KR20160095613A - Composition with which cured product having self-healing property is obtained, and self-healing coat film having cured coating layer thereof - Google Patents

Abstract

The present invention relates to a composition which can form a surface film having satisfactory self-healing properties, excellent film strength and also excellent UV-resistance, and a coating layer formed by curing the composition. More specifically, the present invention aims to provide a self-healing coating film having a coating layer having high total optical transmittance of 90% or higher, a composition which can form a cured product such as a cured film having excellent self-healing properties, film strength and oil resistance, and a self-healing coating film having the cured coating layer. The composition comprises: (A) polyol; (B) polyisocyanate; and (C) at least one amine-based light stabilizer, wherein the OH group of the polyol (A) is 150-400 mgKOH/g, and the hindered amine-based light stabilizer (C) is a compound represented by formula (1).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for producing a cured product having self-repellency and a self-restoration coat film having the cured coating. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming a material having self-repellency and, for example, when it is used as a surface protective film for a liquid crystal display of a mobile device such as a mobile phone or a personal computer, To a composition capable of forming a coating film having both of self-restoration property and excellent coating film hardness and also having UV resistance or oil resistance (oil resistance).

Conventionally, a hard film-treated plastic film has been used as a surface protective film for an optical member such as a liquid crystal panel or a vehicle body of an automobile. In a general hard coat, since the hardness of the coating film is increased by increasing the crosslinking density, the surface of the coating film can be made hard. As a result, the scratch resistance of the surface of the coating film is improved, and damage to the surface of the liquid crystal display or the surface of the vehicle body or the like can be made difficult. However, once a small damage occurs on the surface, it is impossible to return the damage itself to its original state. Therefore, in place of such a hard coat, use of a material having self-repellency has been studied.

Here, the material having self-repellency has a property of imparting rubber elasticity to the coating film by lowering the cross-linking density and recovering small damage caused on the surface by the repulsive force of the rubber elasticity with time. On the other hand, a material having such self-repellent property has a small hardness of the coating film due to a decrease in the crosslinking density, and therefore it is difficult to impart sufficient coating film hardness (scratch resistance) to the surface of the coating film. For this reason, there is a demand for a material having self-repellent properties with improved scratch resistance.

Therefore, in order to form a soft resin layer having self-repellency and scratch resistance, a soft resin layer using a urethane resin obtained from a polyisocyanate and a polyester-based polyol is applied on at least one surface of a hard resin film or sheet A transparent plastic laminate formed thereon has been proposed (Patent Document 1).

In order to provide a material having self-repellency excellent in scratch resistance, a base layer containing a polycarbonate-based resin as a main component and a surface layer and a backside layer of the base layer containing the polymethylmethacrylate- There is proposed a self-repairing film comprising a base sheet provided with a base sheet and a soft resin layer having self-repellency including a polyurethane resin laminated on the surface of the base sheet as main components (Patent Document 2).

However, even with a material having conventional self-repellency, a material having self-repellency with sufficient film hardness can not be obtained. Further, if an external load due to ultraviolet irradiation or the like is applied to the surface of a coating film formed by a material having self-repairing property, the hardness of the coating film may be lowered. Therefore, in addition to sufficient coating film hardness, Is also required. Therefore, it is desired to provide a coating film which exhibits good self-repairability, excellent coating film hardness, and further excellent UV resistance. In addition, since the film obtained from a material having self-repellency is particularly used also as a surface protective film for an optical member, it is preferable that the film exhibits a high total light transmittance. In contrast to this, there is a problem in that a liquid-crystal display or a surface protective film is required to have a property in which grease hardly adheres, that is, oil resistance, and a material having self-repellency of a conventional thermosetting system, there was.

JPH07-195623A JP 2013-144391 A

SUMMARY OF THE INVENTION In view of the above circumstances, it is an object of the present invention to provide a composition capable of forming a surface coating film having both good self-repairability and excellent coating film hardness and having excellent UV resistance, A self-restoration coat film having a coating showing a total light transmittance, and a composition capable of forming a cured product such as a cured coating film having excellent self-repairability, coating film hardness and oil resistance, and a self- .

An aspect of the present invention is a composition containing (A) a polyol, (B) a polyisocyanate and (C) at least one hindered amine light stabilizer, wherein the OH group of the polyol (A) (C) the hindered amine-based light stabilizer is a compound represented by the following general formula (1): " (1) "

Wherein,

n is an integer of 1 to 10,

R is hydrogen or C ₁ to C ₄ Alkyl group,

A is C ₁ to C ₄ Alkyl group or a group represented by the following general formula (2):

A piperidyl group represented by the formula

R 'is hydrogen or C ₁ to C ₄ Alkyl group.

(A) a polyol having an OH group in a range of 150 to 400 mg KOH / g, and (C) a hindered amine light stabilizer having a structure represented by the general formula (1) It is possible to obtain a composition capable of forming a surface coating film having both good self-repairability and excellent coating film hardness and further having excellent UV resistance. Therefore, by coating the composition on a substrate, a coating film having both good self-repairability and excellent coating film hardness and excellent UV resistance can be formed. In addition, the self-restoration coat film having a coating obtained by curing the composition exhibits a high total light transmittance of 90% or more.

An aspect of the present invention is a composition further comprising (D) a surface formulating agent.

An aspect of the present invention is a composition wherein the polyol (A) is a polycaprolactone triol.

As an aspect of the present invention, there is provided the above (C) hindered amine light stabilizer, wherein n is an integer of 5 to 8, R is C ₁ to C ₄ Alkyl group, and R 'is C ₁ to C ₄ Is a composition containing at least one compound represented by the above general formula (1) which is an alkyl group.

An aspect of the present invention resides in that the above (C) hindered amine light stabilizer is bis (1,2,2,6,6-pentamethyl-4-piperidyl) decane diate and methyl 6,6-pentamethyl-4-piperidyl) sebacate.

An aspect of the present invention is a composition wherein the OH group of the polyol (A) is 250 to 350 mg KOH / g.

An aspect of the present invention is a composition comprising (A) a polyol, (B) a polyisocyanate, and (G) a polydialkylsiloxane having a terminal hydroxyl group modified, wherein the polyisocyanate (B) Is a modification of the aliphatic polyisocyanate and / or the corresponding aliphatic polyisocyanate.

An aspect of the present invention is a composition wherein the aliphatic polyisocyanate is an aliphatic polyisocyanate having 3 to 10 carbon atoms.

An aspect of the present invention is a composition wherein the aliphatic polyisocyanate is hexamethylene diisocyanate.

An aspect of the present invention is that the modified body of the aliphatic polyisocyanate is a bifunctional type of hexamethylene diisocyanate and / or an isocyanurate of hexamethylene diisocyanate.

An aspect of the present invention is a composition wherein the OH value of the polyol (A) is 150 to 400 mg KOH / g.

An aspect of the present invention is a composition, wherein the polyol (A) is a polycaprolactone triol.

An aspect of the present invention is a composition further comprising (C) a hindered amine light stabilizer represented by the following general formula (1):

Wherein,

n is an integer of 1 to 10,

R is hydrogen or C ₁ to C ₄ Alkyl group,

A is selected from the group consisting of C ₁ to C ₄ Alkyl group or a group represented by the following general formula (2):

A piperidyl group represented by the formula

R 'is hydrogen or C ₁ to C ₄ Alkyl group.

An aspect of the present invention resides in that the above (C) hindered amine light stabilizer is bis (1,2,2,6,6-pentamethyl-4-piperidyl) decane diate and methyl 6,6-pentamethyl-4-piperidyl) sebacate. ≪ / RTI >

An aspect of the present invention is a composition characterized by further comprising (H) an ultraviolet absorber.

An aspect of the present invention is a composition characterized by further comprising (E) a filler.

An aspect of the present invention is a self-restoration coat film characterized by having a cured coating of the composition.

(A) a polyol having an OH group in a range of 150 to 400 mg KOH / g, (C) a hindered amine light stabilizer having a structure represented by the general formula (1) It is possible to form a coating film having both good self-restoration and excellent coating film hardness on the substrate and having excellent UV resistance. In addition, the film having the film formed by curing the composition exhibits a high total light transmittance of 90% or more. Thus, for example, when a coating film formed from the composition of the present invention is used as a protective film for a liquid crystal display or an automobile body, it is possible to provide a film having both excellent self-repairing property and excellent film hardness, Can be obtained.

According to the aspect of the present invention, the hardness of the coating film formed on the substrate can be further improved by further containing (D) a surface-treating agent in the composition.

According to the aspect of the present invention, the hardness of the coating film formed on the substrate can be further improved by using (A) a polyol having an OH group within the range of 250 to 350 mgKOH / g.

According to an aspect of the present invention, there is provided a process for producing an isocyanate compound, which comprises using an aliphatic polyisocyanate and / or a modified aliphatic polyisocyanate of the corresponding aliphatic polyisocyanate as the isocyanate compound and adding a polydialkylsiloxane having a terminal hydroxyl- As a result, a composition capable of forming a cured product such as a cured coating film having excellent self-repellency and excellent oil resistance can be obtained only by curing by heat treatment without photo-curing as a curing step.

According to the aspect of the present invention, the aliphatic polyisocyanate is an aliphatic polyisocyanate having 3 to 10 carbon atoms, whereby oil resistance can be further improved.

According to an aspect of the present invention, the aliphatic polyisocyanate is hexamethylene diisocyanate or the modified product of aliphatic polyisocyanate is a bifunctional type of hexamethylene diisocyanate and / or hexamethylene diisocyanate By using isocyanurate of cyanate, more excellent oil resistance can be obtained.

According to the aspect of the present invention, the OH value of the polyol (A) is 150 to 400 mgKOH / g, whereby the hardness of the coating film can be improved without compromising the self-restoration and oil resistance.

According to the aspect of the present invention, by further containing the filler (E) in the composition, the hardness of the coating film formed on the substrate can be further improved.

Next, the composition of the present invention will be described. First, the first composition of the present invention will be described. Hereinafter, each component contained in the first composition of the present invention will be described. The first composition of the present invention comprises (A) a polyol having an OH group in the range of 150 to 400 mg KOH / g, (B) a polyisocyanate, (C) And at least one of dodaminedic acid stabilizers.

(A) a polyol

The first composition of the present invention contains a polyol having OH groups in the range of 150 to 400 mg KOH / g as one of the main components for film formation. The polyol is a main raw material for obtaining a polyurethane by reacting with a polyisocyanate. Examples of the polyol include a polyether polyol, a polyester polyol and a polycarbonate polyol. The kind of the polyol in the present invention is not particularly limited as long as it has an OH value in the range of 150 to 400 mgKOH / g, but from the viewpoint of balance between the coating film hardness and the self restorability, the polyester polyol is preferable, Among the polyester polyols, a polycaprolactone polyol obtained by ring-opening a cyclic ester is particularly preferable from the viewpoint of giving a high rebound resilience to the obtained coating layer and good adhesion with the substrate. These polyols may be used singly or in combination of two or more.

Examples of the polycaprolactone polyol include a bifunctional polycaprolactone diol, a trifunctional polycaprolactone triol, and a tetrafunctional polycaprolactone tetraole. From the viewpoint of balance between the film hardness and the self restorability, Polycaprolactone triol is preferred. These polycaprolactone polyols may be used singly or in combination of two or more.

The polyol (A) contained in the first composition of the present invention has OH groups in the range of 150 to 400 mg KOH / g. If the OH value of the polyol is less than 150 mgKOH / g, sufficient film hardness can not be imparted. On the other hand, if the OH group of the polyol is more than 400 mgKOH / g, I will not. The lower limit value of the OH group of the polyol is preferably 200, more preferably 250, from the viewpoint of imparting high hardness by the coating film. On the other hand, the upper limit of the OH value of the polyol is preferably 380, more preferably 350, from the viewpoint of self-restorability.

The mass average molecular weight of the polyol (A) is preferably 300 to 1000, particularly preferably 500 to 900 from the viewpoint of the balance of coating film hardness and self-restoring property. It is also possible to use two or more kinds of polyols having different molecular weights.

Examples of the commercially available polyol (A) having OH groups in the range of 150 to 400 mg KOH / g include PLACCEL 305 (polycaprolactone triol: Daicel Co., Ltd., OH group = 305 mg KOH / g), PLACCEL 308 (polycaprolactone triol: Daicel product, OH group = 195 mgKOH / g), PLACCEL 309 (polycaprolactone triol: Daicel product, OH group = 186 mgKOH / g ) And the like. These polyols may be used alone or in combination of two or more.

(B) a polyisocyanate

The first composition of the present invention contains a polyisocyanate as another main component for forming a coating film, and the polyisocyanate is a main raw material for reacting with a polyol to obtain a polyurethane. The polyisocyanate is not particularly limited and includes, for example, aliphatic polyisocyanates, aromatic polyisocyanates, and alicyclic polyisocyanates. Specific examples include diphenylmethane diisocyanate (2,2'-MDI, 2,4'-MDI, 4,4'-MDI), carbodiimide modified MDI (modified MDI), polymethylene polyphenyl polyisocyanate Carbodiimide diphenylmethane polyisocyanate, xylene diisocyanate, tolylene diisocyanate (2,2'-TDI, 2,4'-TDI, 4,4 '-TDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate, 1,5-naphthalene diisocyanate (NDI), tetramethyl xylene diisocyanate or Aromatic polyisocyanate such as phenylene diisocyanate, aliphatic polyisocyanate such as hexamethylene diisocyanate (HDI), dimer acid diisocyanate or lysine diisocyanate, or Iseporo Rondai Isosai Anei (IPDI), norbornene nendayi isocyanate (NBDI), diphenyl methane diisocyanate between Oh hydrides carbonate (H ₁₂ MDI), xylylene diisocyanate between Oh hydrides carbonate (H ₆ XDI), cyclohexane diamine Alicyclic polyisocyanates such as isocyanate or dicyclohexylmethane diisocyanate, adducts of these polyisocyanates, burette or isocyanurate compounds, and the like can be given These may be used singly or in combination of two or more.

Examples of commercially available polyisocyanates (B) include TAKENATE D-170N (isocyanurate of HDI: manufactured by Mitsui Chemicals, Inc.), MILLIONATE MT (4,4'-MDI: manufactured by Nippon Polyurethane Industry Co., Ltd.), COSMONATE LL (carbodiimide-modified MDI: manufactured by Mitsui Kagaku Polyurethane Co., Ltd.) and the like. These polyisocyanates may be used singly or in combination of two or more.

The amount of the polyisocyanate (B) to be used is not particularly limited, and the isocyanate group of the polyisocyanate (B) relative to the hydroxyl group (OH) of the polyol compound (A) ) Is preferably from 0.6 to 2.5, more preferably from 0.9 to 1.5, in terms of the equivalent ratio (NCO / OH) If the above-mentioned equivalent ratio is lower than 0.6, the material may be poor in heat resistance due to poor curing or crosslinking density. On the other hand, if the equivalent ratio is too high, the coating film becomes too hard and self- . Therefore, the content of the polyisocyanate (B) is preferably 50 to 200 parts by mass, more preferably 65 to 150 parts by mass, per 100 parts by mass of the polyol (A).

(C) Hindered amine light stabilizer

The hindered amine light stabilizer is added in order to impart UV resistance to a coating film formed on a substrate, and a hindered amine light stabilizer having a structure represented by the following general formula (1) is used. The hindered amine light stabilizers may be used singly or in combination of two or more.

Wherein,

n is an integer of 1 to 10,

R is hydrogen or C ₁ to C ₄ Alkyl group,

A is selected from the group consisting of C ₁ to C ₄ Alkyl group or a group represented by the following general formula (2):

A piperidyl group represented by the formula

R 'is hydrogen or C ₁ to C ₄ Alkyl group.

In the above general formula (1), C ₁ to C ₄ , represented by R and R ' Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group and a tert-butyl group.

In the above general formula (1), it is preferable that n is an integer of 5 to 8 and R is C ₁ to C ₄ Alkyl group, and R 'is C ₁ to C ₄ A hindered amine light stabilizer having a structure represented by an alkyl group is preferable. As a hindered amine light stabilizer having such a structure, for example, bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanioate or methyl (1,2,2,6 , 6-pentamethyl-4-piperidyl) sebacate, and the mixture thereof is particularly preferably used.

Examples of the commercially available hindered amine light stabilizer (C) include JF-95 (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate: (Product of Jokoku Chemical Industry Co., Ltd.), JF-90 (bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate manufactured by Joho Kakakakuko Co., Ltd.), Kemistab 29 A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) decane dioate and methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (Manufactured by Chemipro Kasei Co., Ltd.), TINUVIN 292 (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl (1,2,2,6,6 - pentamethyl-4-piperidyl) sebacate: a product of BASF Japan Ltd.). These hindered amine light stabilizers may be used alone, or two or more hindered amine light stabilizers may be used in combination.

The content of the hindered amine light stabilizer (C) is not particularly limited, but the lower limit is preferably 0.5 parts by mass, for example, from the viewpoint of UV resistance to 100 parts by mass of the polyol (A) Preferably 1 part by mass. On the other hand, the upper limit is, for example, preferably 10 parts by mass, more preferably 5 parts by mass, from the viewpoint of the total light transmittance, relative to 100 parts by mass of the polyol (A).

The first composition of the present invention may further contain (D) a surface-treating agent and / or (E) a filler, if necessary.

(D) Surface preparation agent

The surface-formulating agent is not particularly limited as long as it has a function of smoothing the surface of the coating film, and examples thereof include silicone, hydrocarbon, acrylic and the like. Among these surface formulating agents, from the viewpoint of further improving the hardness of the coating film, it is preferable to use a silicon surface-treating agent, and examples thereof include polyether-modified siloxane, polyester- modified polydimethylsiloxane, polyether- Polydimethylsiloxane, polyester-modified polymethylalkylsiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, and hydroxyl-terminated polydimethylsilicone. These surface-treating agents may be used singly or in combination of two or more kinds.

Examples of commercially available products of the surface preparation agent (D) include Silmer OH Di-10 (hydroxyl-terminated polydimethylsilicon: available from SILTECH), Schimer OH Di-50 (hydroxyl- BYK-307 (polyether-modified polydimethylsiloxane: manufactured by BICKEMISA)), BYK-306 (polyether-modified polydimethylsiloxane, manufactured by BICKEMY- BYK-310 (polyester modified polydimethylsiloxane: manufactured by BICKEMISA), BYK-330 (polyether modified polydimethylsiloxane: manufactured by BICKEMISA), and the like. These surface-treating agents may be used singly or in combination of two or more kinds.

The content of the (D) surface-treating agent is not particularly limited, but is preferably 0.005 to 5 parts by mass, more preferably 0.005 to 5 parts by mass, in view of the balance of coating film hardness and haze with respect to 100 parts by mass of the polyol (A) 0.010 to 1 part by mass.

(E) filler

The filler is not particularly limited as long as it has an action of increasing the mechanical strength of the coating film, and examples thereof include an inorganic filler, an organic filler, and an inorganic filler surface-treated with organic acid. Among these fillers, from the viewpoints of improvement in coating film hardness and dispersion stability in the composition, it is preferable to use an inorganic filler having a surface organizing treatment. Examples thereof include nanosilica having methacrylic surface treatment, nanosilica having vinyl surface treatment, Phenyl-surface-treated silica, and the like. These fillers may be used singly or in combination of two or more kinds. When the above-mentioned nano-silica is used, the average primary particle diameter is not particularly limited, but is preferably 1 nm to 200 nm, more preferably 5 nm To 100 nm.

Examples of commercial products of the above (E) filler include YA010C-SM-1 (methacrylic surface treated nanosilica: Admatech Co., Ltd.), YA010C-SV-1 YA010C-SP-3 (phenyl-treated nanosilica, manufactured by Admatech Co., Ltd.), YA050C-SM-1 (methacrylic surface treated nanosilica: manufactured by Admatech Co., (Manufactured by TECH). These fillers may be used singly or in combination of two or more kinds.

The content of the filler (E) is not particularly limited, but is preferably from 0.1 to 200 parts by mass, more preferably from 1 part by mass to 100 parts by mass from the viewpoint of the balance of the coating film hardness and the total light transmittance relative to 100 parts by mass of the polyol (A) To 100 parts by mass.

In addition to the above components, various additives may be appropriately added to the first composition of the present invention, for example, a reaction retarder, an organic solvent, various additives, and the like.

(F) Reaction retarder

The reaction retarder is not particularly limited as long as it can control the reaction time when the polyol (A) is reacted with the polyisocyanate (B) to form the polyurethane. Examples of the reaction retarder include phosphoric ester Can be used. When the reaction retarder is used, the blending amount is not particularly limited, but is preferably 0.005 to 1 part by mass per 100 parts by mass of the polyol (A).

The organic solvent is used for controlling the viscosity and dryness in the composition. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, alcohols such as cyclohexane and methylcyclohexane Petroleum solvents such as aliphatic hydrocarbons, petroleum ether and petroleum naphtha, cellosolves such as cellosolve and butyl cellosolve, carbitols such as carbitol and butyl carbitol, ethyl acetate, butyl acetate, cellosolve acetate , Acetic acid esters such as butylcellosolve acetate, carbitol acetate, diethylene glycol monomethyl ether acetate, and butyl carbitol acetate. When the organic solvent is used, the blending amount is not particularly limited, but is preferably 10 to 30 parts by mass per 100 parts by mass of the polyol (A).

Examples of the various additives include dispersants made of coupling agents such as silane-based, titanate-based, and alumina-based ones, boron trifluoride-amine complexes, dicyanediamides (DICY) and derivatives thereof, organic acid hydrazides, Aminomalononitrile (DAMN) and its derivatives, guanamine and its derivatives, latent curing agents such as amine imides (AI) and polyamines, metal salts of acetylacetone such as acetylacetonate Zn and acetylacetonate Cr, , Tin octylate, quaternary sulfonium salts, triphenylphosphine, imidazole, imidazolium salt and triethanolamine borate.

Next, the second composition of the present invention will be described. The second composition of the present invention is a composition containing (A) a polyol, (B) a polyisocyanate, and (G) a polydialkylsiloxane having a terminal hydroxyl group modified, Wherein the anate is a modification of an aliphatic polyisocyanate and / or a corresponding aliphatic polyisocyanate. The respective components are as follows.

(A) a polyol

The polyol is a component for obtaining a polyurethane by reacting with an aliphatic polyisocyanate described later and / or a modified product of the aliphatic polyisocyanate. The kind of the polyol is not particularly limited, and examples thereof include a polyether polyol, a polyester polyol and a polycarbonate polyol. Of these, polyester polyols are preferable from the viewpoint of balance between coating film hardness and self-restoration property, and polyester polyol is preferable because it gives high rebound resilience to the obtained coating layer and good adhesion with the substrate. Among polyester polyols, Polycaprolactone polyols are particularly preferred.

Examples of the polycaprolactone polyol include a bifunctional polycaprolactone diol, a trifunctional polycaprolactone triol, and a tetrafunctional polycaprolactone tetraole. However, the balance of the film hardness and the self- , Polycaprolactone triol is preferable. These polyols may be used alone or in combination of two or more.

In the second composition of the present invention, the OH group of the polyol (A) is not particularly limited, and for example, the lower limit value thereof is preferably 150 mgKOH / g from the viewpoint of imparting sufficient film hardness, More preferably 200 mgKOH / g, and particularly preferably 250 mgKOH / g, from the viewpoint of imparting hardness. On the other hand, the upper limit value thereof is preferably 400 mgKOH / g from the viewpoint of reliably imparting self-repellency to the cured coating film, more preferably from 380 mgKOH / g from the viewpoint of further improving the self- / g is particularly preferable.

The weight average molecular weight of the polyol (A) is not particularly limited, but is preferably 300 to 1000, particularly preferably 500 to 900 in view of the balance between the film hardness and the self-restorability. Two or more polyols having different mass average molecular weights may be used in combination.

Examples of the commercially available polyol (A) include the various polyols exemplified in the first composition of the present invention. These polyols may be used alone or in combination of two or more.

(B) a polyisocyanate

The polyisocyanate used in the second composition of the present invention is a modified aliphatic polyisocyanate and / or a corresponding aliphatic polyisocyanate. Modified aliphatic polyisocyanates and aliphatic polyisocyanates are components for obtaining a polyurethane by reacting with a polyol. Further, by using a polydialkylsiloxane having a terminal end, which will be described later, in combination with a polydialkylsiloxane modified with a hydroxyl group, a cured product such as a cured film having excellent oil repellency and excellent self- Can be formed.

In the second composition of the present invention, the polyisocyanate may be either an aliphatic polyisocyanate alone, a modified aliphatic polyisocyanate, or an aliphatic polyisocyanate and an aliphatic polyisocyanate May be used in combination.

The aliphatic polyisocyanate is not particularly limited and includes, for example, methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, tri Methyl hexamethylene diisocyanate, methyl pentane diisocyanate, lysine diisocyanate, and the like. Of these, aliphatic polyisocyanates having 3 to 10 carbon atoms are preferable from the standpoint of further improving the oil resistance by the thermal curing process without using the photo-curing process. In view of contributing to weather resistance while improving oil resistance, To 10, more preferably hexamethylene diisocyanate, from the viewpoint of better balance between weather resistance and mechanical properties while further improving oil resistance. These aliphatic polyisocyanates may be used alone or in combination of two or more.

The modified aliphatic polyisocyanate is not particularly limited, and examples thereof include isocyanurate, adduct, burette, bifunctional, and the like of the aliphatic polyisocyanate . Of these, the aliphatic polyisocyanate is preferably an isocyanurate compound or a bifunctional type in view of further improving the oil resistance by a heat curing process without using a photo-curing process. In addition, From the viewpoint of contributing, it is more preferable that the aliphatic polyisocyanate having 3 to 10 carbon atoms is an isocyanurate compound, a bifunctional type, more preferably a hexamethylene diisocyanate of isocyanuric acid And a bifunctional form is particularly preferable. These modified aliphatic polyisocyanates may be used alone or in combination of two or more.

The blending amount of the aliphatic polyisocyanate (B) and / or the modified aliphatic polyisocyanate is not particularly limited, but may be, for example, (A) a ratio of (B) ) The lower limit value of the equivalent ratio (NCO / OH) of the aliphatic polyisocyanate and / or the isocyanate group (NCO / OH) of the modified isocyanate group (NCO) of the aliphatic polyisocyanate is lowered Is preferably 0.6, and particularly preferably 0.9, from the standpoint of reliably preventing the deterioration of the heat resistance by the above-mentioned resin. On the other hand, the upper limit of the equivalent ratio (NCO / OH) is preferably 2.5, and particularly preferably 1.5, from the viewpoint that the hardness of the coating film becomes too high to reliably prevent the self-recovery property from lowering. From the above, the blending amount of the aliphatic polyisocyanate (B) and / or the modified aliphatic polyisocyanate is preferably from 50 to 200 parts by mass, more preferably from 65 to 150 parts by mass, per 100 parts by mass of the polyol (A) The addition is particularly preferred.

(G) a polydialkylsiloxane whose terminal is modified with a hydroxyl group

(G) The polydialkylsiloxane having a terminal hydroxyl group is blended with an aliphatic polyisocyanate and / or a modified product of the aliphatic polyisocyanate, so that the curing process can be carried out without heat curing It is possible to form a cured product such as a cured coating film having excellent oil repellency and excellent oil repellency.

The polydialkylsiloxane includes, for example, polydimethylsiloxane, polydiethylsiloxane, polydipropylsiloxane, polydiisopropylsiloxane, polydibutylsiloxane, polydipentylsiloxane, polydioxysiloxane, polydioxytiloxane , Polymethylethylsiloxane, polymethylpropylsiloxane, polymethylbutylsiloxane, polymethylisopropylsiloxane, polymethylhexylsiloxane, polymethyloctylsiloxane, polyethylpropylsiloxane, and polybutyloctylsiloxane. Of these, a polydimethylsiloxane, that is, a polydimethylsiloxane whose terminal is modified with a hydroxyl group is preferable from the standpoint of surely improving the oil resistance by hardening by heat treatment. The polydialkylsiloxane having the hydroxyl groups at the terminals thereof may be used alone or in combination of two or more.

The number average molecular weight of the polydialkylsiloxane in which the (G) terminus is modified with a hydroxyl group is not particularly limited, but is preferably 300 to 8000 in view of further improving oil resistance and also contributing to heat resistance, and is preferably 500 To 5,000 is particularly preferable.

The blending amount of the polydialkylsiloxane in which the (G) terminus is modified with a hydroxyl group is not particularly limited. For example, the lower limit of the amount is preferably 100 parts by mass of (A) 100 parts by mass of the polyol, 0.10 parts by mass is preferable from the viewpoint of forming a cured product such as a cured coating film which is excellent in oil resistance and 0.20 parts by mass is particularly preferable in that it contributes to heat resistance while improving oil resistance. On the other hand, for example, the upper limit is preferably 1.0 part by mass in view of the transparency of the cured product, and particularly preferably 0.50 parts by mass in order to further improve transparency.

In the second composition of the present invention, a hindered amine light stabilizer (C) may be further blended if necessary. By adding the hindered amine light stabilizer, it is possible to further impart UV resistance to the cured product formed from the second composition of the present invention. Therefore, weather resistance can be imparted to the cured product.

Examples of the hindered amine light stabilizer (C) include compounds such as the compound represented by the general formula (1) compounded in the first composition of the present invention.

In the second composition of the present invention, in the general formula (1), n is an integer of 5 to 8 and R is an integer of 1 to 8, in order to further improve the UV resistance of the cured product, C ₁ to C ₄ Alkyl group, and R 'is C ₁ to C ₄ A hindered amine light stabilizer having a structure represented by an alkyl group is preferable. As a hindered amine light stabilizer having such a structure, for example, bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanioate or methyl (1,2,2,6 , 6-pentamethyl-4-piperidyl) sebacate, and the mixture thereof is particularly preferably used.

Examples of the commercially available hindered amine light stabilizer (C) include various hindered amine light stabilizers exemplified in the first composition of the present invention. These hindered amine light stabilizers may be used alone, or two or more hindered amine light stabilizers may be used in combination.

Although the content of the hindered amine light stabilizer (C) is not particularly limited, the lower limit value is preferably 0.50 parts by mass, for example, from the viewpoint of further improving the UV resistance against 100 parts by mass of the polyol (A) , And 1.0 part by mass are particularly preferable. On the other hand, the upper limit thereof is, for example, preferably 5.0 parts by mass, particularly preferably 3.0 parts by mass, from the viewpoint of transparency of the cured product, relative to 100 parts by mass of the polyol (A).

In the second composition of the present invention, an ultraviolet absorber (H) may be further added if necessary.

(H) ultraviolet absorber, it is possible to prevent the substrate coated with the second composition of the present invention from being deteriorated by UV, and as a result, the weather resistance of the substrate is improved. Further, by blending the ultraviolet absorber (H), it contributes to imparting UV resistance to the cured product of the second composition of the present invention, and consequently contributes to improvement of the weather resistance of the cured product.

The ultraviolet absorber is not particularly limited as long as it has the above-mentioned action, and examples thereof include a benzoate ultraviolet absorber, a benzotriazole ultraviolet absorber, and a benzophenone ultraviolet absorber. Examples of the benzoate ultraviolet absorber include 2,4-di-tert-pentylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4- 3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, 2,6-di-t- butylphenyl-3', 5'- , n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and the like. Examples of the benzotriazole based ultraviolet absorber include 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol] , 2'-methylenebis (4-methyl-6-benzotriazolylphenol), and the like. Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone and the like. These ultraviolet absorbers may be used alone or in combination of two or more.

The content of the ultraviolet absorber (H) is not particularly limited, but the lower limit is preferably 0.50 parts by mass, for example, from the viewpoint of further improving the weatherability of the substrate and the cured product with respect to 100 parts by mass of the polyol (A) 1.0 part by mass is particularly preferable. On the other hand, the upper limit thereof is, for example, preferably 5.0 parts by mass, particularly preferably 3.0 parts by mass, from the viewpoint of transparency of the cured product, relative to 100 parts by mass of the polyol (A).

In the second composition of the present invention, a filler (E) may be further added if necessary.

By adding the filler (E), it contributes to improving the mechanical strength of the cured product. The filler is not particularly limited as long as it has the above-mentioned action. For example, the filler exemplified in the first composition of the present invention may be mentioned.

The content of the filler (E) is not particularly limited, but is preferably from 0.10 to 200 parts by mass, particularly preferably from 1.0 to 100 parts by mass, in view of balance of the mechanical properties and transparency of the cured product with respect to 100 parts by mass of the polyol (A) Do.

In the second composition of the present invention, in addition to the above components, various additives such as urethanization catalysts, various additives, and the like can be appropriately compounded as necessary.

The urethanization catalyst reacts a polyol with an aliphatic polyisocyanate and / or a modified product of the aliphatic polyisocyanate. By the urethanization catalyst, a cured product having no adhesiveness can be obtained and the hardness of the cured product can be improved. Examples of urethanization catalysts include zinc 2-ethylhexanoate, dibutyltin dilaurate, dioctyltin dilaurate, octyltin triallaurate, tin dioctylate, dibutyltin diacetate, dioctyltin di Acetate and the like.

Examples of the various additives that can be blended in the second composition of the present invention include the various additives exemplified in the first composition of the present invention.

The first composition and the second composition of the present invention are not limited to specific methods. For example, the components may be mixed at a predetermined ratio, A kneading means such as a mill, a sand mill or the like, or a stirring means such as a super mixer, a planetary mixer or the like. Prior to the kneading or mixing, if necessary, pre-kneading or premixing may be performed.

Next, the coating method of the first composition and the second composition of the present invention will be described. Here, a method of coating the first composition and the second composition of the present invention on a PET (polyethylene terephthalate) substrate to form a protective film will be described as an example. In addition to the PET substrate, the first and second compositions of the present invention can also be used in combination with other resins such as a polyester resin, a polyamide resin, an epoxy resin, a polyolefin resin, a poly (meth) acrylic resin, a polystyrene resin And the like can be coated on various types of substrates. The thickness of the substrate can also be appropriately set as required.

The first composition and the second composition prepared as described above are applied on a PET substrate to a desired thickness using a bar coater, a screen printing method, a spray coating method or the like, and they are heated at a temperature of about 60 to 170 ° C For 15 to 60 minutes to form a desired self-repellent protective film on the PET substrate.

The first composition and the second composition of the present invention can be used for a surface protective film for space or medical treatment which is difficult to repair damage, in addition to the use as an optical member such as a liquid crystal panel and a surface protecting film for automobile body and the like.

[ Example ]

EXAMPLES Next, examples of the present invention will be described, but the present invention is not limited to these examples unless the scope of the present invention is exceeded. First, examples of the first composition of the present invention will be described below.

Example  1 to 6, Comparative Example  1 to 6

The components shown in the following Table 1 were compounded in the blending ratios shown in Table 1 below and mixed and dispersed at room temperature using three rolls to prepare compositions used in Examples 1 to 6 and Comparative Examples 1 to 6. Then, the thus-prepared composition was coated on a substrate by using a test piece manufacturing process to be described later to prepare a test piece. The amount of each component shown in the following Table 1 indicates the mass part, unless otherwise specified, and the blank part shows no addition.

Details of each component in Table 1 are as follows.

(A) a polyol

PLACCEL 312: Daicel Co., Ltd., polycaprolactone triol (OH group = 135 mg KOH / g)

PLACCEL 308: Daicel product, polycaprolactone triol (OH group = 195 mg KOH / g)

PLACCEL 305: Daicel product, polycaprolactone triol (OH group = 305 mg KOH / g)

PLACCEL 303: Daicel Co., Ltd., polycaprolactone triol (OH group = 540 mgKOH / g)

(B) a polyisocyanate

· Takenate D-170N: product of Mitsui Kagaku Co., Ltd., isocyanurate of hexamethylene diisocyanate

(C) Hindered amine light stabilizer

· Chemist Tab 29: A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate and methyl (1,2,2,6,6-pentamethyl Piperidyl) sebacate < / RTI >

Other light stabilizer

Adekastub LA-57: Adeka product of butane-l, 2,3,4-tetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl)

Adekastab LA-81: Adeka Co., Ltd., carbonic acid bis (2,2,6,6-tetramethyl-1-undecyloxepiperidin-4-yl)

KEMISORB 113: a product of Chemipro Kasei Co., Ltd., 2,4-di-tert-pentylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate

(D) Surface preparation agent

Silmer OH Di-10: manufactured by Siltech Co., hydroxyl-terminated polydimethylsilicone

BYK-306: manufactured by BICKEMIS, polyether-modified polydimethylsiloxane

(E) filler

· YA010C-SM1: manufactured by Adma Tech Co., Ltd., methacrylic surface treated nanosilica

(F) Reaction retarder

JP-508: product of Joho Kakakakako Kogyo Co., Ltd., 2-ethylhexyl acid phosphate

Test piece production process

(1) Test specimens for evaluating coating film hardness and self-

The composition prepared in the same manner as in Examples 1 to 6 and Comparative Examples 1 to 6 was coated on a PET substrate (Tetoron G2, manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 탆 by a bar coater, The coated film of the composition was formed on a PET substrate by drying and curing at 100 캜 for 30 minutes in a drying oven to prepare a test piece. The film thickness of the coating film was 100 탆.

(2) Test piece for evaluating total light transmittance

The composition prepared in the same manner as in Examples 1 to 6 and Comparative Examples 1 to 6 was coated on a glass plate (plate thickness: 2 mm) with a bar coater, and then dried and cured at 100 DEG C for 30 minutes in a drying furnace, The film formed on the substrate was peeled off to prepare a test piece. The film thickness of the film was 100 탆.

evaluation

(1) Film hardness

The test piece on which the coated film was formed was evaluated in accordance with JIS K 56005-4. The evaluation here indicates that the smaller the value of B is, the harder the HB is, the harder the HB is, the harder the HB is, and the higher the value of H, the higher the hardness. A test piece exhibiting a hardness of coat film hardness of "H" or higher is assumed to have excellent coat film hardness.

(2) self-repairability

The brass brush was pressed against the coating film with a load of 1 kg, reciprocated 10 times, and visually inspected for damage within 10 minutes. Evaluation was carried out in the following two steps.

"○": No damage is observed.

"X": When damage is observed.

(3) UV resistance

The test piece having the coated film was introduced into a super-accelerated weather resistance tester SUV-W151 (manufactured by Iwasaki Electric Co., Ltd.) and irradiated with ultraviolet rays at a temperature of 50 ° C and a humidity of 50% (RH) And then the coating film hardness of the test piece was evaluated by the coating film hardness test according to the above (1). As shown in the above (1), the test piece exhibiting the hardness of the coat film harder than " H "

(4) Total light transmittance

The obtained film was measured using a spectrophotometer (Hitachi Spectrophotometer U-4100: Hitachi High Technologies). A film exhibiting a total light transmittance of 90% or more is assumed to exhibit a high total light transmittance.

The evaluation results of Examples 1 to 6 and Comparative Examples 1 to 6 are shown in Table 2.

As shown in Table 2, a composition containing both a polyol having OH groups in the range of 150 to 400 mg KOH / g and a hindered amine light stabilizer having a structure represented by the general formula (1) in the composition In Examples 1 to 6, the coating film on the PET substrate had both hardness and UV resistance of not less than " H " and also had self-restorability of " O ". In Examples 1 to 6, the film as the test piece also exhibited a high total light transmittance of 90% or more. Therefore, in Examples 1 to 6, it is possible to form a coating film having both good self-restoration and excellent coating film hardness on the PET substrate, excellent in UV resistance, and exhibiting a high total light transmittance of 90% A film was obtained.

Further, it is understood from Examples 1 to 5 and Example 6 that in Examples 1 to 5, since the hardness of the coating film and the UV resistance are both "2H" or higher, the hardness of the coating film formed .

From Example 1 and Example 2, it is understood that Example 1 using a polyol having an OH value of 305 mgKOH / g was more effective than Example 2 using a polyol having an OH value of 195 mgKOH / g, By using a polyol having an OH value of 250 to 350 mgKOH / g, the hardness of the formed coating film can be further improved.

In addition, from Example 1 and Example 5, both of the coating film hardness and the UV resistance are higher in Example 5 than in Example 1. Therefore, by using the composition to which the filler is further added, the hardness of the formed coating film can be further improved I could.

On the other hand, in Comparative Example 1 in which a polyol having an OH group of more than 400 mgKOH / g was added as the polyol in the composition, the coating film on the PET substrate had a coating film hardness of "2H" Self-restorability was also " x ". Therefore, in Comparative Example 1, a coating film having good self-repellency and excellent UV resistance was not formed on the PET substrate.

In Comparative Example 2 in which a polyol having an OH value of less than 150 mgKOH / g was added as a polyol in the composition, the self-restorability of the coating film on the PET substrate was " HB ". Therefore, in Comparative Example 2, a coating film having excellent coating film hardness and excellent UV resistance was not formed on the PET substrate.

Further, in Comparative Example 3 in which the hindered amine light stabilizer was not added to the composition, the coating film on the PET substrate had a coating film hardness of " 3H ", but the UV resistance was extremely low as " less than 6B ". Thus, in Comparative Example 3, a coating film excellent in UV resistance was not formed on the PET substrate.

In Comparative Examples 4 and 5 in which other hindered amine light stabilizers having a structure different from that of the general formula (1) were added to the composition, the coating film on the PET substrate had a coating film hardness of "3H" 3B " in Example 4, and " less than 6B " in Comparative Example 5, respectively. Therefore, in Comparative Examples 4 and 5, a coating film excellent in UV resistance was not formed on the PET substrate.

Similarly, in Comparative Example 6 in which another hindered amine light stabilizer having a structure different from that of the general formula (1) was added to the composition, the coating film on the PET substrate had a coating film hardness of "3H" 2 >. Further, the film as the test piece had a total light transmittance of 83% and exhibited a significantly lower total light transmittance than those of Examples 1 to 6 and Comparative Examples 1 to 5. Thus, in Comparative Example 6, a film exhibiting a high total light transmittance of 90% or more could not be obtained.

Next, examples of the second composition of the present invention will be described below.

Example  7 to 12, Comparative Example  7 to 8

The components shown in the following Table 3 were compounded in the blend ratios shown in Table 3 below and mixed and dispersed at room temperature using a three-roll mill to prepare compositions for use in Examples 7 to 12 and Comparative Examples 7 to 8. The numbers in the following Table 3 indicate the parts by mass, and the blank portions indicate no mixing.

Details of the components in Table 3 are as follows.

(B) an aliphatic polyisocyanate and / or a modified product of the aliphatic polyisocyanate

· DURANATE D201: manufactured by Asahi Kasei Kagaku Co., Ltd.

(G) a polydialkylsiloxane whose terminal is modified with a hydroxyl group

· Silmer OH Di-10: manufactured by SILTECH.

· KF-9701: Die cell product.

(H) Ultraviolet absorber

· Chemisub 113: Chemie Pro Kasei Co., Ltd.

Urethanization catalyst

Zn-Octoate 22%: manufactured by DIC Co., Ltd.

Modified polyisocyanates of aromatic polyisocyanates

Takenate D-110: manufactured by Mitsui Kagaku Co., Ltd.

A polydialkylsiloxane whose terminal is modified with a carboxyl group

· X-22-162C: Shin-Etsu Kagakukogyo (Shin-Etsu Chemical Industry Co., Ltd.).

Test piece production process

The compositions prepared in the same manner as in Examples 7 to 12 and Comparative Examples 7 to 8 were coated on a PET substrate (Tetoron DuPont Film Co., Ltd., "Tetoron G2") having a thickness of 100 μm by a bar coater, And then dried and cured at 100 占 폚 for 30 minutes to form a cured film of the composition on the PET substrate to prepare a test piece. The film thickness of the cured coating film was 100 탆.

(1) self-repairability

The brass brush was pressed against the cured coating film under a load of 1.0 kg and reciprocated 10 times, and the presence or absence of damage was visually observed within 10 minutes.

Evaluation was carried out in the following two steps.

&Quot; O: " No damage is observed.

&Quot; x ": Damage is observed.

(2) Oil resistance

A circle with a diameter of 1.0 cm was placed in a circle with a diameter of 1.0 cm and evaluated with naked eyes of the repellent state of the oil spark magic by the Yusung Magic (manufactured by ZEBRA Co., Ltd., " Makki-ultra-fine "). Evaluation was carried out in the following two steps.

&Quot; & cir & ": Repellent of oil magic is observed.

&Quot; x ": no repelling of the oil magic is observed.

(3) Film hardness

The test piece on which the cured coating film was formed was evaluated in accordance with JIS K 5600 5-4.

The evaluation results of Examples 7 to 12 and Comparative Examples 7 to 8 are shown in Table 3 above.

From the results in Table 3, it is understood that, in Examples 7 to 12 in which a modified product of hexamethylene diisocyanate and polydimethylsiloxane modified at the terminal thereof with hydroxyl group were blended, as a curing step, curing by heat treatment It was possible to obtain a cured film having excellent oil repellency and excellent self-repellency without deteriorating the good coat film hardness. Further, in Example 10 in which the urethanization catalyst was added, the hardness of the coating film was further improved.

On the other hand, in place of the modified product of hexamethylene diisocyanate, in place of the modified product of hexamethylene diisocyanate, Comparative Example 7 in which a modified polyisocyanate of aromatic polyisocyanate was blended, or in Comparative Example 7 in which the terminal was replaced with a hydroxyl group, In Comparative Example 8 in which a modified polydialkylsiloxane was blended, oil resistance could not be obtained in all cases.

The composition of the present invention has both excellent self-restoration property and coating film hardness, and it is possible to form a film having a higher total UV transmittance of 90% or more And the second composition has more excellent oil resistance. Therefore, the second composition has a high use value in, for example, a protective film for a liquid crystal display, an automobile body or the like, and a surface protective film for an optical member.

Claims (17)

A composition containing (A) a polyol, (B) a polyisocyanate, and (C) at least one hindered amine light stabilizer,
The OH value of the polyol (A) is 150 to 400 mg KOH / g,
Wherein the hindered amine light stabilizer (C) is a compound represented by the following general formula (1):

Wherein,
n is an integer of 1 to 10,
R is hydrogen or C ₁ to C ₄ Alkyl group,
A is C ₁ to C ₄ Alkyl group or a group represented by the following general formula (2):

A piperidyl group represented by the formula
R 'is hydrogen or C ₁ to C ₄ Alkyl group. The composition according to claim 1, wherein the composition further comprises (D) a surface preparation agent. The composition of claim 1, wherein the polyol (A) is a polycaprolactone triol. The composition according to claim 1, wherein the composition is the hindered amine light stabilizer (C)
Wherein,
n is an integer of 5 to 8,
R is C ₁ to C ₄ Alkyl group, and
R 'is C ₁ to C ₄ A composition comprising at least one compound represented by the above general formula (1) which is an alkyl group. The method of claim 1, wherein the (C) hindered amine light stabilizer is selected from the group consisting of bis (1,2,2,6,6-pentamethyl-4-piperidyl) decane di- 6,6-pentamethyl-4-piperidyl) sebacate. The composition according to claim 1, wherein the OH value of the polyol (A) is 250 to 350 mg KOH / g. A composition containing (A) a polyol, (B) a polyisocyanate, and (G) a polydialkylsiloxane having a terminal hydroxyl group modified,
Wherein the polyisocyanate (B) is a modification of an aliphatic polyisocyanate and / or a corresponding aliphatic polyisocyanate. The composition according to claim 7, wherein the aliphatic polyisocyanate is an aliphatic polyisocyanate having 3 to 10 carbon atoms. 8. The composition of claim 7, wherein the aliphatic polyisocyanate is hexamethylene diisocyanate. The composition according to claim 7, wherein the modified aliphatic polyisocyanate is a bifunctional type of hexamethylene diisocyanate and / or an isocyanurate of hexamethylene diisocyanate. The composition according to claim 7, wherein the OH value of the polyol (A) is 150 to 400 mg KOH / g. The composition according to claim 7, wherein the polyol (A) is a polycaprolactone triol. The composition according to claim 7, further comprising (C) a hindered amine light stabilizer represented by the following general formula (1):

Wherein,
n is an integer of 1 to 10,
R is hydrogen or C ₁ to C ₄ Alkyl group,
A is C ₁ to C ₄ Alkyl group or a group represented by the following general formula (2):

A piperidyl group represented by the formula
R 'is hydrogen or C ₁ to C ₄ Alkyl group. 14. The method of claim 13, wherein the hindered amine light stabilizer (C) is selected from the group consisting of bis (1,2,2,6,6-pentamethyl-4-piperidyl) decane di- 6,6-pentamethyl-4-piperidyl) sebacate. ≪ / RTI > The composition according to claim 7, further comprising (H) an ultraviolet absorber. The composition according to any one of claims 1 to 7, further comprising (E) a filler. A self-restoration coat film comprising a cured coating of the composition of claim 1 or 7.