Curable composition and its cured product

Abstract

Provided is a curable composition whereby it is possible to form a coating film having excellent adhesion to the surface of a substrate, hardness, scratch resistance, and chemical resistance.　This curable composition contains a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton and an isocyanate group other than the isocyanurate skeleton.　The polyol compound (A) preferably includes a compound (a) represented by formula (1). R1 to R3 in the formula are the same or different from each other and are a group represented by formula (1a).

Description

Technical Field

[0001] The present disclosure relates to a curable composition for a decorative film and a cured product thereof. The present disclosure claims the priority of Japanese Patent Application No. 2020-169881 filed in Japan on October 7, 2020, and incorporates the content thereof herein.

Background Art

[0002] Polyurethane resin has flexibility, stretchability, and strength. Therefore, a composition for forming a polyurethane resin is used as a coating agent or the like. For example, a coating agent used for coating a plastic substrate constituting a vehicle member or an electronic device or the like is required to be able to form a film having adhesion to the substrate, hardness, scratch resistance, and the like.

[0003] As such a coating agent, for example, the compositions described in Patent Documents 1, 2, and 3 are known.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] A coating agent containing a solvent volatilizes the solvent in the process of forming a film, which is not preferable because it causes health hazards and air pollution.

[0006] In recent years, as a method of coating a base material constituting a vehicle member, an electronic device, or the like, which serves both as decoration and reinforcement, an in-mold forming method or a three-dimensional surface decoration forming method using a coating agent formed into a film shape (that is, a film coating agent) is known. The film coating agent used in the above method is required to have step followability and to form a film adhered to the base material by curing in a state of following the uneven shape of the base material.

[0007] Furthermore, when the film obtained by using the composition described in the above patent document is touched with a hand to which a chemical such as a sunscreen agent is attached, the appearance may deteriorate due to whitening or chemical liquid marks remaining.

[0008] Therefore, an object of the present disclosure is to provide a curable composition capable of forming a film having adhesion, hardness, scratch resistance, and chemical resistance on the surface of a base material. Another object of the present disclosure is to provide a curable composition capable of forming an active energy ray curable film that is excellent in followability to the surface of a base material and capable of forming a film having excellent adhesion, hardness, scratch resistance, and chemical resistance on the surface of the base material. Another object of the present disclosure is to provide the curable composition having good coating properties without adding a solvent. Another object of the present disclosure is to provide a cured product of the curable composition. Another object of the present disclosure is to provide an active energy ray curable film and a cured product thereof that are excellent in followability to the surface of a base material and capable of forming a film having excellent adhesion, hardness, scratch resistance, and chemical resistance on the surface of the base material by irradiation with active energy rays. Another object of the present disclosure is to provide a method for producing the active energy ray curable film. Another object of the present disclosure is to provide a plastic molded product in which at least a part of the surface of a base material is coated with a film having excellent adhesion, hardness, scratch resistance, and chemical resistance. Another object of the present disclosure is to provide a method for producing the plastic molded product.

Means for Solving the Problems

[0009] As a result of diligent research to solve the above problems, the inventors of this invention have found the following: 1. The polyurethane resin obtained by reacting a polyol compound (A) having an isocyanurate skeleton with a polyisocyanate compound (C) having an isocyanurate skeleton (= a compound having an isocyanurate skeleton and isocyanate groups other than the isocyanurate skeleton) exhibits excellent hardness, scratch resistance, and chemical resistance. 2. The composition obtained by adding an acrylic compound (B) having a hydroxyl group to the polyol compound (A) and polyisocyanate compound (C) has low viscosity and excellent coatability even without the addition of a solvent. 3. The composition obtained by adding an acrylic compound (B) having a hydroxyl group to the polyol compound (A) and polyisocyanate compound (C) can form a cured product through a two-step curing reaction involving thermosetting and photocuring. In other words, it possesses dual curability. 4. The semi-cured product obtained by thermal curing a composition with dual curability exhibits excellent step-following properties. If photocuring is performed after the product has followed the irregularities of the substrate, it is possible to form a coating with excellent adhesion to the irregularities of the substrate, as well as excellent hardness, scratch resistance, and chemical resistance.

[0010] This disclosure has been completed based on these findings.

[0011] In other words, the present disclosure provides a curable composition comprising a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton and isocyanate groups other than the isocyanurate skeleton.

[0012] The disclosure also provides the curable composition wherein the polyol compound (A) is compound (a) represented by the following formula (1). [ka] [R in the formula 1 ~R3 is, the same or different, a group represented by the following formula (1a):

Chemical formula

[0013] The present disclosure also provides the curable composition in which the acrylic compound (B) is a compound (b”) represented by the following formula (2”).

Chemical formula

Chemical formula

[0014] The present disclosure also provides the curable composition in which the polyisocyanate compound (C) is a compound (c) represented by the following formula (3).

Chemical formula

[0015] The disclosure also provides the curable composition comprising the acrylic compound (B) in an amount of 1 to 70 parts by weight per 100 parts by weight of the polyol compound (A).

[0016] The disclosure also provides the curable composition comprising the polyol compound (A) and the acrylic compound (B) in a ratio such that the molar ratio (former / latter) of the hydroxyl groups of the polyol compound (A) to the hydroxyl groups of the acrylic compound (B) is 1.5 to 50.

[0017] The disclosure also provides a curable composition in which the equivalent ratio (NCO / OH) of the NCO group of the polyisocyanate compound (C) to the OH group in the polyol compound (A) and the acrylic compound (B) is in the range of 0.2 to 2.0.

[0018] The present disclosure also provides the curable composition further comprising a photopolymerization initiator (D) in an amount of 1 to 5 parts by weight per 100 parts by weight of the total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C).

[0019] The present disclosure further provides the curable composition comprising a polysiloxane derivative (E) in an amount of 0.1 to 0.5 parts by weight per 100 parts by weight of the total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C).

[0020] This disclosure also provides the curable composition which is a dual-curing coating agent.

[0021] This disclosure also provides an active energy ray curable film containing an (meth)acryloyl group-terminated urethane prepolymer comprising a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton as constituent monomers.

[0022] This disclosure also provides cured products of the curable composition.

[0023] This disclosure also provides cured products of the active energy ray curable film.

[0024] This disclosure also provides a plastic molded article in which a coating made of the cured material covers at least a portion of the surface of a substrate to be coated.

[0025] This disclosure also provides a method for producing an active energy ray curable film, which involves heat-treating a coating film made of the curable composition to produce an active energy ray curable film containing an (meth)acryloyl group-terminated urethane prepolymer comprising a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton as constituent monomers.

[0026] This disclosure also provides a method for manufacturing a plastic molded article, comprising the following steps. Step 1: The activated energy ray-curable film is pressed into the recess of the mold, and then molten plastic is filled into it. Step 2: Solidify or harden the plastic filled into the recesses of the mold. Step 3: Remove the contents from the mold and cure the film by irradiating it with active energy rays. [Effects of the Invention]

[0027] The composition of this disclosure comprises the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C). Therefore, the composition has dual curability, and when the composition is subjected to heat treatment, the urethane bonding reaction between the hydroxyl group and the isocyanate group proceeds, but the radical polymerization reaction of the (meth)acryloyl group does not proceed. As a result, a semi-cured product with active energy ray curability is obtained.

[0028] The aforementioned semi-cured material exhibits excellent conformability to uneven surfaces. When the semi-cured material is made to conform to the irregularities of the substrate and then subjected to light irradiation, a radical polymerization reaction of (meth)acryloyl groups proceeds. This allows for the formation of a cured material that adheres closely to the substrate. Furthermore, the cured material formed in this manner exhibits excellent hardness, scratch resistance, and chemical resistance.

[0029] Because the above-mentioned composition has the above-mentioned properties, it is possible to form a semi-cured product with a good yield without strictly adjusting the thermal curing conditions (e.g., curing temperature and curing time). Furthermore, the film made from the semi-cured product is suitable as a decorative and / or hard coat film coating agent (particularly as a decorative and / or hard coat film coating agent by in-mold molding or three-dimensional surface decorative molding).

[0030] Furthermore, the composition has low viscosity even without containing a solvent. Using the composition, it is possible to provide a coating agent with excellent usability (specifically, a coating agent with excellent applicability, and moreover, is environmentally friendly and safe).

[0031] A plastic molded article having a coating made of a cured product of the composition on at least a portion of the surface of a substrate has high surface hardness and excellent scratch resistance and scratch recovery properties. Furthermore, the coating has excellent adhesion, so even if it is touched with hands that have sunscreen or the like on them, the agent will not penetrate into the gap between the substrate and the coating, and the coating will not peel off. In addition, the coating has excellent chemical resistance, so even if it is touched with hands that have sunscreen or the like on them, the coating will not become cloudy or leave chemical residue.Therefore, the plastic molded article of this disclosure can maintain an excellent appearance for a long period of time. [Modes for carrying out the invention]

[0032] [Curable composition] The curable composition of this disclosure comprises a polyol compound (A), an acrylic compound (B), and a polyisocyanate compound (C). The curable composition of this disclosure may also contain other components in addition to the above components.

[0033] <Polyol compound (A)> Polyol compound (A) is a compound having multiple hydroxyl groups. The number of hydroxyl groups in polyol compound (A) is, for example, two or more, preferably two to four, and particularly preferably three to four. Polyol compound (A) also has an isocyanurate skeleton. Therefore, the resulting cured product has a high crosslinking density and exhibits excellent hardness, scratch resistance, and drug resistance.

[0034] The polyol compound (A) is, for example, compound (a) represented by the following formula (1). [ka] [R in the formula 1 ~R 3 These are the same or different groups represented by the following formula (1a). [ka] (In formula (1a), L 1 , L 2 represents an alkylene group having 1 to 10 carbon atoms, whether identical or different, and m represents a number of 0 or more. However, R 1 ~R 3 The values ​​of m within the equation cannot be 0 at the same time. (The bonds indicated by the wavy lines are bonded to the nitrogen atom in the formula.)

[0035] Examples of the alkylene group having 1 to 10 carbon atoms include linear or branched alkylene groups such as methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, butylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1'-dimethylethylene group, pentylene group, hexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, and desilene group.

[0036] L 1 As such, an alkylene group having 1 to 3 carbon atoms is preferred. Also, L 1 A linear alkylene group is preferred.

[0037] L 2 As such, alkylene groups having 1 to 8 carbon atoms are preferred, and alkylene groups having 4 to 6 carbon atoms are particularly preferred. Also, L 2 A linear alkylene group is preferred.

[0038] In formula (1a), m is the average degree of polymerization of the units shown in parentheses in formula (1a), and is a number greater than or equal to 0. m is, for example, 0 to 7, and is preferably 0 to 4, more preferably 0 to 3, even more preferably greater than 0 and 3 or less, particularly preferably greater than 0 and 2 or less, and most preferably 1 to 2, from the viewpoint that the distance between crosslinking points of the resulting cured product will be shortened, the network structure will be denser, and drug resistance will be improved.

[0039] The number-average molecular weight (Mn: on a standard polystyrene basis) of compound (a) is, for example, less than 800, and is preferably 570-630, more preferably 580-620, and particularly preferably 590-615, from the viewpoint that the distance between crosslinking points in the resulting cured product will be shortened, thereby increasing the density of the network structure and improving drug resistance.

[0040] Furthermore, the molecular weight dispersion (weight-average molecular weight Mw / number-average molecular weight Mn) of compound (a) is preferably 1.0 to 1.5, more preferably 1.0 to 1.3, and even more preferably 1.0 to 1.2.

[0041] The number-average molecular weight and molecular weight dispersion of compound (a) can be measured using the apparatus and conditions described in the examples later.

[0042] The hydroxyl value (KOH mg / g) of compound (a) is, for example, 200 to 400, and among these, preferably 260 to 300, more preferably 270 to 290, and even more preferably 275 to 285, in order to improve the hardness, scratch resistance, and drug resistance of the resulting cured product. The hydroxyl value can be measured by the hydroxyl value measurement method described in JIS-K1557.

[0043] Compound (a) can be produced, for example, by ring-opening polymerization of a lactone starting from the hydroxyl group of formula (1') below. 1 L in equation (1a) 1 It is the same as the three L in equation (1') 1 They may be the same or they may be different. [ka]

[0044] Examples of the aforementioned lactones include α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

[0045] The curable composition of this disclosure may contain one polyol compound (A) alone, or it may contain two or more polyol compounds in combination.

[0046] <Acrylic compound (B)> Acrylic compound (B) is a compound having a hydroxyl group and a (meth)acryloyl group. Acrylic compound (B) is, for example, compound (b') represented by the following formula (2'). [ka] [L in the formula 7 R represents an alkylene group with 1 to 10 carbon atoms. 4 is H or CH3, and R 5 [is H or a group represented by the following formula (2a)] [ka] (In formula (2a), L 6 The '' represents an alkylene group having 1 to 10 carbon atoms, either identical or different, where n is a number greater than or equal to 0. (The wavy bond indicates a bond to the oxygen atom in formula (2').)

[0047] Acrylic compound (B) may also be compound (b) represented by the following formula (2). R in the following formula 4 , R5 The same applies as stated above. [ka]

[0048] The acrylic compound (B) may also be compound (b) represented by the following formula (2"). [ka] [R in the formula 4 R is either H or CH3. 6 This is the group represented by the following formula (2b). [ka] (In formula (2b), L 6 , L 7 The '' represents an alkylene group having 1 to 10 carbon atoms, either identical or different, where n is a number greater than or equal to 0. (The wavy bond indicates a bond to the oxygen atom in formula (2").)

[0049] Said L 6 , L 7 As for alkylene groups with 1 to 10 carbon atoms in L 1 , L 2 Similar examples include alkylene groups with 1 to 10 carbon atoms.

[0050] Said L 6 Among these, alkylene groups having 1 to 8 carbon atoms are preferred, and alkylene groups having 4 to 6 carbon atoms are particularly preferred. Also, L 6 A linear alkylene group is preferred.

[0051] Said L 7 More preferably, an alkylene group having 1 to 8 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is even more preferred, an alkylene group having 2 to 4 carbon atoms is particularly preferred, and an alkylene group having 2 carbon atoms (especially an ethylene group) is particularly preferred. Also, L 7 A linear alkylene group is preferred.

[0052] The aforementioned n is the average degree of polymerization of the units indicated in parentheses in the formula, and is a number greater than or equal to 0. n is, for example, between 0 and 7. From the viewpoint of improving drug resistance by reducing the distance between crosslinking points in the resulting cured product, thereby increasing the density of the network structure, the upper limit of n is preferably 4, more preferably 3, and particularly preferably 2. Also, from the viewpoint of improving the extensibility of the resulting semi-cured product, n is preferably greater than 0, more preferably 0.2 or greater, even more preferably 0.5 or greater, particularly preferably 0.75 or greater, and most preferably 1 or greater.

[0053] Among the groups represented by formula (2b), it is preferable that the group is the same as the group represented by formula (1a) of compound (a), in that the distance between crosslinking points is made uniform, thereby obtaining a cured product with scratch-recovering properties.

[0054] The number-average molecular weight (Mn: on a standard polystyrene basis) of the acrylic compound (B) is preferably 600 or less, more preferably 250 to 500, and even more preferably 300 to 400.

[0055] Furthermore, the molecular weight dispersion (weight-average molecular weight Mw / number-average molecular weight Mn) of the acrylic compound (B) is preferably 1.0 to 1.8, more preferably 1.0 to 1.6, and even more preferably 1.0 to 1.5.

[0056] The number-average molecular weight and molecular weight dispersion of acrylic compound (B) can be measured using the same method as for the number-average molecular weight and molecular weight dispersion of compound (a).

[0057] The hydroxyl value (KOH mg / g) of acrylic compound (B) is, for example, 100 to 300, preferably 140 to 180, more preferably 150 to 170, and even more preferably 155 to 165. The hydroxyl value can be measured using the hydroxyl value measurement method described in JIS-K1557.

[0058] The viscosity of acrylic compound (B) at 25°C and a rotation speed of 20 / s is, from the viewpoint of reducing the viscosity of the curable composition and enabling solvent-free processing, for example, 1000 mPa·s or less, preferably 50 to 500 mPa·s, particularly preferably 50 to 300 mPa·s, most preferably 50 to 200 mPa·s, and especially preferably 50 to 150 mPa·s.

[0059] The curable composition of this disclosure may contain one acrylic compound (B) alone, or it may contain two or more acrylic compounds in combination.

[0060] The curable composition of this disclosure may contain other acrylic compounds (= compounds having a (meth)acryloyl group) in addition to acrylic compound (B), but from the viewpoint of enabling low viscosity and solvent-free formulation, and from the viewpoint of improving the hardness, scratch resistance, and chemical resistance of the resulting cured product, the proportion of acrylic compound (B) in the total amount of acrylic compounds contained in the curable composition is preferably 60% by weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.

[0061] <Polyisocyanate compound (C)> Polyisocyanate compound (C) is a compound having an isocyanurate skeleton. Polyisocyanate compound (C) has isocyanate groups other than the isocyanurate skeleton. Therefore, the resulting cured product has a high crosslinking density and exhibits excellent hardness, scratch resistance, and chemical resistance.

[0062] The polyisocyanate compound (C) is, for example, compound (c) represented by the following formula (3). [ka] [In formula (3), L 3 ~L 5 [These represent identical or different alkylene groups having 1 to 10 carbon atoms.]

[0063] In formula (3), L 3 ~L5 As for alkylene groups with 1 to 10 carbon atoms in L 1 , L 2 Similar examples include alkylene groups with 1 to 10 carbon atoms.

[0064] L 3 ~L 5 Among these, alkylene groups having 3 to 8 carbon atoms are preferred. Also, L 3 ~L 5 A linear alkylene group is preferred.

[0065] The NCO content in the polyisocyanate compound (C) is, for example, 17-25% by weight, preferably 18-24% by weight, and more preferably 19-23% by weight.

[0066] The curable composition of this disclosure may contain one polyisocyanate compound (C) alone, or it may contain two or more in combination.

[0067] The curable composition of this disclosure may contain other isocyanate compounds (i.e., compounds having an isocyanate group) in addition to the polyisocyanate compound (C), but from the viewpoint of improving the hardness, scratch resistance, and drug resistance of the resulting cured product, the proportion of the polyisocyanate compound (C) in the total amount of isocyanate compounds contained in the curable composition is preferably 60% by weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.

[0068] Other isocyanate compounds include, for example, aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; trimers (excluding polyisocyanate compound (C)), allophanates, biuretes, or adducts of the above aliphatic polyisocyanates; aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; polyisocyanates obtained by hydrogenating aromatic polyisocyanates, alicyclic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate; trimers, allophanates, biuretes, or adducts of the above aromatic polyisocyanates or alicyclic polyisocyanates.

[0069] The content of acrylic compound (B) in the curable composition is, for example, 1 to 70 parts by weight per 100 parts by weight of polyol compound (A). The upper limit of the acrylic compound (B) content is preferably 65 parts by weight, more preferably 60 parts by weight, particularly preferably 50 parts by weight, most preferably 40 parts by weight, and especially preferably 25 parts by weight, from the viewpoint of obtaining a semi-cured product with excellent stretchability while maintaining the hardness, scratch resistance, and chemical resistance of the resulting cured product. The lower limit of the acrylic compound (B) content is preferably 3 parts by weight, particularly preferably 5 parts by weight, most preferably 10 parts by weight, and especially preferably 12 parts by weight, from the viewpoint of obtaining a composition with excellent coatability without the addition of a solvent, and obtaining a semi-cured product with sufficient stretchability to exhibit step-following ability.

[0070] The molar ratio (former / latter) of hydroxyl groups of the polyol compound (A) to the acrylic compound (B) in the curable composition is, for example, 1.5 to 50. The lower limit of the molar ratio is preferably 2.0, particularly preferably 4.0, and most preferably 5.0, in order to maintain the hardness, scratch resistance, and chemical resistance of the resulting cured product while the semi-cured product has good stretchability. The upper limit of the molar ratio is preferably 30, more preferably 20, even more preferably 15, particularly preferably 12, and especially preferably 10, in order to obtain a composition that has excellent coatability without the addition of a solvent, and to obtain a semi-cured product that has sufficient stretchability to exhibit step-following ability. If the hydroxyl group content of the polyol compound (A) falls below the above range, the stretchability of the semi-cured product tends to decrease. On the other hand, if the hydroxyl group content of the acrylic compound (B) falls below the above range, the dual curability decreases, and it tends to become difficult to obtain a semi-cured product.

[0071] The curable composition may also contain hydroxyl group-containing compounds (i.e., compounds having at least one hydroxyl group) in addition to the polyol compound (A) and the acrylic compound (B). However, the total proportion of the polyol compound (A) and the acrylic compound (B) in the total amount of hydroxyl group-containing compounds contained in the curable composition is, for example, 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more.

[0072] The content of isocyanate compound (C) in the curable composition is preferably 40 to 160 parts by weight, more preferably 70 to 150 parts by weight, and even more preferably 100 to 140 parts by weight, per 100 parts by weight of polyol compound (A), in order to improve the hardness, scratch resistance, and drug resistance of the resulting cured product.

[0073] The content of the acrylic compound (B) in the curable composition is preferably 1 to 60 parts by weight, more preferably 5 to 40 parts by weight, and even more preferably 8 to 20 parts by weight, per 100 parts by weight of the total of the polyol compound (A), acrylic compound (B), and polyisocyanate compound (C), in order to not significantly reduce the hardness, scratch resistance, and chemical resistance of the resulting cured product and to improve the stretchability of the resulting semi-cured product.

[0074] The equivalent ratio (NCO / OH) of the NCO group of the polyisocyanate compound (C) in the curable composition to the OH group in the polyol compound (A) and acrylic compound (B) is preferably in the range of 0.2 to 2.0, more preferably 0.5 to 1.5, even more preferably 0.7 to 1.3, and particularly preferably 0.9 to 1.2, in terms of improving the hardness, scratch resistance, and chemical resistance of the resulting cured product.

[0075] The total content of polyol compound (A), acrylic compound (B), and isocyanate compound (C) in the curable composition, relative to the total weight of nonvolatile matter (100% by weight), is, for example, 80% by weight or more, preferably 85% by weight or more, and more preferably 90% by weight or more.

[0076] The curable composition may contain, as needed, one or more other components in addition to the polyol compound (A), acrylic compound (B), and polyisocyanate compound (C), and preferably contains a photopolymerization initiator and a surface modifier.

[0077] (Photopolymerization initiator (D)) The photopolymerization initiator (D) is not particularly limited and can be selected and used according to the purpose, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, Examples include benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenyl glyoxylate, benzyl, camphorquinone, etc. Specific examples of photopolymerization initiators (D) include, for example, the trade name "Irgacure 1173" (2-hydroxy-2methyl-1-phenylpropanone, manufactured by IGM Resigns BV). These may be used individually or in combination of two or more types.

[0078] The amount of photopolymerization initiator (D) is, for example, 1 to 5 parts by weight relative to the total amount (100 parts by weight) of the polyol compound (A), acrylic compound (B), and polyisocyanate compound (C). Using 1 to 5 parts by weight of photopolymerization initiator (D) allows for sufficient curing without excess or deficiency.

[0079] Furthermore, the content of the photopolymerization initiator (D) is, for example, 1 to 5 parts by weight per 10 parts by weight of the acrylic compound (B).

[0080] (Surface modifier) Examples of surface modifiers include polysiloxane derivatives (E). Adding a surface modifier to the curable composition provides the effect of smoothing the surface of the coating film.

[0081] Examples of polysiloxane derivatives (E) include compounds having a polydimethylsiloxane skeleton. Among these, polyether-modified polydimethylsiloxane is preferred, as are polyC2 compounds such as polyethylene oxide-added polydimethylsiloxane and polypropylene oxide-added polydimethylsiloxane. 2-4 Alkylene oxide-added polydimethylsiloxanes are particularly preferred.

[0082] The content of the polysiloxane derivative (E) is, for example, 0.1 to 0.5 parts by weight per 100 parts by weight of the total of the polyol compound (A), acrylic compound (B), and polyisocyanate compound (C).

[0083] (Other ingredients) The curable composition may further contain one or more other components. Examples of other components include inorganic particles, surfactants, pigments, dyes, UV absorbers, light stabilizers, defoamers, wetting agents, dispersants, viscoelastic modifiers, thixotropy imparters, preservatives, film-forming agents, plasticizers, penetrating agents, fragrances, bactericides, fungicides, UV absorbers, antioxidants, antistatic agents, flame retardants, matting agents, texture enhancers, and design imparters.

[0084] (Inorganic particles) Examples of inorganic particles include silica, alumina, mica, synthetic mica, talc, calcium oxide, calcium carbonate, zirconium oxide, titanium oxide, barium titanate, kaolin, bentonite, diatomaceous earth, boron nitride, aluminum nitride, silicon carbide, zinc oxide, cerium oxide, cesium oxide, magnesium oxide, glass beads, glass fibers, graphite, carbon nanotubes, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. These can be used individually or in combination of two or more.

[0085] As inorganic particles, silica is preferred because it can improve the chemical resistance and scratch resistance of the coating film.

[0086] The particle size of the inorganic particles is not particularly limited, but from the viewpoint of good appearance, for example, 0.01 nm to 1 μm is preferred.

[0087] The content of other components is not particularly limited, but is preferably 10% by weight or less relative to the total weight (100% by weight) of the nonvolatile content of the curable composition.

[0088] Furthermore, from the viewpoint of reducing environmental impact, the curable composition preferably contains 1% by weight or less of solvent relative to the total weight of nonvolatile matter (100% by weight), more preferably 0.5% by weight or less, and even more preferably 0.1% by weight or less. It is particularly preferable that the curable composition substantially contains no solvent.

[0089] The curable composition has low viscosity because it contains a combination of a polyol compound (A) and an acrylic compound (B) as hydroxyl group-containing compounds. Therefore, it has good coatability even when the solvent content is within the aforementioned range.

[0090] The viscosity of the curable composition at 25°C and a rotation speed of 20 / s is, for example, 500 to 30,000 mPa·s. The lower limit of the viscosity is preferably 1,000 mPa·s, and particularly preferably 2,000 mPa·s, from the viewpoint of forming a coating film of appropriate thickness. The upper limit of the viscosity is preferably 10,000 mPa·s, particularly preferably 6,000 mPa·s, and most preferably 4,000 mPa·s, from the viewpoint of forming a uniform coating film.

[0091] The curable composition can be manufactured by mixing the above components. The curable composition is preferably used as a two-component type; for example, the polyol compound (A) and the polyisocyanate compound (C) are stored separately and mixed at the time of use. This prevents the curable composition from hardening during storage.

[0092] Because the curable composition has the above-described structure, it can form a cured product through a two-step curing reaction involving thermal curing and photocuring. In other words, the curable composition is a dual-curing type composition.

[0093] When the curable composition is subjected to a heat-curing treatment, a urethane bonding reaction proceeds, yielding a semi-cured product that is curable by active energy rays. The semi-cured product has a high elongation at break and excellent step-following properties. The semi-cured product can conform well to the surface shape of a substrate, even if the substrate surface is curved (or non-planar; including uneven or spherical shapes). After the semi-cured product conforms to the surface shape of the substrate, a photocuring treatment is performed to polymerize the (meth)acryloyl groups contained in the semi-cured product, thereby curing the semi-cured product and forming a cured product with excellent adhesion to the substrate, hardness, scratch resistance, and chemical resistance.

[0094] When the curable composition is used in in-mold molding or three-dimensional surface decorative molding, it is preferable to first heat-cur the curable composition to form a film-like semi-cured material, and then apply this to the molding process. Since the film-like semi-cured material has excellent stretchability, it can be made to conform to and adhere to the recesses of the mold.

[0095] Therefore, the curable composition can be used as a dual-curing coating agent. Furthermore, the curable composition can also be used as a material for a film coating agent. A film coating agent is a coating agent molded into a film or sheet. Moreover, the curable composition can also be used as a coating agent (especially a film coating agent) for in-mold molding and three-dimensional surface decoration molding.

[0096] [Semi-cured product] The semi-cured product of this disclosure comprises a (meth)acryloyl group-terminated urethane prepolymer. The urethane prepolymer comprises, as constituent monomers, a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton.

[0097] The urethane prepolymer may contain other monomers as constituent monomers, but the total proportion of the polyol compound (A), acrylic compound (B), and polyisocyanate compound (C) in the total amount of constituent monomers is, for example, 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, most preferably 95% by weight or more, and especially preferably 99% by weight or more.

[0098] The semi-cured product may contain other components in addition to the urethane prepolymer, but the proportion of the urethane prepolymer in the total amount of components is, for example, 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more. The semi-cured product may consist only of the urethane prepolymer.

[0099] The aforementioned semi-cured product is obtained by urethane bonding the hydroxyl groups contained in the polyol compound (A) and the acrylic compound (B) with the isocyanate groups of the polyisocyanate compound (C).

[0100] The urethane bonding reaction proceeds, for example, by heat treatment of the curable composition. The heat treatment conditions are, for example, 100-150°C for about 0.5-12 hours. After the heat treatment is completed, the composition may be further aged at room temperature (1-30°C) for about 12-60 hours.

[0101] The aforementioned semi-cured product exhibits excellent stretchability because the contained urethane prepolymer contains a polyol compound (A) and an acrylic compound (B) as constituent monomers. The elongation at break is, for example, 60% or more, preferably 80% or more, more preferably 100% or more, even more preferably 120% or more, and particularly preferably 125% or more. The elongation at break can be measured using the apparatus and conditions described in the examples that will be explained later.

[0102] Because the semi-cured material has the aforementioned stretchability, it exhibits excellent conformability to uneven surfaces and can conform well to the curved surface of the substrate to be coated (for example, a plastic substrate such as PET). Furthermore, when the semi-cured material is irradiated with active energy rays, the (meth)acryloyl groups polymerize to form a cured product. For this reason, the semi-cured material is suitable as a film coating agent.

[0103] [Cured product] The cured product of this disclosure is a cured product of the curable composition or the semi-cured product. The cured product includes a polymer obtained by urethane bonding the hydroxyl groups and isocyanate groups in the curable composition, and further polymerizing the (meth)acryloyl groups together.

[0104] The cured product is obtained by subjecting the curable composition to thermal curing and photocuring. More specifically, it is obtained by subjecting the curable composition to heat treatment and active energy ray irradiation treatment. The heat treatment conditions are the same as those for the urethane bonding reaction.

[0105] The cured product can also be obtained by subjecting the semi-cured product to photocuring. More specifically, it can be obtained by irradiating the semi-cured product with active energy rays.

[0106] Examples of active energy rays include ultraviolet light and electron beams. Ultraviolet light is preferred from the standpoint of safety, reaction efficiency, and other industrial considerations. Examples of ultraviolet light sources include high-pressure mercury lamps and metal halide lamps. The ultraviolet light irradiation dose is, for example, 100 to 10000 mJ / cm². 2 That is the case.

[0107] The cured product exhibits excellent hardness, chemical resistance, scratch resistance, and scratch recovery properties.

[0108] The cured product has high hardness, and its pencil hardness (by a method in accordance with JIS K5600) is preferably H or higher, more preferably 2H or higher, particularly preferably 3H or higher, and most preferably 4H or higher.

[0109] The cured product exhibits excellent chemical resistance. Furthermore, even when sunscreen is applied, the surface of the cured product does not swell or become cloudy. In other words, the cured product has excellent sunscreen resistance.

[0110] The cured product exhibits excellent scratch resistance. Scratch resistance can be measured using the apparatus and conditions described in the examples.

[0111] When the aforementioned cured material is subjected to a scratch test using steel wool and a load of 500g, with 10 back-and-forth abrasions, the gloss retention rate 2 minutes after the scratch test is, for example, 80% or more, preferably 85% or more, particularly preferably 90% or more, and most preferably 95% or more. Furthermore, when the cured material is subjected to a scratch test using steel wool and a load of 500g, with 20 back-and-forth abrasions, the gloss retention rate 2 minutes after the scratch test is, for example, 80% or more, preferably 85% or more, particularly preferably 90% or more, and most preferably 95% or more.

[0112] Furthermore, the gloss retention rate 2 minutes after the scratch test is calculated using the following formula. Gloss retention rate (%) after 2 minutes following scratch test = (G1) / (G0) × 100 The aforementioned G0 represents the gloss of the cured product before the abrasion test, i.e., the initial gloss of the cured product [Gs(60°)]. The aforementioned G1 indicates the gloss [Gs(60°)] of the cured product after 2 minutes of abrasion testing.

[0113] Furthermore, when a scratch test is performed using steel wool with a load of 500g applied, consisting of 10 back-and-forth abrasions, the gloss retention rate after 24 hours of standing is preferably 80% or more, more preferably 85% or more, particularly preferably 90% or more, and most preferably 95% or more. Furthermore, when the cured material is subjected to a scratch test using steel wool and a load of 500g, with 20 back-and-forth abrasions, the gloss retention rate after being left to stand for 24 hours after the scratch test is preferably 80% or more, more preferably 85% or more, particularly preferably 90% or more, and most preferably 95% or more.

[0114] Furthermore, the gloss retention rate after 24 hours of standing following the scratch test is calculated using the following formula. Gloss retention rate (%) after 24 hours of standing after abrasion test = (G2) / (G0) × 100 The aforementioned G0 represents the gloss of the cured product before the abrasion test, i.e., the initial gloss of the cured product [Gs(60°)]. G2 refers to the gloss [Gs(60°)] of the cured product after the abrasion test, which has been left to stand for 24 hours under constant temperature and humidity conditions of 23°C and 50%RH.

[0115] The cured product possesses the above-mentioned properties. Therefore, by coating a substrate with a film made of the cured product, the substrate can be given hardness, chemical resistance, scratch resistance, and scratch recovery properties. In addition, the substrate can be decorated. That is, by coating with the cured product, the substrate can be given aesthetic appeal and new functions. Examples of substrates include the casings of home appliances (refrigerators, washing machines, air conditioners, televisions, etc.), the casings of electronic devices (personal computers, mobile phones, smartphones, etc.), components that make up musical instruments (pianos, electronic organs, electronic musical instruments, etc.), and vehicle components such as automobiles and railway vehicles (interior materials such as instrument panels, door trims, headlinings, tonneau covers, and exterior materials such as bumpers).

[0116] [Activated energy ray curable film] The active energy ray curable film of this disclosure contains a (meth)acryloyl group-terminated urethane prepolymer comprising a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton as constituent monomers.

[0117] The film can be manufactured, for example, by subjecting a coating made of the curable composition to a heat treatment. The heat treatment conditions are the same as those for the urethane bonding reaction.

[0118] There are no particular limitations on the method for forming the coating film of the curable composition. For example, it can be formed by applying the curable composition to a surface such as a release film or substrate using methods such as screen printing, mask printing, offset printing, inkjet printing, flexographic printing, gravure printing, stamping, dispensing, squeegee printing, silkscreen printing, spraying, or brush application.

[0119] The thickness of the aforementioned film is not particularly limited, but is, for example, 20 to 150 μm.

[0120] The film possesses stretchability derived from the urethane prepolymer. That is, the film has a high elongation at break and excellent conformability to steps. Therefore, the film can conform well to the curved surface of the substrate. Furthermore, when the film is irradiated with active energy rays, the (meth)acryloyl groups copolymerize with each other, resulting in a cured product with excellent hardness, scratch resistance, and chemical resistance.

[0121] Because the aforementioned film has the above-mentioned properties, it is suitable, for example, as a film coating agent, and is particularly suitable as a film coating agent for in-mold molding and three-dimensional surface decorative molding.

[0122] [Plastic molded articles and methods for manufacturing the same] The plastic molded article of this disclosure has a thin film made of a cured product of the curable composition (or a cured product of the active energy ray curable film) covering at least a portion of the surface of the substrate to be coated. That is, the plastic molded article has a coating made of the cured product on at least a portion of the surface of the substrate.

[0123] The aforementioned plastic molded products include, for example, casings for mobile phone terminals, notebook PCs, digital cameras, home appliances, cosmetic containers, and interior and exterior parts for automobiles.

[0124] The thickness of the coating made of the cured material is not particularly limited, and is, for example, 20 to 150 μm.

[0125] The above-mentioned substrate contains at least plastic as a forming material. In addition to plastic, the forming material may also contain materials such as wood, metal, glass, cloth, leather, and silicone.

[0126] The aforementioned plastics include thermoplastic resins and thermosetting resins. These can be used individually or in combination of two or more types.

[0127] Examples of the thermoplastic resins include polyolefin resins such as polyethylene and polypropylene; styrene resins such as polystyrene; polyesters such as polyethylene terephthalate (PET); vinyl chloride resins such as vinyl chloride resin; polyamides such as polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 11, polyamide 12, and polyamide 1212; polyphenylene ethers such as poly(2,6-dimethyl-1,4-phenylene ether); acrylonitrile alone or copolymers such as PAN resin, AS resin, ABS resin, AAS resin, ACS resin, AES resin, and AXS resin; (meth)acrylic resin, polycarbonate, polyacetal, polyphenylene sulfide, polyetheretherketone, polyamideimide, polyimide, polyetherimide, polysulfone, polyethersulfone, and modified products and derivatives of these resins, as well as polymer blends and polymer alloys containing these resins.

[0128] Examples of the thermosetting resins include phenolic resins, urea resins, melamine resins, unsaturated polyesters, furan resins, epoxy resins, polyurethane resins, allyl resins, and polyimides.

[0129] The substrate is preferably a molded article (preferably a three-dimensional molded article) containing a solidified product of the thermoplastic resin and / or a cured product of the thermosetting resin. The surface shape of the substrate is not particularly limited and may be flat or curved (including uneven or spherical shapes). Furthermore, it may contain a combination of flat and curved portions.

[0130] The aforementioned plastic molded product can be manufactured, for example, by applying the curable composition to the surface of a molded substrate and subjecting it to thermal curing and photocuring.

[0131] Furthermore, since the active energy ray curable film has excellent stretchability, by using the active energy ray curable film, it is possible to manufacture plastic molded products with a coating that has excellent adhesion by in-mold molding or three-dimensional surface decoration molding.

[0132] A method for manufacturing a plastic molded article using the aforementioned active energy ray curable film includes, for example, the following steps. Step 1: The activated energy ray-curable film is pressed into the recess of the mold, and then molten plastic is filled into it. Step 2: Solidify or harden the plastic filled into the recesses of the mold. Step 3: Remove the contents from the mold and cure the film by irradiating it with active energy rays.

[0133] (Process 1) Step 1 is the process of adhering the active energy ray-curable film to the recess of the mold, and then filling it with molten plastic.

[0134] As a method for adhering the active energy ray-curable film to the recess of the mold, for example, a mold equipped with suction holes is used, the film is placed on top of the mold, and suction is applied through the suction holes to create a vacuum in the space between the film and the mold, thereby adhering the film to the mold; or a method is used in which the film is placed on top of the mold and compressed air from above the film is used to adhering the film to the mold, and such methods can be used without particular limitation.

[0135] After the film is in close contact with the recess of the mold in this manner, molten plastic is injected into the void of the mold recess.

[0136] (Process 2) Step 2 is the process of solidifying or hardening the plastic filled into the recesses of the mold. The method of solidification or hardening can be appropriately selected depending on the type of plastic. For example, if the plastic is a thermoplastic resin, it can be solidified by cooling the molten plastic to a temperature below its melting point. If the plastic is a thermosetting resin, it can be hardened by heat treatment of the molten plastic.

[0137] After step 2, a solidified or cured plastic (i.e., a substrate) is obtained, which has the active energy ray curable film on its surface.

[0138] (Step 3) Step 3 is the process of removing the contents (i.e., the substrate having the active energy ray-curable film on its surface) from the mold and curing the film by irradiating the removed contents with active energy rays.

[0139] The irradiation conditions for the active energy rays are the same as those used when manufacturing the cured product described above.

[0140] The configurations and combinations thereof in the above embodiments are examples only, and additions, omissions, substitutions, and other modifications can be made as appropriate without departing from the spirit of the invention of this disclosure. The invention of this disclosure is not limited by the embodiments, but is limited only by the claims.

[0141] Furthermore, each aspect disclosed herein can be combined with any other features disclosed herein. [Examples]

[0142] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0143] [Synthesis Example 1] In a five-necked flask equipped with a reflux condenser, thermometer, gas inlet tube, and stirrer, 1306 g of tris(2-hydroxyethyl) isocyanurate, 1694 g of ε-caprolactone, and 6 mg of stannous octylate were added under a nitrogen gas atmosphere, and the internal temperature was then raised to 170°C.

[0144] After confirming that the concentration of ε-caprolactone was less than 1.0% by gas chromatography analysis, the compound was cooled and removed from the five-necked flask. The number-average molecular weight (Mn) of the obtained compound was 611, the molecular weight dispersion (Mw / Mn) was 1.2, the viscosity was 14.3 [Pa·s / 25℃], and the hydroxyl value was 280.1.

[0145] The molecular weight of the obtained compounds was measured using a high-speed GPC instrument. The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were determined by comparison with a polystyrene standard, and the molecular weight dispersion (Mw / Mn) was calculated. The measurement conditions are as follows: • Measurement equipment: High-speed GPC device "HLC-8220GPC", manufactured by Tosoh Corporation • Mobile phase: tetrahydrofuran

[0146] [Example 1] In a 50 mL glass container, the polyol compound (A), acrylic compound (B), polyisocyanate compound (C), photopolymerization initiator (D), and surface modifier (E) were placed as shown in Table 1. The mixture was then mixed and degassed using a rotary / revolving mixer (Awatori Rentaro vacuum type, model: ARV-310, manufactured by Shinky Co., Ltd.) to obtain the composition.

[0147] The obtained composition was poured into a glass plate frame with a 2 mm thick Teflon® spacer sandwiched inside, heat-cured in an oven at 120°C for 3 hours, then dried, and further cured for 48 hours under constant temperature and humidity conditions of 23°C and 50% RH to obtain a semi-cured product.

[0148] Furthermore, the obtained composition was applied to a polyethylene terephthalate film (Cosmoshine A4100 #100, manufactured by Toyobo Co., Ltd.) using an applicator to a film thickness of 30 μm. Subsequently, it was heat-cured in an oven at 120°C for 3 hours, then dried, and further cured for 48 hours under constant temperature and humidity conditions of 23°C and 50% RH to obtain a laminate of a semi-cured product containing an acryloyl group-terminated urethane prepolymer containing the polyol compound (A), acrylic compound (B), and polyisocyanate compound (C) as constituent monomers, and a PET film (semi-cured product / PET film laminate).

[0149] Next, UV irradiation at an irradiation dose of 400 mJ / cm² was applied to the semi-cured side of the semi-cured material / PET film laminate using a 4kW x 1 lamp inverter-type conveyor system (ECS-401GX, manufactured by iGraphics Co., Ltd.). 2 The process was repeated twice to allow the photocuring reaction to proceed, and a laminate of the cured material and PET film (cured material / PET film laminate, hereinafter also simply referred to as the laminate) was obtained.

[0150] [Examples 2-5, Comparative Example 1] A composition, a semi-cured product, and a laminate were obtained in the same manner as in Example 1, except that the composition formulation was changed as shown in Table 1.

[0151] The compositions, semi-cured products, and laminates obtained in the examples and comparative examples were evaluated as follows.

[0152] (viscosity) The viscosity of the compositions obtained in the examples and comparative examples was measured using a rheometer (product name "PHYSICA UDS200", manufactured by Paar Physica) at 25°C and a rotation speed of 20 rpm (mPa·s). In the comparative examples, viscosity measurements were performed for the composition before solvent addition and for the composition after solvent addition.

[0153] (Usability) The usability of the compositions obtained in the examples and comparative examples was evaluated by the following method. Judgment criteria ○: The amount of solvent contained in the composition is less than 1% by weight relative to the total weight of non-volatile matter (100% by weight), and the viscosity of the composition is 4000 mPa·s or less. △: The amount of solvent contained in the composition is less than 1% by weight relative to the total weight of non-volatile matter (100% by weight), and the viscosity of the composition exceeds 4000 mPa·s but is 30,000 or less. ×: The amount of solvent contained in the composition is 1% or more by weight relative to the total weight of nonvolatile matter (100% by weight), or the viscosity of the composition exceeds 30,000 mPa·s.

[0154] (Stretchability) The semi-cured materials obtained in the examples and comparative examples were punched into JIS No. 3 dumbbell shapes and used as samples. Tensile tests were performed using a Tensilon universal testing machine (RTC-1350A (manufactured by A&D Co., Ltd.)) under the following conditions, and the elongation at break (%) was calculated from the following formula. A higher elongation at break indicates better stretchability. Elongation at break (%) = [(Length of sample at break (L) - Length of sample before test (L0)) / Length of sample before test (L0)] × 100 <Tensile Test Conditions> Test environment: 23°C, 50%RH Tensile speed: 500 mm / min The test was performed five times, and the average value was calculated after removing the maximum and minimum values. This average value was then used as the length (L) of the sample at the time of fracture.

[0155] (Adhesion) If the semi-cured product obtained by thermosetting has a high elongation at break, it can conform to the surface shape of the substrate. Furthermore, if the cured product obtained after conforming to the substrate surface and then photocuring has an elongation at break of 70% or less, it exhibits good adhesion to the substrate, resulting in a cured product with excellent adhesion. Therefore, adhesion was evaluated according to the following criteria. <Criteria for determining adhesion> ◎(Excellent): Breaking elongation after heat curing is 100% or more, and breaking elongation after heat curing + photocuring is 80% or less. ○ (Good): Breaking elongation after heat curing is 80% or more and less than 100%, and breaking elongation after heat curing + photocuring is 80% or less. × (Not acceptable): Breaking elongation after heat curing is less than 80%, or breaking elongation after heat curing + photocuring is more than 80%.

[0156] (Pencil hardness) The pencil hardness of the cured film side surface of the laminates obtained in the examples and comparative examples was evaluated by a method in accordance with JIS K5600. Specifically, the hardened surface of the laminate was rubbed with a pencil (pencil lead), and any samples showing scratches were deemed NG (defective). More precisely, the evaluation was performed using a pencil of a certain hardness, and if no scratches were found, the evaluation was repeated with a pencil of the next higher hardness. If scratches were found, the evaluation was re-evaluated with a pencil of the next lower hardness, and if no scratches were found, the evaluation was repeated again with a pencil of the next higher hardness. If reproducibility was confirmed two or more times, the hardness of the hardest pencil that did not cause scratches was defined as the pencil hardness of the hardened coating. • Evaluation pencil: "Pencil Hardness Test Pencil" manufactured by Mitsubishi Pencil Co., Ltd. • Load: 750gf • Scratch distance: 7mm or more Scratch angle: 45° • Measurement environment: 23℃, 50%RH

[0157] (Abrasion resistance and abrasion recovery) The scratch resistance of the hardened film side surface of the laminates obtained in the examples and comparative examples was evaluated by performing a scratch test using a rubbing tester (standard type, manufactured by Nippon Rikagaku Co., Ltd.) with steel wool (B-204, Bonstar industrial #0000) attached, applying a load of 500g and moving it back and forth (10 or 20 times) over the film. Using a gloss meter (Gloss Meter VG7000, manufactured by Nippon Denshoku Industries, Ltd.), the initial gloss (G0) [Gs(60°)] before the scratch test and the gloss (G1) [Gs(60°)] after 2 minutes of the scratch test were measured on the hardened film side surface, and the scratch resistance was evaluated by calculating the gloss retention rate using the following formula. Gloss retention rate (%) after 2 minutes following scratch test = (G1) / (G0) × 100

[0158] Furthermore, the laminated material after scratching was left to stand for 24 hours under constant temperature and humidity conditions of 23°C and 50%RH. The gloss (G2) [Gs(60°)] of the coating after standing was measured, and the gloss retention rate relative to the initial gloss (G0) [Gs(60°)] was calculated using the following formula to evaluate the scratch recovery performance. Scratch recovery performance was evaluated after 10 and 20 passes. Gloss retention rate (%) after 24 hours of standing after abrasion test = (G2) / (G0) × 100

[0159] Judgment criteria ◎ (Good): Gloss retention rate of 90% or higher ○ (Acceptable): Gloss retention rate less than 90%, 80% or more. × (Not acceptable): Gloss retention rate is less than 80% or the coating has peeled off, making gloss measurement impossible.

[0160] (Sunscreen resistance (immersion method)) Test specimens of the laminates obtained in the examples and comparative examples [rectangular, 2 cm] 2 The entire surface of the hardened coating side of the sample was brought into contact with 0.4g of sunscreen cream (Neutrogena's "UltraSheer Dry-Touch SPF45"), which was weighed onto a glass slide (contact amount per unit area between the hardened coating and sunscreen cream: 0.1g / cm²). 2 ). The entire cured film described above was covered with polyvinylidene chloride film and left to stand in an 80°C oven for 5 hours. After wiping off the sunscreen cream, the adhesion state of the cured film was evaluated according to the following criteria. The more difficult the cured film is to peel off, the better its adhesion to the substrate and chemical resistance.

[0161] Judgment criteria ○: The hardened coating did not peel off. ×: Part of the hardened coating has peeled off or the hardened coating has completely peeled off.

[0162] (Sunscreen resistance (intravenous drip method)) 0.025 g / cm³ on the cured film side surface of the laminates obtained in the examples and comparative examples. 2Sunscreen cream (Neutrogena's "UltraSheer Dry-Touch SPF45") was applied in this manner, left to stand in a 50°C oven for 1 hour, then the sunscreen cream was wiped off, and the appearance of the cured film was evaluated according to the following criteria.

[0163] Judgment criteria ◎: There is almost no change in appearance of the hardened coating. ○: Chemical residue remains on the hardened coating. ×: The cured film swells, or the cured film swells and turns white.

[0164] The results above are summarized in Table 1 below. [Table 1]

[0165] Polyol compound (A): Compound obtained by Synthesis Example 1 Acrylic compound (B): Trade name "PLACCEL FA2D" (acrylic acid ester derivative, Mn344, Mw / Mn1.4, hydroxyl value 159-164, viscosity at 25°C 80 mPa·s), manufactured by Daicel Corporation. Polyisocyanate (C): Product name "Takenate D-170N" (isocyanurate modified form of hexamethylene diisocyanate), manufactured by Mitsui Chemicals, Inc. Photopolymerization initiator (D): Trade name "Irgacure 1173" (2-hydroxy-2-methyl-1-phenylpropanone), manufactured by IGM Resigns BV. Surface modifier (E): "BYK-306" (ether-modified polydimethylsiloxane), manufactured by BIC Chemie Japan Co., Ltd. Solvent: Diethylene glycol monoethyl ether acetate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0166] The curable composition obtained in the examples contains both a polyol compound (A) and an acrylic compound (B). Therefore, the curable composition exhibits dual curability, and a semi-cured product is obtained after thermal curing. This semi-cured product has excellent stretchability and good step-following properties. Furthermore, when the semi-cured product is subjected to photocuring treatment, a cured product with high hardness, excellent scratch resistance, scratch recovery properties, and chemical resistance is obtained. In addition, the curable composition obtained in the examples has low viscosity and good applicability even without the addition of solvents.

[0167] On the other hand, the curable composition obtained in Comparative Example 1 does not contain acrylic compound (B) and therefore does not have dual curability. It hardens completely by thermal curing, and the resulting cured product has high hardness, excellent scratch resistance, scratch recovery, and chemical resistance, but low stretchability and does not conform to uneven surfaces. Furthermore, because the curable composition obtained in Comparative Example 1 does not contain acrylic compound (B), its viscosity was too high before the addition of the solvent, making it difficult to apply. In other words, it was difficult to make the curable composition without acrylic compound (B) solvent-free.

[0168] From the above, it can be seen that the curable composition of this disclosure maintains the properties of the resulting cured product (hardness, scratch resistance, scratch recovery, and chemical resistance) while possessing a new property of dual curability, and can form a semi-cured product with good yield even without strictly adjusting the curing conditions, and that the semi-cured product obtained in this way has excellent stretchability. Furthermore, it can be said that the curable composition can be made solvent-free without impairing the coatability, has a low environmental impact, and is highly safe.

[0169] In summary, the structure of this disclosure and its variations are described below. [1] A curable composition comprising a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton and isocyanate groups other than the isocyanurate skeleton. [2] A curable composition comprising a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton. [3] The curable composition according to [1] or [2], wherein the polyol compound (A) is compound (a) represented by the following formula (1). [4] The curable composition according to any one of [1] to [3], wherein the number average molecular weight of the polyol compound (A) is less than 800. [5] The curable composition according to any one of [1] to [4], wherein the acrylic compound (B) is a compound (b) represented by formula (2"). [6] The curable composition according to any one of [1] to [4], wherein the acrylic compound (B) is compound (b') represented by formula (2'). [7] The curable composition according to any one of [1] to [4], wherein the acrylic compound (B) is compound (b) represented by formula (2). [8] The curable composition according to any one of [1] to [7], wherein the polyisocyanate compound (C) is compound (c) represented by formula (3). [9] The curable composition according to any one of [1] to [8], wherein the acrylic compound (B) is contained in an amount of 1 to 70 parts by weight per 100 parts by weight of the polyol compound (A).

[10] A curable composition according to any one of [1] to [9], wherein the polyol compound (A) and the acrylic compound (B) are contained in a ratio such that the molar ratio (former / latter) of the hydroxyl groups of the polyol compound (A) to the hydroxyl groups of the acrylic compound (B) is 1.5 to 50.

[11] The curable composition according to any one of [1] to

[10] , wherein the equivalent ratio (NCO / OH) of the NCO group of the polyisocyanate compound (C) to the OH group in the polyol compound (A) and the acrylic compound (B) is in the range of 0.2 to 2.0.

[12] The curable composition according to any one of [1] to

[11] , further comprising 1 to 5 parts by weight of a photopolymerization initiator (D) per 100 parts by weight of the total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C).

[13] The curable composition according to any one of [1] to

[12] , further comprising 0.1 to 0.5 parts by weight of a polysiloxane derivative (E) per 100 parts by weight of the total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C).

[14] A curable composition according to any one of [1] to

[13] , which is a dual-curing coating agent.

[15] A curable composition according to any one of [1] to

[14] , wherein the viscosity at 25℃ and a rotation speed of 20 / s is 500 to 30,000 mPa·s.

[16] An active energy ray curable film containing an (meth)acryloyl group-terminated urethane prepolymer comprising a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton as constituent monomers.

[17] The active energy ray curable film according to

[16] , wherein the polyol compound (A) comprises a compound (a) represented by the following formula (1).

[18] The active energy ray curable film according to

[16] or

[17] , wherein the number average molecular weight of the polyol compound (A) is less than 800.

[19] The active energy ray curable film according to any one of

[16] to

[18] , wherein the acrylic compound (B) comprises a compound (b) represented by formula (2").

[20] The active energy ray curable film according to any one of

[16] to

[18] , wherein the acrylic compound (B) comprises a compound (b') represented by formula (2').

[21] The active energy ray curable film according to any one of

[16] to

[18] , wherein the acrylic compound (B) comprises compound (b) represented by formula (2).

[22] The active energy ray curable film according to any one of

[16] to

[21] , wherein the polyisocyanate compound (C) comprises compound (c) represented by formula (3).

[23] The active energy ray curable film according to any one of

[16] to

[22] , wherein the acrylic compound (B) is contained in an amount of 1 to 70 parts by weight per 100 parts by weight of the polyol compound (A).

[24] An active energy ray curable film according to any one of

[16] to

[23] , comprising the polyol compound (A) and the acrylic compound (B) in a proportion such that the molar ratio (former / latter) of the hydroxyl groups of the polyol compound (A) to the hydroxyl groups of the acrylic compound (B) is 1.5 to 50.

[25] A cured product of any one of the curable compositions described in [1] to

[15] .

[26] A cured product of an active energy ray curable film as described in any one of

[16] to

[24] . A plastic molded article in which a coating made of the cured product described in

[27]

[25] or

[26] covers at least a portion of the surface of a substrate to be coated. A method for producing an active energy ray curable film, comprising:

[28] Heat-treating a coating film made from any one of the curable compositions described in [1] to

[15] to produce an active energy ray curable film containing an (meth)acryloyl group-terminated urethane prepolymer comprising a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton as constituent monomers.

[29] A method for manufacturing a plastic molded product comprising the following steps. Step 1: A reactive energy ray-curable film described in any one of

[16] to

[24] is pressed into the recess of the mold, and then molten plastic is filled in. Step 2: Solidify or harden the plastic filled into the recesses of the mold. Step 3: Remove the contents from the mold and cure the film by irradiating it with active energy rays.

[30] Use as a dual-curing coating agent of any one of the curable compositions described in [1] to

[15] .

[31] Use as a coating agent for (meth)acryloyl group-terminated urethane prepolymers comprising a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton as constituent monomers.

[32] Use as a film coating agent for a film containing a (meth)acryloyl group-terminated urethane prepolymer comprising a polyol compound (A) having an isocyanurate skeleton, an acrylic compound (B) having a hydroxyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton as constituent monomers. [Industrial applicability]

[0170] The composition of this disclosure has dual curability. When the composition is subjected to heat treatment, a semi-cured product is obtained. The semi-cured product has excellent conformability to the uneven shape of the substrate. Furthermore, when the semi-cured product is subjected to light irradiation treatment, a cured product is obtained. The cured product has excellent hardness, scratch resistance, and chemical resistance. Because the composition has the above properties, it is suitable as a film coating agent.

Claims

1. A curable composition comprising a polyol compound (A) having an isocyanurate skeleton, a compound (B) having a hydroxyl group and a (meth)acryloyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton and isocyanate groups other than the isocyanurate skeleton.

2. The curable composition according to claim 1, wherein the polyol compound (A) is compound (a) represented by the following formula (1). 【Chemistry 1】 [R in the formula 1 ~R 3 These are the same or different groups represented by the following formula (1a). 【Chemistry 2】 (In formula (1a), L 1 , L 2 represents an alkylene group having 1 to 10 carbon atoms, which may be the same or different, and m represents a number of 0 or more. However, R 1 ~R 3 The values ​​of m within the equation cannot be zero at the same time. (The bonds indicated by the wavy lines are bonded to the nitrogen atoms in the formula.)

3. The curable composition according to claim 1 or 2, wherein the compound (B) is a compound (b) represented by the following formula (2"). 【Transformation 3】 [where R in the formula 4 is H or CH 3 . R 6 is a group represented by the following formula (2b)] 【Chemistry 4】 (In formula (2b), L 6 , L 7 The '' represents an alkylene group having 1 to 10 carbon atoms, either identical or different, and n represents a number greater than or equal to 0. (The wavy bond indicates a bond to the oxygen atom in formula (2").)

4. The curable composition according to any one of claims 1 to 3, wherein the polyisocyanate compound (C) is a compound (c) represented by the following formula (3). 【Transformation 5】 [In formula (3), L 3 ~L 5 [These represent identical or different alkylene groups having 1 to 10 carbon atoms.]

5. The curable composition according to any one of claims 1 to 4, wherein the compound (B) is contained in an amount of 1 to 70 parts by weight per 100 parts by weight of the polyol compound (A).

6. A curable composition according to any one of claims 1 to 5, comprising the polyol compound (A) and the compound (B) in a ratio such that the molar ratio (former / latter) of hydroxyl groups of the polyol compound (A) to hydroxyl groups of the compound (B) is 1.5 to 50.

7. The curable composition according to any one of claims 1 to 6, wherein the equivalent ratio (NCO / OH) of the NCO group of the polyisocyanate compound (C) to the OH group in the polyol compound (A) and the compound (B) is in the range of 0.2 to 2.

0.

8. Furthermore, the curable composition according to any one of claims 1 to 7, wherein the photopolymerization initiator (D) is contained in an amount of 1 to 5 parts by weight per 100 parts by weight of the total of the polyol compound (A), the compound (B), and the polyisocyanate compound (C).

9. Furthermore, the curable composition according to any one of claims 1 to 8, wherein the polysiloxane derivative (E) is contained in an amount of 0.1 to 0.5 parts by weight per 100 parts by weight of the total of the polyol compound (A), the compound (B), and the polyisocyanate compound (C).

10. A curable composition according to any one of claims 1 to 9, which is a dual-curing type coating agent.

11. An active energy ray curable film containing a (meth)acryloyl group-terminated urethane prepolymer comprising a polyol compound (A) having an isocyanurate skeleton, a compound (B) having a hydroxyl group and a (meth)acryloyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton as constituent monomers.

12. A cured product of the curable composition according to any one of claims 1 to 10.

13. A cured product of an active energy ray curable film according to claim 11.

14. A plastic molded article in which a coating made of the cured product according to claim 12 or 13 covers at least a portion of the surface of a substrate to be coated.

15. A method for producing an active energy ray curable film, comprising: heat-treating a coating film made from a curable composition according to any one of claims 1 to 10; and producing an active energy ray curable film containing an active energy ray curable film containing a (meth)acryloyl group-terminated urethane prepolymer as constituent monomers, comprising a polyol compound (A) having an isocyanurate skeleton, a compound (B) having a hydroxyl group and a (meth)acryloyl group, and a polyisocyanate compound (C) having an isocyanurate skeleton.

16. A method for manufacturing a plastic molded product comprising the following steps. Step 1: The active energy ray curable film described in claim 11 is placed in close contact with the recess of the mold, and then molten plastic is filled in. Step 2: Solidify or harden the plastic filled into the recesses of the mold. Step 3: Remove the contents from the mold and cure the film by irradiating it with active energy rays.

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