularly limited, but is usually 1 mole of polyoxyalkylene glycol in total. The molar ratio of the hydroxyl group to the hydroxyl group is preferably 0.35, more preferably 0.50, and even more preferably 0.60. The upper limit is preferably 1.00, more preferably 0.98, and even more preferably 0.60. The preferred value is 0.97. If the amount of carbonate compound used exceeds the upper limit, the resulting power The proportion of the ether polycarbonate diol (a2-1) whose terminal groups are not hydroxyl groups is If the molecular weight is less than the lower limit, the molecular weight may not be within the specified range. In some cases, polymerization may not proceed until the

[0039] In producing the polyether polycarbonate diol (a2-1), When a transesterification catalyst is used, the amount used is determined based on the amount of the resulting polycarbonate diol (a2 -1) It is preferable that the amount remaining in the catalyst is such that it does not affect the performance.

[0040] The amount of transesterification catalyst used is determined based on the weight of the raw material polyoxyalkylene glycol. The upper limit of the metal weight ratio is preferably 500 ppm by weight, and 100 ppm by weight. More preferably, it is 50 ppm by weight, and even more preferably, it is 10 ppm by weight. On the other hand, the lower limit is 0.01, which is an amount that provides sufficient polymerization activity. It is preferably 0.1 ppm by weight, more preferably 1 ppm by weight. More preferably, it is ppm.

[0041] The reaction temperature during the transesterification reaction can be any temperature that provides a practical reaction rate. Generally, the lower limit of the reaction temperature is preferably 70°C, and the lower limit of the reaction temperature is preferably 100°C. The upper limit of the reaction temperature is generally 100°C, more preferably 130°C, and even more preferably 130°C. The temperature is usually preferably 250°C, more preferably 230°C, and more preferably 200°C. It is more preferable that the reaction temperature is set to the above upper limit or less. The polycarbonate diol (1) may be colored or an ether structure may be generated, which may cause quality problems. This can prevent problems from occurring.

[0042] Furthermore, ester interchange to produce polyether polycarbonate diol (a2-1) can be carried out. It is preferable to keep the reaction temperature at 180°C or less throughout the entire conversion reaction, and 170°C or less. It is more preferable to keep the temperature at 160°C or lower, and even more preferable to keep the temperature at 160°C or lower. By keeping the temperature below 180°C, it is possible to prevent discoloration under certain conditions. Cut.

[0043] Although the transesterification reaction can be carried out at atmospheric pressure, the transesterification reaction is an equilibrium reaction. By distilling off the low-boiling components produced, the reaction can be biased towards the product system. In the latter half of the reaction, it is usually preferable to carry out the reaction under reduced pressure while distilling off low-boiling components. Alternatively, the pressure may be gradually reduced during the reaction to distill off the low-boiling components produced during the reaction. It is also possible to carry out the reaction by increasing the degree of pressure reduction especially towards the end of the reaction. By-products such as monoalcohols, phenols, and cyclic carbonates can be distilled off. In this case, the upper limit of the reaction pressure at the end of the reaction is preferably 10 kPa. The pressure is preferably 5 kPa, more preferably 1 kPa. In order to effectively distill off the boiling components, inert gases such as nitrogen, argon, and helium are introduced into the reaction system. The reaction can also be carried out while passing an active gas through the reaction system.

[0044] When a low boiling point carbonate compound is used in the transesterification reaction, the carbon The reaction is carried out near the boiling point of the carbonate compound, and as the reaction progresses, the temperature is gradually increased. It is also possible to adopt a method in which the reaction proceeds further. This can prevent the initial distillation of unreacted carbonate compound.

[0045] Furthermore, in order to prevent these raw materials from distilling off, a reflux duct is attached to the reactor to prevent the carbonate compound from being distilled off. It is also possible to carry out the reaction while refluxing the mixture. In this case, the raw materials charged are not lost and the reagents are The ratio of the amounts can be accurately adjusted.

[0046] The polymerization reaction can be carried out in a batch or continuous manner, but the continuous method is preferred due to the stability of the product. The apparatus used may be of any type, such as a tank type, a tubular type, or a column type. A known polymerization vessel equipped with various stirring blades can be used. There are no particular restrictions on the atmosphere, but from the viewpoint of product quality, it is recommended to use an inert gas such as nitrogen gas at normal pressure or It is preferable to carry out the reaction under reduced pressure.

[0047] The polymerization reaction is carried out by: The reaction time required for polymerization is determined by the amount of the polymer used. The presence or absence of polyoxyalkylene glycol, carbonate compound, and catalyst used It is difficult to generalize because it varies greatly depending on the type and the job, but it is usually less than 50 hours. It is preferable that the time is 30 hours or less, more preferably 20 hours or less. It is more preferable that:

[0048] When a catalyst is used in the polymerization reaction, the polyether polycarbonate diol obtained is usually The catalyst remains in the polymer (a2-1), and the remaining catalyst makes it possible to control the polyurethane reaction. In order to suppress the effects of this residual catalyst, A catalyst deactivator such as a phosphorus compound is added in an amount approximately equimolar to the transesterification catalyst to deactivate the transesterification catalyst. Furthermore, after adding the catalyst deactivator, it is preferable to deactivate the catalyst by heat treatment or the like as described below. The transesterification catalyst can be efficiently deactivated.

[0049] Examples of phosphorus compounds used to inactivate the transesterification catalyst include phosphoric acid, Inorganic phosphates such as phosphoric acid, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, Examples include organic phosphates such as triphenyl phosphate and triphenyl phosphite. These may be used alone or in combination of two or more.

[0050] The amount of the phosphorus-based compound used is not particularly limited, but may be determined based on the amount of the transesterification catalyst used. It is sufficient if the molar ratio is approximately equimolar. Specifically, the above ratio is 1 mol per 1 mol of the transesterification catalyst used. The upper limit is preferably 5 mol, more preferably 2 mol, and the lower limit is preferably 0.8 mol. 1.0 mol, more preferably 1.0 mol. When a phosphorus compound is used in an amount less than this, In this case, the transesterification catalyst in the reaction product is not sufficiently inactivated, and the resulting polyether Polycarbonate diol (a2-1) is used as a raw material for producing urethane (meth)acrylate. When used as a diol, the isocyanate group of the polyether polycarbonate diol (1) is In addition, phosphorus exceeding this range may not be able to sufficiently reduce reactivity. When a compound based on the above is used, the resulting polyether polycarbonate diol (a2-1) is It may become discolored.

[0051] The deactivation of the transesterification catalyst by adding a phosphorus compound can be carried out even at room temperature. However, heat treatment is more effective. There is no particular limitation on the temperature of this heat treatment. However, the upper limit is preferably 180°C, more preferably 150°C, and even more preferably 120°C. ° C., particularly preferably 100 ° C., and the lower limit is preferably 50 ° C., more preferably 60 ° C. At temperatures lower than this, the transesterification catalyst may become inactive. Inactivation takes time and is inefficient, and the degree of inactivation may be insufficient. At temperatures above 80°C, the resulting polyether polycarbonate diol (a2-1) The reaction time with the phosphorus compound is not particularly limited, but It usually takes 1 to 5 hours.

[0052] The amount of catalyst remaining in the polyether polycarbonate diol (a2-1) is From the viewpoint of controlling the urethane reaction, the metal equivalent amount should be 100 ppm by weight or less, especially 10 ppm by weight. On the other hand, the required amount of catalyst is 0.01 weight p in terms of metal. pm or more, particularly 0.1 ppm by weight or more, and particularly 5 ppm by weight or more. .

[0053] Polyether polycarbonate diol (a2-1) contains the following as raw materials used in the production: Polyether polycarbonate diol The amount of the carbonate compound remaining in (a2-1) is not limited, but it is preferable that it is small. The upper limit of the weight ratio to the polycarbonate diol (a2-1) is preferably The content is preferably 5% by weight, more preferably 3% by weight, and even more preferably 1% by weight. If the carbonate compound content of the diol polycarbonate (a2-1) is too high, the poly On the other hand, there is no particular lower limit, but it is preferable that or 0.1% by weight, more preferably 0.01% by weight, and even more preferably 0% by weight. .

[0054] Polyether polycarbonate diol (a2-1) is the polyoxyethylene diol used in the production Alkylene glycol may remain. Polyether polycarbonate diol ( The amount of polyoxyalkylene glycol remaining in a2-1) is not limited, but , the smaller the better, and the weight ratio to polyether polycarbonate diol (1) The content is preferably 1% by weight or less, more preferably 0.1% by weight or less, and even more preferably The content of the polyether polycarbonate diol (a2-1) is 0.05% by weight or less. If the amount of polyoxyalkylene glycol remaining is large, the urethane (meth)acrylate and When the soft segment is polymerized, the molecular length of the soft segment may be insufficient, and the desired physical properties may not be obtained.

[0055] The lower limit of the hydroxyl value of polyether polycarbonate diol (a2-1) is usually 22.4 mg-KOH / g, preferably 28.1 mg-KOH / g, more preferably 37.4 mg -KOH / g, the upper limit is usually 187.0 mg-KOH / g, preferably 140.3 mg- KOH / g, more preferably 112.2 mg-KOH / g. If the viscosity is less than 100%, the viscosity will be too high and handling during polyurethane conversion may become difficult. If the above upper limit is exceeded, the flexibility of the resulting urethane (meth)acrylate may be insufficient. There is. The hydroxyl value of the polyether polycarbonate diol (a2-1) is specifically It is measured by the method described in the Examples section of the present application.

[0056] In addition, the hydroxyl value of the polyether polycarbonate diol (a2-1) used in the present invention The lower limit of the number average molecular weight (Mn) calculated from the above is preferably 600, more preferably 80 0, more preferably 1000. On the other hand, the upper limit is preferably 5,000, more preferably Preferably it is 4,000, more preferably 3,000. If the Mn of the urethane diol is less than the lower limit, the urethane (meth)acrylate will not be flexible. On the other hand, if the temperature exceeds the upper limit, the viscosity increases and the polyurethane This may impair handling during conversion.

[0057] <Polyols other than polyether polycarbonate diol (a2-1)> The polyurethane form when producing the urethane (meth)acrylate compound (A) of the present invention In the synthesis reaction, polyether polycarbonate diol (a2-1) and, if necessary, Other polyols may be used in combination. The polyols other than the polyol (a2-1) are those used in the production of ordinary polyurethanes. The polyols are not particularly limited, and examples thereof include polyester polyols, polycaprolactone polyols, Polycarbonate polyols other than the polycarbonate diols of the invention are particularly preferred. The use of polyol (a2-2) having a number average molecular weight of 300 or less improves the elongation and abrasion resistance of the rubber. This is preferable in that the lance can be adjusted.

[0058] <Polyol (a2-2)> Examples of the polyol (a2-2) include ethylene glycol and diethylene glycol. propylene glycol, dipropylene glycol, trimethylene glycol, dimethyl propane, neopentyl glycol, 2,2-diethyl-1,3-propanediol 2-butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylenediol 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-Pentamethylenediol, 1,6-Hexamethylenediol, 3-Methyl-1, 5-Pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, Pentaerythritol diacrylate, 1,9-nonanediol, 2-methyl-1,3-hexanediol aliphatic alcohols such as 1,8-octanediol and 2-methyl-1,8-octanediol; 4-Cyclohexanediol, cyclohexyldimethanol, tricyclodecane dimethano alicyclic diols such as ethanol, bisphenols such as bisphenol A, xylitol and sorbitol These include sugar alcohols such as sorbitol, and these can be used alone or in combination of two or more. You can be there. Among these, from the viewpoint of preventing yellowing of the cured coating film, compounds with structures that do not contain aromatic rings or unsaturated groups are preferred. Preferred are aliphatic alcohols, particularly preferred are neopentyl glycols. It's a call.

[0059] [Hydroxyl group-containing (meth)acrylate (a3)] Examples of the hydroxyl group-containing (meth)acrylate (a3) ​​include 2-hydroxyethyl ( meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxy The alkyl group such as hexyl (meth)acrylate has 1 to 16 carbon atoms (preferably 1 to 1 2) Hydroxyalkyl (meth)acrylate; 2-hydroxyethyl acryloyl acrylate Phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate , caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol Glycidyl (meth)acrylate, fatty acid modified glycidyl (meth)acrylate, polyethylene Polypropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate Compounds having one (meth)acryloyl group such as glycerin di(meth)acrylate, 2-Hydroxy-3-acryloyl-oxypropyl methacrylate, Pentaerythritol Pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate Acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate , dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol Ethritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol Pentaerythritol penta(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate Examples include compounds having two or more (meth)acryloyl groups, such as acrylate. These may be used alone or in combination of two or more.

[0060] Among these, hydroxyl group-containing (meth)acryloyl groups having two or more (meth)acryloyl groups in the molecule are The reason why acrylates can provide a suitable crosslinking structure to the cured coating film and also provide abrasion resistance is that For this reason, glycerin di( meth)acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate It is.

[0061] [Preparation of urethane (meth)acrylate (A)] The urethane (meth)acrylate (A) used in the present invention may be, for example, the above-mentioned polyisocyanate. Anate (a1), polyether polycarbonate diol (a2-1), polyol ( a2-2), a hydroxyl group-containing (meth)acrylate (a3), and It can be produced by separately charging and reacting the components, but polyether polycarbonate Diol (a2-1) and polyol (a2-2), and polyisocyanate (a1) and then reacting the above with each other in advance, and then adding a hydroxyl group-containing (meth)acrylate (a3) ​​to the reaction product. This reaction is useful in terms of the stability of the reaction and the reduction of by-products.

[0062] In order to obtain the urethane (meth)acrylate (A) in a high yield, a polyisocyanate (a1), polyether polycarbonate diol (a2-1), polyol (a2 -2) and the hydroxyl group-containing (meth)acrylate (a3) ​​have the following molar ratio: preferable.

[0063] Alicyclic structure-containing polyisocyanate (a1), polyether polycarbonate diol ( The reaction of (a2-1) with polyol (a2-2) can be carried out by a known reaction method. In this case, for example, the isocyanate group in the polyisocyanate (a1) and the isocyanate group in the polyol Hydroxyl groups ((hydroxyl groups in polyether polycarbonate diol (a2-1) and polyol The molar ratio of isocyanate groups to hydroxyl groups is usually 2: By adjusting the ratio to about 1-15:14, it is possible to obtain a terminal isocyanate with the isocyanate group remaining. The terminal isocyanate group-containing urethane (meth)acrylate can be obtained. The nate group can undergo an addition reaction with a hydroxyl group-containing (meth)acrylate (a3).

[0064] The alicyclic structure-containing polyisocyanate (a1) and polyether polycarbonate diisocyanate (a2) are a reaction product obtained by previously reacting polyol (a2-1) with polyol (a2-2); The addition reaction with the hydroxyl group-containing (meth)acrylate (a3) ​​is also carried out using known reaction means. It is possible.

[0065] The reaction molar ratio of the reaction product to the hydroxyl group-containing (meth)acrylate (a3) ​​can be, for example, The isocyanate (a1) has two isocyanate groups and is a hydroxyl group-containing (meth)acrylate. When (a3) ​​has one hydroxyl group, the reaction product is a hydroxyl group-containing (meth)acrylate. (a3) is about 1:2, and the polyisocyanate (a1) has three isocyanate groups. When the hydroxyl group-containing (meth)acrylate (a3) ​​has one hydroxyl group, the reaction product : hydroxyl group-containing (meth)acrylate (a3) ​​is about 1:3.

[0066] In the addition reaction between this reaction product and the hydroxyl group-containing (meth)acrylate (a3), The reaction is terminated when the residual isocyanate group content in the reaction system reaches 0.3% by weight or less. This gives the urethane (meth)acrylate (A).

[0067] Regarding the reaction conditions, for example, the reaction temperature is In order to obtain A) in a good yield, it is preferable to set the temperature in the range of about 30 to 80°C. In order to control the temperature, it is appropriate to carry out the reaction at 60 to 70°C. The reaction time is usually 2 to 5 minutes. The time is 10 hours, preferably 3 to 8 hours.

[0068] The polyisocyanate (a1) and the polyether polycarbonate diol (a2- 1) with polyol (a2-2), and then reacting the reaction product with a hydroxyl group-containing (meth)acrylate. In the reaction with the acrylate (a3), it is preferable to use a catalyst to promote the reaction. Examples of the catalyst include dibutyltin dilaurate, dibutyltin diacetate, Trimethyltin hydroxide, tetra-n-butyltin, zinc bisacetylacetonate, di Zirconium tris(acetylacetonate)ethyl acetoacetate, Zirconium tetraacetate organometallic compounds such as acetylacetonate, tin octenoate, zinc hexanoate, octenoic acid Zinc stearate, Zinc 2-ethylhexanoate, Zirconium naphthenate, Cobalt naphthenate, Stannous chloride, stannous chloride, metal salts such as potassium acetate, triethylamine, triethylenediamine Amine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1 ,8-diazabicyclo[5,4,0]-7-undecene, N,N,N',N'-tetramethyl Amino acids such as methyl-1,3-butanediamine, N-methylmorpholine, and N-ethylmorpholine In addition to carbon-based catalysts, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc., organic bismuth compounds such as rubismuth dilaurate and dioctyl bismuth dilaurate, Bismuth 2-ethylhexanoate, Bismuth naphthenate, Bismuth isodecanoate, Bismuth decanoate, bismuth laurate, bismuth maleate, bismuth stearate Bismuth salts, bismuth oleate salts, bismuth linoleate salts, bismuth acetate salts, bismuth linoleate salts, Organic acid bismuth salts such as bisneodecanoate, bismuth disalicylate, and bismuth digallate Examples of suitable catalysts include bismuth salts, and among these, dibutyltin dilaurate, 1,8-di Azabicyclo[5,4,0]-7-undecene is preferred. Alternatively, two or more of them may be used in combination.

[0069] The amount of the catalyst is usually 0.01 to 1,000 ppm based on the total amount of the reaction components. The concentration is preferably 0.1 to 500 ppm, and particularly preferably 1 to 300 ppm.

[0070] During the reaction, an organic solvent may be used as needed. Examples of the solvent include acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone. Ketones such as ethanol, cellosolves such as ethyl cellosolve, aromatics such as toluene and xylene acetic acid esters such as methyl acetate, ethyl acetate, and butyl acetate. The organic solvents may be used alone or in combination of two or more kinds.

[0071] The number of ethylenically unsaturated groups contained in the urethane (meth)acrylate (A) is It is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0072] The weight average molecular weight of the urethane (meth)acrylate (A) is preferably 1,000 5,000 to 50,000, more preferably 3,000 to 45,000, and particularly preferably 5, The weight average molecular weight of the urethane (meth)acrylate (1) is 0,000 to 40,000. If the value is too small, the concentration of ethylenically unsaturated groups in the cured coating film will be relatively high, and the cured coating film and When the coating is applied, it tends to be difficult to obtain the extensibility of the coating film, and the urethane (meth)acrylate (A) If the weight average molecular weight is too large, the viscosity will increase and the reaction control will become difficult. In addition, the concentration of ethylenically unsaturated groups in the cured coating film becomes relatively small, resulting in a low crosslink density. Although the cured coating film has good extensibility, its abrasion resistance tends to be low.

[0073] The weight average molecular weight is calculated based on the molecular weight of standard polystyrene. A high-performance liquid chromatograph (Tosoh Corporation, "HLC-8320GPC") was installed with a column: 1 tube of SKguardcolumn SuperHZ-L, 1 tube of TSKgel SuperHZ Two MMs and one TSKgel SuperHZ2000 were used in series, for a total of four. It is measured by

[0074] <Photopolymerization initiator (B)> In the active energy ray-curable resin composition of the present invention, in order to impart curability, It is preferable to further contain a photopolymerization initiator (B).

[0075] There are no particular restrictions on the photopolymerization initiator (B) as long as it generates radicals by the action of light. Examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenone, Nylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy) Phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy- 2-Methyl-1-propan-1-one, 2-methyl-2-morpholino(4-thiomethylfuran) phenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholino (phenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl) Acetophenones such as phenyl]propanone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isopropyl Benzoins such as benzoyl ether; benzophenone, methyl o-benzoylbenzoate, 4-Phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide , 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 2 ,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2- (1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4 benzophenones such as 2-benzoylbenzyltrimethylammonium chloride; 4-Isopropylthioxanthone, 2,4-diethylthioxanthone Santone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthon 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxane Thioxanthones such as thion-9-one mesochloride; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2, 4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethyl acylphosphonoxides such as benzoyl)-phenylphosphine oxide; These photopolymerization initiators (B) may be used alone or in combination of two or more. The above can also be used in combination.

[0076] In addition, triethanolamine and triisopropanol are used as assistants for the photopolymerization initiator (B). Aminobenzophenone (Michler's ketone), 4,4'-dimethylaminobenzophenone Ethylaminobenzophenone, 2-dimethylaminoethylbenzoate, 4-dimethylamino Ethyl benzoate, 4-dimethylaminobenzoate (n-butoxy)ethyl, 4-dimethylamino Isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diaminobenzoate Ethylthioxanthone, 2,4-diisopropylthioxanthone, etc. can also be used in combination. These auxiliary agents may be used alone or in combination of two or more.

[0077] Regarding the content of the photopolymerization initiator (B), When using the ethylenically unsaturated compound (C) described below, the total amount including it shall be 100% by weight. The amount is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight. The content is preferably 1 to 7.5 parts by weight, and more preferably 1 to 7.5 parts by weight. If the content is too small, the curing If the amount is too large, it will cause yellowing of the cured coating film. This makes them prone to coloration problems.

[0078] Ethylenically unsaturated compounds (C) The active energy ray-curable resin composition may contain, as necessary, a photopolymerization initiator (B), Ethylenically unsaturated compounds (C) other than urethane (meth)acrylate compounds (A), It is possible to add polymers such as acrylic resin, surface conditioners, leveling agents, polymerization inhibitors, etc. In addition, dyes, pigments, oils, plasticizers, waxes, drying agents, dispersants, wetting agents, emulsifiers, gels Antioxidants, flame retardants, antistatic agents, electrolyte salts, fillers, stabilizers, reinforcing agents, matting agents , crosslinking agent, UV absorber, weathering agent, light stabilizer, thickener, rust inhibitor, adhesion improver, film-forming agent It is also possible to compound abrasives, organic fine particles, inorganic particles, etc. Compounds that cause crosslinking when heated, specifically epoxy compounds and aziricin compounds Compounds such as melamine compounds, isocyanate compounds, and chelate compounds can also be used.

[0079] Ethylenically unsaturated compounds (excluding urethane (meth)acrylate compounds (A) ] (C) may be, for example, a urethane (meth)acrylate compound (C1) and / or Ethylenically unsaturated monomers (C2) are preferred.

[0080] [Urethane (meth)acrylate compounds (C1)] The urethane (meth)acrylate compound (C1) is represented by the following general formula (2): The urethane (meth)acrylate compound (C1-1) is used for various purposes. This is preferable in that it is easy to impart the required physical properties even when the material is used.

[0081] [ka] (In the above formula (2), R1 represents a urethane bond residue of a polyisocyanate compound, and R2 represents a hydroxyl group. The urethane bond residue of the (meth)acrylate compound contained, and n is an integer of 2 to 10.

[0082] The urethane (meth)acrylate (C1-1) represented by the above formula (2) (hereinafter referred to as "urethane (Meth)acrylate compounds (C1-1) are sometimes abbreviated as "(meth)acrylate compounds (C1-1)". A compound obtained by reacting a acrylate compound with a hydroxyl group-containing (meth)acrylate compound. That is why.

[0083] In the above formula (2), n may be an integer of 2 to 10, preferably 2 to 6, and particularly preferably is 2 to 3.

[0084] Examples of such polyvalent isocyanate compounds include the above-mentioned urethane (meth)acrylates. In the explanation of the polyisocyanate (A), the polyisocyanate compound (a1) is exemplified. The same as above can be mentioned.

[0085] Examples of such hydroxyl group-containing (meth)acrylate compounds include the above-mentioned urethane (meth)acrylates. p) In the explanation of acrylate (A), hydroxyl group-containing (meth)acrylate compounds Examples include the same as those given as examples for (a3).

[0086] The urethane (meth)acrylate compound (C1-1) can be produced by a known general urethane (meth)acrylate method. The compound may be produced in accordance with the method for producing a methacrylate compound.

[0087] The ethylenically unsaturated fatty acid contained in the urethane (meth)acrylate compound (C1-1) The number of the substituted groups is preferably 2 to 30, particularly preferably 2 to 15, and further preferably Preferably 2 to 6. If the number of ethylenically unsaturated groups is too small, the coating film tends not to have sufficient hardness or scratch resistance. If the amount is too high, the coating shrinks during curing, which can lead to poor adhesion to the substrate and make the coating brittle. There is a tendency to

[0088] The weight average molecular weight of the urethane (meth)acrylate compound (C1) is 400 to 800 ,000, more preferably 800 to 50,000, and particularly preferably 1000 to 10, If the weight average molecular weight is too small, the coating hardness and yield strength may be poor. It tends to be difficult to maintain a balance of shrinkage and the weight average molecular weight is too large. If the thickness is too small, it tends to be difficult to maintain scratch resistance and hardness.

[0089] [Ethylenically unsaturated monomer (C2)] The ethylenically unsaturated monomer (C2) is a monomer having one or more ethylenically unsaturated Ethylenically unsaturated monomers having a group (except urethane (meth)acrylate compounds) (C1) is excluded), and examples thereof include monofunctional monomers, bifunctional monomers, trifunctional or higher functional monomers. Examples of the monomer include:

[0090] The monofunctional monomer may be any monomer containing one ethylenically unsaturated group. For example, styrene, vinyltoluene, chlorostyrene, α-methylstyrene, methyl(methyl)styrene, (meth)acrylate, ethyl (meth)acrylate, acrylonitrile, vinyl acetate, 2- Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate acrylate, phenoxyethyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate , 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate ) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclohexyl Dicyclopentenyl (meth)acrylate, n-butyl ( (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, Octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, n-stearyl Benzyl (meth)acrylate, benzyl (meth)acrylate, phenol ethylene oxide Modified (meth)acrylate, nonylphenol propylene oxide modified (meth)acrylate phthalate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, etc. Half ester (meth)acrylate of carboxylic acid derivatives, furfuryl (meth)acrylate, Carbitol (meth)acrylate, benzyl (meth)acrylate, butoxyethyl ( (meth)acrylate, allyl (meth)acrylate, acryloylmorpholine, 2-hydroxybenzoate Hydroxyethyl acrylamide, N-methylol (meth)acrylamide, N-vinylpyrrolidone Rolidone, 2-vinylpyridine, 2-(meth)acryloyloxyethyl acid phosphite ester monoesters, etc.

[0091] In addition to the above monofunctional monomers, Michael adducts of acrylic acid or 2-acrylic acid Also included are triethyloxyethyl dicarboxylic acid monoesters, Michael adducts of acrylic acid Examples include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, and methacrylic acid dimer. acrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc. 2-Acryloyloxyethyl dicarboxylic acid monoesters, which are carboxylic acids with specific substituents Examples of esters include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, Acryloyloxyethyl succinate monoester, 2-acryloyloxyethyl phthalate Monoester, 2-methacryloyloxyethyl phthalate monoester, 2-acryloyl 2-Methacryloyloxyethyl hexahydrophthalic acid monoester, and hydroxyhydrophthalic acid monoesters. Furthermore, oligoester acrylates are also available. Examples include:

[0092] The bifunctional monomer may be any monomer containing two ethylenically unsaturated groups. For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate Acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol Dipropylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol Polyethylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate Butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, propylene glycol Dimethicone-modified bisphenol A di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,6-hexanediol ethylene oxide modified di(meth)acrylate di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate ) acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, di Ethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate Diester di(meth)acrylate, hydroxypivalic acid modified neopentyl glycol Di(meth)acrylate, isocyanuric acid ethylene oxide modified diacrylate, 2- (Meth)acryloyloxyethyl acid phosphate diester and the like.

[0093] The tri- or higher functional monomer is a monomer containing three or more ethylenically unsaturated groups. For example, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, Acrylate, Pentaerythritol Tri(meth)acrylate, Pentaerythritol Dipentaerythritol tetra(meth)acrylate, Dipentaerythritol tetra(meth)acrylate, Di Pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate p) acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, Glycerin polyglycidyl ether poly(meth)acrylate, ethylene isocyanurate Oxide-modified triacrylate, ethylene oxide-modified dipentaerythritol pentaerythritol (meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate ) acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate Ethylene oxide modified pentaerythritol tetra(meth)acrylate, caproic acid Lactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified Dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol erythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra( meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, etc. Examples include:

[0094] These ethylenically unsaturated monomers (C2) may be used alone or in combination of two or more. That's fine.

[0095] In addition, the ethylenically unsaturated monomer (C2) is suitable for use in polymers because it is easy to adjust the physical properties of elongation and scratch resistance. , acryloylmorpholine, dicyclopentenyl (meth)acrylate, trimethylol Propane tri(meth)acrylate, glycerin triacrylate, pentaerythritol Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. It is preferable that the monomer is a mono- to tetra-functional monomer.

[0096] As the ethylenically unsaturated compound (C), a urethane (meth)acrylate compound (C1 Inclusion of (C1) and (C2) when using (C1) and ethylenically unsaturated monomer (C2) in combination The ratio (by weight) of (C1):(C2) is preferably 5:95 to 95:5. It is particularly preferable that (C1):(C2)=20:80 to 80:20.

[0097] The content of the ethylenically unsaturated compound (C) is not particularly limited as long as it does not impair the physical properties. However, the amount of the urethane (meth)acrylate (A) is 0 to 100 parts by weight. parts by weight, more preferably 0 to 95 parts by weight, and particularly preferably 0 to 90 parts by weight, and more preferably 0 to 85 parts by weight.

[0098] Additives The surface conditioner is not particularly limited, and examples thereof include cellulose resins and alkyd resins. Such cellulose resin has the effect of improving the surface smoothness of the coating film. The alkyd resin has the effect of imparting film-forming properties during application.

[0099] As a leveling agent, it has the effect of imparting wettability to the substrate and reducing surface tension. Any known leveling agent can be used, for example, a silicone-modified resin. Examples of the resin that can be used include grease, fluorine-modified resin, and alkyl-modified resin.

[0100] Examples of the polymerization inhibitor include p-benzoquinone, naphthoquinone, toluquinone, 2,5 -Diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butyl hydroquinone Hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t-butyl halides Hydroquinone, pt-butylcatechol, etc.

[0101] Furthermore, the active energy ray-curable resin composition of the present invention may be coated with a suitable viscosity at the time of application, if necessary. To make the composition more uniform, it is also preferable to use an organic solvent for dilution. Examples of the agent include methanol, ethanol, n-propyl alcohol, and isopropyl Alcohol, n-butanol, isobutanol, and other alcohols, acetone, methyl iso Ketones such as butyl ketone, methyl ethyl ketone, cyclohexanone, ethyl cellosolve Cellosolves such as toluene and xylene, aromatics such as propylene glycol monomethyl ether Glycol ethers such as ether, methyl acetate, ethyl acetate, butyl acetate, 2-methyl acetate Acetic acid esters such as 1-methyl-2-thiazolinone, diacetone alcohol, tetrahydrofuran, These organic solvents may be used alone or in combination of two or more. You may do so.

[0102] In producing the active energy ray-curable resin composition of the present invention, P) There are no particular limitations on the method of mixing the acrylate compound (A) and other components. They are not necessarily mixed together, but can be mixed by various methods.

[0103] The active energy ray-curable resin composition of the present invention can be used as a top coating agent or anchor for various substrates. It is effectively used as a curable resin composition for forming a coating film, such as a coating agent. After coating the active energy ray curable resin composition on the substrate (coating the composition diluted with an organic solvent), If the adhesive is dried, it is cured by irradiating it with active energy rays. do.

[0104] <Coating agents, sheets> The active energy ray-curable resin composition of the present invention is, for example, suitable for use as a coating agent. It is used.

[0105] Furthermore, the active energy ray-curable resin composition is used as a coating agent, After coating the substrate to form a coating film, the coating film is cured by irradiating it with active energy rays and then peeled off. By separating the particles, a sheet can be produced.

[0106] In the present invention, the term "sheet" conceptually includes sheets and films. That is why.

[0107] The active energy ray-curable resin composition of the present invention can be applied by, for example, spraying, Wet coating such as shower, dip, roll, spin, screen printing, etc. The coating method is an example of such a method, and the coating is usually carried out on a substrate at room temperature.

[0108] An active energy ray curable resin composition coated on a substrate is cured by an active energy ray curable resin composition. Energy rays include far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X-rays, gamma rays, etc. In addition to electromagnetic waves, electron beams, proton beams, neutron beams, etc. can be used, but the curing speed and input power of the irradiation equipment vary. Curing by ultraviolet irradiation is advantageous in terms of ease of handling, cost, etc. In addition, when electron beam irradiation is used, In this case, curing can be achieved without using the photopolymerization initiator (B).

[0109] The substrate to which the active energy ray-curable resin composition of the present invention is applied is a polypropylene film. Olefin resin, polyester resin, polycarbonate resin, acrylic resin, Acrylonitrile butadiene styrene copolymer (ABS), polystyrene resin, cellulose Plastic substrates such as silicone resins and their molded products (films, sheets, cups, etc.) These composite substrates, or composite substrates of the above materials mixed with glass fiber or inorganic materials, etc., metal ( Aluminum, copper, iron, SUS, zinc, magnesium, and their alloys, etc.), glass, etc. Examples of the substrate include a substrate having a primer layer provided thereon.

[0110] The active energy ray-curable resin composition of the present invention can be used without a solvent. When using an organic solvent, the solid content is usually diluted to 10 to 90% by weight. It is preferable to coat the film.

[0111] The coating thickness (film thickness after curing) is usually determined by adding a photopolymerization initiator ( B) In consideration of light transmission so that the reaction is uniform, a thickness of 3 to 1,000 μm is sufficient, and is preferred. Preferably, it is 5 to 500 μm, and particularly preferably, it is 10 to 200 μm.

[0112] The drying conditions when diluting with the organic solvent are usually 40 to 120°C. ° C. (preferably 50 to 100° C.), and the drying time is usually 1 to 20 minutes (preferably 2 to 10 minutes). minutes).

[0113] When the active energy ray-curable resin composition of the present invention is cured by ultraviolet irradiation, High-pressure mercury lamps, ultra-high-pressure mercury lamps, and carbon arc lamps that emit light in the 50 to 450 nm wavelength range , metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, LEDs or the like, usually 30 to 3000 mJ / cm2 (preferably 100 to 1500 mJ / cm2 ) ultraviolet light. After UV irradiation, heating can be carried out as necessary to ensure complete curing. The heat conditions include, for example, a temperature of 120 to 200°C.

[0114] <<Active Energy Ray-Curable Resin Composition>> The active energy ray-curable resin composition of the present invention contains the specific urethane (meth)acrylate. a photopolymerization initiator (B), the specific ethylenically unsaturated monomer (C), and The above-mentioned various additives can be mixed in predetermined amounts to produce the product. do.

[0115] The active energy ray-curable resin composition of the present invention has the following properties: Hard coating agents applied to the surfaces of electronic components, mobile phones such as smartphones, Surfaces of interior and exterior parts for automobiles, sign poles, barber equipment, amusement equipment, etc. It can be used as a material for forming parts, etc. [Example]

[0116] The present invention will be explained in more detail below with reference to examples, but the present invention does not exceed the gist of the present invention. However, the present invention is not limited to the following examples. In the examples, "parts" and "%" are by weight. The weight average molecular weight, number average molecular weight and viscosity were measured by the above-mentioned methods. The measurements were then carried out.

[0117] [Synthesis of Polyether Polycarbonate Diol] Agitator, distillate trap, pressure regulator, 30mmφ structured packing distillation column, fractionator The prepared 2L glass separable flask was filled with polytetramethylene ether (Mitsubishi Chemical Corporation). Glycol PTMG #250 (number average molecular weight 220): 279 g (1.27 mol), Ethylene carbonate (EC): 125 g (1.42 mol), magnesium(II) acetylacetone Add 108 mg (0.49 mmol) of setonate and reduce the pressure to 5 kPa while stirring. The internal temperature was raised to 150°C, and ethylene glycol and ethylene carbonate were azeotropically mixed. The reaction was carried out while the pressure was reduced to 1 kPa over 17.5 hours, and the reactants were removed from the system by evaporation. At the 7-hour and 14-hour reaction times, 33.2 g and 19.4 g of EC were added to the reaction solution. The number average molecular weight was confirmed to be approximately 2000 by NMR, and it was determined to be polyether polycarbonate. Then, a polyether polycarbonate diol-containing composition was obtained. 0.45 g of an 8.5% aqueous solution of phosphoric acid was added to the mixture to deactivate the catalyst. The remaining monomer was removed at 0.5 kPa and 170°C to obtain polyether polycarbonate. A carbonate diol-containing composition was obtained.

[0118] The obtained polyether polycarbonate diol-containing composition was diluted with water at a flow rate of 100 g / min. The solution is sent to a membrane distillation apparatus and thin-film distillation (temperature: 190°C, pressure: 133 Pa) is carried out to obtain the polyethylene terephthalate. The thin-film distillation apparatus used was a 50 m diameter thin-film distillation apparatus. m, height 200 mm, area 0.0314 m2, internal condenser, jacketed Shibata A special model MS-300 molecular distillation apparatus manufactured by Kagaku Co., Ltd. was used.

[0119] [Production Example 1] A four-neck flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet was 300.0 g of ethyl acetate, 249.9 g of hydrogenated xylylene diisocyanate (a1) (1. 29 mol), neopentyl glycol (a2-1) (weight average molecular weight (Mw): 104) 100.5g (0.96 mol), and 0.04g of dibutyltin dilaurate as a reaction catalyst The mixture was charged and reacted at 70°C. When the residual isocyanate group content reached 4.2% or less, the polyisocyanate was removed. Ether carbonate diol (a2-1) (hydroxyl value 57.9 mg KOH / g) 311 0.7g (0.16 mol) was added and the reaction was continued until the residual isocyanate group was 1.4% or less. At this point, 37.9 g (0.33 mol) of 2-hydroxyethyl acrylate was polymerized. 0.4 g of 2,6-di-tert-butyl-4-methylphenol was further added as an inhibitor. The reaction is stopped when the residual isocyanate group is 0.3% or less. As a result, a urethane acrylate compound (A-1) (weight average molecular weight: 17568) was obtained.

[0120] [Production Example 2] A four-neck flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet was 300.0 g of ethyl acetate, 202.4 g of hydrogenated xylylene diisocyanate (a1) (1. 04 mol), neopentyl glycol (a2-1) (weight average molecular weight (Mw): 104) 72.3 g (0.69 mol) of ethanol and 0.04 g of dibutyltin dilaurate as a reaction catalyst. The mixture was then reacted at 70°C. When the residual isocyanate group content was 5.1% or less, the polyester was Tercarbonate diol (a2-1) (hydroxyl value 57.9 mg KOH / g) 336. 6 g (0.17 mol) was added and the reaction was continued until the residual isocyanate group was 1.6% or less. At this point, the glycerin diacrylate (hydroxyl value 223.0 mg KOH / g) was 88. 7g (0.35 mol), 2,6-di-tert-butyl-4-methyl- Add 0.4 g of phenol and react at 60°C until the residual isocyanate group is 0.3% or less. The reaction was terminated when the weight average molecular weight of the urethane acrylate compound (A-2) was The molecular weight obtained was 18903.

[0121] [Comparative Production Example 1] A four-neck flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet was 300.0 g of ethyl acetate, 281.4 g of hydrogenated xylylene diisocyanate (a1) (1. 45 mol), neopentyl glycol (a2-1) (weight average molecular weight (Mw): 104) 100.6g (0.97 mol), and 0.04g of dibutyltin dilaurate as a reaction catalyst The mixture was charged and reacted at 70°C. When the residual isocyanate group content reached 6.0% or less, the polyisocyanate was removed. Carbonate diol (a2-3) (Asahi Kasei Corporation "Duranol T5650J"): 194.7g (0.24 mol) of hydroxyl group value 139.2mgKOH / g was added and the reaction was continued. When the residual isocyanate group was 2.3% or less, glycerin diacrylate was added. (hydroxyl value 223.0 mg KOH / g) 123.3 g (0.49 mol) as a polymerization inhibitor Then, 0.4 g of 2,6-di-tert-butyl-4-methylphenol was further added and the mixture was heated to 60°C. The reaction is stopped when the residual isocyanate group is 0.3% or less. As a result, an acrylate-based compound (A-3) (weight average molecular weight: 11719) was obtained.

[0122] [Comparative Production Example 2] A four-neck flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet was 300.0 g of ethyl acetate, 299.9 g of hydrogenated xylylene diisocyanate (a1) (1. 54 mol), neopentyl glycol (a2-1) (weight average molecular weight (Mw): 104) 107.2g (1.03 mol), and 0.04g of dibutyltin dilaurate as a reaction catalyst The mixture was charged and reacted at 70°C. When the residual isocyanate group content reached 6.1% or less, the polyisocyanate was removed. Ether diol (a2-4) (Hodogaya Chemical Co., Ltd. "PTG-650SN"): hydroxyl value 161.4 g (0.26 mol) of 178.9 mg KOH / g was added and the reaction was further carried out. When the residual isocyanate group is 2.5% or less, glycerin diacrylate (hydroxyl group 131.4g (0.52 mol) of 2,6-dimethyl-2,6-dichloro-1,6-dichloro ... 0.4 g of di-tert-butyl-4-methylphenol was further charged and reacted at 60°C. The reaction is terminated when the residual isocyanate group is 0.3% or less, and the urethane acrylate is A rate-based compound (A-4) (weight average molecular weight: 10,464) was obtained.

[0123] Example 1 For 100 parts of the resin content of the urethane acrylate compound (A-1) prepared in Production Example 1, 1-hydroxycyclohexyl-phenyl-ketone (BASF) was used as a photo-curing initiator. Add 4 parts of Irgacure 184 (manufactured by Japan Co., Ltd.) to make the solid content 40%. Ethyl acetate was added as a diluting solvent to the above composition to obtain a photocurable resin composition. Got it.

[0124] [Example 2, Comparative Examples 1 and 2] Instead of the urethane acrylate compound (A-1) in Example 1, As described above, the urethane acrylates produced in the above Production Example 2 and the above Comparative Production Examples 1 and 2 A photocurable resin composition was obtained in the same manner as in Example 1, except that a carboxylate compound was used.

[0125] The active energy ray-curable resin composition thus obtained was subjected to the following measurements. A sample was prepared and the elongation, abrasion resistance, and solvent resistance of the sample were evaluated as follows. The results are shown in Table 1 below.

[0126] [Preparation of samples for measuring elongation, abrasion resistance, and solvent resistance] The photocurable resin compositions prepared in the examples and comparative examples were molded into easily moldable polyethylene terephthalate (PET). Polyethylene terephthalate (PET) film (manufactured by Teijin DuPont Films Co., Ltd., easy-to-form PET, thickness 100 After drying at 60°C for 3 minutes, the coating was exposed to a high-pressure mercury lamp. The ultraviolet light was irradiated to an integrated light dose of 800 mJ / cm2 (the irradiation conditions are described in the Functional Development Group). The coating was cured by subjecting the coating to the temperature of 10 μm to hardening, and a coating sample for evaluation was prepared. The following evaluations were carried out using the coating film samples for evaluation obtained above.

[0127] <Elongation> The obtained cured coating film was cut into a size of 40 mm in length and 10 mm in width, and the sample piece was pulled. Testing machine "Force measurement model MX-500N-FA" (IMA A tensile test was carried out in a 180°C atmosphere in accordance with JIS K 7127 using a SUS304 stainless steel sheet (manufactured by DA Co., Ltd.). The pulling speed was 40 mm / min, and the substrate film was pulled together. The elongation was measured and evaluated according to the following criteria. 〇···Breaking elongation of 80% or more. △··· Breaking elongation: 60% or more but less than 80%. × Breaking elongation less than 60%.

[0128] <Scratch resistance> The resulting cured coating was cut into 10cm squares and subjected to the "ROTARY ABRASION TE STER" (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used, and the test was conducted in accordance with JIS K5600-5-9. The abrasion resistance test was carried out using [CS-10] abrasive wheels, with a load of 500g and 500 revolutions. The test was carried out, and the change in haze (ΔH) before and after the test was evaluated according to the following criteria. ○ ΔH is less than 20% × ΔH is 20% or more

[0129] <Chemical resistance> Toluene (Mitsui Bussan Chemicals Co., Ltd., product name "Toluene"), and 1 to 2 drops of methyl ethyl ketone (Idemitsu Kosan Co., Ltd., trade name "MEK") After dropping and leaving to stand for about 1 hour, the coating surface was visually observed. 〇···No change in the paint film or slight traces of solvent are visible. △ Solvent traces are observed on the coating. × Whitening and swelling of the coating film are observed. The coating film dissolves.

[0130] <Overall Judgment> Based on the above-mentioned measurements and evaluations, an overall evaluation was made according to the following criteria. ○···All evaluations were rated as "○". × There was at least one rating of "×".

[0131] [Table 1]

[0132] From the above results, it can be seen that all of the examples have good elongation at 180°C, abrasion resistance, and solvent resistance. It turns out to be excellent. In contrast, in Comparative Example 1, the polycarbonate bone containing polycarbonate diol In Comparative Example 2, a urethane acrylate (A-3) of the same grade was used, and in Comparative Example 3, a polyether polyol was used. The urethane acrylate (A-4) with a polyether skeleton is used, and both are abrasion resistant. In Comparative Example 3, the urethane acrylic resin having a polycarbonate skeleton was used. Polyether-based urethane acrylate containing acrylate (A-3) and polyether polyol It is used in combination with Relate (A-4), but it has good 180°C elongation, abrasion resistance, and solvent resistance. The results were inferior to all others. [Industrial Applicability]

[0133] The present invention provides a cured coating film that has high transparency, good elongation properties, and high abrasion resistance. and an active energy ray-curable resin composition capable of forming a coating film having excellent chemical resistance. Furthermore, the present invention provides a coating agent and a sheet using the same. Therefore, for example, coating agents for home appliances, automotive products, smartphones, Coating agents for sprays, coating agents for touch panels, optical fibers and flexible Furthermore, the coating film is highly transparent and is very useful as an outer coating material for flexible tubular objects. These properties are also excellent, with little deterioration in physical properties at high temperatures and excellent chemical resistance. It can also be used for a variety of purposes.

Claims

1. The present invention relates to a urethane (meth)acrylate compound (A) having a structural unit derived from a polyisocyanate compound (a1), a structural unit derived from a polyol compound (a2), and a structural unit derived from a hydroxyl group-containing (meth)acrylate compound (a3), wherein the polyol compound (a2) contains a polyether polycarbonate diol (a2-1) represented by the following formula (1) and a polyol (a2-2) having a number average molecular weight of 300 or less: the urethane (meth)acrylate compound (A) is a urethane (meth)acrylate compound obtained by bonding the hydroxyl group-containing (meth)acrylate compound (a3) ​​to a remaining isocyanate group of a reaction product obtained by bonding an isocyanate group possessed by a reaction product of a polyol (a2-2) and the polyvalent isocyanate compound (a1) to a hydroxyl group of the polyether polycarbonate diol (a2-1). 【Chemical 1】 (In the above formula (1), R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, n is an integer of 2 to 30, and m is an integer of 1 to 20. In addition, in formula (1), multiple R1s may be the same or different.)

2. The active energy ray-curable composition according to claim 1, wherein the hydroxyl group-containing (meth)acrylate compound (a3) ​​comprises at least one of glycerin di(meth)acrylate and 2-hydroxy-3-acryloyl-oxypropyl methacrylate.

3. 3. The active energy ray-curable resin composition according to claim 1, wherein a weight ratio (a2-1 / a2-2) of the polyether polycarbonate diol (a2-1) to the polyol (a2-2) is 99 / 1 to 50 / 50.

4. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the polyether polycarbonate diol (a2-1) has a number average molecular weight of 500 to 20,000.

5. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the hydroxyl group-containing (meth)acrylate (a3) ​​has one or more (meth)acryloyl groups.

6. A coating agent comprising the active energy ray-curable resin composition according to any one of claims 1 to 5.

7. A sheet having a cured product of the active energy ray-curable resin composition according to any one of claims 1 to 5.

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