JPWO2018052008A1 - Polyrotaxane-containing composition and cured product thereof - Google Patents

Abstract

The present invention provides a polyrotaxane-containing composition capable of obtaining a cured product having both excellent transparency, self-healing property, high hardness, and low tack. The present invention also provides a cured product obtained by curing the polyrotaxane-containing composition. The present invention includes a polyrotaxane, a thiol group, an amino group, and a polyrotaxane comprising a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blocking group that blocks both ends of the linear molecule. A polysiloxane having at least one functional group selected from the group consisting of hydroxyl groups, and a polyrotaxane-containing composition containing a curing agent.

Description

The present invention relates to a polyrotaxane-containing composition and a cured product thereof.

Information terminals such as mobile phones, smartphones, personal computers, and the like cause many scratches during transportation and use, leading to a decrease in design. For this reason, such industrial products are usually subjected to a surface treatment to impart functions such as scratch resistance.
As such a surface treatment, a hard coating and a soft coating are known. As a method classified as a soft coating, self-healing using the elasticity of a film as disclosed in Patent Documents 1 to 3 Mold coating has been developed.

JP-A 63-86762 JP-A-6-180628 Japanese Patent Laid-Open No. 11-42746

Hard coating is to form a high-hardness film with increased cross-linking density of the film, and is excellent in resistance to external load, but because it shrinks when cured, the adhesion with the substrate is reduced, There was a problem that once a scratch was made, the wound would expand.
On the other hand, soft coatings do not have these problems, but because they are soft, they have insufficient resistance to high loads and tend to be tacky, especially in self-healing coatings. .
An object of this invention is to provide the polyrotaxane containing composition which can obtain the hardened | cured material which was excellent in transparency, self-repairability, high hardness, and low tack. Another object of the present invention is to provide a cured product obtained by curing the polyrotaxane-containing composition.
In the present specification, the “self-repair” means that the load from the contact object is restored elastically after unloading to return to the original state, and as a result, no damage remains or is reduced to a minor scar. Means that

The present invention includes a polyrotaxane, a thiol group, an amino group, and a polyrotaxane comprising a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blocking group blocking both ends of the linear molecule. A polysiloxane having at least one functional group selected from the group consisting of hydroxyl groups, and a polyrotaxane-containing composition containing a curing agent.
The present invention is described in detail below.

When the present inventors use a composition containing a polyrotaxane, a polysiloxane having a specific functional group, and a curing agent having a functional group capable of reacting with the polyrotaxane and the polysiloxane, excellent transparency, It has been found that a cured product having both self-repairability, high hardness, and low tack can be obtained, and the present invention has been completed.

The polyrotaxane-containing composition of the present invention contains a polyrotaxane comprising a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blocking group that blocks both ends of the linear molecule. .

The cyclic molecule is a compound that can be included so that a linear molecule penetrates like a skewer in an opening and can move on the linear molecule.
As a method for including the linear molecule by the cyclic molecule, a conventionally known method (for example, a method described in JP-A-2005-154675) can be used.
In the present specification, “cyclic” of the cyclic molecule means substantially cyclic, and may be a complete ring-closed structure as long as it can move on the linear molecule. For example, a spiral structure may be used.

Examples of the cyclic molecule include cyclic polymers such as cyclic polyether, cyclic polyester, and cyclic polyetheramine, and cyclodextrins.
Examples of the cyclic polymer include crown ether and derivatives thereof, calixarene and derivatives thereof, cyclophane and derivatives thereof, cryptand and derivatives thereof, and the like.
The cyclic molecule is appropriately selected depending on the type of linear molecule to be used. However, since it is easily available and many types of blocking groups can be selected, α-cyclodextrin, β-cyclodextrin, γ-cyclo Cyclodextrins such as dextrin are preferred. For example, as will be described later, when polyethylene glycol is selected as the linear molecule, α-cyclodextrin is preferred from the viewpoint of the stability of the resulting clathrate.

When cyclodextrin is used as the cyclic molecule, a part of the hydroxyl group of the cyclodextrin improves the solubility of the polyrotaxane in the organic solvent and the compatibility with the resin used together (hereinafter referred to as “solubility imparting”). It is preferably modified by a group called “group”.
Examples of the solubility-imparting group include an acetyl group, an alkyl group having 1 to 18 carbon atoms, a trityl group, a trimethylsilyl group, a phenyl group, a polyester chain, an oxyethylene chain, and a polyacrylate chain. These modifying groups may be introduced alone or two or more of them may be introduced. When introducing two or more kinds of modifying groups, for example, when introducing an oxyethylene chain and a polyester chain, the hydroxyl group of cyclodextrin is first modified with an oxyethylene chain, and the introduced hydroxyl group at the end of the oxyethylene chain is the starting point. For example, a method of introducing a polyester chain can be used.

In addition to being able to be more soluble in organic solvents and compatible with reactive resins used in combination as needed, since there is a hydroxyl group that can be used as a crosslinking point at the end of the solubility-imparting group, As the solubility-imparting group, polypropylene introduced by performing hydroxypropylation of the hydroxyl group of cyclodextrin using propylene oxide and then performing ring-opening polymerization of ε-caprolactone using the hydroxyl group of the hydroxypropyl group as a reaction initiation point. A caprolactone chain (polyester chain) is preferred.

From the viewpoint of solubility in an organic solvent and compatibility with a reactive resin used in combination as necessary, the introduction rate of the solubility-imparting group is determined based on the total hydroxyl groups of cyclodextrin when cyclodextrin is used as a cyclic molecule. It is preferable that it is 10-90 mol% with respect to it, and it is more preferable that it is 30-70 mol%.

When the inclusion ratio of the amount of inclusion of the cyclic molecule as a percentage with respect to the amount (maximum inclusion amount) that can be included at the maximum when the cyclic molecule includes the linear molecule is included, The preferable lower limit of the contact ratio is 0.1%, the preferable upper limit is 60%, the more preferable lower limit is 1%, the more preferable upper limit is 50%, the still more preferable lower limit is 5%, and the further preferable upper limit is 40%. .
The maximum inclusion amount can be determined by the length of the linear molecule and the thickness of the cyclic molecule. For example, the maximum amount of inclusion when the linear molecule is polyethylene glycol and the cyclic molecule is α-cyclodextrin is experimentally determined (see Macromolecules 1993, 26, 5698-5703).

The linear molecule can be included so as to penetrate the opening of the cyclic molecule in a skewered manner. For example, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyethylene oxide, polyalkylene glycol (polyethylene glycol, polypropylene Glycol), polyvinyl methyl ether, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), casein, gelatin, starch, cellulose resin (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyolefin Resins (polyethylene, polypropylene, polyisobutylene, and copolymers of these with other olefinic monomers), polyester trees , Polyvinyl chloride resin (vinyl chloride-vinyl acetate copolymer, etc.), polystyrene resin (polystyrene, acrylonitrile-styrene copolymer, etc.), acrylic resin (poly (meth) acrylic acid, polymethyl methacrylate, (meth) Acrylate copolymer, acrylonitrile-methyl acrylate copolymer, etc.), polycarbonate resin, polyurethane resin, polyvinyl acetal resin (polyvinyl butyral resin, etc.), polyamide resin (nylon (registered trademark), etc.), polyimide resin, polydiene resin ( Polyisoprene, polybutadiene, etc.), polysiloxane resin (polydimethylsiloxane, etc.), polysulfone resin, polyimine resin (polyethyleneimine, etc.), polyamine resin, polyacetic anhydride resin, polyurea resin, polysulfide tree , Polyphosphazene resin, polyketone resin, polyphenylene resin, polyhaloolefins resin and copolymers thereof, derivatives, modified products and the like. Among these, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinyl methyl ether are preferable, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, Polyethylene and polypropylene are more preferred, and polyethylene glycol is even more preferred.
In the present specification, the “(meth) acryl” means at least one of “acryl” and “methacryl”.

The preferable lower limit of the weight average molecular weight of the linear molecule is 3000, and the preferable upper limit is 300,000. When the weight average molecular weight of the linear molecule is 3000 or more, the amount of movement of the cyclic molecule on the linear molecule is increased, and the resulting coating film is excellent in self-healing properties. When the weight average molecular weight of the linear molecule is 300,000 or less, the solubility in an organic solvent is superior. The more preferable lower limit of the weight average molecular weight of the linear molecule is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 50,000.
In addition, the mass average molecular weight of the said linear molecule is a value calculated | required by polyethyleneglycol conversion, measuring with gel permeation chromatography (GPC). Examples of the column for measuring the mass average molecular weight in terms of polyethylene glycol by GPC include TSKgel SuperAWM-H (manufactured by Tosoh Corporation).
Further, the mass average molecular weight other than the linear molecule is a value determined by polystyrene conversion after measurement by GPC unless otherwise specified. Examples of the column for measuring the mass average molecular weight in terms of polystyrene by GPC include TSKgel SuperHM-M (manufactured by Tosoh Corporation).

In the polyrotaxane used in the present invention, the linear molecule is preferably polyethylene glycol, and the cyclic molecule is preferably a molecule derived from α-cyclodextrin.

The blocking groups are disposed at both ends of the linear molecule included in the cyclic molecule and have a role of preventing the cyclic molecule from leaving. As a method for blocking both ends of a linear molecule with a blocking group, a conventionally known method (for example, a method described in JP-A-2005-154675) can be used.

Examples of the blocking group include dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, pyrenes, anthracenes, and the like having a mass average molecular weight of 1,000 to 1,000,000. Examples include a main chain or a side chain of a polymer.
Of these, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes are preferable, and adamantane groups and trityl groups are more preferable.
Examples of the polymer having a mass average molecular weight of 1,000 to 1,000,000 include polyamide, polyimide, polyurethane, polydimethylsiloxane, and polyacrylic acid ester.
Two or more of these blocking groups may be mixed in the polyrotaxane.

The minimum with preferable content of the said polyrotaxane with respect to the whole polymer structural component in the polyrotaxane containing composition of this invention is 1 mass%, and a preferable upper limit is 90 mass%. By setting the content of the polyrotaxane within this range, the obtained cured product exhibits more excellent hardness (breaking strength) and self-repairability. The more preferable lower limit of the content of the polyrotaxane with respect to the entire polymer component in the polyrotaxane-containing composition of the present invention is 10% by mass, the more preferable upper limit is 80% by mass, the still more preferable lower limit is 20% by mass, and the more preferable upper limit is 75%. % By mass.
In the present specification, the “polymer constituent component” refers to a curing agent and a component that is finally incorporated into a polymer structure by reacting with the curing agent.

In the polyrotaxane-containing composition of the present invention, the content of the polyrotaxane is preferably 10% by mass, more preferably 12% by mass, more preferably 32% by mass, and more preferably 25% by mass.

The polyrotaxane-containing composition of the present invention comprises a polysiloxane having at least one functional group selected from the group consisting of a thiol group, an amino group, and a hydroxyl group (hereinafter also referred to as “polysiloxane according to the present invention”). contains. The polysiloxane according to the present invention reacts with the curing agent together with the polyrotaxane and is incorporated into the polymer structure, so that the cured product obtained using the polyrotaxane-containing composition of the present invention has excellent self-repairability, high hardness, And it shows a low tack. Further, the polysiloxane according to the present invention does not have a great adverse effect on the transparency of the obtained cured product.

The polysiloxane according to the present invention has at least one functional group selected from the group consisting of a thiol group, an amino group, and a hydroxyl group. These functional groups contribute to the reaction with the curing agent. Especially, it is preferable to have a thiol group and / or an amino group from a reactive viewpoint, and it is more preferable to have a thiol group.

The preferable lower limit of the number of functional groups of the polysiloxane according to the present invention is 1.0 mmol / g, and the preferable upper limit is 20 mmol / g. When the number of functional groups of the polysiloxane according to the present invention is within this range, the obtained cured product has a more excellent hardness. The more preferable lower limit of the number of functional groups of the polysiloxane according to the present invention is 2.0 mmol / g, and the more preferable upper limit is 10 mmol / g.
The “number of functional groups of the polysiloxane according to the present invention” means the number of functional groups of the polysiloxane according to the present invention among thiol groups, amino groups, and hydroxyl groups.

Moreover, organopolysiloxane can be used as the polysiloxane according to the present invention.
The polysiloxane according to the present invention preferably has a (poly) silsesquioxane structure.
The (poly) silsesquioxane structure includes a ladder type, a random type, a cage type, and the like, but a random type is preferable from the viewpoint of ease of manufacture.

In addition, you may use the nano silica which has the polysiloxane which has at least 1 sort (s) of functional group selected from the group which consists of a thiol group, an amino group, and a hydroxyl group by surface treatment etc. on the surface. However, such nanosilica is (1) easily aggregated due to its large surface area, and (2) poorly compatible with organic materials such as organic solvents. Turbidity is likely to occur due to aggregation, and can only be added in such an amount that turbidity does not become a problem. (3) Since it does not dissolve in organic solvents or water, only the dispersion form can be handled. Since the solid (powder) obtained by drying the dispersion liquid aggregates during drying, it cannot be dispersed again in an organic solvent or water. (4) It is difficult to perform surface treatment without aggregation. (5) There are cases where the effect of improving the hardness is not sufficiently exhibited without impairing the self-repairing property of the obtained cured product.

The preferable lower limit of the mass average molecular weight of the polysiloxane according to the present invention is 300, and the preferable upper limit is 10,000. When the mass average molecular weight of the polysiloxane according to the present invention is 300 or more, the obtained cured product has more excellent hardness. When the mass average molecular weight of the polysiloxane according to the present invention is 10,000 or less, the compatibility (solubility) with an organic material such as an organic solvent is improved. The more preferable lower limit of the mass average molecular weight of the polysiloxane according to the present invention is 400, and the more preferable upper limit is 7000.
Moreover, the preferable minimum of the molecular weight polydispersity of the polysiloxane concerning this invention is 1.0, a preferable upper limit is 5.0, and a more preferable upper limit is 3.0.
In addition, the mass average molecular weight and the molecular weight polydispersity of the polysiloxane are values obtained by measuring by gel permeation chromatography (GPC) and converted to polystyrene.

The minimum with preferable content of the polysiloxane concerning this invention with respect to the whole polymer structural component in the polyrotaxane containing composition of this invention is 0.5 mass%, and a preferable upper limit is 30 mass%. By making content of the polysiloxane concerning this invention into this range, the hardened | cured material obtained will have more excellent hardness, without impairing self-repairing property, and a tack | tuck can be reduced more. The more preferred lower limit of the polysiloxane content according to the present invention is 1.0 mass%, the more preferred upper limit is 25 mass%, the still more preferred lower limit is 2.0 mass%, and the still more preferred upper limit is 10 mass%.

In the polyrotaxane-containing composition of the present invention, the content of the polysiloxane according to the present invention is preferably 1% by mass, more preferably 1.5% by mass, more preferably 12% by mass, and more preferably 5% by mass. %.

The polysiloxane according to the present invention can be produced by hydrolyzing and condensing alkoxysilanes represented by the following formula (1).

In formula (1), R ¹ represents a thiol group, an amino group, and a hydrocarbon group having 1 to 8 carbon atoms having at least one functional group selected from the group consisting of a hydroxyl group, R ² is A hydrogen atom or a C1-C8 hydrocarbon group is represented. Each R ² may be the same or different.
The hydrocarbon group may be an aliphatic group or may contain an aromatic group.

Examples of the alkoxysilanes represented by the formula (1) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyltributoxysilane, 1 , 4-Dimercapto-2- (trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl) butane, 1,4-dimercapto- 2- (tributoxysilyl) butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercaptopropyltripropoxysilane, 2- Mercaptomethi -3-Mercaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1,2-dimercaptoethyltri Thiol group-containing alkoxysilanes such as butoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N, N′-bis [3- (triethoxysilyl) Propyl] -1,2-ethanediamine, N- [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (triethoxysilyl) propyl] -1,2-ethanediamine, Bis- {3- (trimethoxysilyl) propyl} amine, bis- {3- (triethoxysilyl) propyl} amine, -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, trimethoxy {3- (methylamino) propyl} silane, 3- (N-allylamino) propyltrimethoxysilane, 3- (N-allylamino) propyltriethoxysilane Amino group-containing alkoxysilanes such as 3- (diethylamino) propyltrimethoxysilane, 3- (diethylamino) propyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane, and 3- (phenylamino) propyltriethoxysilane And hydroxyl group-containing alkoxysilanes such as 3-hydroxypropyltrimethoxysilane and 3-hydroxypropyltriethoxysilane. Of these, thiol group-containing alkoxysilanes are preferable, and 3-mercaptopropyltrimethoxysilane is more preferable from the viewpoint of the reactivity of hydrolysis reaction and availability of raw materials. These alkoxysilanes may be used independently and 2 or more types may be used in combination.

Further, the polysiloxane according to the present invention may be a product obtained by hydrolyzing and condensing metal alkoxides in addition to the alkoxysilanes represented by the formula (1).
Examples of the metal alkoxides include trialkylalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, and triphenylethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxy. Dialkyl dialkoxysilanes such as silane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and methyltrimethoxy Silane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxy Alkyltrialkoxysilanes such as run, phenyltriethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, Examples thereof include tetraalkoxytitanium such as tetrabutoxytitanium, and tetraalkoxyzirconium such as tetraethoxyzirconium, tetrapropoxyzirconium, and tetrabutoxyzirconium. These metal alkoxides may be used alone or in combination of two or more.

The hydrolysis reaction can be performed by a conventionally known method using a catalyst. As the catalyst used in the hydrolysis reaction, formic acid is preferable because it has high catalytic activity and can be shared with the catalyst used in the condensation reaction.

The condensation reaction can be performed by a conventionally known method using a catalyst, the reaction temperature is usually about 40 to 150 ° C., preferably 60 to 100 ° C., and the reaction time is usually 30 minutes to 12 minutes. It is about time.
After completion of the condensation reaction, the polysiloxane according to the present invention is obtained by removing the catalyst.

The polyrotaxane-containing composition of the present invention contains a curing agent.
The curing agent has a functional group capable of reacting with the polyrotaxane and the polysiloxane according to the present invention, and functions as a crosslinking agent for crosslinking the polyrotaxane with the polysiloxane according to the present invention. That is, it has a reaction activity with respect to both the hydroxyl group of the polyrotaxane and at least one functional group selected from the group consisting of a thiol group, an amino group, and a hydroxyl group of the polysiloxane according to the present invention. Any one having two or more functional groups shown in one molecule can be used as the curing agent. Specific examples include melamine resins, polyfunctional isocyanate compounds, cyanuric chloride, dibromobenzene, alkoxysilanes, and the like. When using the said melamine resin for the polyrotaxane containing composition of this invention, it is used as a hardening | curing agent instead of the reactive resin mentioned later. In particular, the curing agent preferably contains a polyfunctional isocyanate compound because the resulting cured product can be made more excellent in self-healing properties.
The “polyfunctional isocyanate compound” means a compound having two or more isocyanate groups in one molecule.

Among the polyfunctional isocyanate compounds, examples of the bifunctional isocyanate compound include hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4-dicyclohexyl diisocyanate, and the like. It is done.
Among the polyfunctional isocyanate compounds, the trifunctional or higher functional isocyanate compound is, for example, synthesized from the bifunctional isocyanate compound as a starting material, and is a burette body, a trimethylolpropane adduct body, an isocyanurate body, an allophanate body. And the like.
Among these, from the viewpoint of increasing the hardness (breaking strength) of the obtained cured product, a trifunctional or higher functional isocyanate compound is preferable.
Moreover, since the obtained hardened | cured material can be made into what has the more outstanding hardness, it is preferable to use what protected these polyfunctional isocyanate compounds using the conventionally well-known blocking agent (block isocyanate). However, the blocking agent is not included in the polymer constituents in this specification.
These polyfunctional isocyanate compounds may be used alone or in combination of two or more.

Examples of commercially available polyfunctional isocyanate compounds include Duranate 24A-100 (Asahi Kasei Chemicals, hexamethylene diisocyanate burette), Duranate P-301-75E (Asahi Kasei Chemicals, hexamethylene diisocyanate). Adduct), Duranate TPA-100 (Asahi Kasei Chemicals, isocyanurate of hexamethylene diisocyanate), Takenate D-120N (Mitsui Chemicals, 1,3-bis (isocyanatomethyl) cyclohexane trimethylolpropane Adduct), Takenate D-127N (Mitsui Chemicals, 1,3-bis (isocyanatomethyl) cyclohexane isocyanurate), Takenate D-140N (Mitsui Chemicals, isophorone diisocyanate) Trimethylolpropane adduct of sulfonate), Desmodur XP2679 (manufactured by Sumika Bayer Urethane Co., allophanate body) such as hexamethylene diisocyanate.

Functional groups capable of reacting with functional groups (for example, isocyanate groups) possessed by the curing agent of each component (polyrotaxane, polysiloxane, and preferably used reactive resin, etc.) contained in the polyrotaxane-containing composition of the present invention. The minimum with the preferable number of functional groups of the said hardening | curing agent with respect to 1.0 mol of total substance amounts (a hydroxyl group, a thiol group, an amino group) is 0.5 mol, and a preferable upper limit is 3.0 mol. By adjusting the amount of the curing agent so that the number of functional groups of the curing agent falls within this range, the obtained cured product can have a more excellent hardness (breaking strength). The more preferable lower limit of the number of functional groups of the curing agent is 0.7 mol, the more preferable upper limit is 2.0 mol, the still more preferable lower limit is 1.0 mol, and the still more preferable upper limit is 1.5 mol.
The content of the curing agent is preferably adjusted so that the number of functional groups is in the above-described range. Specifically, the lower limit is preferable with respect to the entire polymer component in the polyrotaxane-containing composition of the present invention. Is 10% by mass, the preferred upper limit is 60% by mass, the more preferred lower limit is 15% by mass, the more preferred upper limit is 50% by mass, the still more preferred lower limit is 25% by mass, and the still more preferred upper limit is 35% by mass.

In the polyrotaxane-containing composition of the present invention, the content of the curing agent has a preferable lower limit of 10% by mass, a more preferable lower limit of 12% by mass, a preferable upper limit of 20% by mass, and a more preferable upper limit of 18% by mass.

When a polyfunctional isocyanate compound is used as a curing agent, a curing catalyst may be used in combination for the purpose of promoting the reaction. Curing catalysts include dibutyltin dilaurate, dioctyltin dilaurate, tri (acetate) butyltin, di (acetate) dibutyltin, acetate tributyltin, methoxytributyltin, tri (2-ethylhexanoate) butyltin, bis Tin catalysts such as (2-ethylhexanoate) dibutyltin, tri (laurate) butyltin, di (octanoate) dibutyltin, tri (octanoate) butyltin, dibutyltin oxide, monobutyltin hydroxide oxide, tetra ( Zirconium-based catalysts such as acetylacetonate) zirconium, titanium-based catalysts such as diisopropoxybis (ethylacetoacetate) titanium, triethylenediamine, triethylamine, N, N, N ′, N′-tetramethylpropylenediamine, N , N, N ' N′-tetrakis (2-hydroxypropyl) ethylenediamine, N-methylmorpholine, 1,2-dimethylimidazole, 1,5-diazabicyclo (4.3.0) nonene-5, 1,8-diazabicyclo (5.4. 0) -undecene-7 (hereinafter also referred to as “DBU”), and various amine salt catalysts such as borane salts, DBU phenol salts, DBU octylates, DBU carbonates of these amine catalysts, Carboxylates such as magnesium naphthenate, lead naphthenate and potassium acetate, trialkylphosphines such as triethylphosphine and tribenzylphosphine, alkoxides of alkali metals such as sodium methoxide, zinc-based organometallic catalysts, etc. A known catalyst can be used.

The polyrotaxane-containing composition of the present invention preferably further contains a reactive resin. By containing the reactive resin, the obtained cured product can have a more excellent hardness (breaking strength), and tack can be further reduced. The reactive resin has a functional group capable of reacting with the functional group of the curing agent, and has at least one selected from the group consisting of a hydroxyl group, an amino group, and a thiol group in the main chain or side chain. Those having a functional group are preferred, those having a hydroxyl group are more preferred, and those having a hydroxyl group in the side chain are more preferred.

The reactive resin may be a homopolymer or a copolymer. In the case of a copolymer, it may be a block copolymer, an alternating copolymer, a random copolymer, or a graft copolymer.

Examples of the reactive resin include vinyl resins, acrylic resins, cellulose resins, polyalkylene oxide resins, polyamine resins, polyolefin resins, polyester resins, and polyurethane resins. Among these, vinyl resins, acrylic resins, and polyester resins are preferable, acrylic resins are more preferable, and acrylic resins having a hydroxyl group in the side chain are more preferable.
The “acrylic resin” is preferably such that 50 mol% or more of the monomer constituents is a (meth) acrylate monomer.
In the present specification, the “(meth) acrylate” means at least one of “acrylate” and “methacrylate”.

Examples of commercially available acrylic resins having a hydroxyl group in the side chain include Alfon UH-2032, Alfon UH-2041 (above, manufactured by Toagosei Co., Ltd.), Cotax LH-408, and Cotax LH. -615, Cotax LH-635, Cotax LH-694 (above, manufactured by Toray Fine Chemical Co., Ltd.), Joncryl 507, Joncryl 552 (above, produced by BASF), Olester Q107, Olester Q202 (above, Mitsui Chemicals, Inc.) Manufactured) and the like.

When synthesizing an acrylic resin having a hydroxyl group in the side chain, examples of monomers constituting the acrylic resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 4 -Hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 7-methyl-8- Hydroxyoctyl (meth) acrylate, 2-methyl-8-hydroxyoctyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, allyl alcohol, methacryl alcohol, and lactones (β-propiolactone, dimethyl) (E.g., adducts with lopiolactone, butyl lactone, γ-valerolactone, ε-caprolactone, γ-caprolactone, γ-caprolactone, crotonolactone, δ-valerolactone, δ-caprolactone, etc.) Saturable monomers can be used.

In addition to the ethylenically unsaturated monomer having a hydroxyl group, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, phenyl acrylate, isobornyl (meth) acrylate, cyclohexyl methacrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dihydrodicyclopentadi Enyl (meth) acrylate, glycidyl (meth) acrylate, styrene, vinyl ketone, vinyl toluene, t-butyl styrene, parachlorostyrene, vinyl naphthalene, (meth) acrylonitrile , Vinyl acetate, may be used in combination ethylenically unsaturated monomer of vinyl propionate.

The polymerization method for polymerizing the monomer constituting the acrylic resin is not particularly limited, and a conventionally known method such as solution radical polymerization can be used. For example, a method of stirring while dropping a suitable radical polymerization initiator and a monomer mixed solution into a suitable solvent at a polymerization temperature of 60 to 160 ° C. over 2 to 10 hours may be mentioned.
Examples of the radical polymerization initiator include azo compounds such as dimethyl-2,2′-azobisisobutyrate, peroxides such as t-butylperoxy-2-ethylhexanoate, and the like. .
The amount of the radical polymerization initiator used is preferably 0.1% by mass, preferably 30% by mass, and more preferably 0.5% by mass with respect to the total amount of monomers. A more preferable upper limit is 25% by mass.
Moreover, the solvent which can be used here does not have a bad influence on reaction, For example, methyl ethyl ketone, propylene glycol monomethyl ether acetate, xylene, etc. are mentioned. Furthermore, in order to adjust the molecular weight, a mercaptan such as lauryl mercaptan or a chain transfer agent such as α-methylstyrene dimer can be used as necessary.

The preferable lower limit of the mass average molecular weight of the reactive resin is 1000, and the preferable upper limit is 50,000. When the mass average molecular weight of the reactive resin is 1000 or more, the obtained cured product can have more excellent hardness (breaking strength). When the reactive resin has a mass average molecular weight of 50,000 or less, the obtained cured product is excellent in self-repairing property, compatibility with polyrotaxane, and transparency. The more preferable lower limit of the mass average molecular weight of the reactive resin is 2000, the more preferable upper limit is 30,000, and the more preferable upper limit is 15000.
The preferred lower limit of the molecular weight polydispersity of the reactive resin is 1.0, the preferred upper limit is 5.0, and the more preferred upper limit is 3.0.
In addition, the molecular weight polydispersity of the reactive resin is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC) in the same manner as the above-described mass average molecular weight.

The preferable lower limit of the number of reactive groups possessed by the reactive resin is 0.3 mmol / g, and the preferable upper limit is 6.0 mmol / g. When the reactive group number of the reactive resin is within this range, the obtained cured product can have a more excellent hardness (breaking strength). The minimum with the preferable reactive group number which the said reactive resin has is 0.5 mmol / g, and a more preferable upper limit is 4.0 mmol / g.
In addition, the reactive group number which the said reactive resin has is calculated | required from a following formula using the hydroxyl value measured according to JISK0070.
Reactive group number [mmol / g] = Hydroxyl value [mgKOH / g] /56.11

The minimum with a preferable glass transition temperature (Tg) of the said reactive resin is -100 degreeC, and a preferable upper limit is 150 degreeC. By setting the Tg of the reactive resin within this range, the obtained cured product can be made more excellent in self-repairability and hardness. The more preferable lower limit of Tg of the reactive resin is −70 ° C., the more preferable upper limit is 120 ° C., the still more preferable lower limit is −50 ° C., and the still more preferable upper limit is 100 ° C.
The Tg of the reactive resin can be measured by differential scanning calorimetry (DSC).

When it contains the said reactive resin, the upper limit with preferable content of the said reactive resin with respect to the whole polymer structural component in the polyrotaxane containing composition of this invention is 80 mass%. By making content of the said reactive resin into this range, the hardened | cured material obtained will be excellent in self-restoration property and hardness, and a tack | tuck can be reduced more. The upper limit with more preferable content of the said reactive resin is 60 mass%, and a still more preferable upper limit is 40 mass%.
Moreover, the upper limit with preferable content of the said reactive resin with respect to 100 mass parts of said polyrotaxanes is 500 mass parts. When the content of the reactive resin is 500 parts by mass or less, the polyrotaxane content is not excessively decreased, and the obtained cured product is excellent in hardness while maintaining excellent self-healing properties. it can. The upper limit with more preferable content of the said reactive resin is 300 mass parts, and a more preferable upper limit is 200 mass parts.

In the polyrotaxane-containing composition of the present invention, the content of the reactive resin has a preferable lower limit of 5% by mass, a more preferable lower limit of 7% by mass, a preferable upper limit of 22% by mass, and a more preferable upper limit of 18% by mass.

Moreover, it is preferable that the polyrotaxane containing composition of this invention contains the organic solvent.
Examples of the organic solvent include halogenated hydrocarbons such as chloroform and dichloromethane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, and 3-octanone; , Ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, n-butyl 3-methyl-3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, acetic acid Esters such as n-butyl, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, γ-butyrolactone, and ethyl lactate Or diethyl ether Ethers such as cyclopentyl methyl ether and tetrahydrofuran, aromatics such as toluene, xylene, monochlorobenzene and dichlorobenzene, and hydrocarbons such as n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane and cycloheptane , Lactams such as N-methyl-2-pyrrolidone and ε-caprolactam, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether Glycol ethers such as acetate, propylene glycol monoethyl ether acetate, etc. Tonitoriru, sulfolane, dimethyl sulfoxide, N, N-dimethylformamide and the like. These organic solvents may be used alone or in combination of two or more.

The content of the organic solvent is not particularly limited, but a preferable upper limit is usually 2000 parts by mass with respect to 100 parts by mass of the solid content in the polyrotaxane-containing composition.

In addition, the polyrotaxane-containing composition of the present invention includes a coupling agent, a leveling agent, a lubricant, an antistatic agent, an antioxidant, a light stabilizer, a heat stabilizer, and an anti-coloring agent as long as the object of the present invention is not impaired. , Metal deactivator, flame retardant, filler, colorant, photocatalyst material, rust inhibitor, water repellent, conductive material, anti-blocking agent, softener, mold release agent, antifoaming agent, fluorescent whitening agent, blue Ingredients may be included.

By polymerizing the polyrotaxane-containing composition of the present invention, a cured product having both excellent transparency, self-healing property, high hardness, and low tack can be produced.
A cured product obtained by curing the polyrotaxane-containing composition of the present invention is also one aspect of the present invention.

The reaction temperature at the time of reacting the polyrotaxane-containing composition of the present invention is within the range in which the polymerization reaction proceeds, and the polyrotaxane may be decomposed. Therefore, it is usually 200 ° C or lower, preferably 180 ° C or lower. More preferably, it is 150 degrees C or less.

The reaction time for reacting the polyrotaxane-containing composition of the present invention is within a range in which the curing (crosslinking) reaction proceeds, a preferred lower limit is 5 minutes, and a preferred upper limit is 10 hours. When the reaction time is 5 minutes or longer, a desired curing reaction is allowed to proceed while preventing the organic solvent from remaining, and the resulting cured product can have more excellent hardness (breaking strength). Even if the reaction time exceeds 10 hours, a sufficient effect cannot be obtained, and polyrotaxane may be decomposed. A more preferred lower limit of the reaction time is 15 minutes, a more preferred upper limit is 6 hours, a still more preferred lower limit is 30 minutes, and a still more preferred upper limit is 5 hours.

Before the polyrotaxane-containing composition of the present invention is reacted to obtain a cured product, the polyrotaxane-containing composition of the present invention may be applied onto a substrate. Thereby, the hardened | cured material of a favorable film | membrane form can be arranged on the base-material surface.

Examples of the method for applying the polyrotaxane-containing composition of the present invention on a substrate include dip coating, spin coating, flow coating, roll coating, gravure coating, flexographic printing, screen printing, and inkjet. Examples of the coating method include a printing method, a bar coating method, a spray method, and a reverse coating method.

The shape of the substrate on which the polyrotaxane-containing composition of the present invention is applied is appropriately selected according to the purpose, such as a film shape or a board shape.
Examples of the material of the base material include inorganic base materials such as glass, metal plates, and ceramics, poly (cyclo) olefin resin, polycarbonate resin, (meth) acrylic resin, polyester resin, and polystyrene resin. , Epoxy resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyacetal resins, polyamide resins, polyimide resins, fluorine resins, silicone resins, polysulfone resins, polyethersulfone resins, polyether ketones Organic base materials such as a resin, a polyether ether ketone resin, and a polyphenylene sulfide resin can be used.

Moreover, you may wash | clean the base-material surface before coating the polyrotaxane containing composition of this invention for the purpose of preventing delamination and a coating nonuniformity. As a method for cleaning the substrate surface, for example, ultrasonic cleaning, UV cleaning, seric powder cleaning, acid cleaning, alkali cleaning, surfactant cleaning, organic solvent cleaning, etc. may be performed alone or in combination. Can do. After completion of the cleaning, rinsing and drying are performed so that the cleaning agent does not remain, whereby a cured product having a good film form can be obtained on the substrate.

ADVANTAGE OF THE INVENTION According to this invention, the polyrotaxane containing composition which can obtain the hardened | cured material which was excellent in transparency, self-repairability, high hardness, and low tack can be provided. Moreover, according to this invention, the hardened | cured material which hardened this polyrotaxane containing composition can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Hereinafter, the polyrotaxane used in the production examples was prepared with reference to the method described in JP2011-241401A.

(Production Example 1)
(Production of polyrotaxane (PR-1))
As a linear molecule, polyethylene glycol (mass average molecular weight 35000), as a cyclic molecule, after introducing a hydroxypropyl group, α-cyclodextrin grafted with ε-caprolactone (hydroxypropyl group introduction rate 51 mol%), 300 g of a 35% by mass xylene solution of polyrotaxane having an adamantaneamine group as a blocking group (inclusion rate of cyclic molecules of 25%, mass average molecular weight of 470000, hydroxyl value of 74 mgKOH / g) is added to a large amount of methanol, stirred, and centrifuged. The precipitate was taken out by a separation method. The obtained precipitate was dissolved in a small amount of acetone, added to a large amount of methanol, stirred and reprecipitated, and the precipitate was taken out by centrifugation. The obtained precipitate was dried to obtain 99.8 g of polyrotaxane (PR-1).

(Production Example 2)
(Production of polyrotaxane (PR-2))
As a linear molecule, polyethylene glycol (mass average molecular weight 11000), as a cyclic molecule, after introducing a hydroxypropyl group, α-cyclodextrin grafted with ε-caprolactone (hydroxypropyl group introduction rate 51 mol%), 300 g of a 35 mass% xylene solution having a polyrotaxane having an adamantaneamine group as a blocking group (inclusion rate of cyclic molecules 28%, mass average molecular weight 160000, hydroxyl value 92 mgKOH / g) is added to a large amount of methanol, stirred, and centrifuged. The precipitate was taken out by a separation method. The amount of ε-caprolactone used was 78% by mass of the amount used in Production Example 1. The obtained precipitate was dissolved in a small amount of acetone, added to a large amount of methanol, stirred and reprecipitated, and the precipitate was taken out by centrifugation. The obtained precipitate was dried to obtain 98.3 g of polyrotaxane (PR-2).

(Production Example 3)
(Production of reactive resin A (acrylic resin))
3200 g of propylene glycol monomethyl ether acetate was added to a 200 mL glass container equipped with a stirrer, a nitrogen inlet tube, a cooling condenser, a thermometer, and a dropping funnel, and heated to 130 ° C. under a nitrogen atmosphere. In the container, using a dropping funnel, 15.0 g of propylene glycol monomethyl ether acetate, 15.0 g of tert-butylperoxy-2-ethylhexanoate, 16.7 g of styrene, 11.0 g of 2-ethylhexyl acrylate, 2-ethylhexyl A solution in which 22.0 g of methacrylate, 32.8 g of 2-hydroxyethyl methacrylate, and 0.83 g of methacrylic acid were mixed was dropped at a constant rate over 3 hours. Thereafter, the mixture was kept at 130 ° C. for 0.5 hour, and 1.67 g of tert-butylperoxy-2-ethylhexanoate dissolved in 4.17 g of propylene glycol monomethyl ether acetate was added dropwise at a constant rate in 30 minutes. Furthermore, by continuing heating at 130 ° C. for 1 hour, a reactive resin A (acrylic resin) was obtained (resin solid content 66.1%, mass average molecular weight 3900, molecular weight polydispersity 2.09, hydroxyl group number). (Solid) 2.42 mmol / g, Tg 19 ° C.).

(Production Example 4)
(Production of curing agent A)
In a 200 mL glass container equipped with a stirrer, a nitrogen inlet tube, a cooling condenser, and a thermometer, 38.4 g of 3,5-dimethylpyrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) as a blocking agent and Duranate TPA- as a polyfunctional isocyanate compound 100 (100% manufactured by Asahi Kasei Chemicals Co., Ltd., isocyanate group content: 23.1%) is added, heated to 90 ° C. under a nitrogen atmosphere, and stirred for 2 hours while maintaining the internal temperature, thereby blocking as a curing agent Isocyanate (curing agent A) was obtained (isocyanate group content 14.9%). In addition, as a result of measuring by FT-IR, since the peak derived from the isocyanate group in the vicinity of 2250 cm ⁻¹ disappeared, it was confirmed that the isocyanate group was protected.

(Production Example 5)
(Production of polysiloxane A)
In a 200 mL glass container equipped with a stirrer, a nitrogen inlet tube, a cooling condenser, and a thermometer, 40.0 g (0.204 mol) of 3-mercaptopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), methyltrimethoxysilane ( 32.5 g (0.239 mol) manufactured by Tokyo Chemical Industry Co., Ltd., 10 g of toluene and 60 g of 1,2-dimethoxyethane were added, and the mixture was stirred at room temperature for 5 minutes. To this solution, 23.9 g (1.327 mol) of water and 3.63 g (0.079 mol) of formic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, followed by hydrolysis at room temperature for 30 minutes. After stirring at 75 ° C for 1 hour, slowly reduce the pressure to 5 mmHg so as not to bump at 70 ° C. After reaching 5 mmHg, stir for 1 hour to retain methanol, water, toluene, 1,2-dimethoxyethane and formic acid. To give 44.9 g of condensate (solid content 93.5%). To this, 1.58 g of toluene and 9.49 g of 1,2-dimethoxyethane were added and diluted to obtain 56.0 g of polysiloxane (polysiloxane A) according to the present invention (solid content 75%, thiol group number ( Solid) 4.85 mmol / g, weight average molecular weight 1900, molecular weight polydispersity 1.6).

(Production Example 6)
(Production of polysiloxane B)
In a 200 mL glass container equipped with a stirrer, a nitrogen introducing tube, a cooling condenser, and a thermometer, 34.0 g (0.173 mol) of 3-mercaptopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), methyltrimethoxysilane ( 45.5 g (0.334 mol) of Tokyo Chemical Industry Co., Ltd., 10 g of toluene and 60 g of 1,2-dimethoxyethane were added and stirred at room temperature for 5 minutes. To this solution, 27.4 g (1.522 mol) of water and 3.98 g (0.086 mol) of formic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, followed by hydrolysis at room temperature for 30 minutes. After stirring at 75 ° C for 1 hour, slowly reduce the pressure to 5 mmHg so as not to bump at 70 ° C. After reaching 5 mmHg, stir for 1 hour to retain methanol, water, toluene, 1,2-dimethoxyethane and formic acid. To give 48.8 g of condensate (solid content 91.0%). To this, 2.47 g of toluene and 14.8 g of 1,2-dimethoxyethane were added and diluted to obtain 66.1 g of polysiloxane (polysiloxane B) according to the present invention (solid content 72%, thiol group number ( Solid) 3.89 mmol / g, weight average molecular weight 2700, molecular weight polydispersity 2.1).

(Production Example 7)
(Production of polysiloxane C)
Methyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.0 g (0.147 mol) and toluene 20 g are added to a 100 mL glass container equipped with a stirrer, nitrogen introducing tube, cooling condenser and thermometer, and stirred at room temperature for 5 minutes. did. To this solution, 7.93 g (0.440 mol) of water and 1.00 g (0.022 mol) of formic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, followed by hydrolysis at room temperature for 30 minutes. After stirring at 75 ° C. for 1 hour, the pressure is slowly reduced to 5 mmHg so as not to bump at 70 ° C. After reaching 5 mmHg, the mixture is stirred for 1 hour to distill off methanol, water, toluene and formic acid. 8 g (91.2% solids) was obtained. To this, 22.1 g of toluene was added and diluted to obtain 32.8 g of other polysiloxane (polysiloxane C) (solid content 30%, mass average molecular weight 3200, molecular weight polydispersity 1.8).

(Examples 1-24, Comparative Examples 1-10)
Each material was added at a ratio shown in Tables 1 to 3 to a 50 mL sample bottle equipped with a stir bar and stirred until uniform. After adding 200 mg of 1% by weight DBTDL (dibutyltin dilaurate) / xylene solution, the mixture was stirred at 20 ° C. for 5 minutes to obtain a composition.
In addition, the hardening | curing agent B in a table | surface is Duranate TPA-100 (Asahi Kasei Chemicals company make, isocyanate group content rate 23.1%), Reactive resin B is Joncryl 507 (BASF company make, resin solid content 80.2%, Mass average molecular weight 2200, molecular weight polydispersity 2.08, number of hydroxyl groups (solid) 2.64 mmol / g, Tg-7 ° C., nano silica is NANOBYK-3650 (by Big Chemie Japan, solid content 31%, average particle Diameter D50 = 20 nm).
In the table, “the number of functional groups of the curing agent” specifically refers to the substance of the isocyanate group of the curing agent with respect to 1 mol of the total amount of hydroxyl group and thiol group of the polyrotaxane, polysiloxane, and reactive resin. Means quantity.

Using the obtained composition liquid on an glass plate (length 100 mm, width 100 mm, thickness 2 mm) whose surface was washed with acetone using an applicator (manufactured by Sheen Instruments Ltd, “Micrometer Adjustable Film Applicator, 1117/200”). Coated. After leaving still at 40 ° C. for 10 minutes under a nitrogen atmosphere, curing and drying at 100 ° C. for 30 minutes and then 140 ° C. for 15 minutes, a test piece in which a cured product in the form of a thin film was arranged on a substrate Obtained.

<Evaluation>
The following evaluation was performed about each test piece obtained by the Example and the comparative example. The results are shown in Tables 1-3.

(transparency)
Each test piece obtained in Examples and Comparative Examples was visually observed. As a result, the transparency was evaluated as “◯” when the cured product was transparent without turbidity and “X” when turbidity was confirmed in the cured product.

(Pencil hardness)
(25 ° C)
About each test piece obtained by the Example and the comparative example, the pencil hardness test (based on JISK5600) was implemented at 25 degreeC. The sample was allowed to stand at 25 ° C. for 12 hours immediately after the test, and then the pencil hardness was determined.
(80 ° C)
Similarly to the above, a pencil hardness test was conducted at 25 ° C., and after dipping in an 80 ° C. hot water bath for 10 seconds, the sample was cooled to 25 ° C. and the pencil hardness was judged.

(Self-healing)
Each test piece obtained in Examples and Comparative Examples was placed on an electronic balance with the cured product surface facing upward at 25 ° C., and the cured product surface was brass brushed (4 rows of bristle material, with bristles) After 10 reciprocal scratches in a state where the load was 1000 ± 100 g with a length of 70 mm, a wire diameter of 0.14 mm, and a hair length of 16 mm, the repair behavior of the wound was visually observed. About the time until the wound is repaired, “immediate repair”, “within 5 seconds”, “within 10 seconds”, “within 30 seconds”, “within 45 seconds”, “within 1 minute”, “within 5 minutes” And self-repairability was evaluated by the evaluation criteria of “within 40 minutes”. Moreover, even if it confirmed after leaving still for 12 hours, the case where the damage | wound remained was evaluated as "no repairability".

(Tackiness)
The PET film was slid onto the cured product surface of each test piece obtained in the examples and comparative examples while pressing with a finger. The tackiness was evaluated as “◯” when slipping, and “×” when resistance was large and difficult to slip.

When Examples 1-24 are compared with Comparative Examples 1-10, each Example containing the polysiloxane according to the present invention is 25 ° C. and / or compared with each Comparative Example not including the polysiloxane according to the present invention. The pencil hardness at 80 ° C. is improved and the self-repairing property is maintained. In addition, tackiness is also improved.
Comparative Example 8 is a system using another polysiloxane other than the polysiloxane according to the present invention, and no significant improvement in pencil hardness was observed. Moreover, the obtained hardened | cured material was cloudy.
Moreover, in the comparative example 9 which does not contain a polyrotaxane, the self-repair property was not recognized.
Comparative Example 10 is a system using general nano silica instead of the polysiloxane according to the present invention. In this case, although the pencil hardness was improved, the self-repairing property was impaired, and the obtained composition and cured product were turbid.

ADVANTAGE OF THE INVENTION According to this invention, the polyrotaxane containing composition which can obtain the hardened | cured material which was excellent in transparency, self-repairability, high hardness, and low tack can be provided. Moreover, according to this invention, the hardened | cured material which hardened this polyrotaxane containing composition can be provided.

Claims (5)

A polyrotaxane comprising a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blocking group that blocks both ends of the linear molecule;
A polysiloxane having at least one functional group selected from the group consisting of a thiol group, an amino group, and a hydroxyl group, and
A polyrotaxane-containing composition containing a curing agent. The polyrotaxane-containing composition according to claim 1, wherein the curing agent contains a polyfunctional isocyanate compound. Furthermore, the polyrotaxane containing composition of Claim 1 or 2 containing reactive resin. The polyrotaxane-containing composition according to claim 3, wherein the reactive resin has a hydroxyl group. Hardened | cured material which hardened | cured the polyrotaxane containing composition of Claim 1, 2, 3 or 4.