JP5950107B2 - Method for producing self-healing material, and method for producing composition for producing self-healing material - Google Patents

Description

  The present invention relates to a self-healing material that can naturally repair a wound generated on a surface, a self-healing member protected with the self-healing material, and a composition for producing the self-healing material.

  Liquid resins that are cured by energy rays, particularly ultraviolet rays, are widely used as various protective films taking advantage of good handling due to being liquid, high manufacturability and high weather resistance due to high-speed curing.

  For example, in order to prevent the mobile phone, the flat panel of the display and its casing, the car body of the automobile, and the like from being damaged, a hard coat treatment is performed on the surfaces thereof. However, when the hard coat is damaged, it is difficult to repair the hard coat, and the merchandise value of the article is significantly reduced due to the loss of the appearance and function of the article. In recent years, a material that can naturally repair a scratch even if the surface is scratched has been proposed.

  For example, Patent Document 1 discloses a self-repair comprising an amorphous polymer having a dangling chain and a crosslinked structure, and an amorphous polymer having a glass transition temperature of room temperature or higher by dynamic viscoelasticity measurement. A functional resin body is disclosed.

  Patent Document 2 discloses a photocurable composition for producing a self-healing material containing a diene oligomer having a predetermined structure and a photopolymerization initiator.

JP 2010-260979 A JP 2010-260905 A

  However, the self-healing material of Patent Document 1 described above does not autonomously exhibit self-healing ability, and it is necessary to raise the temperature of the material in which the scratch has occurred above the glass transition temperature. In addition, since the cross-linked polymer is dissolved in a solvent, in order to obtain a good coated surface, there is a drawback that the selection range of the solvent accompanying the dissolution of the cross-linked polymer is narrowed. For this reason, it is considered that the self-healing material of Patent Document 1 is difficult to apply in practice.

  On the other hand, in Patent Document 2 described above, a diene oligomer having a predetermined structure is used. However, since the diene oligomer has a double bond in the molecular chain, the curing rate is reduced and the cured film obtained is obtained. There was a disadvantage that the weather resistance of the was low. For this reason, the self-healing material of Patent Document 2 is considered to be difficult to apply in practice.

  Therefore, some aspects according to the present invention solve the above-mentioned problems, and are excellent in curability and transparency and self-healing material excellent in autonomous self-healing action, and protected by the self-healing material. A self-healing member and a composition for producing the self-healing material are provided.

  The present invention can be realized as the following aspects or application examples.

[Application Example 1]
One aspect of the self-healing material according to the present invention is:
Curing reaction of a composition containing urethane (meth) acrylate obtained by reacting at least one polyol selected from an aliphatic polyol and a polyol having a cyclic structure, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. A self-healing material having molecular chains formed by
The composition adjusts the ratio of the number of hydroxyl groups [OH] of the polyol to the number of isocyanate groups [NCO] of the polyisocyanate within the range of [NCO] / [OH] = 1.0 to 2.0 or less. It contains the polyfunctional urethane (meth) acrylate (A) made to react by this.

[Application Example 2]
In the self-healing material of Application Example 1,
In the composition, the ratio of the number of hydroxyl groups [OH] of the polyfunctional urethane (meth) acrylate (A) and the polyol to the number of isocyanate groups [NCO] of the polyisocyanate is [NCO] / [OH] = 0.3. The monofunctional urethane (meth) acrylate (B) prepared by the reaction within the range of 1.0 or less can be contained.

[Application Example 3]
In the self-healing material of Application Example 2,
The blending ratio when the total amount of the polyfunctional urethane (meth) acrylate (A) and the monofunctional urethane (meth) acrylate (B) in the composition is 100 parts by mass is a polyfunctional urethane (on a mass basis). (Meth) acrylate (A): Monofunctional urethane (meth) acrylate (B) = 100: 0 to 50:50.

[Application Example 4]
In the self-healing material of any one of Application Examples 1 to 3,
The urethane group concentration is 2.0 mmol / g or more, and the cross-linking or entanglement density obtained by dynamic viscoelasticity measurement can be 0.2 to 2.5 mmol / cm ³ .

[Application Example 5]
One aspect of the self-healing member according to the present invention is:
A coating film made of the self-healing material of any one of Application Examples 1 to 4 is formed on the surface of the substrate.

[Application Example 6]
In the self-healing member of Application Example 5,
The thickness of the coating may be 50 μm or less.

[Application Example 7]
One aspect of the composition for producing the self-healing material according to the present invention is:
A composition containing urethane (meth) acrylate obtained by reacting at least one polyol selected from an aliphatic polyol and a polyol having a cyclic structure, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. ,
The reaction was performed by adjusting the ratio of the number of hydroxyl groups [OH] of the polyol to the number of isocyanate groups [NCO] of the polyisocyanate within the range of [NCO] / [OH] = 1.0 to 2.0 or less. It contains polyfunctional urethane (meth) acrylate (A).

[Application Example 8]
In the composition for producing the self-healing material of Application Example 7,
The ratio of the number of hydroxyl groups [OH] of the polyfunctional urethane (meth) acrylate (A) and the polyol to the number of isocyanate groups [NCO] of the polyisocyanate is [NCO] / [OH] = 0.3 or more and 1.0 or less. The monofunctional urethane (meth) acrylate (B) that has been adjusted and reacted in the range of can be contained.

[Application Example 9]
In the composition for producing the self-healing material of Application Example 8,
The blending ratio when the total amount of the polyfunctional urethane (meth) acrylate (A) and the monofunctional urethane (meth) acrylate (B) is 100 parts by mass is the polyfunctional urethane (meth) acrylate (A ): Monofunctional urethane (meth) acrylate (B) = in the range of 100: 0 to 50:50.

  The self-healing material according to the present invention has excellent curability and transparency, and can autonomously exhibit excellent self-healing ability. Therefore, by applying the self-healing material to the surface of products that require transparency and scratch resistance (mobile devices, leather products, automobile instrument panels, etc.), it is possible to effectively prevent the appearance and functions from being impaired. it can.

It is explanatory drawing which shows typically the self-healing material which concerns on this Embodiment. 2 is a photograph showing a scratch disappearance test of a self-healing member according to Example 1. FIG. 2 is a photograph showing a scratch disappearance test of a self-healing member according to Example 1. FIG. 2 is a photograph showing a scratch disappearance test of a self-healing member according to Example 1. FIG.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modifications implemented in the range which does not change the summary of this invention are also included. In the present specification, (meth) acrylate represents acrylate and methacrylate.

1. Self-healing material 1.1. Structure and Features The self-healing material according to the present embodiment is obtained by reacting at least one polyol selected from an aliphatic polyol and a polyol having a cyclic structure, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. It has a molecular chain formed by curing reaction of a composition containing urethane (meth) acrylate.

FIG. 1 is an explanatory view schematically showing a self-repairing material according to the present embodiment. As shown in FIG. 1, a self-healing material 100 according to the present embodiment includes a three-dimensional crosslinked structure 10a serving as a basic skeleton formed of polyfunctional urethane (meth) acrylate, and a monofunctional structure in the three-dimensional crosslinked structure 10a. And a long-chain branched chain 10b formed by physically and / or chemically cross-linking urethane (meth) acrylate. In the self-healing material 100 shown in FIG. 1, each of the crosslinking points 12 represents a chemical bond of urethane (meth) acrylate with (meth) acrylate, but the three-dimensional crosslinked structure 10a and the branched chain 10b as the basic skeleton are , They may be connected via a covalent bond or may be connected via a non-covalent bond. And the urethane group contained in this structure interacts, The physical bridge | crosslinking point (not shown) by a noncovalent bond is formed. Accordingly, there are two types of physical crosslinking points and chemical crosslinking points in the three-dimensional crosslinked structure 10a. As described above, the self-healing material 100 according to the present embodiment has cross-linking points due to covalent bonds and cross-linking (entanglement) points due to non-covalent bonds. In the present invention, “non-covalent bond” means a hydrogen bond other than a covalent bond, an ionic bond, a hydrophobic bond, or a bond by van der Waals force.

  The self-healing material 100 can maintain the solvent resistance by forming a network by covalent bonds as described above. Further, the self-healing material 100 can exhibit an elastic property by non-covalent bonding between urethane groups contained in the molecular chain. Furthermore, the self-healing material 100 is considered to exhibit pseudo viscous properties due to the presence of the branched chain 10b. The self-healing mechanism of the self-healing material 100 having such a structure and characteristics is not preferred to be bound by theory because there are still many opaque parts, but is presumed as follows. Since the self-healing material 100 has appropriate elastic properties as described above, if the self-healing material is damaged by some physical external force, the covalent bond is not cut and the strength is lower. It is considered that the noncovalent bond between the molecular chains is broken and then recombined by a noncovalent bond. Further, when the branched chain 10b is present, it can move so as to close the wound received by the branched chain 10b, so that the self-repair ability is considered to be further improved. That is, the self-healing material 100 is a non-covalent bond, such as a hydrogen bond, an ionic bond, a hydrophobic bond, or a van der Waals force. Since the chain can move freely, it is considered that better self-healing ability is expressed.

  The molecular chain contained in the self-healing material 100 is a urethane formed by reacting at least one polyol selected from an aliphatic polyol and a polyol having a cyclic structure, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. It is a molecular chain formed by a curing reaction of a composition containing (meth) acrylate. According to the self-healing material containing such a molecular chain, it has excellent transparency and curability and can autonomously exhibit excellent self-healing properties.

  Although details will be described later, the urethane (meth) acrylate obtained by the above reaction is a polyfunctional urethane (meth) acrylate (A) having two or more reactive groups ((meth) acryloyl group) or one reaction. The monofunctional urethane (meth) acrylate (B) having a functional group ((meth) acryloyl group) or both. When the composition containing these urethane (meth) acrylates is subjected to a curing reaction, the three-dimensional crosslinked structure 10a is formed from the polyfunctional urethane (meth) acrylate (A). The monofunctional urethane (meth) acrylate (B) is physically and / or chemically crosslinked to further form a long-chain branched chain 10b. In the structure thus obtained, a large number of urethane groups serving as polar group portions are present. The urethane groups are non-covalently bonded (in this case, hydrogen bonds) to form a physical cross-linking point.

  The self-healing material according to the present embodiment preferably has a urethane group concentration of 2.0 mmol / g or more, more preferably 2.5 mmol / g or more and 4 mmol / g or less, and 2.5 mmol / g or more. Particularly preferred is 3.5 mmol / g or less. When the urethane group concentration is within the above range, the physical cross-linking points due to the interaction between the molecular chains are sufficiently formed, so that it has appropriate elastic properties and further improves the self-healing ability. On the other hand, if the urethane group concentration is less than the above range, the physical cross-linking points are not sufficiently formed, so that the self-healing ability tends to decrease.

The self-healing material according to the present embodiment preferably has a cross-linking or entanglement density determined by dynamic viscoelasticity measurement in the range of 0.2 to 2.5 mmol / cm ³ , and 0.3 to 2.3 m.
more preferably in the range of mol / cm ^3, and particularly preferably in the range of 0.4~2.0mmol / cm ^3. When the cross-linking or entanglement density is within the above range, each molecular chain can move freely, so that self-repair ability is further improved. When the cross-linking or entanglement density exceeds the above range, the molecular chain is difficult to move, so that the self-repairing ability tends to decrease. On the other hand, if the cross-linking or entanglement density is less than the above range, the physical cross-linking points due to the interaction between the molecular chains are not sufficiently formed, so that the self-healing ability tends to decrease.

The crosslinking or entanglement density can be calculated from the following formula (1) by obtaining an equilibrium elastic modulus E ′ (MPa) in a rubber-like flat region of a measurement sample using a dynamic viscoelasticity measuring apparatus.
n = E ′ / 3RT (1)
Here, n: cross-linking or entanglement density (mol / cm ³ ), E ′: equilibrium elastic modulus (MPa), R: gas constant (8.314 J / (K · mol)), T: absolute temperature (K) is there.

  The self-healing material according to the present embodiment completely loses fluidity, is not a gel, does not have a surface hardness up to a hard coat, but does not easily scratch even if rubbed with a nail or the like have. Furthermore, there is no tack (stickiness), and no foreign matter adheres due to the adhesiveness of the surface, or the self-healing material adhesive does not peel or adhere when the surfaces are pressed again and separated. When the self-repairing material according to the present embodiment is damaged, the wound is repaired autonomously within a few minutes. The surface hardness of the self-healing material is selected according to the application and purpose, but as one guideline, it is preferable that the guide value when measured with an Asker hardness tester (TYPE EP) is 3 or more. As a hardness meter, “Asker rubber hardness meter TYPE EP” manufactured by Kobunshi Keiki Co., Ltd. can be used.

  Next, a composition for producing a molecular chain contained in the self-healing material according to the present embodiment (hereinafter also simply referred to as “composition”) will be described in detail.

1.2. Composition for producing molecular chains 1.2.1. Urethane (meth) acrylate The composition according to the present embodiment reacts at least one polyol selected from an aliphatic polyol and a polyol having a cyclic structure, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate. Containing urethane (meth) acrylate. Such urethane (meth) acrylate is produced, for example, as follows.

  First, the polyisocyanate and the hydroxyl group-containing (meth) acrylate are stirred in the presence of an organometallic catalyst or a basic catalyst and an antioxidant to add the isocyanate group of the polyisocyanate and the hydroxyl group of the hydroxyl group-containing (meth) acrylate. By reacting, the isocyanate group of the polyisocyanate and the hydroxyl group of the hydroxyl group-containing (meth) acrylate are urethane-bonded. Here, the blending ratio of the polyisocyanate and the hydroxyl group-containing (meth) acrylate is such that the total number of isocyanate groups in the polyisocyanate is greater than the total number of hydroxyl groups in the hydroxyl group-containing (meth) acrylate in the reaction system.

As the organometallic catalyst, non-tin organometallic compounds can be used in addition to known organotin compounds. For example, an organic titanium compound, an organic zirconium compound, etc. are mentioned. Each structure includes alkoxide, chelate, acylate and the like. Among these, an acetylacetone chelate of an organic zirconium compound is preferable, and specifically, Zr (CH ₃ COCHCOCH ₃ ) ₄ is preferable.

Next, the residual isocyanate group of the polyisocyanate and the hydroxyl group of the polyol are stirred while heating, and the residual isocyanate group of the polyisocyanate is added to the hydroxyl group of the polyol. This residual isocyanate group and the hydroxyl group of the polyol are urethane-bonded to produce urethane (meth) acrylate.

  In the above production example, the hydroxyl group-containing (meth) acrylate is added to the polyisocyanate and then the polyol is reacted. However, after the polyisocyanate and the polyol are reacted, the hydroxyl group-containing (meth) acrylate is reacted. Or they may be reacted at once.

  Moreover, the solvent used by said manufacture example is not specifically limited. Examples of the solvent include methyl ethyl ketone, or a mixed solvent such as methyl ethyl ketone / cyclohexanone, methyl ethyl ketone / ethyl acetate, methyl ethyl ketone / butyl acetate, methyl ethyl ketone / ethylene glycol monobutyl ether, and n-butanol / butyl acetate. In the above production examples, the solvent may be used when necessary, and can be synthesized without the solvent.

  In the above urethane (meth) acrylate production method, the ratio of the number of hydroxyl groups [OH] of the polyol to the number of isocyanate groups [NCO] of the polyisocyanate is [NCO] / [OH] = 1.0 to 2.0 or less. The polyfunctional urethane (meth) acrylate (A) having two or more reactive groups ((meth) acryloyl group) can be produced by adjusting the reaction to the range. When the polyfunctional urethane (meth) acrylate (A) thus obtained is subjected to a curing reaction, a three-dimensional crosslinked structure having a urethane group is formed.

  In the method for producing the urethane (meth) acrylate, the ratio of the number of hydroxyl groups [OH] of the polyol to the number of isocyanate groups [NCO] of the polyisocyanate is [NCO] / [OH] = 0.3 or more and 1.0 or less. The monofunctional urethane (meth) acrylate (B) having one reactive group ((meth) acryloyl group) can be produced by adjusting the reaction within the range. The monofunctional urethane (meth) acrylate (B) thus obtained is physically or chemically cross-linked to the three-dimensional cross-linked structure, whereby a long branched chain having a urethane group is formed.

  The composition according to this embodiment can produce a self-healing material having self-healing ability if it contains a polyfunctional urethane (meth) acrylate (A). It is preferable to contain both functional urethane (meth) acrylate (B), and it is more preferable that they are mix | blended in the following ratios.

  That is, when the total amount of the polyfunctional urethane (meth) acrylate (A) and the monofunctional urethane (meth) acrylate (B) is 100 parts by mass, the polyfunctional urethane (meth) acrylate (A): monofunctional on a mass basis. Urethane (meth) acrylate (B) is preferably in the range of 100: 0 to 50:50, more preferably in the range of 90:10 to 75:25. By blending within the above range, the urethane group concentration and crosslinking or entanglement density of the resulting self-healing material can be made a preferable range, and the interaction between the molecular chains and the ease of rheological movement of the molecular chains. A good balance can be achieved. Thereby, the self-healing ability of the self-healing material can be expressed more effectively.

The polyol used in the present embodiment is not particularly limited as long as it is at least one polyol selected from an aliphatic polyol and a polyol having a cyclic structure. For example, hydroxy-terminated polyester, polyether polyol, polyester polyol , Polycarbonate polyol, polyolefin polyol, polyester carbonate polyol, polyether carbonate polyol, polyester amide polyol and the like. Among these, polyether polyol is preferable from the viewpoint of the hardness of the obtained molecular chain being moderate and exhibiting good elasticity. These polyols may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the polyether polyol include polytetramethylene glycol (PTMG), polypropylene glycol (PPG), polyethylene glycol (PEG), polyoxyethylene-propylene glycol (EO-PO), polyoxyethylene-bisphenol A ether, polyoxypropylene -Ethylene glycol modified diol of bisphenol A, bisphenol A, etc. are mentioned.

  The polyol preferably has a number average molecular weight of 200 to 4,000, more preferably 300 to 2,000, and particularly preferably 400 to 1,000. When the number average molecular weight is within the above range, the hardness of the obtained molecular chain is moderate, which is preferable in view of good elasticity. The number average molecular weight is a relative value obtained by converting the number average molecular weight measured by gel permeation (GPC) into polystyrene.

  In addition, when the polyol to be used has crystallinity, solidification due to crystallization can be prevented by synthesizing urethane (meth) acrylate and then dissolving it in a solvent. The solvent is not particularly limited, but is preferably a ketone or alcohol solvent, and more preferably methyl ethyl ketone.

  The polyisocyanate used in the present embodiment is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups in one molecule, but the hardness increases as the number of reactive groups added increases, while self Diisocyanate is preferred because the repair ability tends to decrease.

  Examples of the diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, 1 , 5-naphthalene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-phenylene diisocyanate and other aromatic diisocyanates; ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6- Aliphatic diisocyanates such as hexamethylene diisocyanate; cycloaliphatic such as isophorone diisocyanate and norbornene diisocyanate Isocyanates, and the like. These diisocyanates may be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing (meth) acrylate used in the present embodiment include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate, and glycerin di ( Examples include meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tetramethylol methane triacrylate, and the like.

1.2.2. Photopolymerization initiator It is preferable to add a photopolymerization initiator that generates active radical species by radiation (light) irradiation to the composition according to the present embodiment.

The photopolymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radical species to initiate the polymerization reaction. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2, 2 -Dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4, 4′-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydro Ci-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1- Methyl vinyl) phenyl) propanone) and the like.

  Examples of commercially available photopolymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Darocur 1116, 1173, Lucyrin TPO, 8893 (or more Ubecril P36 (manufactured by UCB); Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B (above, manufactured by Lamberti) and the like.

  The addition amount of the photopolymerization initiator in the composition according to the present embodiment is preferably 0.01 to 20 parts by mass, more preferably 0.1 when the total of urethane (meth) acrylate is 100 parts by mass. It is in the range of -10 parts by mass.

1.2.3. Antifouling agent It is preferable to add an antifouling agent to the composition according to the present embodiment. As the antifouling agent, a nonionic surfactant (C) comprising a fatty acid ester (hereinafter also referred to as “fatty acid ester surfactant (C)”) is suitable. The fatty acid ester surfactant (C) is blended for the purpose of making the fingerprint attached to the self-healing material obtained in the present invention less visible and improving the wiping property of the fingerprint.

  In the composition according to the present embodiment, it is preferable to use a fatty acid ester surfactant (C) having an HLB in the range of 2 to 7, and a fatty acid ester surfactant having an HLB in the range of 2 to 4 ( More preferably, C) is used. Moreover, since it can couple | bond and fix with the binder component in the composition of this invention by providing a (meth) acryloyl group to fatty acid ester surfactant (C), fatty acid ester surfactant It is possible to prevent (C) from bleeding out on the surface of the self-healing material. This improves the durability of the resulting self-healing material. Furthermore, the fatty acid ester surfactant (C) preferably has a linear or branched monovalent or divalent hydrocarbon group having 6 to 30 carbon atoms. By having a hydrocarbon group having 6 to 30 carbon atoms, it is possible to further improve fingerprint adhesion prevention and fingerprint wiping properties in the obtained self-repairing material. Here, “fingerprint adhesion preventing property” means the difficulty of seeing with the naked eye when a fingerprint is adhered to the film surface.

Here, the HLB (Hydrophile-Lipophile Balance) value is an important index indicating the characteristics of the surfactant and indicates the degree of hydrophilicity or lipophilicity. The HLB value can be obtained by the following calculation formula.
HLB = 7 + 11.7Log (MW / MO)
Here, MW is the molecular weight of the hydrophilic group, and MO is the molecular weight of the lipophilic group. MW + MO = M (molecular weight of surfactant).

  As a method for imparting a (meth) acryloyl group to the fatty acid ester surfactant (C), for example, it can be obtained by converting a hydroxyl group of a fatty acid ester surfactant having a hydroxyl group into a (meth) acryloyl group. Specifically, the fatty acid ester surfactant (C) can be obtained by reacting a hydroxyl group of the fatty acid ester surfactant with a compound having a (meth) acryloyl group.

  As the compound having a (meth) acryloyl group, for example, a compound having an isocyanate group and a (meth) acryloyl group can be used. By using such a compound, the hydroxyl group of the fatty acid ester surfactant and the isocyanate group react to form a urethane bond, whereby a (meth) acryloyl group is introduced.

  Specific examples of the compound having an isocyanate group and a (meth) acryloyl group include 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl]. Ethyl isocyanate and the like can be used. It can also be obtained by reacting a diisocyanate compound with a compound containing a hydroxyl group and a (meth) acryloyl group. Examples of such diisocyanate compounds include isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate and the like.

  Specific examples of the fatty acid ester-based surfactant having a hydroxyl group include polyoxyalkylene hydrogenated castor oil and polyoxyalkylene fatty acid ester, and polyoxyethylene hydrogenated castor oil and polyoxyethylene fatty acid ester are preferable.

  Examples of commercially available polyoxyethylene hydrogenated castor oil include EMALEX HC series (manufactured by Nippon Emulsion Co., Ltd.) and Neugen HC series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

  Examples of commercially available polyoxyethylene fatty acid esters include EMALEX GWIS-100EX (glyceryl isostearate, manufactured by Nippon Emulsion Co., Ltd.), Neugen GIS series (produced by Daiichi Kogyo Seiyaku Co., Ltd.), and the like.

  The reaction between the fatty acid ester-based surfactant having a hydroxyl group and the compound having an isocyanate group and a (meth) acryloyl group can be carried out as follows. That is, it is a reaction between an isocyanate compound and a hydroxyl group-containing compound. Usually, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2, 6, It is preferable to use 0.01 to 1 part by weight of a urethanization catalyst such as 7-trimethyl-1,4-diazabicyclo [2.2.2] octane with respect to 100 parts by weight of the total amount of the reactants. Moreover, in the reaction of these compounds, it can also carry out without a catalyst. The reaction temperature is usually from 0 to 90 ° C, preferably 40 to 80 ° C. The reaction may be carried out without a solvent or by dissolving in a solvent.

  The fatty acid ester surfactant (C) can have, for example, a structure represented by the following formula (1).

In formula (1), the meaning of each symbol is as follows. X represents an optionally substituted (m ¹ + m ² ) -valent hydrocarbon group having 3 to 10 carbon atoms. A plurality of Y ¹ and Y ² each independently represent a divalent group or a single bond containing an ether bond, an ester bond, or a urethane bond, and at least one of Y ¹ and Y ² has a structure derived from a fatty acid. . Z represents a group having one or more (meth) acryloyl groups. A plurality of R ¹¹ and R ¹² each independently represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms. m ¹ and m ² are each an integer of 0 to 10, and n ¹ and n ² are each independently an integer of 0 to 20. However, m ¹ and m ² are not 0 at the same time.

  The fatty acid ester surfactant (C) can be synthesized as follows. It can be obtained by reacting a surfactant having a hydroxyl group with an isocyanate compound having (meth) acryloyl group or (meth) acrylic acid at a ratio such that the HLB after the reaction falls within a desired range. For example, when a surfactant having three hydroxyl groups is used as a raw material, when the HLB of the raw material surfactant is 5, an isocyanate compound having a (meth) acryloyl group of 1/3 molar equivalent of the hydroxyl group or ( It is only necessary to react the (meth) acrylic acid. When the HLB of the raw material surfactant is 9, it is preferable to react an isocyanate compound or (meth) acrylic acid having a (meth) acryloyl group having an equimolar equivalent of a hydroxyl group.

  The content of the fatty acid ester surfactant (C) in the composition according to the present embodiment is in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). It is more preferable that it is in the range of 1 to 5 parts by mass. By setting the content of the fatty acid ester surfactant (C) in the above range, sufficient fingerprint wiping properties can be obtained. When the fatty acid ester surfactant (C) does not have a (meth) acryloyl group, the hardness of the self-healing material may be reduced. It is preferable to set it as 10-50 mass parts with respect to a total of 100 mass parts of (A) and a component (B).

1.2.4. Slip agent You may add a slip agent to the composition which concerns on this Embodiment as needed. By adding a slip agent, the surface slipperiness is improved, so that the resulting self-healing material is hardly damaged.

  As the slip agent used in the present embodiment, a compound having a siloxane skeleton is preferable. A compound having a siloxane skeleton has an effect of improving the surface slipperiness and improving the scratch resistance of the resulting self-healing material, and can also impart antifouling properties. These effects further enhance the self-healing ability of the self-healing material. As the slip agent, either a non-reactive slip agent or a reactive slip agent may be used, or a mixture thereof may be used. Examples of non-reactive slip agents include SH8400, SH190 manufactured by Toray Dow Corning Co., Ltd. Examples of the reactive slip agent include BYK-371 and BYK-3500 manufactured by Big Chemie Japan.

The addition amount of the slip agent in the composition according to the present embodiment is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts when the total of urethane (meth) acrylate is 100 parts by mass. It is in a range of 0.5 to 8 parts by mass, particularly preferably 0.5 to 8 parts by mass.

1.2.5. Other monomer The composition which concerns on this Embodiment may also contain another monomer component other than said component as needed. As the other monomer components, known ones can be widely used, but those that are copolymerizable with the polyfunctional urethane (meth) acrylate (A) and the monofunctional urethane (meth) acrylate (B) are preferable. In particular, a monomer having a substituent selected from the group consisting of a cyclic ether group, a hydroxy group, and an aromatic hydrocarbon group and having one or two vinyl groups or (meth) acryloyl groups or both in one molecule, Since there exists an effect which improves adhesiveness with an acryl-type base material, it is preferable. Here, the acrylic base material is a polyalkyl (meth) acrylate such as polymethyl methacrylate (PMMA) (hereinafter sometimes abbreviated as PMMA), a mixture of PMMA and a polystyrene copolymer, or PMMA. And a mixture of acrylonitrile-styrene copolymer, a copolymer of methyl (meth) acrylate and styrene, a copolymer of methyl (meth) acrylate and styrene acrylonitrile, and the like. Specific examples of such monomers include two radically polymerizable groups such as resorcin diethoxydivinyl ether, bisphenol A diethoxydivinyl ether, bisphenol S diethoxydivinyl ether, divinylbenzene, and pentaerythritol di (meth) acrylate. Functional monomer; (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol mono (Meth) acrylate, glycerin mono (meth) acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, hydroxyethyl vinyl Ether, hydroxybutyl vinyl ether, a monofunctional monomer and the like having one radical polymerizable group such as cyclohexanedimethanol monovinyl ether. The monomer illustrated above may be used individually by 1 type, and can also use 2 or more types together. The blending amount of the other monomer components is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, and particularly preferably 25 to 50% by mass in the total polymerizable components. If it is less than 5% by mass, the adhesion to the substrate may be insufficient. On the other hand, when it exceeds 80 mass%, the speed of self-repair may decrease.

1.2.6. Other Additives The composition according to the present embodiment includes a monofunctional monomer, a polyfunctional monomer, a non-polymerizable oligomer, a polymerizable oligomer, a non-reactive polymer, a polymerizable polymer, an oxidation agent as necessary in addition to the above components. Inhibitors, UV absorbers, light stabilizers, silane coupling agents, coating surface improvers, thermal polymerization inhibitors, leveling agents, surfactants, colorants, storage stabilizers, plasticizers, lubricants, mold release agents, solvents , Fillers, anti-aging agents, wettability improvers, antifouling agents, water repellents, and the like.

1.2.7. Production Method of Composition The composition according to the present embodiment can be prepared by adding each of the above components and mixing at room temperature or under heating conditions. Specifically, it can be prepared using a known mixer such as a mixer, a kneader, or a ball mill. However, when mixing under heating conditions, it is preferable to carry out at a temperature lower than the decomposition start temperature of the polymerization initiator or polymerizable unsaturated group. The composition according to the present embodiment is preferably mixed in a container where radiation (light) is blocked because the curing reaction proceeds by radiation (light).

2. Self-healing member The self-healing member according to the present embodiment has a structure in which a film made of the above-mentioned self-healing material is formed on the surface of a base material. Since the film made of the self-healing material is formed on the surface of the base material, it is possible to prevent the appearance and function of the base material from being damaged by autonomously repairing the scratches attached to the surface. Moreover, since the self-healing material described above has transparency, when an opaque base material is used, a self-healing member that allows the base material to be seen through can be obtained. On the other hand, when a transparent substrate is used, a transparent self-repairing member can be obtained.

  The self-healing member according to the present embodiment can be manufactured, for example, by applying the above-described composition to the surface of a base material and curing it with heat and / or radiation (light) to form a film. .

  The kind of base material is not specifically limited, The thickness of a base material can also be suitably changed with a use. In addition, when the above-mentioned composition is directly applied to the surface of the substrate and cured, and the adhesion between the substrate and the self-healing material is inferior, corona discharge treatment, plasma is applied to the substrate surface in advance. You may perform processes, such as a process and an easily bonding process.

  The application method to the substrate is a normal method such as spray coating, bar coating, dipping coating, flow coating, shower coating, roll coating, spin coating, transfer method, vacuum pressure method, brush coating, etc. can do.

  The thickness of the coating is the thickness after drying and curing, and is preferably 1 to 1,000 μm, more preferably 5 to 500 μm, and particularly preferably 10 to 50 μm. The reason why the film thickness is thicker than normal hard coat is that the wound can no longer be repaired when the scratch reaches the substrate, so the film thickness (volume) is such that the scratch does not easily reach the substrate. It is because it is desirable to have.

  In the conventional self-healing member, the thickness of the film made of the self-healing material usually needs to exceed 100 μm, at least 50 μm. In addition, when the thickness of the film was 50 μm or less, it was necessary to separately provide a primer layer or the like as the lower layer of the film. The reason why such a thickness is necessary is that conventional self-healing materials often have low hardness, so that scratches are prevented from reaching the substrate, and the volume effect is utilized (the coating layer is recessed). 2 points of securing room). On the other hand, even when the self-healing member according to the present invention is a single layer having a thickness of about 10 μm made of a self-healing material, the scratches are not treated because the hardness is higher than that of the conventional self-healing material. And sufficient self-repair ability can be expressed. That is, the self-healing member according to the present invention is superior to the conventional self-healing member in that the thickness of the coating can be further reduced.

  When a film is formed by curing with heat, it is preferable to further add a thermosetting agent to the composition. On the other hand, in the case of forming a film by curing by irradiating with radiation (light), the organic added when synthesizing urethane (meth) acrylate as necessary before irradiating with radiation (light) You may provide the process of volatilizing and removing volatile components, such as a solvent, at the temperature of 0-200 degreeC.

The radiation (light) is not particularly limited as long as it can be cured in a short time, but ultraviolet rays and electron beams are preferable for reasons such as availability of an irradiation apparatus. As an ultraviolet ray source, a mercury lamp, a halide lamp, a laser, or the like can be used, and as an electron beam source, a method using thermoelectrons generated from a commercially available tungsten filament can be used. . When ultraviolet rays or electron beams are used as the radiation, the preferred irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, preferable irradiation conditions of the electron beam are an acceleration voltage of 10 to 300 kV, an electron density of 0.02 to 0.30 mA / cm ² , and an electron beam irradiation amount of 1 to 10 Mrad.

3. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, “%” represents mass%, and “part” represents mass part.

3.1. Example of synthesis of urethane (meth) acrylate 3.1.1. Synthesis Example 1: Production of polyfunctional urethane (meth) acrylate (U-1) In a reaction vessel equipped with a stirrer, 28.28 g of tolylene diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol, 0.08 g of dibutyltin dilaurate (trade name KS-1200A-1 manufactured by Kyodo Yakuhin Kogyo Co., Ltd.) and 99.95 g of methyl ethyl ketone were charged and cooled with ice until the liquid temperature became 10 ° C. or lower while stirring them. 18.85 g of hydroxyethyl acrylate was added dropwise while controlling the liquid temperature to be 20 ° C. or lower, and the mixture was further reacted for 1 hour with stirring. Next, 52.82 g of polytetraethylene glycol having a number average molecular weight of 650 (manufactured by Hodogaya Chemical Co., Ltd.) was charged, and stirring was continued at a liquid temperature of 70 to 75 ° C. for 3 hours. The reaction was terminated when the following occurred. Thus, the solution containing polyfunctional urethane (meth) acrylate (U-1) was obtained.

3.1.2. Synthesis Example 2: Production of polyfunctional urethane (meth) acrylate (U-2) In a reaction vessel equipped with a stirrer, 35.49 g of tolylene diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol, 0.08 g of dibutyltin dilaurate (trade name KS-1200A-1 manufactured by Kyodo Yakuhin Kogyo Co., Ltd.) and 99.95 g of methyl ethyl ketone were charged and cooled with ice until the liquid temperature became 10 ° C. or lower while stirring them. 23.66 g of hydroxyethyl acrylate was added dropwise while controlling the liquid temperature to be 20 ° C. or lower, and the mixture was further reacted by stirring for 1 hour. Next, 40.80 g of polyethylene glycol having a number average molecular weight of 400 (manufactured by NOF Corporation) was charged, and stirring was continued for 3 hours at a liquid temperature of 70 to 75 ° C., so that the residual isocyanate became 0.1% by mass or less. Time was the end of the reaction. Thus, the solution containing polyfunctional urethane (meth) acrylate (U-2) was obtained.

3.1.3. Synthesis Example 3: Production of polyfunctional urethane (meth) acrylate (U-3) In a reaction vessel equipped with a stirrer, 14.139 g of tolylene diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol, 0.06 g of dibutyltin dilaurate (trade name “KS-1200A-1” manufactured by Kyodo Yakuhin Kogyo Co., Ltd.) and 49.974 g of methyl ethyl ketone were charged, and the mixture was ice-cooled until the liquid temperature became 10 ° C. or lower while stirring. 9.426 g of hydroxyethyl acrylate was added dropwise while controlling the liquid temperature to be 20 ° C. or lower, and the mixture was further reacted for 1 hour with stirring. Next, 26.409 g of polytetraethylene glycol having a number average molecular weight of 650 (manufactured by Hodogaya Chemical Co., Ltd.) was charged, and stirring was continued at a liquid temperature of 70 to 75 ° C. for 3 hours. The reaction was terminated when the following occurred. In this way, a solution containing urethane (meth) acrylate (U-3) was obtained.

3.1.4. Synthesis Example 4: Production of polyfunctional urethane (meth) acrylate (U-4) In a reaction vessel equipped with a stirrer, 27.13 g of tolylene diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol, 0.08 g of dibutyltin dilaurate (trade name KS-1200A-1 manufactured by Kyodo Yakuhin Kogyo Co., Ltd.) and 99.95 g of methyl ethyl ketone were charged and cooled with ice until the liquid temperature became 10 ° C. or lower while stirring them. 18.12 g of hydroxyethyl acrylate was dropped while controlling the liquid temperature to be 20 ° C. or lower, and the reaction was further stirred for 1 hour. Next, 54.66 g of an ethylene glycol-modified diol (manufactured by NOF Corporation) of bisphenol A having a number average molecular weight of 700 is charged, and stirring is continued for 3 hours at a liquid temperature of 70 to 75 ° C. The reaction was terminated when it became less than%. In this way, a solution containing polyfunctional urethane (meth) acrylate (U-4) was obtained.

3.1.5. Synthesis Example 5: Production of polyfunctional urethane (meth) acrylate (U-5) In a reaction vessel equipped with a stirrer, 17.52 g of tolylene diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol, 0.08 g of dibutyltin dilaurate (trade name KS-1200A-1 manufactured by Kyodo Yakuhin Kogyo Co., Ltd.) and 99.95 g of methyl ethyl ketone were charged and cooled with ice until the liquid temperature became 10 ° C. or lower while stirring them. 49.62 g of tetramethylol methane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added dropwise while controlling the liquid temperature to be 20 ° C. or lower, and the mixture was further reacted by stirring for 1 hour. Next, 32.732 g of polytetramethylene glycol having a number average molecular weight of 650 (manufactured by Hodogaya Chemical Co., Ltd.) is charged, and stirring is continued at a liquid temperature of 70 to 75 ° C. for 3 hours. The reaction was terminated when Thus, the solution containing polyfunctional urethane (meth) acrylate (U-5) was obtained.

3.1.6. Synthesis Example 6: Production of urethane (meth) acrylate (U-6) In a reaction vessel equipped with a stirrer, 10.90 g of tolylene diisocyanate as a polyisocyanate and 400 bisphenol A EO-modified glycol having a number average molecular weight of 400 as a polyol (Nichi Oil Co., Ltd.) 15.60 g made by company), 22.44 g polyester polyol having a number average molecular weight of 1000 (product name: P1010, manufactured by Kuraray Co., Ltd.) as a polyol, 0.024 g 2,6-di-t-butyl-p-cresol, dibutyltin 0.08 g of dilaurate (trade name KS-1200A-1 manufactured by Kyodo Pharmaceutical Co., Ltd.) and 150 g of methyl ethyl ketone were charged, and stirring was continued at a liquid temperature of 60 to 75 ° C. for 3 hours while stirring them. Thereafter, 1.05 g of tetramethylol methane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added dropwise as the hydroxyl group-containing (meth) acrylate, and stirring was continued at a liquid temperature of 60 to 75 ° C. for 3 hours while stirring them. The reaction was terminated when the residual isocyanate was 0.01% by mass or less. In this way, a solution containing urethane (meth) acrylate (U-6) was obtained.

3.1.7. Synthesis Example 7: Production of polyfunctional urethane (meth) acrylate (U-7) In a reaction vessel equipped with a stirrer, 13.460 g of tolylene diisocyanate, 0.012 g of 2,6-di-t-butyl-p-cresol, Charge 49.974 g of methyl ethyl ketone, 20.629 g of EO-modified diol (manufactured by NOF Corporation) of bisphenol A having a number average molecular weight of 400, and 12.893 g of polytetramethylene glycol (manufactured by Hodogaya Chemical Co., Ltd.) having a number average molecular weight of 1000. The solution was ice-cooled while stirring until the liquid temperature became 15 ° C. or lower. Thereto was added dropwise 0.060 g of dibutyltin dilaurate (trade name KS-1200A-1 manufactured by Kyodo Yakuhin Kogyo Co., Ltd.), and the mixture was reacted for 3 hours while controlling the liquid temperature to be 35 ° C. or lower. Then, after dropping 2.991 g of hydroxyethyl acrylate, stirring was continued for 4 hours at a liquid temperature of 70 to 75 ° C., and the reaction was terminated when the residual isocyanate was 0.01% by mass or less. In this way, a solution containing urethane acrylate (U-7) was obtained.

3.1.8. Synthesis Example 8: Production of polyfunctional urethane (meth) acrylate (U-8) In a reaction vessel equipped with a stirrer, 13.167 g of tolylene diisocyanate, 0.012 g of 2,6-di-t-butyl-p-cresol, Charged 49.974 g of methyl ethyl ketone, 18.161 g of bisphenol A EO-modified diol having a number average molecular weight of 400 (manufactured by NOF Corporation) and 15.134 g of polytetramethylene glycol having a number average molecular weight of 1000 (manufactured by Hodogaya Chemical Co., Ltd.). The solution was ice-cooled while stirring until the liquid temperature became 15 ° C. or lower. Thereto, 0.060 g of dibutyltin dilaurate (trade name “KS-1200A-1”, manufactured by Kyodo Yakuhin Kogyo Co., Ltd.) was dropped and reacted for 3 hours while controlling the liquid temperature to be 35 ° C. or lower. Thereafter, 3.511 g of hydroxyethyl acrylate was dropped, and stirring was continued for 4 hours at a liquid temperature of 70 to 75 ° C., and the reaction was terminated when the residual isocyanate was 0.01% by mass or less. In this way, a solution containing urethane acrylate (U-8) was obtained.

3.1.9. Synthesis Example 9: Production of polyfunctional urethane (meth) acrylate (U-9) In a reaction vessel equipped with a stirrer, 14.728 g of tolylene diisocyanate, 0.012 g of 2,6-di-t-butyl-p-cresol, 49.974 g of methyl ethyl ketone, 20.315 g of EO modified diol (manufactured by NOF Corporation) of bisphenol A having a number average molecular weight of 400, and 11.004 g of polytetramethylene glycol (manufactured by Hodogaya Chemical Co., Ltd.) having a number average molecular weight of 650 are charged. The solution was ice-cooled while stirring until the liquid temperature became 15 ° C. or lower. Thereto, 0.060 g of dibutyltin dilaurate (trade name “KS-1200A-1”, manufactured by Kyodo Yakuhin Kogyo Co., Ltd.) was dropped and reacted for 3 hours while controlling the liquid temperature to be 35 ° C. or lower. Thereafter, 3.927 g of hydroxyethyl acrylate was dropped, and stirring was continued for 4 hours at a liquid temperature of 70 to 75 ° C., and the reaction was terminated when the residual isocyanate was 0.01% by mass or less. In this way, a solution containing urethane acrylate (U-9) was obtained.

3.1.10. Synthesis Example 10: Production of polyfunctional urethane (meth) acrylate (U-10) In a reaction vessel equipped with a stirrer, 16.000 g of isophorone diisocyanate, 0.012 g of 2,6-di-t-butyl-p-cresol, methyl ethyl ketone 49.974 g, EO-modified diol of bisphenol A having a number average molecular weight of 400 (made by NOF Corporation) 19.194 g, polytetramethylene glycol having a number average molecular weight of 1000 (made by Hodogaya Chemical Co., Ltd.) 11.997 g, While stirring them, the solution was cooled on ice until the liquid temperature became 15 ° C. or lower. Thereto, 0.060 g of dibutyltin dilaurate (trade name “KS-1200A-1”, manufactured by Kyodo Yakuhin Kogyo Co., Ltd.) was dropped and reacted for 3 hours while controlling the liquid temperature to be 35 ° C. or lower. Thereafter, 2.783 g of hydroxyethyl acrylate was dropped, and stirring was continued for 4 hours at a liquid temperature of 70 to 75 ° C., and the reaction was terminated when the residual isocyanate was 0.01% by mass or less. In this way, a solution containing urethane acrylate (U-10) was obtained.

3.1.11. Synthesis Example 11 Production of Urethane (Meth) acrylate (U-11) In a reaction vessel equipped with a stirrer, 12.25 g of tolylene diisocyanate as a polyisocyanate and bisphenol A EO-modified glycol having a number average molecular weight of 400 as a polyol (Nissan Co., Ltd.) 19.22 g made by company), 17.60 g polytetramethylene glycol (made by Hodogaya Chemical Co., Ltd.) having a number average molecular weight of 1000 as a polyol, 0.024 g 2,6-di-t-butyl-p-cresol, dibutyl 0.08 g of tin dilaurate and 150 g of methyl ethyl ketone were charged, and stirring was continued at a liquid temperature of 60 to 75 ° C. for 3 hours while stirring them. Thereafter, 0.93 g of glycerol monomethacrylate (manufactured by NOF Corporation) was dropped as a hydroxyl group-containing (meth) acrylate, and stirring was continued for 3 hours at a liquid temperature of 60 to 75 ° C. while stirring these, The reaction was terminated when it became 0.01% by mass or less. In this way, a solution containing urethane (meth) acrylate (U-11) was obtained. Gel permeation chromatography (HLC-8200GPC manufactured by Tosoh Corporation, TSKgel-G4000HXL × 1, TSKGel-G3000HXL × 1, TSKGel manufactured by Tosoh Corp.) -G2000 × 2, TSK guard column H _XL -L × 1), the number average molecular weight in terms of standard polystyrene was 450,000.

3.1.12. Synthesis Example 12 Production of Urethane (Meth) acrylate (U-12) In a reaction vessel equipped with a stirrer, 14.65 g of isophorone diisocyanate as polyisocyanate and bisphenol A EO-modified glycol having a number average molecular weight of 400 as polyol (NOF Corporation) 18.00 g of polytetramethylene glycol (manufactured by Hodogaya Chemical Co., Ltd.) as a polyol, 16.48 g, 0.024 g of 2,6-di-t-butyl-p-cresol, dibutyltin 0.08 g of dilaurate and 150 g of methyl ethyl ketone were charged, and stirring was continued for 3 hours at a liquid temperature of 60 to 75 ° C. while stirring them. Thereafter, 0.87 g of glycerin monomethacrylate (manufactured by NOF Corporation) was dropped as a hydroxyl group-containing (meth) acrylate, and stirring was continued at a liquid temperature of 60 to 75 ° C. for 3 hours while stirring these. The reaction was terminated when it became 0.01% by mass or less. In this way, a solution containing urethane (meth) acrylate (U-12) was obtained. Gel permeation chromatography (HLC-8200GPC manufactured by Tosoh Corporation, TSKgel-G4000HXL × 1, TSKGel-G3000HXL × 1, TSKGel manufactured by Tosoh Corp.) -G2000 × 2, TSK guard column H _XL -L × 1), the number average molecular weight in terms of standard polystyrene was 260,000.

3.1.13. Synthesis Example 13: Production of urethane (meth) acrylate (U-13) A reaction vessel equipped with a stirrer was charged with 11.46 g of tolylene diisocyanate as polyisocyanate and bisphenol A EO-modified glycol having a number average molecular weight of 400 as polyol (Nissan Co., Ltd.) 15.73 g made by company), 21.95 g polypropylene glycol (Asahi Glass Urethane Co., Ltd.) having a number average molecular weight of 1000 as polyol, 0.024 g 2,6-di-t-butyl-p-cresol, dibutyltin dilaurate 0 0.08 g and methyl ethyl ketone 150 g were charged, and stirring was continued for 3 hours at a liquid temperature of 60 to 75 ° C. while stirring them. Thereafter, 0.87 g of glycerin monomethacrylate (manufactured by NOF Corporation) is added dropwise as a hydroxyl group-containing (meth) acrylate, and stirring is continued at a liquid temperature of 60 to 75 ° C. for 3 hours while stirring these. The reaction was terminated when it became 0.01% by mass or less. In this way, a solution containing urethane (meth) acrylate (U-13) was obtained. Gel permeation chromatography (HLC-8200GPC manufactured by Tosoh Corporation, TSKgel-G4000HXL × 1, TSKGel-G3000HXL × 1, TSKGel manufactured by Tosoh Corp.) -G2000 × 2, TSK guard column H _XL -L × 1), the number average molecular weight in terms of standard polystyrene was 350,000.

3.1.14. Synthesis Example 14: Production of urethane (meth) acrylate (U-14) In a reaction vessel equipped with a stirrer, isophorone diisocyanate 18.150 g, 2,6-di-t-butyl-p-cresol 0.024 g, dibutyltin dilaurate (Kyodo Pharmaceutical Co., Ltd., trade name “KS-1200A-1”) 0.06 g and methyl ethyl ketone 49.974 g, number average molecular weight 400 bisphenol A EO-modified diol (manufactured by NOF Corporation) 21.925 g, number Polytetramethylene glycol having an average molecular weight of 1000 (made by Hodogaya Chemical Co., Ltd.) 3.364 g, polypropylene glycol having a number average molecular weight of 1000 (made by Asahi Glass Urethane Co., Ltd.) 3.364 g, glycerol monomethacrylate (made by NOF Corporation, product) Name "Blemmer GLM") 3.213g While stirring these, stirring was continued for 4 hours at a liquid temperature of 70 to 75 ° C., and the reaction was terminated when the residual isocyanate was 0.01% by mass or less. In this way, a solution containing urethane methacrylate (U-14) was obtained. Gel permeation chromatography (HLC-8200GPC manufactured by Tosoh Corporation, TSKgel-G4000HXL × 1, TSKGel-G3000HXL × 1, TSKGel manufactured by Tosoh Corp.) -G2000 × 2, TSK guard column H _XL -L × 1), the number average molecular weight in terms of standard polystyrene was 380,000.

3.1.16. Synthesis Example 15: Production of monofunctional urethane (meth) acrylate (B-1) In a reaction vessel equipped with a stirrer, 18.50 g of tolylene diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol, 0.08 g of dibutyltin dilaurate and 99.95 g of methyl ethyl ketone were charged, and these were cooled with ice until the liquid temperature became 10 ° C. or lower while stirring. 12.33 g of hydroxyethyl acrylate was dropped while controlling the liquid temperature to be 20 ° C. or lower, and the reaction was further stirred for 1 hour. Next, 69.11 g of polytetramethylene glycol having a number average molecular weight of 650 (manufactured by Hodogaya Chemical Co., Ltd.) was charged, and stirring was continued at a liquid temperature of 70 to 75 ° C. for 3 hours. The reaction was terminated when Thus, the solution containing monofunctional urethane (meth) acrylate (B-1) was obtained.

3.1.17. Synthesis Example 16: Production of monofunctional urethane (meth) acrylate (B-2) In a reaction vessel equipped with a stirrer, 25.20 g of tolylene diisocyanate, 0.024 g of 2,6-di-t-butyl-p-cresol, 0.08 g of dibutyltin dilaurate and 99.95 g of methyl ethyl ketone were charged, and these were cooled with ice until the liquid temperature became 10 ° C. or lower while stirring. 16.83 g of hydroxyethyl acrylate was dropped while controlling the liquid temperature to be 20 ° C. or lower, and the reaction was further stirred for 1 hour. Next, 57.94 g of polyethylene glycol having a number average molecular weight of 400 (manufactured by NOF Corporation) was charged, and stirring was continued at a liquid temperature of 70 to 75 ° C. for 3 hours. Time was the end of the reaction. In this way, a solution containing the monofunctional urethane (meth) acrylate (B-2) was obtained.

3.2. Production of fatty acid ester surfactant (antifouling agent) 3.2.1. Synthesis Example 17 Production of Compound (C-1)
In formula (2), R ¹ is a group represented by the following formula (3). a + b + c = 7.

To a three-necked flask equipped with a stirrer, 2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemical Co., Yoshinox BHT) 0.030 g, pentaerythritol triacrylate (Shin Nakamura Chemical Co., Ltd., NK ester A-TMM-3LM-N) 21.60 g, tolylene diisocyanate (Mitsui Chemical Polyurethane Co., Ltd., TOLDY-100) 8.05 g, and methyl isobutyl ketone (Mitsubishi Chemical Co., Ltd.) 50.00 g were charged. Dioctyltin dilaurate (Kyodo Pharmaceutical Co., Ltd., KS-1200)
-A) After adding 0.292 g, the mixture was stirred at room temperature for 2 hours. Subsequently, 20.03 g of polyoxyethylene hydrogenated castor oil (Nippon Emulsion Co., Ltd., EMALEX HC-7; HLB value 6) was added. The reaction solution was heated to 60 ° C. and stirred for 2 hours to obtain compound (C-1). Moreover, since the acrylation reaction proceeds almost quantitatively, the HLB of the compound (C-1) determined from the charged amount is 3.

3.3. Production of self-healing member Examples 1 to 43 and Comparative Example 1 were prepared by adding each material so as to have the composition shown in Tables 1 to 5 and stirring for 2 hours at room temperature in a container shielded from ultraviolet rays. Each composition of -6 was obtained.

Subsequently, in Examples 1 to 38 and Comparative Examples 1 to 6, the obtained compositions were applied on a PET film having a thickness of 188 μm with a bar coater so as to have the film thicknesses described in Tables 1 to 4. After evaporating the solvent in an oven at 80 ° C., it is cured at 1,000 mJ / cm ² in the air using a UV curing device (manufactured by Eye Graphics) or heat-treated at 140 ° C. for 5 minutes. And cured. That is, Example 16 and Example 28 were heat-cured, and other examples and comparative examples were UV-cured. The surface hardness of the obtained cured film was measured with “Asker Rubber Hardness Meter TYPE EP” manufactured by Kobunshi Keiki Co., Ltd., and it was confirmed that the pointer value was 3 or more.

On the other hand, the self-restoring members according to Examples 39 to 43 were produced as follows. On an acrylic base material having a thickness of 3 mm, the compositions obtained in Examples 39, 40, 42, and 43 so as to have the film thicknesses shown in Table 5 were sprayed by Anest Iwata (model W-101-101G). In Example 41, the composition obtained so as to have the film thickness described in Table 5 was applied with a bar coater. Then, after volatilizing the solvent in an 80 ° C. oven, it was cured at 1,000 mJ / cm ² under air using a UV curing device (manufactured by Eye Graphics). The surface hardness of the obtained cured film was measured with “Asker Rubber Hardness Meter TYPE EP” manufactured by Kobunshi Keiki Co., Ltd., and it was confirmed that the pointer value was 3 or more.

3.4. Evaluation test 3.4.1. State of composition The composition obtained in the above section "3.3. Production of self-healing member" is allowed to stand under the conditions of a temperature of 23 ° C and a humidity of 50%, and a solidified material is generated after 7 days. It was confirmed visually whether or not. The evaluation criteria are as follows. The results are also shown in the table.
○: A transparent and uniform solution.
X: A coagulated substance is generated in the solution.

3.4.2. Measurement of cross-linking or entanglement density Equilibrium elastic modulus E ′ (MPa) in a rubber-like flat region of a self-healing member obtained using a dynamic viscoelasticity measuring device (RHEOVIBRON MODEL DDV-01FP manufactured by A & D Corporation) ) By substituting the obtained equilibrium elastic modulus E ′ (MPa) into the following formula (4), the crosslinking or entanglement density n was calculated. The results are also shown in the table.
n = E ′ / 3RT (4)
Here, n: cross-linking or entanglement density (mol / cm ³ ), R: gas constant (8.314 J / (K · mol)), T: absolute temperature (K), E ′: equilibrium elastic modulus (MPa) is there.

3.4.3. Breaking strength, breaking elongation and tensile product About the self-healing member according to Examples 17 to 28 and Comparative Example 6, using a tensile tester (manufactured by Shimadzu Corporation, model “AGS-50G”), breaking the test piece The strength and elongation at break were measured under the following measurement conditions. Further, from the values of the obtained breaking strength and breaking elongation, the following formula (5
) To calculate the tensile product. The results are also shown in Table 3.
Tensile product = (breaking strength) × (breaking elongation) (5)
<Measurement conditions>
Tensile speed: 50 mm / distance between marked lines (measurement distance): 25 mm
Measurement temperature: 23 ° C
Relative humidity: 50%

3.4.4. Measurement of total light transmittance Using a color haze meter (Color Cute i and Haze Computer HZ-2 manufactured by Suga Test Instruments Co., Ltd.), all of the obtained self-restoring members (including PET film) according to JIS K7105 The light transmittance (%) was measured. The results are also shown in the table.

3.4.5. Measurement of haze Using a color haze meter (Color Cute i and Haze Computer HZ-2, manufactured by Suga Test Instruments Co., Ltd.), the haze value (%) of the obtained self-restoring member (including PET film) according to JIS K7105 ) Was measured. The results are also shown in the table.

3.4.6. Bonding test After the surfaces of the cured films of the obtained self-healing member were bonded together, they were peeled off and the state of both surfaces was observed visually. The results are also shown in the table. In the table, “Yes” is indicated when the adhesive material is found on both cured surfaces, and “None” is indicated when no adhesive material is found on both cured surfaces.

3.4.7. Scratch Resistance Test Using # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), the surface of the cured film was repeatedly rubbed 10 times under the condition of a load of 100 g / cm ² in accordance with JIS K5400. Thereafter, the surface state of the cured film was visually observed. The evaluation criteria are as follows. The results are also shown in the table.
○: No scratch is observed on the surface of the cured film.
X: Scratches are observed on the surface of the cured film.

3.4.8. Scratch disappearance test A brass brush (manufactured by TRUSCO NAKAYAMA Co., Ltd., product number TB-5008-10) was used to scratch the surface of the cured film repeatedly by scratching 10 times. Thereafter, it was visually confirmed whether or not the scratches on the surface of the cured film disappeared within 3 minutes. The evaluation criteria are as follows. The results are also shown in the table.
○: The wound disappeared within 3 minutes.
X: It took 3 minutes or more for the scratches to disappear, or the scratches did not disappear.

3.4.9. Curling property The self-healing member obtained in “3.2. Production of self-healing member” was cut into a 10 cm × 10 cm square, and the average value of the amount of warping at the four corners was measured. The evaluation criteria are as follows. The results are also shown in the table.
A: The average value of the amount of warping was 1 mm or less.
X: The average value of the amount of warping exceeded 1 mm.

3.4.10. Fingerprint wiping property The back surface of the self-healing member obtained in Examples 29 to 38 was blacked out, and a fingerprint was adhered to the cured film surface of the self-healing member. Thereafter, the fingerprint was wiped off with a tissue and evaluated according to the following evaluation criteria.
○: Can be wiped off.
X: Cannot be wiped off.

3.4.11. Appearance of coating film The self-healing members obtained in Examples 39 to 43 were visually observed and evaluated according to the following evaluation criteria.
◯: A yuzu skin-like appearance cannot be confirmed in the cured film 180 mm × 100 mm.
X: The skin-like surface appearance can be confirmed partially or entirely in the cured film 180 mm × 100 mm.

3.4.12. Cross-cut test The self-healing members obtained in Examples 39 to 43 were evaluated according to JIS K5600-5-6. A sample that peeled off at all or only a part was evaluated as “good”, and a sample that completely peeled off was evaluated as “failed”.

The abbreviations described in Tables 1 to 5 are as follows, and only the solid content is described in the compositions of Tables 1 to 5.
U-1: polyfunctional urethane (meth) acrylate produced in Synthesis Example 1 ([NCO] / [O
H] = 2.00)
U-2: polyfunctional urethane (meth) acrylate produced in Synthesis Example 2 ([NCO] / [OH] = 2.00)
U-3: polyfunctional urethane (meth) acrylate produced in Synthesis Example 3 ([NCO] / [OH] = 2.00)
U-4: polyfunctional urethane (meth) acrylate produced in Synthesis Example 4 ([NCO] / [OH] = 2.00)
U-5: polyfunctional urethane (meth) acrylate produced in Synthesis Example 5 ([NCO] / [OH] = 2.00)
U-6: polyfunctional urethane (meth) acrylate produced in Synthesis Example 6 ([NCO] / [OH] = 1.02)
U-7: polyfunctional urethane (meth) acrylate produced in Synthesis Example 7 ([NCO] / [OH] = 1.20)
U-8: polyfunctional urethane (meth) acrylate produced in Synthesis Example 8 ([NCO] / [OH] = 1.25)
U-9: polyfunctional urethane (meth) acrylate produced in Synthesis Example 9 ([NCO] / [OH] = 1.25)
U-10: polyfunctional urethane (meth) acrylate produced in Synthesis Example 10 ([NCO] / [OH] = 1.20)
U-11: Polyurethane (meth) acrylate produced in Synthesis Example 11 ([NCO] / [OH] = 1.43, number average molecular weight: 450,000)
U-12: Polyurethane (meth) acrylate produced in Synthesis Example 12 ([NCO] / [OH] = 1.07, number average molecular weight: 260,000)
U-13: Polyurethane (meth) acrylate produced in Synthesis Example 13 ([NCO] / [OH] = 1.07, number average molecular weight: 350,000)
U-14: Polyurethane (meth) acrylate produced in Synthesis Example 14 ([NCO] / [OH] = 1.33, number average molecular weight: 380,000)
B-1: Monofunctional urethane (meth) acrylate produced in Synthesis Example 15 ([NCO] / [OH] = 1.00)
B-2: monofunctional urethane (meth) acrylate produced in Synthesis Example 16 ([NCO] / [OH] = 1.00)
-Dipentaerythritol hexaacrylate: Nippon Kayaku Co., Ltd., KAYARAD DPHA
Tetraethylene glycol diacrylate: Kyoeisha Chemical Co., Ltd., light acrylate 4EG-A
Polypropylene glycol monomethacrylate: manufactured by NOF Corporation, Blemmer PP 800
・ Irg. 184: manufactured by BASF Japan, photopolymerization initiator / perbutyl Z: manufactured by NOF Corporation, thermosetting agent / BYK371: manufactured by Big Chemie Japan, slip agent / SH8400: manufactured by Toray Dow Corning, slip agent / SH190: manufactured by Toray Dow Corning Co., Ltd., slip agent / BYK3500: manufactured by Big Chemie Japan, slip agent / HEMA: 2-hydroxyethyl methacrylate / THF-A: tetrahydrofurfuryl methacrylate

In addition, the number average molecular weight (Mn) of polyurethane (meth) acrylate (U-11 to U-14) is measured by gel permeation column chromatography (GPC), and the retention capacity is measured by the standard polystyrene method. It calculated | required by converting into an average molecular weight (Mn). The specific measurement conditions are as follows.
・ Model used: Tosoh Corporation, HLC-8200GPC
Solvent: Tetrahydrofuran Column: Tosoh Corporation, TSKGel-G4000HXL × 1, TSKGel-G3000HXL × 1, TSKGel-G2000 × 2, TSK guard column H _XL- L × 1

3.5. Evaluation results From the results of Table 1, according to the self-repairing members of Examples 1 to 16 according to the present invention, they have excellent transparency and are hardly scratched from the results of the scratch resistance test (that is, the hardness is high). ) And the results of the wound disappearance test showed that the self-repairing ability was excellent. In particular, when the urethane group concentration of the self-healing material is 2.0 mmol / g or more and the cross-linking or entanglement density is in the range of 0.2 to 2.5 mmol / cm ³ , the self-healing ability of the self-healing material is effective. It turns out that it is demonstrated. As described above, the self-healing member according to the present invention is different from the conventional self-healing member in that it has both high hardness and excellent self-healing property.

  In Examples 17 to 28 described in Table 3, the number of moles of the hydroxyl group-containing (meth) acrylate is decreased, and a composition containing a urethane polymer obtained by synthesizing a polyisocyanate and a polyol is subjected to a curing reaction. Is formed. This urethane-based polymer has an aggregated layer (hard layer) based on the intermolecular interaction of urethane groups and the stacking action of the bisphenol A skeleton, and a long chain segment (soft layer) such as polytetramethylene glycol. From Examples 17 to 28, it was found that such self-healing members exhibited high toughness and stretchability due to the entanglement of molecular chains based on the polymer structure. Since these self-healing members exhibit high stretchability, it is considered that they are suitable for in-mold molding materials, particularly vacuum / pressure forming materials that require stretchability.

  Examples 29 to 38 listed in Table 4 are obtained by adding an antifouling agent to the self-healing member according to the present invention. From these results, it was found that the self-healing member to which the antifouling agent according to the present invention was added exhibited good fingerprint wiping properties. Such a self-healing member is excellent in scratch resistance and autonomous self-healing ability, and can also prevent the adhesion of fingerprints. It is considered suitable as a material.

  Examples 39 to 43 shown in Table 5 are obtained by applying the composition for forming a self-restoring member according to the present invention to an acrylic base material, and evaluating the adhesion to the base material and the self-healing performance. . The acrylic substrate used here is a (meth) acrylic copolymer containing methyl methacrylate (MMA) and 2- (hydroxymethyl) methyl acrylate (MHMA) at a ratio of 40/10 (wt / wt). A polymer and a styrene-acrylonitrile copolymer containing styrene and acrylonitrile at a ratio of 73/27 (mol / mol) are contained at a ratio of 90/10 (wt / wt). From these results, it was found that according to the composition according to the present invention, a self-repairing member in which the surface coating film and the acrylic base material are in good contact with each other and high self-repairing properties are obtained can be obtained. Since acrylic materials are relatively inexpensive and excellent in transparency, and have low hygroscopicity and excellent dimensional stability, such self-healing members are used for external components of display devices and front panels of portable information terminals. It is thought that it is suitable for a coating material or an anti-scratch film used by sticking to these.

2 to 4 are photographs showing a state of a scratch disappearance test of the self-restoring member according to Example 1. FIG. FIG. 2 is a photograph showing a state immediately after the surface of the self-restoring member is scratched with a brass brush. FIG. 3 is a photograph showing a state 3 seconds after the surface of the self-healing member was scratched with a brass brush. FIG. 4 is a photograph showing a state 3 minutes after the surface of the self-healing member is scratched with a brass brush. From the photographs of FIGS. 2 to 4, it was confirmed that the scratches attached to the surface of the self-healing member according to Example 1 were progressing after 3 seconds and could not be visually confirmed within 3 minutes. It turns out that it has disappeared to the extent.

  On the other hand, in the self-recoverable members of Comparative Examples 1 to 3, a material obtained by combining a hard skeleton with one end long-chain methacrylate is used. In the scratch resistance test of Comparative Example 1, the obtained self-restoring member had curls, and when the curls were extended, the cracks were partially formed, so that the test could not be performed. In the scratch disappearance test of Comparative Example 1, the cured film of the obtained self-restoring member was not scratched at all. On the other hand, the scratches attached in Comparative Examples 2 and 3 did not disappear at all.

  In the self-healing members of Comparative Examples 4 to 5, a material in which a soft skeleton was combined with one-end long-chain methacrylate was used, but the attached scratch did not disappear at all.

  In Comparative Example 6, the composition containing only the monofunctional urethane (meth) acrylate (B-1) with [NCO] / [OH] = 1.00 was cured and reacted, but a film having sufficient hardness was obtained. Couldn't get.

  The self-healing material according to the present invention has excellent curability and transparency, and can autonomously exhibit excellent self-healing ability. Therefore, self-healing according to the present invention is applied to the surface of various articles such as products requiring transparency and scratch resistance, such as portable information devices, portable communication terminals, leather products, automobile instrument panels, home appliances, personal computers, etc. By applying the material, it is possible to effectively prevent the appearance and function from being impaired.

DESCRIPTION OF SYMBOLS 10a ... Three-dimensional crosslinked structure by polyfunctional urethane (meth) acrylate, 10b ... Branch chain by monofunctional urethane (meth) acrylate, 12 ... Cross-linking point, 100 ... Self-healing material

Claims (8)

At least one polyol selected from polytetramethylene glycol, polytetraethylene glycol, ethylene glycol-modified diol of bisphenol A and polyethylene glycol having a number average molecular weight of 400 to 1000, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate And a method for producing a self-healing material formed by a curing reaction of a composition containing urethane (meth) acrylate obtained by reacting,
The urethane (meth) acrylate has a urethane group concentration of 2.414 mmol / g or more and 4.02 mmol / g or less,
The composition adjusts the ratio of the number of hydroxyl groups [OH] of the polyol to the number of isocyanate groups [NCO] of the polyisocyanate within the range of [NCO] / [OH] = 1.0 to 2.0 or less. A method for producing a self-healing material, comprising the polyfunctional urethane (meth) acrylate (A) reacted in the step.   In the composition, the ratio of the number of hydroxyl groups [OH] of the polyfunctional urethane (meth) acrylate (A) and the polyol to the number of isocyanate groups [NCO] of the polyisocyanate is [NCO] / [OH] = 0.3. The manufacturing method of the self-healing material of Claim 1 containing the monofunctional urethane (meth) acrylate (B) adjusted and reacted within the range of 1.0 or more and below. The blending ratio when the total amount of the polyfunctional urethane (meth) acrylate (A) and the monofunctional urethane (meth) acrylate (B) in the composition is 100 parts by mass is a polyfunctional urethane (on a mass basis). The method for producing a self-healing material according to claim 2, which is within the range of (meth) acrylate (A): monofunctional urethane (meth) acrylate (B) = 90 : 10 to 50:50. The self-healing material, cross-linking or entanglements density was determined by dynamic viscoelasticity measurement is 0.2~2.5mmol / cm ^3, the self-repairing material according to any one of claims 1 to 3 Manufacturing method. The manufacturing method of the self-healing material according to any one of claims 1 to 4, wherein the film thickness of the self-healing material is 1 to 1000 µm. At least one polyol selected from polytetramethylene glycol, polytetraethylene glycol, ethylene glycol-modified diol of bisphenol A and polyethylene glycol having a number average molecular weight of 400 to 1000, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate And a method for producing a composition containing urethane (meth) acrylate obtained by reacting
The urethane (meth) acrylate has a urethane group concentration of 2.414 mmol / g or more and 4.02 mmol / g or less,
The composition adjusts the ratio of the number of hydroxyl groups [OH] of the polyol to the number of isocyanate groups [NCO] of the polyisocyanate within the range of [NCO] / [OH] = 1.0 to 2.0 or less. The manufacturing method of the composition for manufacturing the self-healing material containing the polyfunctional urethane (meth) acrylate (A) made to react by this. In the composition, the ratio of the number of hydroxyl groups [OH] of the polyfunctional urethane (meth) acrylate (A) and the polyol to the number of isocyanate groups [NCO] of the polyisocyanate is [NCO] / [OH] = 0.3. The manufacturing method of the composition for manufacturing the self-healing material of Claim 6 containing the monofunctional urethane (meth) acrylate (B) adjusted and reacted in the range of 1.0 or more and below. The blending ratio when the total amount of the polyfunctional urethane (meth) acrylate (A) and the monofunctional urethane (meth) acrylate (B) in the composition is 100 parts by mass is a polyfunctional urethane (on a mass basis). The method for producing a composition for producing a self-healing material according to claim 7 , which is within the range of (meth) acrylate (A): monofunctional urethane (meth) acrylate (B) = 90 : 10 to 50:50. .