JP2017066263A - Composition for giving cured product having self-repairing property and oil resistance, and self-repairing coat film comprising cured coat thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition which can form a coat having excellent self-repairing property and excellent oil resistance and a self-repairing coat film comprising a cured coat thereof.SOLUTION: The present invention provides a composition comprising (A) polyol, (B) aliphatic polyisocyanate and/or a modified body of the aliphatic polyisocyanate, and (C) polydialkylsiloxane having a terminal modified with a hydroxy group.SELECTED DRAWING: None

Description

  The present invention relates to a composition for forming a material having self-healing properties and oil resistance, and is used, for example, as a liquid crystal display of a mobile device such as a mobile phone or a personal computer, or as a surface protective film for an automobile body, etc. In such a case, the present invention relates to a composition capable of forming a coating film having excellent self-healing properties and oil resistance.

  Conventionally, a plastic film subjected to a hard coat treatment has been used as an optical member such as a liquid crystal panel or a surface protective film for an automobile body. In a general hard coat, the hardness of the coating film is increased by increasing the crosslinking density, so that the surface of the coating film can be hardened. Thereby, the abrasion resistance of the surface of a coating film improves, and it can make it hard to damage a surface, such as a screen of a liquid crystal display, or a car body. However, once a small scratch is made on the surface, it is impossible to restore the scratch itself. Therefore, in place of such a hard coat, use of a material having a self-repairing property has been studied.

  Here, the self-healing material is a property that imparts rubber elasticity to the coating film by lowering the crosslinking density and recovers small scratches generated on the surface over time using the repulsive force of this rubber elasticity. It is what has. On the other hand, such a self-healing material is difficult to impart sufficient coating film hardness (scratch resistance) to the surface of the coating film because the hardness of the coating film decreases as the crosslinking density decreases. It is. Therefore, there is a demand for a material having self-repairing properties with improved scratch resistance.

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

  In addition, in order to provide a material having excellent scratch resistance and self-healing properties, a base material layer containing a polycarbonate resin as a main component and a surface of the base material layer containing a polymethyl methacrylate resin as a main component A self-healing film comprising a base sheet having a layer and a back layer and a soft resin layer having a self-healing property containing a polyurethane-based resin laminated as a main component on the surface of the base sheet has been proposed (Patent Document 2).

  On the other hand, liquid crystal displays and surface protection films are also required to have a characteristic that oil stains are difficult to adhere, that is, oil resistance, and conventional thermosetting self-healing materials provide sufficient oil resistance. There was a problem that it was not.

JP 07-195623 A JP 2013-144391 A

  In view of the above circumstances, an object of the present invention is to provide a composition capable of forming a cured product such as a cured coating film having excellent self-repairing properties and excellent oil resistance, and a self-repairing coating film having the cured coating film. With the goal.

  An aspect of the present invention contains (A) a polyol, (B) an aliphatic polyisocyanate and / or a modified product of the aliphatic polyisocyanate, and (C) a polydialkylsiloxane having a terminal modified with a hydroxyl group. It is a composition characterized by this.

  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 the composition wherein the aliphatic polyisocyanate is hexamethylene diisocyanate.

  An embodiment of the present invention is a composition characterized in that the modified product 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 the composition characterized in that the polyol (A) has an OH group value of 150 to 400 mgKOH / g.

  An aspect of the present invention is the composition characterized in that the polyol (A) is polycaprolactone triol.

The aspect of the present invention further includes (D) the general formula (1).
(Where
n is an integer of 1 to 10,
R is hydrogen or _C 1 -C ₄ alkyl group,
A _is, C 1 -C ₄ alkyl group or the following general formula (2)

And a hindered amine light stabilizer represented by the following formula: R 'represents hydrogen or a C ₁ -C ₄ alkyl group).

  In an embodiment of the present invention, the (D) hindered amine light stabilizer is bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate and methyl (1,2,2,6,6). -Pentamethyl-4-piperidyl) A composition comprising sebacate.

  An embodiment of the present invention is a composition further comprising (E) an ultraviolet absorber.

  An embodiment of the present invention is a composition characterized by further containing (F) a filler.

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

  According to the aspect of the present invention, as the curing step, an aliphatic polyisocyanate and / or a modified product of the aliphatic polyisocyanate is used as the isocyanate compound, and a polydialkylsiloxane having a terminal modified with a hydroxyl group is blended. It is possible to obtain a composition capable of forming a cured product such as a cured coating film having excellent self-repairing property and excellent oil resistance, only by curing by heat treatment without performing photocuring.

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

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

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

  Next, the composition of the present invention will be described. The composition of the present invention contains (A) a polyol, (B) an aliphatic polyisocyanate and / or a modified product of the aliphatic polyisocyanate, and (C) a polydialkylsiloxane having a terminal modified with a hydroxyl group. To do. Each of the above components is as follows.

(A) Polyol A polyol is a component for obtaining a polyurethane by reacting with an aliphatic polyisocyanate and / or a modified product of the aliphatic polyisocyanate described later. Although the kind of polyol is not specifically limited, For example, polyether polyol, polyester polyol, polycarbonate polyol etc. are mentioned. Among these, polyester polyol is preferable from the viewpoint of the balance between the coating film hardness and self-repairing property, and among the polyester polyols, it is cyclic from the viewpoint of imparting high rebound resilience and good adhesion to the substrate to the resulting coating layer. Polycaprolactone polyols obtained by ring opening of esters are particularly preferred.

  Examples of the polycaprolactone polyol include a bifunctional polycaprolactone diol, a trifunctional polycaprolactone triol, and a tetrafunctional polycaprolactone tetraol. From the viewpoint, polycaprolactone triol is preferable. The said polyol may be used independently and may use 2 or more types together.

  (A) The OH group value of the polyol is not particularly limited, but the lower limit is preferably 150 mg KOH / g from the viewpoint of imparting sufficient coating film hardness, and 200 mg KOH / g from the point of imparting higher coating film hardness. More preferred is 250 mg KOH / g. On the other hand, the upper limit is preferably 400 mgKOH / g from the viewpoint of reliably imparting self-repairing properties to the cured coating film, more preferably 380 mgKOH / g, and particularly preferably 350 mgKOH / g from the point of further improving self-repairing properties. .

  (A) Although the mass mean molecular weight of a polyol is not specifically limited, 300-1000 are preferable from the point of the balance of coating-film hardness and self-repairability, and 500-900 are especially preferable. Two or more polyols having different mass average molecular weights can be used in combination.

  (A) What is marketed as a polyol includes, for example, PLACEL 305 (polycaprolactone triol: manufactured by Daicel Corporation, OH group value = 305 mgKOH / g), PLACEL 308 (polycaprolactone triol: manufactured by Daicel Corporation), OH group value = 195 mgKOH / g), PLACEL 309 (polycaprolactone triol: manufactured by Daicel Corporation, OH group value = 186 mgKOH / g), and the like. These polyols may be used alone or in combination of two or more.

(B) Aliphatic polyisocyanate and / or modified product of aliphatic polyisocyanate The aliphatic polyisocyanate and the modified product of aliphatic polyisocyanate are components for reacting with a polyol to obtain polyurethane. In addition, by using together with a polydialkylsiloxane having a terminal modified with a hydroxyl group, which will be described later, as a curing step, only by curing by heat treatment without performing photocuring, while having excellent self-repairing properties, oil resistance A cured product such as an excellent cured coating film can be formed.

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

  The aliphatic polyisocyanate is not particularly limited, and examples thereof include methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylpentane diisocyanate, and lysine diisocyanate. Among these, the aliphatic polyisocyanate having 3 to 10 carbon atoms is preferable from the viewpoint of further improving the oil resistance only by the thermosetting process without using the photocuring process, and the weather resistance while further improving the oil resistance. A linear aliphatic polyisocyanate having 3 to 10 carbon atoms is more preferable in terms of contribution, and hexamethylene diisocyanate is particularly preferable in terms of improving weather resistance and mechanical properties in a well-balanced manner while further improving oil resistance. These aliphatic polyisocyanates may be used alone or in combination of two or more.

  In addition, the modified product of the aliphatic polyisocyanate is not particularly limited, and examples thereof include isocyanurate bodies, adduct bodies, biuret bodies, and bifunctional types of the above aliphatic polyisocyanates. Among these, from the point of improving oil resistance only by heat curing step without using photocuring step, isocyanurate body, bifunctional type of aliphatic polyisocyanate is preferable, and weather resistance while further improving oil resistance Isocyanurate, bifunctional type of aliphatic polyisocyanate having 3 to 10 carbon atoms is more preferable from the point of contributing to the property, and isocyanurate type, bifunctional type of hexamethylene diisocyanate from the point of improving heat resistance. Is particularly preferred. These modified polyisocyanates of aliphatic polyisocyanate may be used alone or in combination of two or more.

  The blending amount of the (B) aliphatic polyisocyanate and / or the modified product of the aliphatic polyisocyanate is not particularly limited. For example, (B) (B) the aliphatic polyisocyanate and / or the hydroxyl group (OH) of the polyol Alternatively, the lower limit of the isocyanate group (NCO) equivalent ratio (NCO / OH) of the modified polyisocyanate of aliphatic polyisocyanate is 0 from the point of reliably preventing a decrease in heat resistance due to poor curing or a decrease in crosslink density. .6 is preferred, and 0.9 is particularly preferred. On the other hand, the upper limit value of the equivalent ratio (NCO / OH) is preferably 2.5, and particularly preferably 1.5, from the viewpoint of reliably preventing the coating film hardness from becoming too high and reducing the self-repairing property. From the above, the blending amount of the (B) aliphatic polyisocyanate and / or the modified product of the aliphatic polyisocyanate is preferably 50 to 200 parts by mass, and 65 to 150 parts by mass with respect to 100 parts by mass of the (A) polyol. Particularly preferred.

(C) Polydialkylsiloxane modified with a hydroxyl group at the end (C) Polydialkylsiloxane modified with a hydroxyl group at the end is blended with an aliphatic polyisocyanate and / or a modified product of the aliphatic polyisocyanate, As a curing step, a cured product such as a cured coating film having excellent oil resistance while having excellent self-repairing property can be formed only by curing by heat treatment without performing photocuring.

  Examples of the polydialkylsiloxane include polydimethylsiloxane, polydiethylsiloxane, polydipropylsiloxane, polydiisopropylsiloxane, polydibutylsiloxane, polydipentylsiloxane, polydihexylsiloxane, polydioctylsiloxane, polymethylethylsiloxane, polymethylpropylsiloxane, Examples include polymethylbutylsiloxane, polymethylisopropylsiloxane, polymethylhexylsiloxane, polymethyloctylsiloxane, polyethylpropylsiloxane, polybutyloctylsiloxane, and the like. Among these, polydimethylsiloxane, that is, polydimethylsiloxane having a terminal modified with a hydroxyl group is preferable from the viewpoint of reliably improving oil resistance only by curing by heat treatment. These polydialkylsiloxanes whose ends are modified with a hydroxyl group may be used alone or in combination of two or more.

  (C) The number average molecular weight of the polydialkylsiloxane modified with a hydroxyl group at the end is not particularly limited, but is preferably 300 to 8000 from the viewpoint of contributing to heat resistance while further improving oil resistance, and further improves heat resistance. 500-5000 is especially preferable from the point made to do.

  (C) Although the compounding quantity of the polydialkylsiloxane by which the terminal was modified by the hydroxyl group is not specifically limited, For example, the lower limit is (A) 100 mass parts of polyol is cured by heat treatment without performing photocuring. Only 0.10 parts by mass from the point of reliably forming a cured product such as a cured coating film having excellent oil resistance, and 0.20 parts by mass from the point of contributing to heat resistance while further improving oil resistance Is particularly preferred. On the other hand, for example, the upper limit is preferably 1.0 part by mass from the viewpoint of transparency of the cured product, and particularly preferably 0.50 part by mass from the viewpoint of further improving the transparency.

  Moreover, in this invention, you may mix | blend (D) hindered amine light stabilizer further as needed. By adding a hindered amine light stabilizer, UV resistance can be further imparted to the cured product formed from the composition of the present invention. Therefore, weather resistance can be imparted to the cured product.

(D) As a hindered amine light stabilizer, for example, the following general formula (1)
(Where
n is an integer of 1 to 10,
R is hydrogen or _C 1 -C ₄ alkyl group,
A _is, C 1 -C ₄ alkyl group or the following general formula (2)
And R ′ represents hydrogen or a C ₁ -C ₄ alkyl group. ) Can be mentioned.

In the general formula (1), as the _C 1 -C ₄ alkyl groups represented by R and R ', a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, sec- butyl group, an isobutyl group, A tert-butyl group is mentioned.

From the viewpoint of further improving the UV resistance of the cured product, in general formula (1), n is an integer of 5 to 8, R is _C 1 -C ₄ alkyl group, and R 'is _C 1 ~ It hindered amine light stabilizer having a structure represented by C ₄ alkyl group is preferred. Examples of hindered amine light stabilizers having such a structure include bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate and methyl (1,2,2,6,6-pentamethyl). -4-piperidyl) sebacate and the like, and the use of these mixtures is particularly preferable.

  As a commercial item of the (D) hindered amine light stabilizer, for example, JF-95 (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate: manufactured by Johoku Chemical Industry Co., Ltd.), JF-90 (bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate: manufactured by Johoku Chemical Industry Co., Ltd.), Chemistab 29 (bis (1,2,2,6,6-pentamethyl-4) Mixture of piperidyl) decandioate 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: manufactured by BASF Japan Ltd.), etc. Can be mentioned. These hindered amine light stabilizers may be used alone or in combination of two or more.

  The content of the (D) hindered amine light stabilizer is not particularly limited, but the lower limit is, for example, 0.50 parts by mass from the viewpoint of further improving UV resistance with respect to 100 parts by mass of the polyol (A). 1.0 part by mass is preferable and particularly preferable. On the other hand, the upper limit is, for example, preferably 5.0 parts by weight and particularly preferably 3.0 parts by weight with respect to 100 parts by weight of the polyol (A) in terms of transparency of the cured product.

  In this invention, you may mix | blend (E) ultraviolet absorber further as needed.

  (E) By mix | blending a ultraviolet absorber, it can prevent that the board | substrate which coats the composition of this invention deteriorates by UV, and, as a result, the weather resistance of a board | substrate improves. Moreover, by mix | blending (E) ultraviolet absorber, it contributes to providing UV tolerance to the hardened | cured material of the composition of this invention, and, as a result, contributes to the improvement of the weather resistance of hardened | cured material.

  An ultraviolet absorber will not be specifically limited if it has the said effect | action, For example, a benzoate type ultraviolet absorber, a benzotriazole type ultraviolet absorber, a benzophenone type ultraviolet absorber, etc. are mentioned. Examples of the benzoate ultraviolet absorber include 2,4-di-tert-pentylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 2,6-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, n-hexadecyl-3, 5-di-t-butyl-4-hydroxybenzoate and the like can be mentioned. Examples of the benzotriazole UV absorber include 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol], 2,2 ′. -Methylenebis (4-methyl-6-benzotriazolylphenol) and the like can be mentioned. Examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-normal-octyloxybenzophenone, 2-hydroxy-4methoxybenzophenone, and the like. These ultraviolet absorbers may be used alone or in combination of two or more.

  Although content of the said (E) ultraviolet absorber is not specifically limited, The lower limit is 0.50 from the point which improves the weather resistance of a board | substrate and hardened | cured material more with respect to 100 mass parts of (A) polyol, for example. Part by mass is preferable, and 1.0 part by mass is particularly preferable. On the other hand, the upper limit is, for example, preferably 5.0 parts by weight and particularly preferably 3.0 parts by weight with respect to 100 parts by weight of the polyol (A) in terms of transparency of the cured product.

  In this invention, you may mix | blend (F) filler further as needed.

  (F) Adding a filler contributes to improving the mechanical strength of the cured product. A filler will not be specifically limited if it has the said effect | action, For example, an inorganic filler, an organic filler, the inorganic filler by which the surface organic-treatment was carried out, etc. are mentioned. Among these, from the viewpoint of improvement in coating film hardness and dispersion stability in the composition, surface-treated inorganic fillers are preferable, methacrylic surface-treated nanosilica, vinyl surface-treated nanosilica, and phenyl surface-treated. Silica is particularly preferred. These fillers may be used alone or in combination of two or more.

  In addition, when using the above-mentioned surface-organized nano silica, the average primary particle size is not particularly limited, but is preferably 1.0 nm to 200 nm, for example, from the viewpoint of dispersing the filler in the composition. Particularly preferred is 0 nm to 100 nm.

  Examples of commercially available (F) fillers include YA010C-SM-1 (Nanosilica treated with methacrylic surface: manufactured by Admatechs Co., Ltd.), YA010C-SV-1 (Nanosilica treated with vinyl surface: AD Co., Ltd.). MAT010), YA010C-SP-3 (phenyl surface-treated nano silica: manufactured by Admatechs), YA050C-SM-1 (methacrylic surface-treated nano silica: manufactured by Admatechs), and the like. it can.

  The content of the filler (F) is not particularly limited, but is preferably 0.10 to 200 parts by mass with respect to 100 parts by mass of the polyol (A) from the viewpoint of the balance between mechanical properties and transparency of the cured product. 0.0-100 mass parts is especially preferable.

  Furthermore, in addition to the above-mentioned components, various additive components such as a urethanization catalyst and various additives can be appropriately blended with the composition of the present invention as necessary.

  The urethanization catalyst reacts with a polyol and an aliphatic polyisocyanate and / or a modified product of the aliphatic polyisocyanate. By the urethanization catalyst, a tack-free cured product can be obtained, and the hardness of the cured product can be improved. Examples of the urethanization catalyst include zinc 2-ethylhexanoate, dibutyltin dilaurate, dioctyltin dilaurate, octyltin trilaurate, tin dioctylate, dibutyltin diacetate, and dioctyltin diacetate.

  Examples of various additives include dispersants such as coupling agents such as silane, titanate, and alumina, boron trifluoride-amine complex, dicyandiamide (DICY) and its derivatives, organic acid hydrazide, and diaminomaleonitrile (DAMN). ) And derivatives thereof, guanamine and derivatives thereof, amine imide (AI) and latent curing agents such as polyamines, metal salts of acetylacetone such as acetylacetonate Zn and acetylacetonate Cr, enamines, tin octylates, quaternary sulfonium salts And thermosetting accelerators such as triphenylphosphine, imidazole, imidazolium salt and triethanolamine borate.

  The production method of the composition of the present invention is not limited to a specific method. For example, after blending each of the above components in a predetermined ratio, at room temperature, a kneading means such as a three roll, ball mill, sand mill, or super mixer, It can be produced by kneading or mixing with a stirring means such as a planetary mixer. Further, prior to the kneading or mixing, if necessary, preliminary kneading or premixing may be performed.

  Next, an example of how to use the composition of the present invention will be described. Here, a method for forming a protective film by applying the composition of the present invention on a substrate (for example, a PET (polyethylene terephthalate) substrate) will be described as an example. The composition produced as described above is applied on a substrate to a desired thickness using a method such as a bar coater, a screen printing method, or a spray coating method, and a drying furnace or the like having a temperature of about 60 to 170 ° C. It can be dried and cured by heating for about 15 to 60 minutes to form a desired protective film having self-repairing properties and oil resistance on the substrate.

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

  Next, examples of the present invention will be described. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Examples 1-6, Comparative Examples 1-2
The components used in Examples 1 to 6 and Comparative Examples 1 to 2 are blended at the blending ratios shown in Table 1 below and mixed and dispersed at room temperature using three rolls. A product was prepared. In addition, the number of the mixing | blending in following Table 1 shows a mass part, and a blank part shows no mixing | blending.

The details of each component in Table 1 are as follows.
(A) Polyol / PLACCEL 305T: OH group value 305 mgKOH / g, manufactured by Daicel Corporation.

(B) Aliphatic polyisocyanate and / or modified product of this aliphatic polyisocyanate / Takenate D-170N: manufactured by Mitsui Chemicals, Inc.
・ Duranate D201: manufactured by Asahi Kasei Chemicals Corporation.

(C) Polydialkylsiloxane modified with a hydroxyl group at the end. Silmer OH Di-10: manufactured by SILTECH.
・ KF-9701: manufactured by Daicel Corporation.

(D) Hindered amine light stabilizer / Kemistab 29: manufactured by Chemipro Kasei Co., Ltd.

(E) Ultraviolet absorber, KEMISORB 113: manufactured by Chemipro Kasei Co., Ltd.

(F) Filler YA010C-SM-1: manufactured by Admatechs Corporation.

Urethane catalyst / Zn-Octoate 22%: manufactured by DIC Corporation.

Modified aromatic polyisocyanate, Takenate D-110, manufactured by Mitsui Chemicals, Inc.
Polydialkylsiloxane modified with carboxyl group at the end X-22-162C: manufactured by Shin-Etsu Chemical Co., Ltd.

Test piece preparation process Each of the compositions prepared as in Examples 1 to 6 and Comparative Examples 1 and 2 was applied on a PET substrate having a thickness of 100 μm (manufactured by Teijin DuPont Films Ltd., “Tetron G2”) with a bar coater. Then, a cured coating film of the composition was formed on a PET substrate by drying and curing at 100 ° C. for 30 minutes in a drying furnace, and a test piece was prepared. The film thickness of the cured coating film was 100 μm.

(1) Self-healing property A brass brush was pressed against the cured coating film with a load of 1.0 kg, moved 10 times, and visually evaluated for scratches within 10 minutes. Evaluation was performed in the following two stages.
“◯”: No scratches are observed.
“×”: Scratches are observed.

(2) Oil resistance An oil-based magic (manufactured by ZEBRA, “Mckey extra-fine”) was used to draw a circle with a diameter of 1.0 cm, and the repelling condition of the oil-based magic was visually evaluated. Evaluation was performed in the following two stages.
“◯”: Oily magic repelling is observed.
“×”: No oily magic repelling is observed.

(3) Coating film hardness The test piece in which the cured coating film was formed was evaluated based on JISK5600 5-4.

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

  From the results of Table 1, in Examples 1 to 6 in which a modified product of hexamethylene diisocyanate and a polydimethylsiloxane having a terminal modified with a hydroxyl group were blended, only curing by heat treatment without performing photocuring as a curing step, It was possible to obtain a cured coating film excellent in oil resistance while having excellent self-healing properties without impairing good coating film hardness. Moreover, in Example 4 which added the urethanization catalyst, the coating-film hardness improved more.

  On the other hand, in place of the modified product of hexamethylene diisocyanate, Comparative Example 1 in which a modified product of aromatic polyisocyanate was blended, or in place of polydimethylsiloxane having a terminal modified with a hydroxyl group, the terminal was modified with a carboxyl group In Comparative Example 2 in which polydialkylsiloxane was blended, oil resistance could not be obtained.

  The composition of the present invention has self-healing properties and excellent oil resistance, so that it requires self-healing properties and needs to prevent the adhesion of oil stains, such as liquid crystal displays and automobile bodies. It is highly useful in protective films such as surface protective films for optical members.

Claims (11)

(A) a polyol;
(B) an aliphatic polyisocyanate and / or a modified product of the aliphatic polyisocyanate;
(C) a polydialkylsiloxane having a terminal modified with a hydroxyl group;
The composition characterized by containing.   The composition according to claim 1, wherein the aliphatic polyisocyanate is an aliphatic polyisocyanate having 3 to 10 carbon atoms.   The composition according to claim 1 or 2, wherein the aliphatic polyisocyanate is hexamethylene diisocyanate.   The composition according to any one of claims 1 to 3, wherein the modified product of the aliphatic polyisocyanate is a bifunctional type of hexamethylene diisocyanate and / or an isocyanurate of hexamethylene diisocyanate.   5. The composition according to claim 1, wherein the polyol (A) has an OH group value of 150 to 400 mgKOH / g.   The composition according to claim 1, wherein the (A) polyol is polycaprolactone triol. Furthermore, (D) General formula (1)
(Where
n is an integer of 1 to 10,
R is hydrogen or _C 1 -C ₄ alkyl group,
A _is, C 1 -C ₄ alkyl group or the following general formula (2)

In a represented by piperidyl group, and R 'is a hindered amine light stabilizer represented by hydrogen or C ₁ -C ₄ alkyl group), of claims 1 to 6, characterized in that it contains The composition according to any one of the above.   The (D) hindered amine light stabilizer is bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate and methyl (1,2,2,6,6-pentamethyl-4-piperidyl). 8. The composition of claim 7, comprising a mixture with) sebacate.   The composition according to any one of claims 1 to 8, further comprising (E) an ultraviolet absorber.   Furthermore, (F) a filler is contained, The composition of any one of the Claims 1 thru | or 9 characterized by the above-mentioned.   A self-repair coat film comprising a cured film of the composition according to claim 1.