Curable Composition and Cured Product Thereof

Abstract

The present invention provides a curable composition which can form a coating film having adhesion to a substrate surface, hardness, abrasion resistance and chemical resistance. The curable composition of the present disclosure comprises: 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 contains a compound (a) represented by the following formula (1). In the formula, R 1 ~R 3 are the same or different and are groups represented by the following 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 priority to Japanese Patent Application No. 2020-169881 filed in Japan on October 7, 2020, the contents of which are incorporated herein by reference. Background Art

[0002] Polyurethane resin has flexibility, elasticity, and strength. Therefore, the composition for polyurethane resin molding is used for coating agents, etc. For example, for coating agents used for coating plastic substrates constituting vehicle components or electronic devices, it is required to form a coating having adhesion to the substrate, hardness, and scratch resistance.

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

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 04-130119

[0007] Patent Document 2: Japanese Patent Application Publication No. 2011-137145

[0008] Patent Document 3: Japanese Patent Application No. 2015-530295 Summary of the invention

[0009] Problems to be solved by the invention

[0010] In the case of a coating agent containing a solvent, the solvent volatilizes during the film formation process, but this is not preferred because it may cause health damage and air pollution.

[0011] In addition, in recent years, as a method of coating a substrate constituting a vehicle component or an electronic device in a manner that takes into account both decoration and reinforcement, an in-mold molding method and a three-dimensional surface decoration molding method using a coating agent that forms a film (i.e., a film coating agent) are known. The film coating agent used in the above method is required to have height difference tracking properties and be cured while following the concave-convex shape of the substrate, thereby forming a coating that is closely attached to the substrate.

[0012] Furthermore, when a coating 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 has adhered, the coating film may deteriorate in appearance due to whitening or residual traces of the chemical solution.

[0013] Therefore, an object of the present disclosure is to provide a curable composition capable of forming a coating having adhesion to a substrate surface, hardness, abrasion resistance, and chemical resistance.

[0014] Another object of the present disclosure is to provide a curable composition capable of forming an energy ray-curable film, the energy ray-curable film having excellent followability to the surface of a substrate and capable of forming a film having excellent adhesion, hardness, scratch resistance, and chemical resistance to the surface of the substrate.

[0015] Another object of the present disclosure is to provide the curable composition having good coatability even without adding a solvent.

[0016] Another object of the present disclosure is to provide a cured product which is a cured product of the curable composition.

[0017] Another object of the present disclosure is to provide an energy ray-curable film and a cured product thereof, the energy ray-curable film having excellent followability to the surface of a substrate and capable of forming a film having excellent adhesion, hardness, scratch resistance, and chemical resistance to the surface of the substrate by irradiation with energy rays.

[0018] Another object of the present disclosure is to provide a method for producing the energy ray-curable film.

[0019] Another object of the present disclosure is to provide a plastic molded article in which at least a part of the surface of the substrate is covered with a film having excellent adhesion, hardness, scratch resistance, and chemical resistance.

[0020] Another object of the present disclosure is to provide a method for producing the plastic molded article.

[0021] Technical Solution

[0022] The present inventors have conducted intensive studies to solve the above problems and have found the following.

[0023] 1. A 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 an isocyanate group other than the isocyanurate skeleton) has excellent hardness, scratch resistance, and chemical resistance.

[0024] 2. A composition obtained by adding an acrylic compound (B) having a hydroxyl group to the polyol compound (A) and the polyisocyanate compound (C) has a low viscosity and excellent coatability even without adding a solvent.

[0025] 3. A composition obtained by adding an acrylic compound (B) having a hydroxyl group to the polyol compound (A) and the polyisocyanate compound (C) can form a cured product through a two-stage curing reaction of thermal curing and photo-curing. That is, it has dual curability.

[0026] 4. The semi-cured product obtained by thermally curing the composition having dual curability has excellent height difference followability. If it is photocured after following the unevenness of the substrate, a coating film excellent in adhesion to the unevenness of the substrate, and excellent in hardness, scratch resistance, and chemical resistance can be formed.

[0027] The present disclosure has been completed based on these insights.

[0028] That is, 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 an isocyanate group other than the isocyanurate skeleton.

[0029] The present disclosure also provides the above curable composition, wherein the polyol compound (A) is a compound (a) represented by the following formula (1).

[0030] [Chemical formula 1]

[0031]

[0032] [In the formula, R 1 ~R 3 are the same or different and are groups represented by the following formula (1a).]

[0033] [Chemical formula 2]

[0034]

[0035] (In formula (1a), L 1 , L 2 are the same or different and represent an alkylene group having 1 to 10 carbon atoms, and m represents a number of 0 or more. Among them, m in R 1 ~R 3 is not 0 at the same time. The wavy bonding bond is bonded to the nitrogen atom in the formula.)

[0036] The present disclosure also provides the above curable composition, wherein the acrylic compound (B) is a compound (b") represented by the following formula (2").

[0037] [Chemical formula 3]

[0038]

[0039] [In the formula, R 4 is H or CH 3 . R 6 is a group represented by the following formula (2b).]

[0040] [Chemical formula 4]

[0041]

[0042] (In formula (2b), L 6 and L 7 are the same or different and represent an alkylene group having 1 to 10 carbon atoms, and n represents a number of 0 or more. The wavy bonding bond is bonded to the oxygen atom in formula (2").)

[0043] The present disclosure also provides the curable composition, wherein the polyisocyanate compound (C) is a compound (c) represented by the following formula (3).

[0044] [Chemical formula 5]

[0045]

[0046] [In formula (3), L 3 to L 5 are the same or different and represent an alkylene group having 1 to 10 carbon atoms.]

[0047] The present disclosure also provides the curable composition, wherein the acrylic compound (B) is contained in a range of 1 to 70 parts by weight with respect to 100 parts by weight of the polyol compound (A).

[0048] The present disclosure also provides the curable composition, wherein the polyol compound (A) and the acrylic compound (B) are contained in a ratio such that the molar ratio (the former / latter) of the hydroxyl group of the polyol compound (A) to the hydroxyl group of the acrylic compound (B) is 1.5 to 50.

[0049] The present disclosure also provides the curable composition, 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.

[0050] The present disclosure also provides the curable composition, wherein 1 to 5 parts by weight of a photopolymerization initiator (D) is further contained with respect to 100 parts by weight in total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C).

[0051] The present disclosure also provides the curable composition, wherein 0.1 to 0.5 parts by weight of a polysiloxane derivative (E) is further contained with respect to 100 parts by weight in total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C).

[0052] The present disclosure also provides the curable composition, wherein the curable composition is a dual-curing type coating agent.

[0053] The present disclosure also provides a radiation-curable film containing a (meth)acryloyl-terminated urethane prepolymer, the (meth)acryloyl-terminated urethane prepolymer including 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.

[0054] The present disclosure also provides a cured product which is a cured product of the curable composition.

[0055] The present disclosure also provides a cured product which is a cured product of the radiation-curable film.

[0056] The present disclosure also provides a plastic molded article, wherein at least a part of the surface of a substrate to be coated is coated with a coating film formed of the cured product.

[0057] The present disclosure also provides a method for producing a radiation-curable film, wherein a coating film formed of the curable composition is subjected to a heat treatment to produce a radiation-curable film containing a (meth)acryloyl-terminated urethane prepolymer, the (meth)acryloyl-terminated urethane prepolymer including 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.

[0058] The present disclosure also provides a method for producing a plastic molded article, the production method including the following steps.

[0059] Step 1: The radiation-curable film is brought into close contact with a concave portion of a mold, and then molten plastic is filled.

[0060] Step 2: The plastic filled in the concave portion of the mold is solidified or cured.

[0061] Step 3: The content is taken out of the mold, and active energy rays are irradiated to cure the film.

[0062] Advantages of the Invention

[0063] The composition of the present disclosure includes: the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C). Therefore, the composition has dual curability. When the composition is subjected to a heat treatment, a urethane bonding reaction between a hydroxyl group and an isocyanate group occurs, but a radical polymerization reaction of (meth)acryloyl groups does not occur. Thus, a semi-cured product having radiation curability can be obtained.

[0064] The semi-cured product has excellent height difference followability. When the semi-cured product follows the unevenness of the substrate and then light irradiation treatment is performed, a radical polymerization reaction of (meth)acryloyl groups occurs. Thereby, a cured product that adheres closely to the substrate can be formed. In addition, the cured product thus formed is excellent in hardness, scratch resistance, and chemical resistance.

[0065] Since the composition has the above characteristics, a semi-cured product can be formed with a good yield even without strictly adjusting the thermal curing conditions (for example, curing temperature, curing time). Moreover, the film composed of the semi-cured product is suitable as a film coating agent for decoration and / or hard coating (especially a film coating agent for decoration and / or hard coating achieved by in-mold forming method or three-dimensional surface decoration forming method).

[0066] In addition, the composition has a low viscosity even without containing a solvent. If the composition is used, a coating agent with excellent usability (specifically, excellent coating property, and excellent environmental protection and safety) can be provided.

[0067] A plastic molded article having a coating film composed of a cured product of the composition on at least a part of the surface of the substrate has a high surface hardness, excellent scratch resistance and scratch recovery property. In addition, the coating film has excellent adhesion. For example, even when touched with a hand attached with a sunscreen agent or the like, the agent does not enter the gap between the substrate and the coating film to peel off the coating film. In addition, the coating film has excellent chemical resistance. Therefore, for example, even when touched with a hand attached with a sunscreen agent or the like, the coating film does not become cloudy or leave a chemical solution trace. Therefore, the plastic molded article of the present disclosure can maintain an excellent appearance for a long time. Detailed Description

[0068] [Curable Composition]

[0069] The curable composition of the present disclosure contains: a polyol compound (A), an acrylic compound (B), and a polyisocyanate compound (C). The curable composition of the present disclosure may contain other components in addition to the above components.

[0070] [Polyol Compound (A)]

[0071] The polyol compound (A) is a compound having a plurality of hydroxyl groups. The number of hydroxyl groups possessed by the polyol compound (A) is, for example, 2 or more, preferably 2 to 4, and particularly preferably 3 to 4. The polyol compound (A) also has an isocyanurate skeleton. Therefore, the crosslinking density of the obtained cured product is high, showing excellent hardness, scratch resistance, and chemical resistance.

[0072] The polyol compound (A) is, for example, a compound (a) represented by the following formula (1).

[0073] [Chemical Formula 6]

[0074]

[0075] [In the formula, R 1 ~R 3 are the same or different and are groups represented by the following formula (1a).]

[0076] [Chemical formula 7]

[0077]

[0078] (In formula (1a), L 1 , L 2 are the same or different and represent an alkylene group having 1 to 10 carbon atoms, and m represents a number of 0 or more. Among them, m in R 1 ~R 3 is not 0 at the same time. The wavy bonding bond is bonded to the nitrogen atom in the formula.)

[0079] Examples of the alkylene group having 1 to 10 carbon atoms include linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, butylene, 1-methyltrimethylene, 2-methyltrimethylene, 1,1'-dimethylethylene, pentylene, hexylene, heptylene, octylene, 2-ethylhexylene, nonylene, and decylene.

[0080] As L 1 , an alkylene group having 1 to 3 carbon atoms is preferred. In addition, as L 1 , a linear alkylene group is preferred.

[0081] As L 2 , an alkylene group having 1 to 8 carbon atoms is preferred, and an alkylene group having 4 to 6 carbon atoms is particularly preferred. In addition, as L 2 , a linear alkylene group is preferred.

[0082] In formula (1a), m is the average value of the degree of polymerization of the unit shown in the parentheses of formula (1a) and is a number of 0 or more. m is, for example, 0 to 7, and from the viewpoint of densifying the mesh structure and improving drug resistance by shortening the distance between crosslinking points of the obtained cured product, it is preferably 0 to 4, more preferably 0 to 3, further preferably more than 0 and 3 or less, particularly preferably more than 0 and 2 or less, and most preferably 1 to 2.

[0083] The number average molecular weight (Mn: standard polystyrene conversion) of compound (a) is, for example, less than 800, and from the viewpoint of densifying the mesh structure and improving drug resistance by shortening the distance between crosslinking points of the obtained cured product, it is preferably 570 to 630, more preferably 580 to 620, and particularly preferably 590 to 615.

[0084] In addition, the molecular weight dispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of the compound (a) is preferably 1.0 to 1.5, more preferably 1.0 to 1.3, and still more preferably 1.0 to 1.2.

[0085] It should be noted that the number-average molecular weight and molecular weight dispersity of the compound (a) can be measured by the apparatus and conditions described in the examples below.

[0086] The hydroxyl value (KOH mg / g) of the compound (a) is, for example, 200 to 400. Among them, from the aspect of improving the hardness, scratch resistance, and chemical resistance of the obtained cured product, it is preferably 260 to 300, more preferably 270 to 290, and still more preferably 275 to 285. It should be noted that the hydroxyl value can be measured by the hydroxyl value measurement method described in JIS-K1557.

[0087] The compound (a) can be produced, for example, by ring-opening polymerization of a lactone starting from the hydroxyl group of the following formula (1'). L in the formula (1') 1 is the same as L in the formula (1a). 1 The three Ls in the formula (1') 1 can be the same or different.

[0088] [Chemical formula 8]

[0089]

[0090] Examples of the lactone include α-ethyl lactone, β-propyl lactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and the like.

[0091] The curable composition of the present disclosure may contain a single polyol compound (A) or may contain two or more polyol compounds (A) in combination.

[0092] <Acrylic compound (B)>

[0093] The acrylic compound (B) is a compound having a hydroxyl group and a (meth)acryloyl group. The acrylic compound (B) is, for example, a compound (b') represented by the following formula (2').

[0094] [Chemical formula 9]

[0095]

[0096] [In the formula, L 7 represents an alkylene group having 1 to 10 carbon atoms, R 4 is H or CH 3 , and R 5 is H or a group represented by the following formula (2a).]

[0097] [Chemical Formula 10]

[0098]

[0099] (In formula (2a), L 6 is the same or different and represents an alkylene group having 1 to 10 carbon atoms, and n represents a number of 0 or more. The wavy bonding bond is bonded to the oxygen atom in formula (2').)

[0100] The acrylic compound (B) may also be a compound (b) represented by the following formula (2). R in the following formula 4 and R 5 are the same as those described above.

[0101] [Chemical Formula 11]

[0102]

[0103] The acrylic compound (B) may also be a compound (b") represented by the following formula (2").

[0104] [Chemical Formula 12]

[0105]

[0106] [In the formula, R 4 is H or CH 3 . R 6 is a group represented by the following formula (2b).

[0107] [Chemical Formula 13]

[0108]

[0109] (In formula (2b), L 6 and L 7 are the same or different and represent an alkylene group having 1 to 10 carbon atoms, and n represents a number of 0 or more. The wavy bonding bond is bonded to the oxygen atom in formula (2").)

[0110] Examples of the alkylene group having 1 to 10 carbon atoms as the L 6 and L 7 are the same as those of the alkylene group having 1 to 10 carbon atoms in L 1 and L 2 .

[0111] As the L 6 , among them, an alkylene group having 1 to 8 carbon atoms is preferable, and an alkylene group having 4 to 6 carbon atoms is particularly preferable. In addition, as L 6 , a linear alkylene group is preferable.

[0112] As the L 7 , more preferably an alkylene group having 1 to 8 carbon atoms, still more preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably an alkylene group having 2 to 4 carbon atoms, and especially preferably an alkylene group having 2 carbon atoms (especially ethylene). Further, as the L 7 , a linear alkylene group is preferred.

[0113] The n is the average value of the degree of polymerization of the unit shown in the parentheses in the formula, and is a number of 0 or more. For example, n is 0 to 7. From the viewpoint of densifying the mesh structure and improving the chemical resistance by shortening the distance between crosslinking points of the obtained cured product, the upper limit value of n is preferably 4, more preferably 3, and particularly preferably 2. Further, from the viewpoint of improving the stretchability of the obtained semi-cured product, n is preferably more than 0, more preferably 0.2 or more, still more preferably 0.5 or more, particularly preferably 0.75 or more, and most preferably 1 or more.

[0114] As the group represented by the formula (2b), in terms of obtaining a cured product having scratch recovery properties by making the distance between crosslinking points uniform, it is preferably the same group as the group represented by the formula (1a) of the compound (a).

[0115] The number average molecular weight (Mn: standard polystyrene conversion) of the acrylic compound (B) is preferably 600 or less, more preferably 250 to 500, and still more preferably 300 to 400.

[0116] In addition, the molecular weight dispersity (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 still more preferably 1.0 to 1.5.

[0117] It should be noted that the number average molecular weight and molecular weight dispersity of the acrylic compound (B) can be measured by the same method as the number average molecular weight and molecular weight dispersity of the compound (a).

[0118] The hydroxyl value (KOHmg / g) of the acrylic compound (B) is, for example, 100 to 300, preferably 140 to 180, more preferably 150 to 170, and still more preferably 155 to 165. It should be noted that the hydroxyl value can be measured by the hydroxyl value measurement method described in JIS-K1557.

[0119] From the viewpoint of reducing the viscosity of the curable composition and enabling solvent-free, the viscosity of the acrylic compound (B) at 25 ° C and a rotation speed of 20 / s is, 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.

[0120] The curable composition of the present disclosure may contain one acrylic compound (B) alone, or may contain two or more acrylic compounds (B) in combination.

[0121] In addition to the acrylic compound (B), the curable composition of the present disclosure may also contain other acrylic compounds (i.e., compounds having a (meth)acryloyl group). From the viewpoints of low viscosity and the ability to be solvent-free, as well as improving the hardness, scratch resistance, and chemical resistance of the resulting cured product, the proportion of the 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.

[0122] <Polyisocyanate compound (C)>

[0123] The polyisocyanate compound (C) is a compound having an isocyanurate skeleton. The 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.

[0124] The polyisocyanate compound (C) is, for example, a compound (c) represented by the following formula (3).

[0125] [Chemical formula 14]

[0126]

[0127] [In formula (3), L 3 ~L 5 are the same or different and represent an alkylene group having 1 to 10 carbon atoms].

[0128] In formula (3), as the alkylene group having 1 to 10 carbon atoms for L 3 ~L 5 , examples similar to the alkylene group having 1 to 10 carbon atoms for L 1 , L 2 can be cited.

[0129] As L 3 ~L 5 , preferably an alkylene group having 3 to 8 carbon atoms. In addition, as L 3 ~L 5 , a linear alkylene group is preferred.

[0130] The NCO content in the polyisocyanate compound (C) is, for example, 17 to 25% by weight, preferably 18 to 24% by weight, and more preferably 19 to 23% by weight.

[0131] The curable composition of the present disclosure may contain one polyisocyanate compound (C) alone, or may contain two or more polyisocyanate compounds (C) in combination.

[0132] In addition to the polyisocyanate compound (C), the curable composition of the present disclosure may contain other isocyanate compounds (i.e., compounds having an isocyanate group). However, from the viewpoint of improving the hardness, scratch resistance, and chemical 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.

[0133] Examples of other isocyanate compounds include aliphatic polyisocyanates such as 1,6 - hexamethylene diisocyanate, 2,2,4 - trimethylhexamethylene diisocyanate, and 2,4,4 - trimethylhexamethylene diisocyanate; trimers (excluding polyisocyanate compound (C)), urethane compounds, biuret compounds, or adducts of the above - mentioned aliphatic polyisocyanates; aromatic polyisocyanates such as toluene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; polyisocyanates obtained by hydrogenating aromatic polyisocyanates, alicyclic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate; trimers, urethane compounds, biuret compounds, or adducts of the above - mentioned aromatic polyisocyanates or the above - mentioned alicyclic polyisocyanates, etc.

[0134] The content of the acrylic compound (B) in the curable composition is, for example, 1 to 70 parts by weight relative to 100 parts by weight of the polyol compound (A). From the viewpoints of maintaining the hardness, scratch resistance, and chemical resistance of the resulting cured product and obtaining a semi - cured product with excellent stretchability, the upper limit value of the content of the acrylic compound (B) 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. In addition, from the viewpoints of obtaining a composition with excellent coatability even without adding a solvent and obtaining a semi - cured product with stretchability sufficient to exhibit height difference followability, the lower limit value of the content of the acrylic compound (B) 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.

[0135] In the curable composition, the molar ratio (the former / latter) of the hydroxyl groups of the polyol compound (A) to the hydroxyl groups of the acrylic compound (B) is, for example, 1.5 to 50. From the aspects of maintaining the hardness, abrasion resistance, and chemical resistance of the obtained cured product and the semi-cured product having good stretchability, the lower limit value of the molar ratio is preferably 2.0, particularly preferably 4.0, and most preferably 5.0. Further, from the viewpoints of obtaining a composition having excellent coatability even without adding a solvent and obtaining a semi-cured product having stretchability sufficient to exhibit height difference followability, the upper limit value of the molar ratio is preferably 30, more preferably 20, further preferably 15, particularly preferably 12, and especially preferably 10. If the content of the hydroxyl groups of the polyol compound (A) is lower than the above range, the stretchability of the semi-cured product tends to decrease. On the other hand, if the content of the hydroxyl groups of the acrylic compound (B) is lower than the above range, the double curability decreases and it becomes difficult to obtain a semi-cured product.

[0136] In addition to the polyol compound (A) and the acrylic compound (B), the curable composition may contain a hydroxyl group-containing compound (i.e., a compound having at least one hydroxyl group). However, the proportion of the total of the polyol compound (A) and the acrylic compound (B) in the total amount of the hydroxyl group-containing compounds contained in the curable composition is, for example, 60% by weight or more, preferably 70% by weight or more, further preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more.

[0137] From the aspect of improving the hardness, abrasion resistance, and chemical resistance of the obtained cured product, the content of the isocyanate compound (C) in the curable composition is preferably 40 to 160 parts by weight, more preferably 70 to 150 parts by weight, and further preferably 100 to 140 parts by weight with respect to 100 parts by weight of the polyol compound (A).

[0138] From the aspect of improving the stretchability of the obtained semi-cured product without significantly reducing the hardness, abrasion resistance, and chemical resistance of the obtained cured product, 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 further preferably 8 to 20 parts by weight with respect to 100 parts by weight of the total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C).

[0139] From the viewpoint of improving the hardness, abrasion resistance and chemical resistance of the resulting cured product, the equivalent ratio (NCO / OH) of the NCO groups of the polyisocyanate compound (C) in the curable composition to the OH groups in the polyol compound (A) and the acrylic compound (B) is preferably in the range of 0.2 to 2.0, more preferably 0.5 to 1.5, still more preferably 0.7 to 1.3, and particularly preferably 0.9 to 1.2.

[0140] The total content of the polyol compound (A), the acrylic compound (B) and the isocyanate compound (C) relative to the total weight (100% by weight) of the nonvolatile components in the curable composition is, for example, 80% by weight or more, preferably 85% by weight or more, and still more preferably 90% by weight or more.

[0141] In addition to the polyol compound (A), the acrylic compound (B) and the polyisocyanate compound (C), the curable composition may further contain one or more other components as needed, and preferably contains a photopolymerization initiator and a surface conditioner.

[0142] (Photopolymerization initiator (D))

[0143] As the photoinitiator (D), there is no particular limitation, and it can be selected and used according to the purpose. For example, the following can be cited: 1-hydroxycyclohexyl phenyl 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-morpholinopropan-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzil dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, methyl phenyl glyoxylate, benzil, camphorquinone, etc. Specifically, for example, the product name "Irgacure1173" (2-hydroxy-2-methyl-1-phenylpropanone, manufactured by IGM Resigns B.V.) can be cited. They can be used alone or in combination of two or more.

[0144] The content of the photoinitiator (D) is, for example, 1 to 5 parts by weight based on the total amount (100 parts by weight) of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C). If the amount of the photoinitiator (D) used is 1 to 5 parts by weight, sufficient curing can be carried out without being excessive or insufficient.

[0145] In addition, the content of the photoinitiator (D) is, for example, 1 to 5 parts by weight based on 10 parts by weight of the acrylic compound (B).

[0146] (Surface conditioner)

[0147] As the surface conditioner, for example, a polysiloxane derivative (E) can be cited. If a surface conditioner is added to the curable composition, an effect of making the surface of the coating film smooth can be obtained.

[0148] As the polysiloxane derivative (E), for example, a compound having a polydimethylsiloxane skeleton can be cited. Among them, polyether-modified polydimethylsiloxane is preferred, and poly(ethylene oxide) adduct polydimethylsiloxane, poly(propylene oxide) adduct polydimethylsiloxane, etc., poly(epoxy C) are particularly preferred.2-4 Alkane - added polydimethylsiloxane.

[0149] The content of the polysiloxane derivative (E) is, for example, 0.1 to 0.5 parts by weight with respect to the total 100 parts by weight of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C).

[0150] (Other components)

[0151] The curable composition may further contain one or more other components. As other components, for example, the following can be cited: inorganic particles, surfactants, pigments, dyes, ultraviolet absorbers, light stabilizers, defoamers, wetting agents, dispersants, viscoelasticity modifiers, thixotropy imparting agents, preservatives, film - forming agents, plasticizers, penetrants, fragrances, fungicides, mildew inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, matting agents, touch - feel improvers, design - imparting agents, etc.

[0152] (Inorganic particles)

[0153] As inorganic particles, for example, the following can be cited: silica, alumina, mica, synthetic mica, talc, calcium oxide, calcium carbonate, zirconia, 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, aluminum hydroxide, etc. They can be used alone or in combination of two or more.

[0154] As inorganic particles, from the viewpoint of improving the chemical resistance and scratch resistance of the coating film, silica is preferred.

[0155] The particle size of the inorganic particles is not particularly limited, and from the viewpoint of good appearance, for example, it is preferably 0.01 nm to 1 μm.

[0156] The content of other components is not particularly limited, and is preferably 10% by weight or less with respect to the total weight of the non - volatile components of the curable composition (100% by weight).

[0157] In addition, from the viewpoint of reducing the environmental burden, for the curable composition, the content of the solvent is preferably 1% by weight or less, more preferably 0.5% by weight or less, and further preferably 0.1% by weight or less with respect to the total weight of the non - volatile components (100% by weight). The curable composition is particularly preferably substantially free of solvents.

[0158] The curable composition contains the polyol compound (A) and the acrylic compound (B) as hydroxyl - containing compounds in combination, and thus has a low viscosity. Therefore, even when the content of the solvent is in the above range, the curable composition has good coatability.

[0159] 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. From the viewpoint of forming a coating film with an appropriate thickness, the lower limit value of the viscosity is preferably 1000 mPa·s, particularly preferably 2000 mPa·s. From the viewpoint of forming a uniform coating film, the upper limit value of the viscosity is preferably 10,000 mPa·s, particularly preferably 6000 mPa·s, and most preferably 4000 mPa·s.

[0160] The curable composition can be produced by mixing the above components. It should be noted that the curable composition is preferably used in the form of a two-component type. For example, it is preferable to store the polyol compound (A) and the polyisocyanate compound (C) separately and mix them at the time of use. Thereby, curing of the curable composition during storage can be prevented.

[0161] Since the curable composition has the above constitution, a cured product can be formed through a curing reaction in two stages of thermal curing and photocuring. That is, the curable composition is a dual-curing type composition.

[0162] When the curable composition is subjected to a thermal curing treatment, a urethane bonding reaction proceeds to obtain a semi-cured product having photoenergy ray curability. The semi-cured product has a large elongation at break and excellent height difference followability. Even for a substrate having a curved surface (or non-planar surface; including concave-convex shapes and spherical shapes), the semi-cured product can well follow its surface shape. After the semi-cured product follows the surface shape of the substrate, a photocuring treatment is carried out to polymerize the (meth)acryloyl group contained in the semi-cured product, whereby the semi-cured product is cured, and a cured product having excellent adhesion, hardness, scratch resistance, and chemical resistance to the substrate can be formed.

[0163] When the curable composition is used in in-mold molding or three-dimensional surface decoration molding, it is preferable to previously subject the curable composition to a thermal curing treatment to form a film-like semi-cured product, and carry out the molding on the film-like semi-cured product. The film-like semi-cured product has excellent stretchability, and thus can follow and adhere to the concave portion of the mold.

[0164] Therefore, the curable composition can be used as a dual-curing type coating agent. In addition, the curable composition can also be used as a material for a film coating agent. It should be noted that a film coating agent refers to a coating agent formed into a film shape or a sheet shape. Furthermore, the curable composition can also be used as a coating agent (particularly a film coating agent) for in-mold molding and three-dimensional surface decoration molding.

[0165] [Semi-cured product]

[0166] The semi-cured product of the present disclosure contains a (meth)acryloyl-terminated urethane prepolymer. The urethane prepolymer 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 as constituent monomers.

[0167] In addition to the above, the urethane prepolymer may further contain other monomers as constituent monomers. The total proportion of the polyol compound (A), acrylic compound (B), and polyisocyanate compound (C) in the total amount of the 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.

[0168] In addition to the urethane prepolymer, the semi-cured product may further contain other constituent components. The proportion of the urethane prepolymer in the total amount of the constituent 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 be composed only of the urethane prepolymer.

[0169] The semi-cured product is obtained by subjecting the hydroxyl groups contained in the polyol compound (A) and the acrylic compound (B) to urethane bonding with the isocyanate groups of the polyisocyanate compound (C).

[0170] The urethane bonding reaction is carried out, for example, by heating the curable composition. The heating treatment conditions are, for example, 0.5 to 12 hours at 100 to 150 °C. After the heating treatment, it may be further aged at room temperature (1 to 30 °C) for about 12 to 60 hours.

[0171] Regarding the semi-cured product, since the contained urethane prepolymer contains the polyol compound (A) and the acrylic compound (B) as constituent monomers, it has excellent stretchability, and the elongation at break is, for example, 60% or more, preferably 80% or more, more preferably 100% or more, further preferably 120% or more, and particularly preferably 125% or more. It should be noted that the elongation at break can be measured by the apparatus and conditions described in the examples below.

[0172] Since the semi-cured product has the above stretchability, it has excellent height difference followability and can well follow the curved surface of a substrate to be coated (for example, a plastic substrate such as PET). In addition, when the semi-cured product is irradiated with active energy rays, the (meth)acryloyl groups polymerize with each other to form a cured product. Therefore, the semi-cured product is suitable as a film coating agent.

[0173] [Cured product]

[0174] The cured product of the present disclosure is the cured product of the curable composition or the semi-cured product. The cured product contains a polymer obtained by subjecting the hydroxyl groups in the curable composition and isocyanate groups to urethane bonding and then polymerizing (meth)acryloyl groups with each other.

[0175] The cured product is obtained by subjecting the curable composition to thermal curing and photo-curing. More specifically, the cured product 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 in the urethane bonding reaction.

[0176] The cured product is also obtained by subjecting the semi-cured product to photo-curing. More specifically, it is obtained by subjecting the semi-cured product to active energy ray irradiation treatment.

[0177] Examples of the active energy ray include ultraviolet rays or electron beams, etc. From the viewpoints of industrial properties such as safety and reaction efficiency, etc., it is preferable to use ultraviolet rays. Examples of the irradiation source of ultraviolet rays include high-pressure mercury lamps, metal halide lamps, etc. The irradiation amount of ultraviolet rays is, for example, 100 to 10,000 mJ / cm 2 .

[0178] The cured product is excellent in hardness, chemical resistance, scratch resistance, and scratch recovery.

[0179] The cured product has high hardness, and the pencil hardness (by the method according to JIS K5600) is, for example, preferably H or more, more preferably 2H or more, particularly preferably 3H or more, and most preferably 4H or more.

[0180] The cured product is excellent in chemical resistance. Moreover, even if a sunscreen agent adheres, the surface of the cured product does not swell or become cloudy. That is, the cured product is excellent in sunscreen agent resistance.

[0181] The cured product is excellent in scratch resistance. It should be noted that the scratch resistance can be measured by the apparatus and conditions described in the examples.

[0182] In the case of performing a scratch test of 10 reciprocations on the cured product under the state of using steel wool and applying a load of 500 g, 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.

[0183] In addition, when a rubbing test is performed 20 times reciprocally on the cured product while using steel wool and applying a load of 500 g, the gloss retention rate 2 minutes after the rubbing test is, for example, 80% or more, preferably 85% or more, particularly preferably 90% or more, and most preferably 95% or more.

[0184] It should be noted that the gloss retention rate 2 minutes after the rubbing test is calculated according to the following formula.

[0185] Gloss retention rate 2 minutes after rubbing test (%) = (G1) / (G0) × 100

[0186] The G0 represents the gloss of the cured product before the rubbing test, that is, the initial gloss [Gs(60°)] of the cured product.

[0187] The G1 represents the gloss [Gs(60°)] of the cured product 2 minutes after the rubbing test.

[0188] In addition, when a rubbing test is performed 10 times reciprocally while using steel wool and applying a load of 500 g, the gloss retention rate after leaving the cured product standing for 24 hours after the rubbing test is, for example, preferably 80% or more, more preferably 85% or more, particularly preferably 90% or more, and most preferably 95% or more.

[0189] In addition, when a rubbing test is performed 20 times reciprocally on the cured product while using steel wool and applying a load of 500 g, the gloss retention rate after leaving the cured product standing for 24 hours after the rubbing test is, for example, preferably 80% or more, more preferably 85% or more, particularly preferably 90% or more, and most preferably 95% or more.

[0190] It should be noted that the gloss retention rate after leaving the cured product standing for 24 hours after the rubbing test is calculated according to the following formula.

[0191] Gloss retention rate after leaving the cured product standing for 24 hours after rubbing test (%) = (G2) / (G0) × 100 The G0 represents the gloss of the cured product before the rubbing test, that is, the initial gloss [Gs(60°)] of the cured product.

[0192] The G2 represents the gloss [Gs(60°)] of the cured product after leaving the cured product after the rubbing test standing for 24 hours under the constant temperature and humidity conditions of 23°C and 50% RH.

[0193] The cured product has both of the above characteristics. Therefore, if a substrate is coated with a coating film composed of the cured product, the substrate can be imparted with hardness, chemical resistance, scratch resistance, and scratch recovery properties. In addition, the substrate can also be decorated. That is, if the substrate is coated with the cured product, beauty and new functions can be imparted to the substrate. It should be noted that examples of the substrate include: the housing of home appliances (such as refrigerators, washing machines, air conditioners, televisions, etc.); the housing of electronic devices (such as personal computers, mobile phones, smart phones, etc.); the components constituting musical instruments (such as pianos, electronic organs, electronic musical instruments, etc.); vehicle components for vehicles such as automobiles or railway vehicles (interior materials such as instrument panels, door trim panels, headliners, and cabin covers, and exterior materials such as bumpers).

[0194] [Energy ray curable film]

[0195] The energy ray curable film of the present disclosure contains a (meth)acryloyl-terminated urethane prepolymer, and the (meth)acryloyl-terminated urethane prepolymer includes 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.

[0196] The film can be manufactured, for example, by subjecting a coating film composed of the curable composition to a heat treatment. The heat treatment conditions are the same as those in the urethane bonding reaction.

[0197] As a method for forming the coating film of the curable composition, there is no particular limitation. For example, it can be formed by coating the curable composition on the surface of a release film, a substrate, etc. using the following methods: screen printing method, mask printing method, offset printing method, inkjet printing method, flexographic printing method, gravure printing method, stamping, dispensing, squeegee printing method, screen printing method, spraying, brush coating, etc.

[0198] The thickness of the film is not particularly limited and is, for example, 20 to 150 μm.

[0199] The film has stretchability derived from the above urethane prepolymer. That is, the film has a large elongation at break and excellent height difference followability. Therefore, the film can follow the curved surface of the substrate well. In addition, when the film is irradiated with energy rays, (meth)acryloyl groups copolymerize with each other to form a cured product having excellent hardness, scratch resistance, and chemical resistance.

[0200] The film has the above characteristics, and therefore is suitable as a film coating agent, for example, and is particularly suitable as a film coating agent for in-mold forming and three-dimensional surface decoration forming.

[0201] [Plastic molded product and its manufacturing method]

[0202] In the case of the plastic molded article of the present disclosure, a film formed of a cured product of the curable composition (or a cured product of the active energy ray curable film) covers at least a part of the surface of a substrate as an object to be coated. That is, in the case of the plastic molded article, a coating film formed of the cured product is provided on at least a part of the substrate surface.

[0203] The plastic molded article includes, for example: cases of mobile phone terminals, notebook PCs, digital cameras, etc.; household electrical appliances, cosmetic containers, interior and exterior parts of automobiles, etc.

[0204] The thickness of the coating film formed of the cured product is not particularly limited, and is, for example, 20 to 150 μm.

[0205] In the case of the above-mentioned substrate, at least plastic is contained in the forming material. In addition to plastic, the forming material may further contain, for example, materials such as wood, metal, glass, cloth, leather, and silicone.

[0206] The plastics include thermoplastic resins and thermosetting resins. They may be used alone or in combination of two or more.

[0207] Examples of the thermoplastic resin 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, polyamide 1212; polyphenylene ethers such as poly(2,6-dimethyl-1,4-phenylene ether); homopolymers or copolymers of acrylonitrile such as PAN resin, AS resin, ABS resin, AAS resin, ACS resin, AES resin, AXS resin; (meth)acrylic resins, polycarbonate, polyacetal, polyphenylene sulfide, polyether ether ketone, polyamideimide, polyimide, polyetherimide, polysulfone, polyethersulfone, and modified products or derivatives of these resins, and further polymer blends or polymer alloys containing these resins.

[0208] Examples of the thermosetting resin include: phenolic resin, urea resin, melamine resin, unsaturated polyester, furan resin, epoxy resin, polyurethane resin, allyl resin, polyimide, etc.

[0209] The substrate is preferably a molded article (preferably a three-dimensional molded article) containing a cured 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 a flat surface or a curved surface (including concave-convex shapes and spherical shapes). Further, it may also include a combination of a flat surface portion and a curved surface portion.

[0210] The plastic molded article can be manufactured, for example, by coating the surface of the formed substrate with the above curable composition and performing thermal curing and photocuring.

[0211] In addition, the active energy ray curable film has excellent stretchability. Therefore, if the active energy ray curable film is used, a plastic molded article having a film with excellent adhesion can be manufactured by an in-mold forming method or a three-dimensional surface decoration forming method.

[0212] A method for manufacturing a plastic molded article using the active energy ray curable film includes, for example, the following steps.

[0213] Step 1: Bring the active energy ray curable film into close contact with the concave portion of the mold, and then fill with molten plastic.

[0214] Step 2: Solidify or cure the plastic filled in the concave portion of the mold.

[0215] Step 3: Take out the content from the mold and irradiate with active energy rays to cure the film.

[0216] (Step 1)

[0217] Step 1 is a step of bringing the active energy ray curable film into close contact with the concave portion of the mold and then filling with molten plastic.

[0218] As a method for bringing the active energy ray curable film into close contact with the concave portion of the mold, for example, the following methods can be used without particular limitation: using a mold having suction holes, disposing the film on the upper part of the mold, and performing suction from the suction holes to make the space between the film and the mold in a vacuum state, thereby bringing the film into close contact with the mold; disposing the film on the upper part of the mold and bringing the film into close contact with the mold by compressed air from the upper part of the film, etc.

[0219] After bringing the film into close contact with the concave portion of the mold in this way, molten plastic is injected into the gap of the mold concave portion.

[0220] (Step 2)

[0221] Step 2 is a step of solidifying or curing the plastic filled in the concave portion of the mold. The method of solidifying or curing can be appropriately selected according to the type of plastic. For example, when the plastic is a thermoplastic resin, it can be solidified by cooling the molten plastic to a temperature below the melting point. In addition, when the plastic is a thermosetting resin, it can be cured by performing a heat treatment on the molten plastic.

[0222] After Step 2, a solidified or cured plastic (i.e., a substrate) having the active energy ray curable film on its surface is obtained.

[0223] (Process 3)

[0224] Process 3 is a process of taking out the content (i.e., the substrate having the active energy ray curable film on the surface) from the mold and irradiating the taken-out content with active energy rays to cure the film.

[0225] The irradiation conditions of the active energy rays are the same as those of the active energy ray irradiation when manufacturing the above-mentioned cured product.

[0226] Each configuration and the combination of each configuration in the above-described embodiment are examples, and additions, omissions, replacements, and other changes of the configuration can be appropriately made without departing from the gist of the invention of the present disclosure. The invention of the present disclosure is not limited by the embodiment, but is limited only by the claims.

[0227] In addition, the various aspects disclosed in this specification can be combined with any other features disclosed in this specification.

[0228] Examples

[0229] Hereinafter, the present disclosure will be described more specifically by way of examples, but the present disclosure is not limited by these examples.

[0230] [Synthesis Example 1]

[0231] Under a nitrogen atmosphere, 1306 g of tris(2-hydroxyethyl)isocyanurate, 1694 g of ε-caprolactone, and 6 mg of stannous octoate were put into a five-necked flask equipped with a reflux condenser, a thermometer, a mixed gas inlet tube, and a stirring device, and then the internal temperature was raised to 170 °C.

[0232] After confirming that the concentration of ε-caprolactone became less than 1.0% by analysis based on gas chromatography, it was cooled and taken out from the five-necked flask. The number average molecular weight (Mn) of the obtained compound was 611, the molecular weight dispersity (Mw / Mn) was 1.2, the viscosity was 14.3 [Pa·s / 25 °C], and the hydroxyl value was 280.1.

[0233] It should be noted that the molecular weight of the obtained compound was measured using a high-speed GPC device, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined by comparison with a polystyrene standard, and the molecular weight dispersity (Mw / Mn) was calculated.

[0234] The measurement conditions are as follows.

[0235] · Measurement device: High-speed GPC device "HLC-8220GPC", manufactured by Tosoh Corporation.

[0236] · Mobile phase: Tetrahydrofuran.

[0237] [Example 1]

[0238] A polyol compound (A), an acrylic compound (B), a polyisocyanate compound (C), a photopolymerization initiator (D), and a surface conditioner (E) as shown in Table 1 were placed in a 50 mL glass container, and mixed and defoamed using a rotation / revolution mixer (THINKYMIXER vacuum type, model: ARV-310, manufactured by THINKY Co., Ltd.) to obtain a composition.

[0239] The obtained composition was cast onto a glass plate frame sandwiching a 2 mm thick Teflon (registered trademark) spacer, heat cured in an oven at 120°C for 3 hours, then dried, and further cured at a constant temperature and humidity of 23°C and 50% RH for 48 hours to obtain a semi-cured product.

[0240] Furthermore, the obtained composition was applied to a polyethylene terephthalate film (Cosmo Shine A4100#100, manufactured by Toyobo Co., Ltd.) using an applicator in a film thickness of 30 μm. Subsequently, the composition was heat cured at 120° C. for 3 hours in an oven, and then dried, and then cured for 48 hours under constant temperature and humidity conditions of 23° C. and 50% RH to obtain a laminate (semi-cured material / PET film laminate) of a semi-cured material including an acryl-terminated urethane prepolymer containing the polyol compound (A), an acrylic compound (B), and a polyisocyanate compound (C) as constituent monomers and a PET film.

[0241] Next, the semi-cured material side of the semi-cured material / PET film laminate was irradiated with a 4 kW x 1 lamp inverter type conveyor (ECS-401GX, manufactured by EYE GRAPHICS Co., Ltd.) at a dose of 400 mJ / cm 2 UV irradiation was performed twice to allow a photocuring reaction to proceed, thereby obtaining a laminate of a cured product and a PET film (cured product / PET film laminate, hereinafter also referred to as a laminate).

[0242] [Examples 2 to 5, Comparative Example 1]

[0243] Except having changed the formulation of the composition as described in Table 1, it carried out similarly to Example 1, and obtained the composition, semi-cured material, and laminated body.

[0244] The compositions, semi-cured products, and laminated bodies obtained in Examples and Comparative Examples were evaluated as follows.

[0245] (Viscosity)

[0246] Regarding the viscosities of the compositions obtained in the examples and comparative examples, a rheometer (trade name "PHYSICA UDS200", manufactured by Paar Physica) was used to measure the viscosities (mPa·s) at 25°C and a rotational speed of 20 / s. It should be noted that in the comparative examples, the viscosities of the composition before adding the solvent and the composition after adding the solvent were measured.

[0247] (Usability)

[0248] The usability of the compositions obtained in the examples and comparative examples was evaluated by the following method.

[0249] Judgment criteria

[0250] ○: The amount of the solvent contained in the composition is less than 1% by weight relative to the total weight (100% by weight) of the non-volatile components, and the viscosity of the composition is 4000 mPa·s or less.

[0251] Δ: The amount of the solvent contained in the composition is less than 1% by weight relative to the total weight (100% by weight) of the non-volatile components, and the viscosity of the composition exceeds 4000 mPa·s and is 30,000 or less.

[0252] ×: The amount of the solvent contained in the composition is 1% by weight or more relative to the total weight (100% by weight) of the non-volatile components, or the viscosity of the composition exceeds 30,000 mPa·s.

[0253] (Tensile property)

[0254] The semi-cured products obtained in the examples and comparative examples were punched into JIS No. 3 dumbbell-shaped objects as specimens, and a Tensilon universal testing machine (RTC-1350A (manufactured by A&D Co., Ltd.)) was used to conduct a tensile test under the following conditions, and the elongation at break (%) was calculated according to the following formula. The greater the elongation at break, the more excellent the tensile property.

[0255] Elongation at break (%) = [(Length of the specimen at break (L) - Length of the specimen before the test (L0)) / Length of the specimen before the test (L0)] × 100

[0256] <Tensile test conditions>

[0257] Test atmosphere: 23°C, 50% RH.

[0258] Tensile speed: 500 mm / min.

[0259] The number of tests was set to 5 times, and the maximum value and the minimum value were excluded to obtain the average value, and this average value was adopted as the length of the specimen at break (L).

[0260] (Adhesion)

[0261] When the elongation at break of the semi-cured product obtained by heat curing is large, it can follow the surface shape of the substrate. In addition, in the case of photo-curing after following the substrate surface, if the elongation at break of the obtained cured product is 70% or less, good adhesiveness to the substrate is exhibited, and a cured product with excellent conformity can be obtained. Therefore, the conformity is evaluated based on the following criteria.

[0262] <Conformity judgment criteria>

[0263] ◎(Excellent): The elongation at break after heat curing is 100% or more, and the elongation at break after heat curing + photo-curing is 80% or less.

[0264] ○(Good): The elongation at break after heat curing is 80% or more and less than 100%, and the elongation at break after heat curing + photo-curing is 80% or less.

[0265] ×(Non-conforming): The elongation at break after heat curing is less than 80%, or the elongation at break after heat curing + photo-curing exceeds 80%.

[0266] (Pencil hardness)

[0267] The pencil hardness of the cured film side surface of the laminate obtained in the examples and comparative examples was evaluated using the method based on JIS K5600.

[0268] That is, the cured product side surface of the laminate was rubbed with a pencil (the core of the pencil), and it was regarded as NG (defective) when a scratch was confirmed on the surface. Specifically, evaluation was performed using a pencil of a certain hardness. If no scratch was left, the operation of evaluating with a pencil of a higher hardness was repeated. If a scratch was confirmed, re-evaluation was performed using a pencil of one hardness lower than it. In addition, if no scratch was confirmed, evaluation was performed again using a pencil of a higher hardness. In the case where reproducibility was confirmed two or more times, the hardness of the hardest pencil that did not leave a scratch was taken as the pencil hardness of the cured film.

[0269] · Pencil for evaluation: "Pencil for pencil hardness test" manufactured by Mitsubishi Pencil Co., Ltd.

[0270] · Load: 750 gf.

[0271] · Scratch distance: 7 mm or more.

[0272] · Scratch angle: 45°.

[0273] · Measurement environment: 23°C, 50% RH.

[0274] (Abrasion resistance and abrasion recovery)

[0275] The abrasion resistance of the cured film side surface of the laminates obtained in the examples and comparative examples was evaluated by an abrasion test as follows: Steel wool (B-204, Bonstar industrial grade #0000) was attached to a friction tester (standard type, manufactured by Rika Kogyo Co., Ltd., Japan), and reciprocating motion (10 or 20 reciprocations) was performed on the film under a load of 500 g. Using a gloss meter (Gloss Meter VG7000, manufactured by Nippon Denshoku Industries Co., Ltd., Japan), the initial gloss (G0) [Gs(60°)] before the abrasion test and the gloss (G1) [Gs(60°)] 2 minutes after the abrasion test of the cured film side surface were measured. The gloss retention rate was calculated according to the following formula, and the abrasion resistance was evaluated therefrom.

[0276] Gloss retention rate (%) 2 minutes after abrasion test = (G1) / (G0) × 100

[0277] In addition, the abraded laminate was allowed to stand for 24 hours under constant temperature and humidity conditions of 23°C and 50% RH, and the gloss (G2) [Gs(60°)] of the film after standing was measured. The gloss retention rate relative to the initial gloss (G0) [Gs(60°)] was calculated according to the following formula, and the abrasion recovery was evaluated therefrom. The abrasion recovery was evaluated separately after 10 reciprocations and 20 reciprocations.

[0278] Gloss retention rate (%) 24 hours after standing after abrasion test = (G2) / (G0) × 100 Judgment criteria

[0279] ◎ (Good): Gloss retention rate is 90% or more.

[0280] ○ (Qualified): Gloss retention rate is less than 90% and 80% or more.

[0281] × (Unqualified): Gloss retention rate is less than 80% or the coating film is peeled off and the gloss cannot be measured.

[0282] (Resistance to sunscreen agent (immersion method))

[0283] The entire cured film side surface of the test pieces [rectangular, 2 cm 2 of the laminates obtained in the examples and comparative examples was brought into contact with 0.4 g of sunscreen (Neutrogena "UltraSheer Dry-Touch SPF45") measured on a glass slide (contact amount per unit area of the cured film and the sunscreen: 0.1 g / cm 2 ).

[0284] Cover the above-mentioned cured coating film integrally with a polyvinylidene chloride film, leave it standing in an oven at 80 °C for 5 hours, wipe off the sunscreen, and evaluate the adhesion state of the cured coating film using the following criteria. The less likely the cured coating film is to peel off, the better the adhesion to the substrate and the drug resistance.

[0285] Judgment criteria

[0286] ○: The cured coating film has not peeled off.

[0287] ×: A part of the cured coating film has peeled off or the cured coating film has completely peeled off.

[0288] (Resistance to sunscreen agent (drop method))

[0289] On the side surface of the cured coating film of the laminate obtained in the examples and comparative examples, apply sunscreen ("UltraSheer Dry-Touch SPF45" manufactured by Neutrogena) so as to be 0.025 g / cm 2 . After leaving it standing in an oven at 50 °C for 1 hour, wipe off the sunscreen, and evaluate the appearance of the cured coating film using the following criteria.

[0290] Judgment criteria

[0291] ◎: For the cured coating film, the appearance has hardly changed.

[0292] ○: Traces of the liquid medicine remain on the cured coating film.

[0293] ×: The cured coating film swells, or the cured coating film swells and turns white.

[0294] The above results are summarized in Table 1 below.

[0295] [Table 1]

[0296]

[0297]

[0298] Polyol compound (A): The compound obtained by Synthesis Example 1.

[0299] Acrylic compound (B): Trade name "PLACCEL FA2D" (acrylate derivative, Mn 344, Mw / Mn 1.4, hydroxyl value 159 - 164, viscosity at 25 °C 80 mPa·s), manufactured by DAICEL CORPORATION.

[0300] Polyisocyanate (C): Trade name "TAKENATE D-170N" (isocyanurate-modified product of hexamethylene diisocyanate), manufactured by Mitsui Chemicals, Inc.

[0301] Photoinitiator (D): Trade name “Irgacure 1173” (2-hydroxy-2-methyl-1-phenylpropanone), manufactured by IGM Resigns B.V.

[0302] Surface conditioner (E): “BYK-306” (ether-modified polydimethylsiloxane), manufactured by BYK-Chemie Japan Co., Ltd.

[0303] Solvent: Diethylene glycol monoethyl ether acetate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0304] The curable composition obtained in the examples has both the polyol compound (A) and the acrylic compound (B). Therefore, it can be known that: the curable composition has dual curability, and a semi-cured product can be obtained after thermal curing. The semi-cured product has excellent stretchability and good height difference followability. In addition, it can be known that: when the semi-cured product is subjected to photocuring treatment, a cured product with high hardness, excellent abrasion resistance, abrasion recovery property, and chemical resistance can be obtained. In addition, the curable composition obtained in the examples has a low viscosity and has good coatability even without adding a solvent.

[0305] On the other hand, it can be known that: the curable composition obtained in Comparative Example 1 does not contain the acrylic compound (B), so it does not have dual curability and is completely cured by thermal curing. The obtained cured product has high hardness, excellent abrasion resistance, abrasion recovery property, and chemical resistance, but has low stretchability and does not have height difference followability. In addition, the curable composition obtained in Comparative Example 1 does not contain the acrylic compound (B), so the viscosity is too high in the state before adding the solvent and it is difficult to coat. That is, it is difficult to achieve solvent-free in the curable composition without the acrylic compound (B).

[0306] From the above, it can be known that: the curable composition of the present disclosure maintains the properties of the obtained cured product (hardness, abrasion resistance, abrasion recovery property, and chemical resistance) and has dual curability as a new property. Even without strictly adjusting the curing conditions, a semi-cured product can be formed with a good yield, and the obtained semi-cured product has excellent stretchability. In addition, it can be known that: the curable composition can be solvent-free without impairing the coatability, has a small environmental burden, and excellent safety.

[0307] As a summary of the above, the constitution of the present disclosure and its modifications are noted below.

[0308] [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 an isocyanate group other than the isocyanurate skeleton.

[0309] [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.

[0310] [3]The curable composition according to [1] or [2], wherein the polyol compound (A) is a compound (a) represented by the following formula (1).

[0311] [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.

[0312] [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").

[0313] [6]The curable composition according to any one of [1] to [4], wherein the acrylic compound (B) is a compound (b') represented by formula (2').

[0314] [7]The curable composition according to any one of [1] to [4], wherein the acrylic compound (B) is a compound (b) represented by formula (2).

[0315] [8]The curable composition according to any one of [1] to [7], wherein the polyisocyanate compound (C) is a compound (c) represented by formula (3).

[0316] [9]The curable composition according to any one of [1] to [8], wherein the acrylic compound (B) is contained in a range of 1 to 70 parts by weight relative to 100 parts by weight of the polyol compound (A).

[0317]

[10] The 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 (the former / the latter) of the hydroxyl group of the polyol compound (A) to the hydroxyl group of the acrylic compound (B) is 1.5 to 50.

[0318]

[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.

[0319]

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

[11] , wherein 1 to 5 parts by weight of a photopolymerization initiator (D) is further contained based on 100 parts by weight in total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C).

[0320]

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

[12] , wherein 0.1 to 0.5 part by weight of a polysiloxane derivative (E) is further contained based on 100 parts by weight in total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C).

[0321]

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

[13] , wherein the curable composition is a dual-curing type coating agent.

[0322]

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

[14] , wherein the curable composition has a viscosity of 500 to 30,000 mPa·s at 25°C and a rotation speed of 20 / s.

[0323]

[16] A radiation-curable film containing a (meth)acryloyl-terminated urethane prepolymer, wherein the (meth)acryloyl-terminated urethane prepolymer 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 as constituent monomers.

[0324]

[17] The radiation-curable film according to

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

[0325]

[18] The radiation-curable film according to

[16] or

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

[0326]

[19] The radiation-curable film according to any one of

[16] to

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

[0327]

[20] The radiation-curable film according to any one of

[16] to

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

[0328]

[21] The radiation-curable film according to any one of

[16] to

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

[0329]

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

[16] to

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

[0330]

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

[16] to

[22] , wherein the acrylic compound (B) is contained in a range of 1 to 70 parts by weight with respect to 100 parts by weight of the polyol compound (A).

[0331]

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

[16] to

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

[0332]

[25] A cured product, which is a cured product of the curable composition according to any one of [1] to

[15] .

[0333]

[26] A cured product, which is a cured product of the active energy ray-curable film according to any one of

[16] to

[24] .

[0334]

[27] A plastic molded article, wherein at least a part of the surface of a substrate to be coated is coated with a coating film made of the cured product according to

[25] or

[26] .

[0335]

[28] A method for manufacturing an active energy ray-curable film, wherein a coating film composed of the curable composition according to any one of [1] to

[15] is heat-treated to manufacture an active energy ray-curable film containing a (meth)acryloyl-terminated urethane prepolymer, and the (meth)acryloyl-terminated urethane prepolymer 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 as constituent monomers.

[0336]

[29] A method for manufacturing a plastic molded article, wherein the manufacturing method has the following steps.

[0337] Step 1: Bring the active energy ray-curable film according to any one of

[16] to

[24] into close contact with a concave portion of a mold, and then fill molten plastic.

[0338] Step 2: Solidify or cure the plastic filled in the concave portion of the mold.

[0339] Step 3: Take out the content from the mold and irradiate active energy rays to cure the film.

[0340]

[30] Use of a curable composition as a dual-curable coating agent, which is the use of the curable composition as described in any one of [1] to

[15] as a dual-curable coating agent.

[0341]

[31] Use of a (meth)acryloyl-terminated urethane prepolymer as a coating agent, wherein the (meth)acryloyl-terminated urethane prepolymer 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 as constituent monomers.

[0342]

[32] Use of a film as a film coating agent, wherein the film contains a (meth)acryloyl-terminated urethane prepolymer, and the (meth)acryloyl-terminated urethane prepolymer 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 as constituent monomers.

[0343] Industrial availability

[0344] The composition of the present disclosure has dual curability. When the composition is subjected to a heat treatment, a semi-cured product can be obtained. The semi-cured product has excellent followability to the uneven shape of the substrate. In addition, when the semi-cured product is subjected to a light irradiation treatment, a cured product can be obtained. The cured product has excellent hardness, scratch resistance, and chemical resistance. Since the composition has the above characteristics, it is suitable as a film coating agent.

Claims

1. A curable composition, the 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 an isocyanate group other than the isocyanurate skeleton, Based on 100% by weight of the total weight of the non-volatile components in the curable composition, the total content of the polyol compound (A), the acrylic compound (B), and the isocyanate compound (C) is 90% by weight or more, The polyol compound (A) is a compound (a) represented by the following formula (1), R in the formula 1 ~R 3 are the same or different and are groups represented by the following formula (1a). In formula (1a), L 1 , L 2 which are the same or different, represent an alkylene group having 1 to 10 carbon atoms, and m represents a number of 0 or more. wherein, R 1 ~R 3 m in them is not 0 at the same time, and the wavy bonding bond is bonded to the nitrogen atom in the formula; The acrylic compound (B) is a compound (b") represented by the following formula (2"), R in the formula 4 is H or CH 3 ; R 6 is a group represented by the following formula (2b), In formula (2b), L 6 , L 7 which are the same or different, represent an alkylene group having 1 to 10 carbon atoms, n represents a number of 0 or more, and the wavy bonding bond is bonded to the oxygen atom in formula (2").

2. The curable composition according to claim 1, wherein, The polyisocyanate compound (C) is a compound (c) represented by the following formula (3), In formula (3), L 3 to L 5 are the same or different and represent an alkylene group having 1 to 10 carbon atoms.

3. The curable composition according to claim 1 or 2, wherein, Based on 100 parts by weight of the polyol compound (A), the acrylic compound (B) is contained in a range of 1 to 70 parts by weight.

4. The curable composition according to claim 1 or 2, wherein, The polyol compound (A) and the acrylic compound (B) are contained in a ratio such that the molar ratio of the hydroxyl group of the polyol compound (A) to the hydroxyl group of the acrylic compound (B), i.e., the former / latter, is 1.5 to 50.

5. The curable composition according to claim 1 or 2, wherein, The equivalent ratio of the NCO group of the polyisocyanate compound (C) to the OH group in the polyol compound (A) and the acrylic compound (B), i.e., NCO / OH, is in the range of 0.2 to 2.

0.

6. The curable composition according to claim 1 or 2, wherein, Based on 100 parts by weight of the total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C), a photoinitiator (D) is further contained in an amount of 1 to 5 parts by weight.

7. The curable composition according to claim 1 or 2, wherein, Based on 100 parts by weight of the total of the polyol compound (A), the acrylic compound (B), and the polyisocyanate compound (C), a polysiloxane derivative (E) is further contained in an amount of 0.1 to 0.5 parts by weight.

8. The curable composition according to claim 1 or 2, wherein, The curable composition is a dual-curing type coating agent.

9. A radiation curable film, the radiation curable film containing a (meth)acryloyl-terminated urethane prepolymer, the (meth)acryloyl-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, The total proportion of the polyol compound (A), the acrylic compound (B), and the isocyanate compound (C) in the total amount of the constituent monomers is 90% by weight or more, The polyol compound (A) is a compound (a) represented by the following formula (1), R in the formula 1 ~R 3 are the same or different and are groups represented by the following formula (1a): In formula (1a), L 1 and L 2 which are the same or different, represent an alkylene group having 1 to 10 carbon atoms, and m represents a number of 0 or more. wherein, R 1 ~R 3 m in them is not 0 at the same time, and the wavy bonding key is bonded to the nitrogen atom in the formula; the acrylic compound (B) is a compound (b") represented by the following formula (2"), R in the formula 4 is H or CH 3 , R 6 is a group represented by the following formula (2b), In formula (2b), L 6 , L 7 which may be the same or different, each represents an alkylene group having 1 to 10 carbon atoms, n represents a number of 0 or more, and the wavy bonding bond is bonded to the oxygen atom in formula (2").

10. A cured product, which is a cured product of the curable composition according to any one of claims 1 to 8.

11. A cured product, which is a cured product of the active energy ray curable film according to claim 9.

12. A plastic molded article, wherein, a coating film composed of the cured product according to claim 10 or 11 covers at least a part of the surface of a substrate as an object to be coated.

13. A method for manufacturing an active energy ray curable film, wherein, a coating film composed of the curable composition according to any one of claims 1 to 8 is subjected to a heat treatment to manufacture an active energy ray curable film containing a (meth)acryloyl-terminated urethane prepolymer, and the (meth)acryloyl-terminated urethane prepolymer 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 as constituent monomers.

14. A method for manufacturing a plastic molded article, wherein, the manufacturing method has the following steps: Step 1: bringing the active energy ray curable film according to claim 9 into close contact with a concave portion of a mold, and then filling molten plastic; Step 2: solidifying or curing the plastic filled in the concave portion of the mold; and Step 3: taking out the content from the mold and irradiating active energy rays to cure the film.

Images