JP6596852B2 - Curable resin composition and laminated structure - Google Patents

Description

  The present invention relates to a curable resin composition and a laminated structure in which a cured product layer obtained by curing the composition is formed on a substrate.

The curable resin composition is immediately cured by irradiation with active energy rays to form a cured film having excellent strength and chemical resistance. Therefore, the curable resin composition is used as a paint or a coating material for protecting various surfaces. In recent years, it is used for optical films or sheets such as antireflection films, polarizing films, and prism sheets used in image display devices such as liquid crystal displays, as well as housings, display panels, switch buttons, and the like of electronic devices and home appliances. Use in insert molding or in-mold transfer films is expanding.
The curable resin composition used for such applications is required to have high hardness and scratch resistance in order to prevent the appearance and performance from being damaged by scratches or dents. Among them, in recent years, as a means to improve the resistance to scratches, rather than improving hardness, by improving flexibility and resilience, even if minor scratches or dents occur, the scratches are restored over time Thus, it has been practiced to have a property of disappearing (hereinafter referred to as self-repairing property).

Since the self-repairing property is a useful property in various applications, it can be applied to a wide range of applications. Higher resilience and quicker repair time, especially when used in parts of a household appliance such as housing, panels, image display devices, etc. Tend to be preferred.
In addition, since various types of base materials are used depending on the application, it is necessary that the adhesiveness to those base materials is good. As a general method for imparting adhesion, a method of increasing the wet spread, penetration into the substrate, and affinity with the substrate by blending a monofunctional or bifunctional monomer with low viscosity into the curable resin This technique can be used for self-healing resins as well.

However, in order to express self-repairability, it is necessary to have both flexibility and hardness in an appropriate balance, and it is necessary to design a molecule so that an appropriate crosslinking density is obtained when a cured film is formed. When a monofunctional or bifunctional monomer is added to provide adhesion, the crosslink density is reduced when a cured film is formed, so that a problem that the self-repairing property is not sufficiently expressed may occur. For this reason, various attempts have been made to provide good adhesion to a substrate while sufficiently exhibiting self-repairing properties in actual use.
For example, Patent Document 1 includes a hydroxyl group-containing (meth) acrylate compound, a polyol, a urethane (meth) acrylate composed of an isocyanate having an aromatic ring structure, and a monomer having one ethylenically unsaturated group. A curable resin composition is disclosed. However, the composition described in Patent Document 1 is excellent in adhesion and is excellent in hardness due to the incorporation of an aromatic ring structure, but is insufficient in flexibility and Since instant restoration was not recognized, it was not fully satisfied in actual use.

Patent Document 2 discloses a resin composition containing urethane (meth) acrylate, polyol, and monofunctional (meth) acrylate. However, the composition described in Patent Document 2 can be expected to have excellent effects on adhesion and flexibility by including a polyol as a plasticizer. Although restored and lost over time, it does not have sufficient hardness when used in the above-mentioned image display devices, electronic devices and home appliance housings, etc., so a pencil, pen, metal brush Since scratches remain when contacted with a material having a high hardness and sharpness such as self-healing, the self-repairing property was not sufficiently satisfied in actual use.
Patent Document 3 discloses a resin composition containing urethane (meth) acrylate, a monofunctional ethylenically unsaturated compound, and a polyfunctional (meth) acrylate monomer. However, the resin composition described in Patent Document 3 is suitably used for lens sheets such as lenticular lenses and Fresnel lenses, and has an aromatic ring structure in order to have excellent hardness and high refractive index. However, although it exhibits excellent resilience against deformation, it does not have the flexibility to exhibit flaw resilience as described in this application, and it does not have the flexibility to display image display devices, electronic devices, and home appliances as described above. It was not suitable for use on the body.

JP 2014-141654 A JP 2007-314779 A JP 2004-131520 A

  As described above, the problem of the present invention is that a curable resin composition that cures rapidly by irradiation with active energy rays and exhibits excellent self-repairability in actual use, excellent adhesion to a plastic substrate, and curl resistance. And a laminate in which a cured product of the composition is formed.

As a result of intensive studies to solve the above problems, the present inventor has found that polyoxyalkylene mono (meth) acrylate having a specific alkylene oxide chain length, polyether polyol having a specific alkylene oxide chain length, and isocyanurate of a diisocyanate compound. A curable resin composition containing urethane (meth) acrylate obtained by reacting a modified product and polyoxyalkylene mono (meth) acrylate having a specific alkylene oxide chain length in a specific ratio solves the above problem. As a result, the present invention has been completed.
That is, the present invention includes the following [1] and [2].

（式中、Ｒ¹は水素原子またはメチル基を示し、Ｒ²は炭素原子数２〜４のアルキレン基を示し、ａはＲ²Ｏの平均付加モル数であり、２〜８を示す。）
（ａ２）下記式（２）で表されるポリエーテルジオール

（式中、Ｒ³は炭素原子数２〜４のアルキレン基を示し、ｂはＲ³Ｏの平均付加モル数であり、２〜１６を示す。）
（ａ３）下記式（３）で表されるジイソシアネート化合物のイソシアヌレート変性体

（式中、Ｒ⁴は炭素数４〜１０のアルキレン基を示す。）
（Ｂ）成分：下記式（４）で表される単官能エチレン性不飽和化合物

（式中、Ｒ⁵は水素原子またはメチル基を示し、Ｒ⁶は炭素原子数２〜４のアルキレン基を示し、ｃはＲ⁶Ｏの平均付加モル数であり、０〜２を示す。）
［２］前記の［１］に記載の硬化性樹脂組成物を硬化して得られる硬化物層、および基材の少なくとも二層で構成され、前記基材の少なくとも一方の面に前記硬化物層が形成されてなる積層構造体。 [1] A curable resin composition containing the following components (A) and (B) in a mass ratio of (A) :( B) = 50: 50 to 95: 5.
Component (A): The following components (a1) to (a3)
The equivalent ratio of hydroxyl group of (a1) / hydroxyl group of (a2) is 2.0 to 59.0,
The equivalent ratio of the hydroxyl groups of (a1) and (a2) / isocyanate groups of (a3) is 0.9 to 1.1.
Urethane (meth) acrylate (a1) obtained by reacting at a reaction ratio of (1) Polyoxyalkylene mono (meth) acrylate represented by the following formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 4 carbon atoms, and a represents the average number of moles of R ² O added and represents 2 to 8)
(A2) polyether diol represented by the following formula (2)

(In the formula, R ³ represents an alkylene group having 2 to 4 carbon atoms, b represents the average number of added moles of R ³ O, and represents 2 to 16).
(A3) Isocyanurate-modified product of diisocyanate compound represented by the following formula (3)

(In the formula, R ⁴ represents an alkylene group having 4 to 10 carbon atoms.)
Component (B): monofunctional ethylenically unsaturated compound represented by the following formula (4)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alkylene group having 2 to 4 carbon atoms, and c represents an average added mole number of R ⁶ O, and represents 0 to 2).
[2] A cured product layer obtained by curing the curable resin composition according to the above [1], and a substrate, and the cured product layer on at least one surface of the substrate. A laminated structure in which is formed.

  The curable resin composition of the present invention is rapidly cured by irradiation with active energy rays, and exhibits excellent self-repairability in actual use, excellent adhesion to a plastic substrate, and curl resistance. Therefore, the curable resin composition of the present invention can be used for various paints, coating materials, optical films or sheets such as antireflection films, polarizing films, and prism sheets used in image display devices such as liquid crystal displays, electronic devices, It is useful for applications such as insert molding or in-mold transfer film used for housings of home appliances, display panels, switch buttons and the like.

  The present invention is described in detail below. The curable resin composition of the present invention is characterized by comprising a specific urethane (meth) acrylate as the component (A) and a specific monofunctional ethylenically unsaturated compound as the component (B).

<Urethane (meth) acrylate (A)>
The urethane (meth) acrylate (A) used in the curable resin composition of the present invention comprises a polyoxyalkylene mono (meth) acrylate as the component (a1), a polyether polyol as the component (a2), and a diisocyanate compound as the component (a3). It is a compound obtained by urethanation reaction using the modified isocyanurate.

  The polyoxyalkylene mono (meth) acrylate (a1) is a compound obtained by ring-opening addition polymerization of a C2-C4 alkylene oxide to a hydroxyalkyl (meth) acrylate.

  Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Among these, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable. These hydroxyalkyl (meth) acrylates may be used alone or in combination of two or more.

  Examples of the alkylene oxide having 2 to 4 carbon atoms used for the ring-opening addition polymerization include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. Among these, ethylene oxide and propylene oxide are preferable from the viewpoint of reactivity. These alkylene oxides may be used alone or in combination of two or more. When using 2 or more types together, you may make it react in a block form and may make it react in a random form.

  The number of moles of alkylene oxide added relative to the polyoxyalkylene mono (meth) acrylate is 2 in order to suppress curing shrinkage when forming a coating film and to provide appropriate flexibility for developing self-repairing properties. It is -8 mol, Preferably it is 3-6 mol. By setting the number of added moles within this range, it is possible to obtain a good crosslink density when a coating film is formed, and to have good self-repairability, curl resistance, and flexibility.

  The polyoxyalkylene mono (meth) acrylate (a1) can be generally produced according to a known method. For example, a hydroxyalkyl (meth) acrylate, an alkylene oxide, a ring-opening polymerization catalyst, and a polymerization inhibitor or an organic solvent as necessary are charged into a reaction vessel, and a predetermined temperature is maintained for reaction. At this time, the alkylene oxide may be allowed to react while adding dropwise other raw materials first and then dropwise. Further, after the reaction, the catalyst may be adsorbed using a known adsorbent, and the adsorbent may be removed by filtration, or the salt generated by neutralization with an acid or alkali may be removed by filtration.

  Examples of the polyoxyalkylene mono (meth) acrylate (a1) include polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxybutylene mono (meth) acrylate, and polyoxyethylene polyoxypropylene mono (Meth) acrylate, polyoxyethylene polyoxybutylene mono (meth) acrylate, polyoxypropylene polyoxybutylene mono (meth) acrylate and the like. These (a1) components may be used independently and may use 2 or more types together.

  Examples of the polyether polyol (a2) include polyethylene glycol, polypropylene glycol, and polybutylene glycol. Of these, polyethylene glycol and polypropylene glycol are preferred. These polyether polyols may be used alone or in combination of two or more.

  The number of repeating units of the alkylene oxide of the polyether polyol (a2) is 2 to 16 mol, preferably 3 in order to impart moderate flexibility when a coating film is formed and to exhibit self-healing properties. ~ 12 moles. By setting the repeating unit of the alkylene oxide in this range, it is possible to impart an appropriate flexibility to the coating film and to exhibit good self-repairing properties.

  As the diisocyanate compound used in the isocyanurate-modified product (a3) of the diisocyanate compound, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate as aliphatic diisocyanate, Examples of the alicyclic diisocyanate include isophorone diisocyanate and dicyclohexylmethane-4,4′-diisocyanate, and examples of the aromatic diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate. Among these, aliphatic diisocyanate and alicyclic diisocyanate are preferable, and aliphatic diisocyanate is particularly preferable from the viewpoint of yellowing resistance and self-healing properties. Specifically, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate are preferable, and 1,6-hexamethylene diisocyanate is particularly preferable.

  In general, the isocyanurate-modified product (a3) of the diisocyanate compound can be produced according to a known method. For example, an isocyanurate-forming catalyst such as the diisocyanate compound or quaternary ammonium salt and an organic solvent as required are charged into a reaction vessel, and the isocyanurate-forming reaction is carried out while maintaining a predetermined temperature. Further, after the reaction, it is preferable to stop the isocyanuration reaction by introducing a reaction terminator for the purpose of improving the storage stability of the product. Furthermore, it is preferable to remove the unreacted diisocyanate compound by distillation.

  Examples of commercially available products of the isocyanurate-modified product (a3) of the diisocyanate compound include “Duranate TPA-100”, “Duranate TKA-100”, “Duranate TLA-100” manufactured by Asahi Kasei Chemicals Corporation, "Sumijoule N3300", "Death Module N3600", "Death Module N3790BA", "Death Module N3900", "Death Module Z4700BA" manufactured by Sumika Bayer Urethane Co., Ltd., "Takenate D-" manufactured by Mitsui Takeda Chemical Co., Ltd. 170N "," Bernock DN-980 "," Bernock DN-981 "," Bernock DN-990 "," Bernock DN-992 ", manufactured by DIC Corporation," Coronate HX "," Nippon Polyurethane Co., Ltd. " Coronate HXR, Coronate HX V "and the like.

  In the production of the urethane (meth) acrylate (A), the blending ratio of the polyoxyalkylene mono (meth) acrylate (a1) and the polyether polyol (a2) is the flexibility, hardness, and hardness of the urethane (meth) acrylate described later. From the viewpoint of handling properties, the equivalent ratio of hydroxyl group of (a1) / hydroxyl group of (a2) is 2.0 to 59.0, preferably 3.0 to 15.0. By setting the equivalent ratio in this range, it is possible to obtain a urethane acrylate having good handling properties without causing problems such as gelation in the later-described urethanization.

  In the production of urethane (meth) acrylate (A), the equivalent ratio of hydroxyl group to isocyanate group is the sum of hydroxyl groups of (a1) and (a2) / equivalent of isocyanate group of (a3) from the viewpoint of storage stability of the product. The ratio is preferably 0.9 to 1.1, more preferably 0.95 to 1.05.

  In the production of the urethane (meth) acrylate (A), the method of the urethanization reaction is not particularly limited, but it can be generally produced according to a known method. For example, the components (a1), (a2), and (a3) are charged into a reaction vessel, and a urethanization catalyst, a polymerization inhibitor, a yellowing inhibitor, and an organic solvent are charged as required. React in At this time, there are no particular limitations on the method of adding the components (a1), (a2), and (a3), but all of these may be charged all at once or may be added to the system in small amounts and allowed to react. Alternatively, after reacting either the component (a1) or the component (a2) with the component (a3) first, the remaining components may be added and reacted.

  In the urethanization reaction, it is preferable to use a urethanization catalyst because the reaction time can be shortened. Examples of the urethanization catalyst include organic tin compounds such as dibutyltin dilaurate, organic bismuth compounds such as dibutylbismuth dilaurate, tertiary amines such as triethylamine, and quaternary ammonium such as tetraalkylammonium bromide. These urethanization catalysts are used in an amount of 0.005 to 1.0% by weight based on the total amount of reaction raw materials.

The urethanization reaction is usually performed in the range of 30 to 100 ° C. The end point of the urethanization reaction can be confirmed by disappearance of the infrared absorption spectrum at 2270 cm ⁻¹ indicating the isocyanate group, or by determining the isocyanate group content by the method described in JIS K 7301.

<Monofunctional ethylenically unsaturated compound (B)>
Examples of the monofunctional ethylenically unsaturated compound (B) used in the curable resin composition of the present invention include (meth) acrylic acid, hydroxyalkyl (meth) acrylate, or polyoxyalkylene mono (meth) acrylate. Polyoxyalkylene mono (meth) acrylate is a compound obtained by ring-opening addition polymerization of C2-C4 alkylene oxide to hydroxyalkyl (meth) acrylate.

  Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Among these, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable. These hydroxyalkyl (meth) acrylates may be used alone or in combination of two or more.

  The number of added moles of alkylene oxide in the polyoxyalkylene mono (meth) acrylate is 1 to 2 and preferably 1 from the viewpoint of improving the adhesion to the substrate. By setting the number of added moles within this range, good adhesion can be imparted.

  The blending ratio of the urethane (meth) acrylate (A) and the monofunctional ethylenically unsaturated compound (B) is (A) when the total mass of the component (A) and the component (B) is 100% by mass (A ) :( B) = 50: 50 to 95: 5, preferably 60:40 to 90:10. By making the compounding quantity of (A) component and (B) component into this range, self-restoring property and adhesiveness can be expressed with good balance.

<Photopolymerization initiator>
You may mix | blend a photoinitiator with the curable resin composition of this invention. Examples of the photopolymerization initiator include benzoin and benzoin alkyl ethers such as benzoin and benzoin methyl ether; aromatic ketones such as benzophenone and benzoylbenzoic acid; benzyl ketals such as benzyldimethyl ketal and benzyldiethyl ketal; 1-hydroxycyclohexyl Acetophenones such as phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) An acyl phosphine oxide such as phenyl phosphine oxide may be mentioned. Among these, acetophenone such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 Acylphosphine oxide such as 1,4,6-trimethylbenzoyl) phenylphosphine oxide is preferred, and acetophenone such as 1-hydroxycyclohexyl phenyl ketone is more preferred.

  Furthermore, the curable resin composition of the present invention includes a (meth) acrylic polymer, a surface conditioner, a leveling agent, a filler, a pigment, and a silane coupling agent as long as the effects of the present invention are not inhibited as optional components. An antistatic agent, an antifoaming agent, an antifouling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a photopolymerization initiator, an organic solvent, and the like can be blended.

  The curable resin composition of the present invention can be obtained by blending and mixing the urethane (meth) acrylate (A), the monofunctional ethylenically unsaturated compound (B), and other optional components as necessary.

<Configuration and production method of laminate>
The laminate of the present invention is composed of at least two layers of a cured product layer of a curable resin composition containing a urethane (meth) acrylate (A) and a monofunctional ethylenically unsaturated compound (B), and a substrate. The cured product of the curable resin composition is formed on at least one surface of the substrate.

  Although it does not specifically limit as said base material, The thing of materials, such as a plastics, glass, a metal, wood, paper, can be used. Among these, plastic is preferable, for example, polyethylene (PE) resin, polypropylene (PP) resin, polybutadiene resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate resin, polyethylene naphthalate (PEN) resin, triacetyl cellulose (TAC). Resin, polymethyl methacrylate (PMMA) resin, polycarbonate (PC) resin, cycloolefin polymer, ethylene vinyl acetate copolymer (EVA) resin, polyvinyl chloride (PVA) resin, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile styrene (AS) ) Resins and the like. Further, the shape of the plastic resin is not particularly limited, but a thin film or a thick resin plate is generally used.

  As a method for applying a curable resin to a substrate, as a method for applying a curable resin composition to a substrate, a gravure coating method, a roll coating method, a flow coating method, a bar coating method, or the like, Printing methods such as gravure printing and screen printing can be applied. Although the thickness of hardened | cured material is not specifically limited, Usually, it is the range of 1-200 micrometers, the range of 3-100 micrometers is preferable, and the range of 5-50 micrometers is more preferable. By making the film thickness within this range, the curability of the curable resin composition and the scratch recovery property of the cured product can be kept good.

As a method for curing the curable resin composition, a light ray selected from the group of active energy rays such as infrared rays, visible rays, ultraviolet rays, X-rays, γ rays and electron beams can be selected. As a method of irradiating active energy rays, a normal curing method of a curable resin composition can be used. When ultraviolet rays are used as the active energy ray irradiation device, electrodeless lamps such as H bulbs manufactured by Fusion UV Systems Co., Ltd. having a spectral distribution in the wavelength range of 200 to 450 nm, low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps Xenon lamp, gallium lamp, metal halide lamp and the like. The dose of the active energy rays are usually 10~3,000mJ / cm ² as the accumulated light quantity is preferably ^{50~2,000mJ / cm 2, 100~1,000mJ / cm} 2 is more preferable. The atmosphere at the time of irradiation may be air or may be cured in an inert gas such as nitrogen or argon.

  Synthesis examples, examples, and comparative examples are given below to specifically describe the embodiment. Note that the present invention is not limited to this.

(Synthesis Example 1: Synthesis of urethane (meth) acrylate (A-1))
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, polyoxyethylene monoacrylate (in formula (1), R ¹ = hydrogen atom, R ² = C ₂ H ₄ , a = 4.5, hydroxyl value (OHV) = 201 mgKOH / g) is 753.3 g, polyethylene glycol (R ³ = C ₂ H ₄ in formula (2), b = 9) as component (a2) is 60.0 g, (A3) Isocyanurate modified product of hexamethylene diisocyanate (hereinafter referred to as “HDI”) as component (trade name: Duranate TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd., isocyanate group content = 23.1%, 545.5 g of "TPA-100"), dibutyltin dilaurate (trade name: Neostan U-100, manufactured by Nitto Kasei Co., Ltd., hereinafter "DBTDL" The notation) 0.20g, hydroquinone monomethyl ether (hereinafter, the notation) and "MEHQ" was 0.20g charged. Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing dry air, after confirming that the isocyanate group content is 0.05% or less by the method of JIS K 7301, urethane acrylate (A-1) was obtained. The yield was 1333.4 g.

(Synthesis Examples 2 to 4, Comparative Synthesis Examples 1 to 4)
Using the polyoxyalkylene mono (meth) acrylate, polyether diol, isocyanurate modified form of diisocyanate compound, urethanization catalyst, and polymerization inhibitor described in Table 1, the same operation as in Example 1 was carried out to obtain the present invention. Urethane acrylates A′-1 to A′-4 different from the urethane acrylates A-2 to A-4 used and the urethane acrylate used in the present invention were obtained.

(Comparative Synthesis Example 5: Synthesis of urethane (meth) acrylate (A′-5))
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, polyoxyethylene monoacrylate (in formula (1), R ¹ = hydrogen atom, R ² = C ₂ H ₄ , a = 4.5, hydroxyl value = 201mgKOH / g) 558.0g, R 3 = C 2 H 4 in (a2) polyethylene glycol (formula (2 as component), b = 9) 12.0 g, a DBTDL 0.11 g , 0.11 g of MEHQ was added. Next, HDI was slowly added dropwise over 5 hours as component (a3) while blowing dry air, and 168.0 g was charged while maintaining the internal temperature at 60 ° C. After confirming that the isocyanate group content was 0.05% or less by the method of JIS K 7301, a urethane acrylate (A′-5) different from the urethane acrylate used in the present invention was obtained. The yield was 738.0 g.

The abbreviations in Table 1 indicate the following compounds.
-TPA-100: Isocyanurate modified product of 1,6-hexamethylene diisocyanate, trade name "Duranate TPA-100" manufactured by Asahi Kasei Chemicals Co., Ltd.-HDI: 1,6-hexamethylene diisocyanate-DBTDL: dibutyltin dilaurate, trade name "Neostan U-100" manufactured by Nitto Kasei Co., Ltd. MEHQ: Hydroquinone monomethyl ether

<Examples 1 to 11 and Comparative Examples 1 to 8: Production of laminated structure in which cured products are laminated>
The urethane (meth) acrylate (A), monofunctional ethylenically unsaturated compound (B), and photopolymerization initiator obtained in the above synthesis examples were blended in the proportions shown in Tables 2 and 3, and uniformly dissolved and cured. A functional resin composition was obtained. Subsequently, this curable resin composition is dried on a PET substrate (Cosmo Shine A4300, substrate thickness 100 μm, manufactured by Toyobo Co., Ltd.) or PC substrate (JIS 6735 compliant, thickness 2 mm) with a dry film thickness of 20 μm. It applied so that it might become. Furthermore, the laminated structure which has hardened | cured material was obtained by irradiating the ultraviolet-ray of the integrated light quantity 500mJ / cm < ² > in an atmospheric condition using an ultraviolet irradiation device [The fusion UV systems Japan Co., Ltd. make, light source H bulb]. The following evaluation was implemented about the obtained laminated structure.

<Curing property>
The cured film surface of the laminated structure obtained using the PET base material was traced with a finger to examine the presence or absence of stickiness. The judgment criteria are as follows.
○: There is no stickiness.
X: There is stickiness.

<Self-healing>
When the cured film surface of the laminated structure obtained using the PET base material was rubbed 5 times with a brass brush at a load of 500 g, the surface state of the cured film was visually determined. The judgment criteria are as follows.
A: The wound is repaired within 1 second.
○: The wound is repaired within 1 to 5 seconds.
Δ: The wound is repaired within 5 to 60 seconds.
X: A wound is not repaired even if it is left still for 60 seconds or more.

<Curl resistance>
When the laminated structure obtained using a PET base material is cut into 10 cm × 10 cm, left to stand at 25 ° C. and 60 RH% for 1 hour, and then placed on a horizontal table with the cured product face up The height of each of the four sides that floated was measured, and the curl resistance was determined from the average value according to the following criteria.
A: The average height is less than 2 mm.
○: The average height is 2 mm or more and less than 5 mm.
(Triangle | delta): The average value of height is 5 mm or more and less than 20 mm.
X: The average value of height is 20 mm or more.

<Adhesion>
After leaving the laminated structure obtained using the PET substrate and the PC substrate for 1 hour under the conditions of 25 ° C. and 60 RH%, in accordance with JIS K 5600, a 1 mm square grid with a cutter knife When 100 pieces were produced and peeled at a stroke after a commercially available cellophane tape was adhered to the surface, the number of grids remaining without peeling was determined according to the following criteria.
A: The number of remaining grids is 100.
A: The number of remaining grids is 80 to 99.
Δ: The number of remaining grids is 50 to 79.
X: The number of remaining grids is 49 or less.

The abbreviations in Tables 2 and 3 represent the following compounds.
Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, trade name “Irgacure 184, manufactured by BASF Japan Ltd.”
B-1: In the formula (4), R ⁵ = hydrogen atom, R ⁶ = C ₂ H ₄ , c = 1
B-2: In the formula (4), R ⁵ = hydrogen atom, R ⁶ = C ₃ H ₆ , c = 1
B-3: In the formula (4), R ⁵ = hydrogen atom, R ⁶ = C ₂ H ₄ , c = 2
B′-1: In formula (4), R ⁵ = hydrogen atom, R ⁶ = C ₂ H ₄ , c = 4.5

  In addition, regarding the evaluations of “self-repairability”, “curl resistance”, and “adhesion” in Tables 2 and 3, the lower numerical values indicate actual measurement values.

From the results of Table 2, the curable resin compositions of Examples 1 to 11 according to the present invention were excellent in any physical properties of curability, self-repairability, curl resistance, and adhesion.
On the other hand, in Comparative Example 1, when the component (B) was not included and only the component (A) was used, the adhesion to the substrate was insufficient. In Comparative Example 2, the blending ratio exceeds the range, and when the amount of the component (B) is increased with respect to the component (A), the crosslinked structure is not sufficiently formed, and the self-repairability is insufficient because the crosslinking density is lowered. The scratches did not recover instantly. In Comparative Example 3, when the component (a2) was not included in the component (A), the crosslinking structure was insufficient, so that self-healing properties were exhibited, but the repair time was slightly long. In Comparative Example 4, the ratio of (a1) / (a2) in urethanization was low beyond the range, and when the proportion of the polyether was increased, gelation occurred during the synthesis and subsequent evaluation was impossible. there were.

  In Comparative Example 5, when the polyether chain length of the component (a2) was increased beyond the range, the strength of the cured film was reduced, so that the scratches attached with the brass brush became ruptured scratches and self-repairing properties were expressed. There wasn't. In Comparative Example 6, when chain extension was not performed by adding the polyether of the component (a1), the flexibility of the coating film was remarkably lowered and no self-healing property was exhibited. Further, since the curl resistance was insufficient, the influence of curing shrinkage was increased, and curling occurred. In Comparative Example 7, when the component (a3) was an isocyanate having a different structure, the strength was lowered because it did not have an isocyanurate structure, and self-repairability was not exhibited. In Comparative Example 8, when the polyether chain length of the component (B) was increased beyond the range, the adhesion to the PET substrate was sufficient, but it did not adhere sufficiently to the PC substrate. It was.

Claims (2)

A curable resin composition containing the following components (A) and (B) in a mass ratio of (A) :( B) = 50: 50 to 95: 5.
Component (A): The following components (a1) to (a3) are mixed with an equivalent ratio of hydroxyl group of (a1) / hydroxyl group of (a2) of 2.0 to 59.0, hydroxyl group of (a1) and (a2) / Urethane (meth) acrylate obtained by reacting (a3) with an isocyanate group equivalent ratio of 0.9 to 1.1

(A1) Polyoxyalkylene mono (meth) acrylate represented by the following formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 4 carbon atoms, and a represents the average number of moles of R ² O added and represents 2 to 8)

(A2) polyether diol represented by the following formula (2)

(In the formula, R ³ represents an alkylene group having 2 to 4 carbon atoms, b represents the average number of added moles of R ³ O, and represents 2 to 16).

(A3) Isocyanurate-modified product of diisocyanate compound represented by the following formula (3)

(In the formula, R ⁴ represents an alkylene group having 4 to 10 carbon atoms.)

Component (B): monofunctional ethylenically unsaturated compound represented by the following formula (4)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alkylene group having 2 to 4 carbon atoms, and c represents an average added mole number of R ⁶ O, and represents 0 to 2).   A cured product layer obtained by curing the curable resin composition according to claim 1, and at least two layers of a substrate, and the cured product layer is formed on at least one surface of the substrate. Laminated structure.