JP2011144338A - Water-based paint and water-based coating film using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide water-based paint having improved dispersibility in a solvent. <P>SOLUTION: The water-based paint containing a modified polyrotaxane has a cyclic molecule having a modified group formed with all or a part of the modified group converted into carboxylate; a straight chain molecule including the cyclic molecules in a skewing state; and blocker groups which are located at both ends of the straight chain molecule and prevent elimination of the cyclic molecule. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aqueous coating material and an aqueous coating film formed using the aqueous coating material. These water-based paints are mainly used for automobile bodies, resin molded products used indoors and outdoors, woodwork products such as stairs, floors, furniture, aluminum wheels that have been subjected to plating, vapor deposition, sputtering, etc., door mirrors, etc. It is suitably used for products and the like. More specifically, the present invention contains a water-dispersible polyrotaxane, and is excellent in smoothness, scratch resistance, water resistance, acid resistance, bird dropping resistance and stretchability, and atmospheric precipitation such as acid rain and bird droppings. The present invention relates to a water-based paint that enables protection of the paint film and a water-based paint film formed using the water-based paint. The present invention also relates to a carboxylate-modified polyrotaxane aqueous dispersion (emulsion, dispersion) used as a material for the water-based paint.

  In the case of resin molded products such as polycarbonate and acrylic, or various metal products, if the physical properties such as hardness, weather resistance, stain resistance, solvent resistance, and corrosion resistance do not meet the required levels, these physical properties In order to compensate for this, surface treatment may be applied. For such surface treatments, curable paints such as room temperature drying paints and two-component urethane paints are usually used, but the surface treatment films with such paints are easily scratched and scratched. This is easily noticeable.

  In addition, in order to improve the design as a product, various parts may be subjected to metal mirror surface treatment such as plating, vapor deposition, and sputtering. Scratches are easily attached, and the attached scratches are easily noticeable. For this reason, such a mirror-finished film is usually further subjected to a surface treatment with a paint as described above. However, the paint-treated film is also easily damaged as described above, and the attached scratch is conspicuous. There is a drawback that it is easy.

  In recent years, the top coat for automobiles has been increasingly oriented toward high durability so that the paint appearance of new cars can be maintained over a long period of time. There is a need for scratch resistance that does not cause scratches due to, for example.

  As a paint capable of forming such a scratch-resistant coating film, a water-based paint using a hydrophilic polyrotaxane has been conventionally known (for example, see Patent Document 1).

  In addition, large products such as automobiles are exposed to atmospheric pollutants such as wind, rain, moisture, sunlight, air, iron powder, bird droppings, and smoke during the period until they reach the consumer's hands. Prone to contamination. For this reason, a coating film protective agent is conventionally applied on the painted surface of automobiles, etc., and the coating surface protective agent is removed immediately before passing to consumers, thereby preventing contamination of the painted surface and commercial value. Is being done.

  As is clear from its application, the above-mentioned coating film protective agent is durable so that it cannot be easily removed by rain or moisture, and when it is necessary to remove it, it can be easily removed by organic solvent, water, or hand-wiping. It must be easy to remove.

  Examples of conventional coating film protective agents include a wax solvent dispersion type, a wax-solid powder solvent dispersion type that can be removed by hand, and an aqueous emulsion type in which wax is emulsified and dispersed.

Among these coating film protective agents, coating film protective agents that volatilize organic solvents during coating and drying, and coating film protective agents that require organic solvents during removal, are particularly pollutant and other resources. In recent years, it has been regarded as a problem in terms of waste, economy and safety.

  Therefore, a strippable paint type using a hydrophilic polyrotaxane that does not volatilize an organic solvent and can be peeled off when it is not used has been studied (for example, see Patent Document 2).

JP 2007-99973 A JP 2007-106867 A

  However, the water-based paint disclosed in Patent Document 1 and the strippable paint-type coating film protective agent disclosed in Patent Document 2 are hydrophilic, although there are no problems in terms of scratch resistance, base protection and removability. Since the solvent type in which the conductive polyrotaxane can be dispersed is limited, an additive that is soluble in the limited solvent type is selected, so the degree of freedom in selecting the material of the additive is low.

  This invention is made | formed in view of the said subject in such a conventional water-system paint, and it aims at providing the water-system paint which the dispersibility to a solvent improved.

  The present invention is also an aqueous system excellent in various performances to be provided as a paint, such as smoothness, scratch resistance, base protection, removability, water resistance, moisture resistance, acid resistance, bird dropping resistance, stretchability, etc. An object is to provide a water-based paint capable of forming a coating film.

  An object of the present invention is to provide a water-based coating film excellent in smoothness, scratch resistance, base protection, removability, water resistance, moisture resistance, acid resistance, bird dropping resistance, and stretchability.

  As a result of further intensive studies to solve the above problems, the present inventors have focused on excellent stretchability, viscoelasticity, and mechanical strength based on the pulley effect of polyrotaxane. That is, when all or part of the modification group of the polyrotaxane modified with all or part of the hydroxyl group of the cyclic molecule is modified with a carboxylate, the dispersible solvent species can be expanded, It was found that the dispersibility was improved. Further, the modified polyrotaxane can be dispersed in water or an aqueous solvent, and the range of application to products requiring durability is widened. It has been found that the above object can be achieved by applying such a modified polyrotaxane to a paint. The present invention has been completed.

  That is, the above object can be achieved by a water-based paint containing a modified polyrotaxane in which all or part of the modifying group of the cyclic molecule is modified with a carboxylate.

  The aqueous paint containing the modified polyrotaxane of the present invention is a paint having improved dispersibility of the modified polyrotaxane in water or an aqueous solvent. Moreover, since the modified | denatured polyrotaxane can be disperse | distributed to various solvent seed | species in the water-based paint of this invention, the freedom degree of material selection, such as an additive, spreads.

  In addition, the water-based coating film formed using the water-based paint of the present invention is excellent in smoothness, scratch resistance, base protection, removability, water resistance, moisture resistance, acid resistance, bird dropping resistance, and stretchability. .

1 is a schematic diagram conceptually showing the basic structure of a modified polyrotaxane according to the present invention. It is a schematic diagram which shows notionally a crosslinked structure type modified polyrotaxane. It is a schematic sectional drawing which shows the structural example of the laminated coating film containing the clear coating film of this invention. It is a schematic sectional drawing which shows the structural example of the coating protective film of this invention.

  The present invention includes a cyclic molecule having a modifying group and in which all or a part of the modifying group is modified into a carboxylate, a linear molecule that includes the cyclic molecule in a skewered manner, and the linear Provided is a water-based paint comprising a modified polyrotaxane having a blocking group which is disposed at both ends of a molecule and prevents the elimination of the cyclic molecule. In the present specification, a cyclic molecule having a modifying group and obtained by modifying all or part of the modifying group into a carboxylate salt is also simply referred to as “modified cyclic molecule”. Also simply called “cyclic molecule”. The linear molecule that includes the cyclic molecule in a skewered manner is also simply referred to as “linear molecule”. Furthermore, a blocking group that is disposed at both ends of the linear molecule and prevents the elimination of the cyclic molecule is also simply referred to as a “blocking group”.

  The present invention uses a modified polyrotaxane having a cyclic molecule, a linear molecule, and a blocking group, wherein a modified group is introduced into the cyclic molecule and at least a part of the modified group is modified to a carboxylate. There is a feature in doing. In such a modified polyrotaxane, since at least a part of the modifying group introduced into the cyclic molecule is converted to a carboxylate, the dispersibility in water or an aqueous solvent is further improved. In addition, this modified polyrotaxane can diversify the types of aqueous solvents that can be used by improving the dispersibility in water and aqueous solvents. For this reason, when the water-based paint of the present invention is used, for example, for the formation of a surface paint film or a surface protective film on an object such as a clear paint film or a paint protective film of a vehicle body, the water-based paint film obtained is excellent. Shows smoothness. In addition, polyrotaxane can exhibit excellent stretchability, viscoelasticity, and mechanical strength based on the pulley effect due to its structure, and this effect is maintained even with a modified polyrotaxane. For this reason, when the water-based paint of the present invention is used, for example, in the formation of a surface paint film or a surface protective film on an object such as a clear paint film or a paint protective film on a vehicle body, It can also exhibit scratch resistance, chipping resistance, bird dropping resistance, and stretchability. In the present invention, the modifying group may have any of hydrophilic, hydrophobic, and amphiphilic properties, but is preferably a hydrophobic modifying group.

  Hereinafter, the present invention will be described in detail. In the present specification, “mass” and “weight”, “mass%” and “wt%”, “mass part” and “part by weight” are synonyms, and “%” is a mass percentage unless otherwise specified. (Mass%) is meant. Moreover, when there is no notice in particular regarding the measurement of a physical property etc., it measures at room temperature (20-25 degreeC) / 40-50% of relative humidity.

  As described above, the modified polyrotaxane according to the present invention is obtained by modifying at least a part of the modifying group of the cyclic molecule into a carboxylate, and such modification improves dispersibility in water or an aqueous solvent. . The water-based paint of the present invention contains the modified polyrotaxane.

FIG. 1 is a schematic diagram conceptually showing the basic structure of a modified polyrotaxane according to the present invention. In FIG. 1, the modified polyrotaxane 1 includes a cyclic molecule 2, a linear molecule 3 penetrating through the opening of the cyclic molecule 2, and a blocking group 4 bonded to both ends of the linear molecule 3. Become. Here, the blocking group 4 serves to prevent the cyclic molecule 2 from detaching from the linear molecule 3. With the above structure, when an external stress is applied, the cyclic molecule 2 freely moves along the linear molecule 3 (pulley effect). For this reason, the water-based coating film formed using the water-based paint of the present invention is excellent in stretchability and viscoelasticity, and has excellent characteristics that the film is not cut or easily damaged. Therefore, the water-based coating film formed using the water-based paint of the present invention is excellent in scratch resistance (chipping resistance), bird dropping resistance, stretchability, and base protection. The cyclic molecule 2 has a modifying group 2a, and all or part of the modifying group is modified with a carboxylate 2b. Thus, the presence of the carboxylate improves the dispersibility of the modified polyrotaxane in water or an aqueous solvent and can be suitably blended as a component of the aqueous paint. Therefore, the water-based paint of the present invention is a paint using water or a water-based solvent corresponding to various applications. Moreover, since the modified polyrotaxane can be uniformly dispersed in the water-based paint, the water-based coating film formed using the water-based paint is also excellent in smoothness.

  In addition, the expression of dispersibility in water and aqueous solvents as described above is based on the reaction field of water or aqueous solvent, typically a cross-linking field, with respect to polyrotaxanes that have been hardly soluble or insoluble in water or aqueous solvents. Is to provide. That is, the modified polyrotaxane according to the present invention has improved reactivity so that crosslinking with other polymers can be easily performed in the presence of water or an aqueous solvent.

  As described above, the modified polyrotaxane according to the present invention is a polyrotaxane having a cyclic molecule, a linear molecule, and a blocking group, wherein a modifying group is introduced into the cyclic molecule and at least a part of the modifying group is carboxylated. It has a structure modified to an acid salt.

  Here, the cyclic molecule is not particularly limited as long as it has a cyclic structure and is included in a linear molecule and exerts a pulley effect. In the present specification, the “annular structure” does not necessarily have a closed ring shape. That is, it is sufficient that the cyclic molecule has a substantially cyclic structure, for example, a “C” shape.

  The cyclic molecule preferably has a reactive group. This facilitates the introduction of modifying groups and the like. Examples of such a reactive group include, but are not limited to, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, a thiol group, and an aldehyde group. The reactive group is preferably a group that does not react with the blocking group when a blocking group described later is formed (blocking reaction). Considering such points, the reactive group is preferably a hydroxyl group, an epoxy group, or an amino group, and particularly preferably a hydroxyl group.

Specifically, examples of the cyclic molecule include cyclodextrin, crown ethers, benzocrowns, dibenzocrowns, dicyclohexanocrowns, and derivatives and modified products thereof. Of these, cyclodextrin and cyclodextrin derivatives are preferably used. Here, the types of cyclodextrin and cyclodextrin derivatives are not particularly limited. The cyclodextrin may be any of α-type, β-type, γ-type, δ-type, and ε-type. The cyclodextrin derivative may be any of α-type, β-type, γ-type, δ-type, and ε-type. The cyclodextrin derivative is intended to be a chemical modification such as amino, tosyl, methyl, propyl, monoacetyl, triacetyl, benzoyl, sulfonyl, and monochlorotriazinyl. It is. More specific examples of cyclodextrins and cyclodextrin derivatives that can be used in the present invention include α-cyclodextrin (glucose number = 6), β-cyclodextrin (glucose number = 7), γ-cyclodextrin (glucose). Cyclodextrin; dimethylcyclodextrin, glucosylcyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2,6-di-O-methyl-α-cyclodextrin, 6-O-α- Maltosyl-α-cyclodextrin, 6-O-α-D-glucosyl-α-cyclodextrin mono, hexakis (2,3,6-tri-O-acetyl) -α-cyclodextrin, hexakis (2,3,6 -Tri-O-methyl) -α-cyclodextrin, hexakis (6-O-toshi ) -Α-cyclodextrin, hexakis (6-amino-6-deoxy) -α-cyclodextrin, hexakis (2,3-acetyl-6-bromo-6-deoxy) -α-cyclodextrin, hexakis (2, 3,6-tri-O-octyl) -α-cyclodextrin, mono (2-O-phosphoryl) -α-cyclodextrin, mono [2, (3) -O- (carboxylmethyl)]-α-cyclodextrin , Octakis (6-Ot-butyldimethylsilyl) -α-cyclodextrin, succinyl-α-cyclodextrin, glucuronylglucosyl-β-cyclodextrin, heptakis (2,6-di-O-methyl) -β Cyclodextrin, heptakis (2,6-di-O-ethyl) -β-cyclodextrin, heptakis (6-O-sulfur E) -β-cyclodextrin, heptakis (2,3-di-O-acetyl-6-O-sulfo) -β-cyclodextrin, heptakis (2,3-di-O-methyl-6-O-sulfo) -Β-cyclodextrin, heptakis (2,3,6-tri-O-acetyl) -β-cyclodextrin, heptakis (2,3,6-tri-O-benzoyl) -β-cyclodextrin, heptakis (2, 3,6-tri-O-methyl) -β-cyclodextrin, heptakis (3-O-acetyl-2,6-di-O-methyl) -β-cyclodextrin, heptakis (2,3-O-acetyl- 6-bromo-6-deoxy) -β-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, hydroxypropyl-β-cyclodextrin, 2-hydroxypro Ru-β-cyclodextrin, (2-hydroxy-3-N, N, N-trimethylamino) propyl-β-cyclodextrin, 6-O-α-maltosyl-β-cyclodextrin, methyl-β-cyclodextrin, Hexakis (6-amino-6-deoxy) -β-cyclodextrin, bis (6-azido-6-deoxy) -β-cyclodextrin, mono (2-O-phosphoryl) -β-cyclodextrin, hexakis [6- Deoxy-6- (1-imidazolyl)]-β-cyclodextrin, monoacetyl-β-cyclodextrin, triacetyl-β-cyclodextrin, monochlorotriazinyl-β-cyclodextrin, 6-O-α-D- Glucosyl-β-cyclodextrin, 6-O-α-D-maltosyl-β-cyclodextrin, Sinyl-β-cyclodextrin, succinyl- (2-hydroxypropyl) -β-cyclodextrin, 2-carboxymethyl-β-cyclodextrin, 2-carboxyethyl-β-cyclodextrin, butyl-β-cyclodextrin, sulfopropyl -Β-cyclodextrin, 6-monodeoxy-6-monoamino-β-cyclodextrin, silyl [(6-Ot-butyldimethyl) 2,3-di-O-acetyl] -β-cyclodextrin, 2- Hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, butyl-γ-cyclodextrin, 3A-amino-3A-deoxy- (2AS, 3AS) -γ-cyclodextrin, mono-2-O- (P-toluenesulfonyl) -γ-cyclodextrin, Mono-6-O- (p-toluenesulfonyl) -γ-cyclodextrin, mono-6-O-mesitylenesulfonyl-γ-cyclodextrin, octakis (2,3,6-tri-O-methyl) -γ-cyclo Dextrin, octakis (2,6-di-O-phenyl) -γ-cyclodextrin, octakis (6-Ot-butyldimethylsilyl) -γ-cyclodextrin, octakis (2,3,6-tri-O— Acetyl) -γ-cyclodextrin, and the like. Here, the above-mentioned cyclic molecules such as cyclodextrin can be used singly or in combination of two or more. Among the cyclic molecules, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and derivatives thereof are preferable. From the viewpoint of inclusion, α-cyclodextrin and derivatives thereof should be used. Is particularly preferred.

  The number (inclusion amount) of the cyclic molecule included in the linear molecule is not particularly limited, and can be appropriately selected depending on the dispersibility in a desired solvent, the type of the modifying group, and the like. Specifically, the number (inclusion amount) of the cyclic molecule included in the linear molecule is 0.06 to 0 when the maximum inclusion amount that the linear molecule can include the cyclic molecule is 1. 0.61 is preferable, 0.11 to 0.48 is more preferable, and 0.24 to 0.41 is particularly preferable.

  In the present specification, the "maximum inclusion amount that a linear molecule can include a cyclic molecule" means the number of cyclic molecules when the cyclic molecule is included in the linear molecule without a gap. It can be calculated by an equation.

  Here, the chain length of the linear molecule can be easily determined from its molecular weight (weight average molecular weight). The thickness of the cyclic molecule is also known, for example, about 0.7 nm in the case of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

  In the present invention, the cyclic molecule has a modifying group. By introducing the modifying group into the cyclic molecule, the dispersibility in a solvent can be improved to some extent, and the reactivity with other polymers can be improved. Here, the modifying group included in the cyclic molecule is preferably the following modifying group. For example, an alkyl group, a benzyl group, a benzene derivative-containing group, an acyl group, a silyl group, a trityl group, a tosyl group, or the like, wherein the group is bonded to a urethane bond, an ester bond or an ether bond, or the two groups are the above Examples thereof include a group bonded through any bond.

  Further, when the modified polyrotaxane according to the present invention has a plurality of cyclic molecules, it is not necessary that all of the reactive groups of the cyclic molecules are modified with a modifying group. In other words, as long as the modified polyrotaxane as a whole exhibits dispersibility in a desired solvent by modification to the next carboxylate, there may be any partial presence of a cyclic molecule having a hydroxyl group that is not modified by the modifying group. . Further, when the modified polyrotaxane has a plurality of cyclic molecules, the modifying group may be introduced uniformly or non-uniformly throughout the cyclic molecule. However, considering various properties to be provided as a coating material, such as dispersibility in solvents, mechanical strength, and excellent stretchability and viscoelasticity based on the pulley effect, the modifying group is uniform throughout the cyclic molecule (substantially Are preferably introduced in such a way that the same number or ratio of modifying groups are present in each cyclic molecule).

  Here, the average modification degree by the modifying group of the cyclic molecule is not particularly limited, and can be appropriately selected depending on the dispersibility in a desired solvent, the kind of the cyclic molecule, and the like. The average degree of modification by the modifying group of the cyclic molecule is preferably 0.02 or more, more preferably 0.04 or more, when the maximum number that the reactive group of the cyclic molecule can be modified is 1. It is especially preferable that it is 0.06 or more. Note that insoluble bumps (protrusions derived from adhesion of foreign substances) may be generated during coating film formation. In the present specification, the “maximum number of reactive groups of a cyclic molecule that can be modified” means the total number of reactive groups that the cyclic molecule had before modification with the modifying group. The “average degree of modification” is the ratio of the total number of reactive groups modified to the total number of reactive groups in one cyclic molecule of the modified polyrotaxane. For example, when α-cyclodextrin is used as a cyclic molecule, since α-cyclodextrin has 18 hydroxyl groups as reactive groups, the total number of reactive groups of polyrotaxane before modification is 18 × (number of α-cyclodextrins). It becomes. Of these, assuming that a total of n reactive groups are modified with a modifying group, the average modification degree is n / (18 × (number of α-cyclodextrin)).

  In the present invention, at least a part of the modifying group is modified to a carboxylate. By such modification, dispersibility in water or an aqueous solvent can be improved. Here, it is not necessary for all of the modifying groups to be modified to carboxylate. In other words, as long as the modified polyrotaxane, which is the final product, exhibits dispersibility in a desired solvent, there may be any partial modification groups that are not modified in the carboxylate. In addition, when the modified polyrotaxane has a plurality of cyclic molecules, the carboxylate may be modified evenly by modifying the modifying group so as to be uniform over the entire cyclic molecule or in a non-uniform state. Good. However, in consideration of various properties to be provided as a coating material such as dispersibility in a solvent, mechanical strength, and excellent stretchability and viscoelasticity based on the pulley effect, the carboxylate is uniform over the entire cyclic molecule. Thus, it is preferable to modify the modifying group. That is, it is preferred that substantially the same number of carboxylates be present for each cyclic molecule.

  The degree of modification of the modifying group by the carboxylate is not particularly limited, and can be appropriately selected depending on the dispersibility in a desired solvent, the type of the modifying group, and the like. The degree of modification of the modifying group by the carboxylate is preferably 10 to 50%, more preferably 20 to 40%, based on the total number of modifying groups. If it is such a range, the dispersibility to sufficient solvent, especially sufficient dispersibility to water or an aqueous solvent can be shown. In addition, although the modification degree of the modifying group by the carboxylate is described in detail below, it can be appropriately controlled by the addition amount of the acid anhydride and the amine compound.

  The carboxylate is not particularly limited as long as the dispersibility in water or an aqueous solvent can be improved. Specifically, the carboxylate has a group represented by the following formula (1).

In the above formula ^{(1), R 1, R} 2 and ^{R 3} represents a hydrogen atom or a hydrocarbon group which may have a branched chain having 1 to 8 carbon atoms. Here, R ¹ , R ² and R ³ may be the same or different from each other. The hydrocarbon group which may have a branched chain having 1 to 8 carbon atoms is not particularly limited, but for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec A linear or branched chain having 1 to 8 carbon atoms, such as -butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, etc. An alkyl group; a cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; phenyl, benzyl, phenethyl, o-, m- or p-tolyl, 2, 3 -Or 2,4-xylyl, mesityl, naphthyl, anthryl, phenanthryl, biphenylyl, benzhydryl, trityl and pyrenyl, etc. An aryl group having 6 to 20 carbon atoms can be mentioned. Among these, R ¹ , R ² and R ³ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group, A hydrogen atom and an ethyl group are even more preferable, and an ethyl group is particularly preferable. R ⁴ represents a modifying group obtained by modifying a hydroxyl group of a hydroxyalkyl group with a lactone derivative. Preferably, R ⁴ represents a modifying group obtained by modifying a hydroxyl group of a hydroxypropyl group with a lactone derivative. With such a carboxylate form, the resulting modified polyrotaxane exhibits particularly excellent dispersibility in water and aqueous solvents.

  The modified polyrotaxane according to the present invention further has a linear molecule that includes the cyclic molecule in a skewered manner. The linear molecule may be substantially linear, and may have a branched chain as long as the cyclic molecule as a rotor can be rotated and can be included so as to exert a pulley effect. Further, although it is affected by the size of the cyclic molecule, the length of the linear molecule (molecular weight of the linear molecule) is not particularly limited as long as the cyclic molecule can exhibit the pulley effect.

  The material of the linear molecule is not particularly limited, but preferably has a reactive group at both ends. Thereby, it can be made to react easily with the said blocking group, and a blocking group can be introduce | transduced into the both ends of a linear molecule. Such a reactive group is not particularly limited and can be appropriately changed depending on the type of linear molecule or blocking group employed, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, and a thiol group. .

Such a linear molecule is not particularly limited. Specifically, the linear molecules include polyalkylenes such as polyethylene and polypropylene; polyesters such as polycaprolactone and polyvalerolactone; polyethers such as polyethylene glycol and polypropylene glycol; polyamides; poly (meth) Acrylics; and linear molecules having a benzene ring. Of these linear molecules, polyester and polyether are preferable, polyethylene glycol, polypropylene glycol, and polycaprolactone are more preferable, and polyethylene glycol is particularly preferable from the viewpoint of dispersibility in water or an aqueous solvent.

Further, the molecular weight (weight average molecular weight) of the linear molecule is not particularly limited, and can be appropriately selected depending on the kind of the cyclic molecule, the inclusion amount, and the like. The molecular weight of the linear molecule is preferably in the range of 10,000 to 60,000, more preferably 15,000 to 40,000, and particularly preferably 20,000 to 35,000. Within such a range, a sufficient number of cyclic molecules can be included in the linear molecule. If the molecular weight of the linear molecule is less than 10,000, the pulley effect due to the cyclic molecule may not be sufficiently obtained, and the elongation percentage of the coating film may decrease. In such a case, when the modified polyrotaxane is used as a coating film, the scratch resistance of the coating film may be lowered. Moreover, when molecular weight exceeds 50,000, the dispersibility to water or an aqueous solvent may fall. In such a case, the smoothness of the coating film may be inferior when the modified polyrotaxane is used as the coating film. The molecular weight is determined by gel permeation chromatography (GPC: Gel
Permeation Chromatography) and other known methods.

  The modified polyrotaxane according to the present invention further has blocking groups arranged at both ends of the linear molecule in order to prevent elimination of the cyclic molecule. The blocking group is not particularly limited as long as it is a group that is arranged at both ends of a linear molecule and can maintain a state in which a cyclic molecule is pierced by a linear molecule. For example, a group having “bulkyness” or a group having “ionicity” can be used. Here, the “group” means various groups including a molecular group and a polymer group. The group having “bulkyness” is a group that mainly prevents the elimination of the cyclic molecule depending on its size, and examples thereof include a spherical shape and a side wall-shaped group. In addition, the group having “ionicity” is mainly caused by the interaction of the ionicity of the cyclic molecule, for example, the repulsive action, and the cyclic molecule is skewed into the linear molecule due to the ionicity of the blocking group. It is a group that maintains the state.

  Examples of the substance having such a blocking group include compounds having a dinitrophenyl group such as 2,4-dinitrophenyl group and 3,5-dinitrophenyl group, adamantanes such as cyclodextrins and adamantamine, and trityl. Examples thereof include compounds having a group, fluoresceins, and pyrenes; and derivatives and modified products thereof. Note that the substance having a blocking group is not limited to the above as long as it can prevent the elimination of the cyclic molecule.

The method for producing the modified polyrotaxane according to the present invention is not particularly limited. Below, although the preferable form of the manufacturing method of the modification | denaturation polyrotaxane based on this invention is described, this invention is not limited to the following method. As a preferable form of the manufacturing method of the modified polyrotaxane according to the present invention, the following steps (1) to (4) are included.
(1) A step of mixing a cyclic molecule and a linear molecule, penetrating through the opening of the cyclic molecule with a linear molecule in a skewered manner, and enclosing the cyclic molecule in the linear molecule to obtain a pseudopolyrotaxane;
(2) By blocking both ends (both ends of the linear molecule) of the linear molecule of the pseudopolyrotaxane obtained in (1) above with a blocking group, the cyclic molecule is not detached from the linear molecule. Adjusting to obtain a polyrotaxane;
(3) a step of obtaining a modified polyrotaxane by modifying a reactive group (for example, a hydroxyl group) of the polyrotaxane cyclic molecule obtained in (2) above with a modifying group; and (4) obtained in (3) above. A step of further modifying the modifying group of the modified polyrotaxane into a carboxylate.

First, a cyclic molecule and a linear molecule are mixed, and the opening of the cyclic molecule is penetrated by the linear molecule in a skewered manner so that the cyclic molecule is included in the linear molecule to obtain a pseudopolyrotaxane.

  Here, the linear molecule may be oxidized before mixing with the cyclic molecule. For example, when a linear molecule has a hydroxyl group as a reactive group, when the linear molecule is oxidized, a carboxyl group is introduced into at least a part (preferably a terminal part). In this way, by oxidizing the linear molecule in advance, the reactivity with both ends of the pseudo-polyrotaxane linear molecule is increased in the next step (2), so that it is easy to introduce a blocking group to oxidize the cyclic molecule. There is an advantage of preventing.

  At this time, the oxidation method of the linear molecule is not particularly limited, and a known oxidation method can be used. Examples thereof include TEMPO (2,2,6,6-tetramethyl-piperidinyloxy radical). The oxidation conditions are not particularly limited, and known oxidation conditions can be applied similarly or appropriately modified.

  The details of the oxidation method of a linear molecule, the formation of an inclusion complex between a linear molecule and a cyclic molecule oxidized with a carboxylic acid group at the end, and the blocking reaction using adamantaneamine are disclosed in International Publication WO 2005-052026. It is described in. The polyrotaxane used in the present invention was prepared with reference to the above International Publication.

  Next, the reactive group (for example, hydroxyl group) of the polyrotaxane cyclic molecule obtained above is modified with a modifying group to obtain a modified polyrotaxane.

  Here, the method for introducing the modifying group into the cyclic molecule of polyrotaxane is not particularly limited. For example, an alkylene oxide is added to the polyrotaxane obtained above to react the reactive group of the cyclic molecule with the alkylene oxide. Here, the polyrotaxane is preferably dissolved in a suitable solvent. In this case, the suitable solvent is not particularly limited as long as it can dissolve the polyrotaxane, but considering the solubility, an alkaline solution is preferable. For example, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. are mentioned.

  In the above method, the alkylene oxide is not particularly limited, but an alkylene oxide having 2 to 4 carbon atoms is preferable. Specific examples include ethylene oxide, propylene oxide, and butylene oxide. Of these, propylene oxide and butylene oxide are more preferable. One of these alkylene oxides may be used alone, or two or more thereof may be used in the form of a mixture. The addition amount of the alkylene oxide is not particularly limited, and is preferably such an amount that the degree of modification by the modifying group of the cyclic molecule as described above is obtained. Specifically, the amount of alkylene oxide added is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, based on the total number of reactive groups in the polyrotaxane.

  Addition of alkylene oxide and reaction conditions are not particularly limited, but it is preferably carried out usually at 10 to 30 ° C. in an aqueous sodium hydroxide solution. Detailed conditions are described in International Publication WO2005-080469.

Next, a lactone derivative is added to the hydroxyalkylated polyrotaxane to further modify the hydroxyalkyl of the cyclic molecule with the lactone derivative. Here, the lactone derivative is not particularly limited. Examples include ε-caprolactone, γ-butyrolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, and the like. Of these, ε-caprolactone, γ-butyrolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone and δ-valerolactone are preferred, and ε-caprolactone is particularly preferred. One of these lactone derivatives may be used alone, or two or more thereof may be used in the form of a mixture. The addition amount of the lactone derivative is not particularly limited, and is preferably such an amount that the degree of modification by the modifying group of the cyclic molecule as described above is obtained. Specifically, the addition amount of the lactone derivative is preferably 1 to 4.5 times, more preferably 3.5 to 4.5 times the weight of the polyrotaxane.

  The addition / reaction conditions for the lactone derivative are not particularly limited. For example, a lactone derivative is added to the hydroxyalkylated polyrotaxane to carry out the reaction. In this case, the reaction may be performed only with the hydroxyalkylated polyrotaxane and the lactone derivative, but it is preferable to perform the reaction in the presence of a catalyst. The catalyst which can be used here is not particularly limited, and a known catalyst can be used. For example, 2-ethylhexanoic acid tin etc. are mentioned. Moreover, it is preferable to perform the said reaction normally at 80-100 degreeC for 4 hours. In addition, you may stir the said reaction so that a solution may become uniform. Here, the stirring may be performed before the above reaction or simultaneously with the above reaction, but it is preferable to add the catalyst after stirring in advance before the reaction. After the above addition and, if necessary, stirring, precipitation with an appropriate solvent, centrifugation, dialysis, freeze drying, hot air drying, vacuum distillation, vacuum drying, vacuum drying, and the like may be performed. Thereby, the modified polyrotaxane in which the modifying group of the cyclic molecule is modified with the lactone derivative is obtained.

  Next, the modifying group of the modified polyrotaxane is further modified to a carboxylate to obtain the modified polyrotaxane according to the present invention. Thereby, the modified polyrotaxane according to the present invention is particularly improved in dispersibility in water or an aqueous solvent. Here, the modification method of the modified group of the modified polyrotaxane into the carboxylate is not particularly limited. Specifically, an acid anhydride is added to the modified polyrotaxane and reacted. Here, the acid anhydride is an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, or a t-butylene group, and is a straight chain or branched chain having 1 to 4 carbon atoms. Examples thereof include acid anhydrides having at least any one of a chain alkylene group, a phenylene group, and a naphthalene group, and an aryl group having 6 to 20 carbon atoms. More specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, acid anhydrides of terephthalic acid and the like can be mentioned. Of these, succinic acid and isophthalic anhydride are preferable, and succinic anhydride is more preferable. The acid anhydrides may be used alone or in the form of a mixture of two or more.

  The mixing ratio of the acid anhydride and the modified polyrotaxane is not particularly limited, and is preferably an amount that gives a modification degree of the modifying group by the carboxylate as described above. Specifically, the acid anhydride is mixed with respect to 100 parts by mass of the modified polyrotaxane, preferably 1 to 10 parts by mass, more preferably 5 to 8 parts by mass. Moreover, the addition amount of the acid anhydride is not particularly limited, and is preferably an amount that gives a modification degree of the modifying group by the carboxylate as described above. Specifically, the amount of acid anhydride added is preferably 10 to 50 mol%, more preferably 20 to 40 mol%, based on the total number of reactive groups in the polyrotaxane.

The reaction between the acid anhydride and the modified polyrotaxane may be performed in the absence of a solvent or in a solvent, but is preferably performed in a solvent. In this case, the solvent is not particularly limited as long as it can dissolve the modified polyrotaxane and the acid anhydride. Specifically, toluene and dehydrated toluene. The said solvent may be used independently or may be used with the form of a 2 or more types of mixture. Moreover, the addition amount of the said solvent will not be restrict | limited especially if the said reaction advances. Specifically, the amount is such that the concentration of the modified polyrotaxane in the solvent is 10 to 25% by mass. The reaction conditions are not particularly limited as long as the reaction between the acid anhydride and the modified polyrotaxane proceeds. Preferably, the mixture of the acid anhydride and the modified polyrotaxane is reacted at 30 to 80 ° C. for 2 to 3 hours. In addition, you may stir the said reaction so that a solution may become uniform. Here, stirring may be performed either before the above reaction or simultaneously with the above reaction, but it is preferable to carry out the reaction while stirring. Thereby, carboxylic acid can be uniformly introduced into the modifying group. After the above addition and, if necessary, stirring, precipitation with an appropriate solvent, centrifugation, dialysis, freeze drying, hot air drying, vacuum distillation, vacuum drying, vacuum drying, and the like may be performed. Thereby, a carboxylic acid-modified polyrotaxane in which the modifying group of the cyclic molecule is modified with a carboxylic acid is obtained.

Thereafter, an amine compound is added to the carboxylic acid-modified polyrotaxane and reacted (neutralized) to obtain the modified polyrotaxane according to the present invention. Here, the amine compound is not particularly limited and is appropriately selected depending on the structure of the desired modified polyrotaxane. Specifically, examples of the amine compound include ammonia; primary amines such as methylamine and ethylamine; secondary amines such as dimethylamine and diethylamine; tertiary amines such as trimethylamine and triethylamine. Of these, tertiary amines are preferred, and trimethylamine and triethylamine are particularly preferred. The above amine compounds may be used alone or in the form of a mixture of two or more. In addition, when using ammonia among the said amine compounds, the method of blowing ammonia gas in the solution containing a carboxylic acid modification polyrotaxane etc. can be used. By such a method, the carboxyl group of the carboxylic acid-modified polyrotaxane is modified to a carboxylate, and a modified polyrotaxane in which R ^{1 to} R ³ in the above formula (1) are hydrogen atoms can be produced.

  The mixing ratio of the amine compound and the carboxylic acid-modified polyrotaxane is not particularly limited, and is preferably an amount that provides the degree of modification of the modifying group by the carboxylate as described above. Specifically, the amine compound is mixed so that it is preferably 1 to 10 parts by mass, more preferably 5 to 8 parts by mass with respect to 100 parts by mass of the carboxylic acid-modified polyrotaxane. Moreover, the addition amount of the amine compound is not particularly limited, and is preferably such an amount that the degree of modification of the modifying group by the carboxylate is as described above. Specifically, the addition amount of the amine compound is preferably 10 to 50 mol%, more preferably 20 to 40 mol%, based on the total number of reactive groups in the polyrotaxane.

  The neutralization reaction of the carboxylic acid-modified polyrotaxane with the amine compound may be performed in the absence of a solvent or in a solvent, but is preferably performed in a solvent. In this case, as the solvent, the solvent of the carboxylic acid-modified polyrotaxane obtained by the above reaction may be used as it is, or when the amine compound is liquid, the amine compound may be used as the solvent. Moreover, it is preferable that the pH of the solution after neutralization reaction is about 7-8. As a result, the carboxylic acid can be appropriately modified (neutralized) into the carboxylate. After the above reaction, precipitation with an appropriate solvent, centrifugation, dialysis, freeze drying, hot air drying, vacuum distillation, vacuum drying, vacuum drying and the like may be performed. Thereby, the modified polyrotaxane according to the present invention in which the modifying group of the cyclic molecule is modified with the carboxylate is obtained.

  For the purpose of better understanding the above method, the modification group of the modified polyrotaxane is modified to a carboxylate salt when succinic anhydride is used as the acid anhydride of the dicarboxylic acid and triethylamine is used as the amine compound. The reaction to be performed is shown in the following reaction formula 1. In addition, the following reaction formula 1 aims at understanding the present invention more clearly, and does not limit the present invention.

  The modified polyrotaxane according to the present invention can be produced by the method as described above. In the above method, the modification with the modifying group and the modification of the carboxylate were performed after producing the polyrotaxane, but the present invention is not limited to this order. For example, after modifying the hydroxyl group of the cyclic molecule with a modifying group in advance, and further modifying the modifying group with a carboxylate salt, the modified cyclic molecule is included in the linear molecule, and is further attached to both ends of the linear molecule. Even when a blocking group is introduced, a modified polyrotaxane excellent in dispersibility in water or an aqueous solvent can be obtained. Alternatively, after the hydroxyl group of the cyclic molecule is previously modified with a modifying group, the modified cyclic molecule is included in a linear molecule, and in this state, the modifying group is modified with a carboxylate salt. Even if blocking groups are introduced at both ends, a modified polyrotaxane excellent in dispersibility in water or an aqueous solvent can be obtained. Alternatively, after modifying the hydroxyl group of the cyclic molecule with a modifying group in advance, the modified cyclic molecule is included in the linear molecule, and after introducing blocking groups at both ends of the linear molecule, Even when the carboxylate is modified, a modified polyrotaxane excellent in dispersibility in water or an aqueous solvent can be obtained.

In the present invention, the modified polyrotaxane may have a crosslinked structure as long as it can be dispersed in water or the above aqueous solvent. Such a modified polyrotaxane having a crosslinked structure (also referred to as “crosslinked structure-type modified polyrotaxane”) can be used in place of or in combination with the non-crosslinked modified polyrotaxane. Examples of such a crosslinked structure type modified polyrotaxane include a modified polyrotaxane crosslinked with a polymer having a relatively low molecular weight, typically a polymer having a molecular weight of about several thousand. Here, in general, the crosslinked structure type modified polyrotaxane refers to a crosslinked polyrotaxane and another polymer, which will be described in detail below. However, when the coating film is formed, the modified polyrotaxane forms a coating film such as a polymer. Cross-linked with ingredients. This coating film-forming component is bonded to the polyrotaxane via the polyrotaxane cyclic molecule.

  In the present invention, the crosslinked structure type modified polyrotaxane may have other functional groups in addition to the modifying group and the carboxylate. Thereby, the reactivity with another polymer can be improved. Such a functional group is not particularly limited, but it is preferably three-dimensionally structured to be outside a cyclic molecule, for example, cyclodextrin, and can be easily reacted using this functional group when bonded or crosslinked with a polymer. . Such a functional group can be appropriately changed depending on, for example, the type of solvent used when a crosslinking agent is not used. On the other hand, when using a crosslinking agent, it can change suitably according to the kind of the crosslinking agent to be used.

  Furthermore, in the present invention, specific examples of the functional group may include, for example, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, a thiol group, and an aldehyde group, but are not limited thereto. . In the modified polyrotaxane according to the present invention, the above-mentioned functional groups may be used alone or in combination of two or more.

  Such functional groups are particularly residues of compounds bonded to the hydroxyl group of cyclodextrin, and those having a hydroxyl group, a carboxyl group, an amino group, an epoxy group, or an isocyanate group are good, and there are various reactions. From the viewpoint of properties, a hydroxyl group is preferred. Examples of the compound that forms such a functional group include ε-caprolactone, but are not limited thereto. For example, if the effect of improving the dispersibility of the polyrotaxane in water or an aqueous solvent is not significantly reduced, the compound that forms the functional group may be a polymer. From the viewpoint of dispersibility, for example, the molecular weight is about several thousand. It is desirable that

FIG. 2 is a schematic view conceptually showing such a crosslinked structure-type modified polyrotaxane. In the figure, the crosslinked structure-type modified polyrotaxane 6 has the above-mentioned polyrotaxane 1 and polymer 7, and this polyrotaxane 1 Are linked to the polymer 7 and the polymer 7 ′ by the crosslinking point 8 via the cyclic molecule 2. The cyclic molecule 2 shown in this figure has a modifying group 2a and a carboxylate 2b as shown in FIG. When the cross-linked structure-modified polyrotaxane 6 having such a configuration is loaded with a deformation stress in the direction of arrow XX ′ in FIG.
The crosslinked structure type modified polyrotaxane 6 can be deformed and absorb this stress as shown in FIG. That is, as shown in FIG. 2 (B), the cyclic molecule 2 can move along the linear molecule 3 due to the pulley effect, so that it can be easily deformed, and internal absorption of the stress is possible. . As described above, the crosslinked structure type modified polyrotaxane has a pulley effect as shown in the figure, and has excellent stretchability, viscoelasticity, and mechanical strength as compared with a conventional gel-like material. Moreover, the modified polyrotaxane (carboxylate-modified polyrotaxane), which is a precursor of the crosslinked structure-type modified polyrotaxane, has improved dispersibility in water and aqueous solvents as described above, such as crosslinking in water and aqueous solvents. Is easy.

  As described above, since the water-based paint of the present invention uses a crosslinked structure-type modified polyrotaxane, it has excellent dispersibility in water and water-based solvents, and therefore exhibits excellent smoothness when forming a coating film. In addition, the polyrotaxane can exhibit excellent stretchability, viscoelasticity, and mechanical strength based on the pulley effect due to its structure, and this effect is maintained even with the crosslinked structure-type modified polyrotaxane. For this reason, the water-based paint of the present invention can also exhibit excellent scratch resistance, chipping resistance, bird dropping resistance, and stretchability when forming a coating film.

  The water-based paint of the present invention contains the water-based paint material of the present invention and the crosslinked structure type modified polyrotaxane, and the coating film of the present invention is formed by solidifying the water-based paint. The crosslinked structure type modified polyrotaxane can be easily obtained under conditions where water or an aqueous solvent is present, and in particular, can be easily obtained by crosslinking the modified polyrotaxane and a water-soluble coating film forming component.

  When the water-based paint of the present invention contains a crosslinked structure-type modified polyrotaxane, the modifying group, carboxylate or other functional group of the crosslinked structure-type modified polyrotaxane reacts with the film-forming component during coating film formation, By forming the structural-type modified polyrotaxane, a coating film having excellent scratch resistance and chipping resistance is obtained. In addition, cracks and the like hardly occur, and the weather resistance, contamination resistance, adhesion, and the like are excellent. Therefore, the water-based paint material of the present invention is a paint using a water-soluble coating film polymer, particularly a car paint required for car wash resistance, scratch resistance, chipping resistance, impact resistance and weather resistance, It can also be applied to paints for home appliances, and can exhibit an excellent pulley effect in these applications.

  From another point of view, the crosslinked structure-type modified polyrotaxane is obtained by combining the coating film-forming component and the polyrotaxane without impairing the physical properties of the coating film-forming component that is a crosslinking target of the modified polyrotaxane (carboxylate-modified polyrotaxane). It can be said that it was complexed.

  Therefore, as described below, by forming a crosslinked structure-type modified polyrotaxane in the coating film, a coating film having the physical properties of the coating film forming component and the physical properties of the hydrophilic polyrotaxane itself can be obtained, such as a polymer species. By selecting, a coating film having a desired mechanical strength can be obtained.

Here, the crosslinking of the modified polyrotaxane used in the present invention will be described. That is, the crosslinked structure type modified polyrotaxane is typically
(A) A modified polyrotaxane, which is a water-based coating material, is mixed with other coating film forming components,
(B) at least a part of the coating film-forming component is physically and / or chemically crosslinked;
(C) It can be formed by bonding at least a part of the coating film-forming component and the modified polyrotaxane via a cyclic molecule (curing reaction).

  In addition, since a crosslinked structure type modified polyrotaxane can be dispersed in water or an aqueous solvent, the steps (a) to (c) can be smoothly performed in water, an aqueous solvent, and a mixed solvent thereof. Moreover, these processes can be performed more smoothly by using a curing agent.

  In the steps (b) and (c), it is preferable to chemically cross-link. For example, the hydroxyl group contained in the cyclic molecule of the modified polyrotaxane as described above and the melamine resin which is an example of the paint forming component have a urethane bond. By repeating the formation, a crosslinked structure-type modified polyrotaxane is obtained. Moreover, you may implement the (b) process and the (c) process substantially simultaneously.

  The mixing step (a) depends on the coating film forming component to be used, but can be carried out in a solvent such as water or an aqueous solvent or without these solvents. Further, the solvent can be removed by heat treatment or the like when forming the coating film.

  The modified polyrotaxane according to the present invention can further improve dispersibility in water or an aqueous solvent by further modifying at least part of the modifying group introduced into the cyclic molecule into a carboxylate. Moreover, the kind of aqueous solvent which can be used can also be diversified by the improvement of the dispersibility to a solvent.

  As described above, since the water-based paint of the present invention uses a modified polyrotaxane excellent in dispersibility in a solvent, it exhibits excellent smoothness when forming a coating film. Polyrotaxane can exhibit excellent stretchability, viscoelasticity, and mechanical strength based on the pulley effect due to its structure, and this effect is maintained even with a modified polyrotaxane. For this reason, the water-based paint of the present invention can also exhibit excellent scratch resistance, chipping resistance, bird dropping resistance, and stretchability when forming a coating film.

The water-based paint of the present invention contains the water-based paint material of the present invention, that is, the above-described modified polyrotaxane (carboxylate-modified polyrotaxane), and the coating film of the present invention is formed by solidifying the water-based paint. Is.

  Here, the aqueous solvent means a solvent that interacts with water and has a strong affinity for water. Specifically, alcohols such as isopropyl alcohol, butyl alcohol, and ethylene glycol; ether esters such as cellosolve acetate, butyl cellosolve acetate, and diethylene glycol monoethyl ether; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Examples include glycol ethers such as propylene glycol monomethyl ether. These aqueous solvents may be used alone or in the form of a mixture of two or more. Further, it may be used as a mixture of an aqueous solvent and water. The modified polyrotaxane according to the present invention exhibits good dispersibility even in a solvent in which two or more of these are mixed. Of these, water, alcohols, and glycol ethers are preferably used, and water and glycol ethers are more preferably used. The water is not particularly limited, and any of tap water, deionized water, distilled water, filtered water and the like can be used. In addition, the solvent used in the water-based paint of the present invention may contain a slight amount of an organic solvent such as toluene as long as it has a strong affinity for water as a whole.

  In addition, the content of the modified polyrotaxane in the aqueous paint of the present invention is not particularly limited as long as it is an amount that can be dispersed in water or an aqueous solvent. Specifically, the content of the modified polyrotaxane is preferably 1 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 60% with respect to the coating film forming component (solid content) of the water-based paint. It is the range of mass%. Here, when the content of the modified polyrotaxane is less than 1% by mass, the pulley effect of the modified polyrotaxane cannot be sufficiently obtained, and the elongation rate of the coating film is lowered and the desired scratch resistance cannot be obtained. There is. On the contrary, when it exceeds 90 mass%, the smoothness as a coating film is impaired due to film formation on the surface, and the appearance may be deteriorated.

  The water-based paint of the present invention contains a modified polyrotaxane as an essential component, but may further contain other components. In this case, as other components, components used in ordinary water-based paints can be used in the same manner, and the type is not particularly limited. Specific examples include surfactants and aqueous solvents. Here, since an aqueous solvent is the same as that of the said illustration, description is abbreviate | omitted here. Moreover, it does not restrict | limit especially as surfactant, A well-known surfactant can be used. For example, alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate, saturated fatty acid salt, Anions such as saturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid surfactants, N-acyl amino acid surfactants, alkyl phosphate esters or salts thereof, alkenyl phosphate esters or salts thereof Surfactant: polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl Nonionic surfactants such as luglycoxide, fatty acid glycerin monoester, and alkylamine oxide; cationic surfactants such as quaternary ammonium salts; and amphoteric surfactants such as carboxyl-type amphoteric surfactants and sulfobetaine-type amphoteric surfactants Surfactant etc. are mentioned. Of these, nonionic surfactants are preferred, and polyoxyethylene octylphenyl ether is preferred. At this time, the content of the surfactant is not particularly limited, and may be the same amount as that usually used for water-based paints. Specifically, the content of the surfactant is 0.01 to 0.03% by mass with respect to the total mass of the water-based paint.

Further, the water-based paint of the present invention can be used in various forms depending on the application. For example, it can be obtained by blending the modified polyrotaxane according to the present invention into an existing water-based paint such as an acrylic melamine clear paint or a two-pack type urethane resin paint so as to have the above-mentioned content. In other words, in addition to the water, the aqueous solvent, and the surfactant, the modified polyrotaxane according to the present invention includes at least one selected from the group consisting of a resin component, a curing agent, an additive, a pigment, a brightening agent, and a solvent. It can obtain by mix | blending based on a conventional method and mixing.

  The resin component is not particularly limited, but the main chain or side chain is a hydroxyl group, amino group, carboxyl group, epoxy group, vinyl group, thiol group or photocrosslinking group, and any combination thereof. Those having a group are preferred. Among the above, examples of the photocrosslinking group include cinnamic acid, coumarin, chalcone, anthracene, styrylpyridine, styrylpyridinium salt, and styrylquinoline salt. Two or more kinds of resin components may be mixed and used. In this case, it is preferable that at least one kind of resin component is bonded to the polyrotaxane via a cyclic molecule.

  Such a resin component may be a homopolymer or a copolymer. In the case of a copolymer, it may be composed of two or more monomers, and may be a block copolymer, an alternating copolymer, a random copolymer or a graft copolymer.

  Specific examples include polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and other cellulose resins, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resins, Polyvinyl resins such as polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch and copolymers thereof, polyolefin resins such as polyethylene, polypropylene and copolymers with other olefin monomers, polyester resins such as alkyd resins, Polyvinyl chloride resin, polystyrene resin such as polystyrene and acrylonitrile-styrene copolymer resin, polymethyl methacrylate And acrylic resins such as (meth) acrylic acid ester copolymers, acrylonitrile-methyl acrylate copolymers, polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, and derivatives or modified products thereof. , Polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon (registered trademark), polyimides, polydienes such as polyisoprene and polybutadiene, and polydimethylsiloxane Siloxanes, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and these , And the like derivatives. As the derivative, those having the above-described hydroxyl group, amino group, carboxyl group, epoxy group, vinyl group, thiol group, photocrosslinking group, and a group related to a combination thereof are preferable. The resin component may be used alone or in the form of a mixture of two or more.

The said hardening | curing agent in particular is not restrict | limited, The hardening | curing agent normally used with a water-system coating material can be used similarly. Specifically, melamine resin, polyisocyanate compound (for example, hexamethylene diisocyanate), blocked isocyanate compound, cyanuric chloride, trimesoyl chloride, terephthaloyl chloride, epichlorohydrin, dibromobenzene, glutaraldehyde, phenylene diisocyanate, Examples include trilein diisocyanate, divinyl sulfone, 1,1′-carbonyldiimidazole or alkoxysilanes. The said hardening | curing agent may be used independently or may be used with the form of 2 or more types of mixtures. Further, the curing agent is not particularly limited with respect to molecular weight or the like. Preferably, a curing agent having a molecular weight of less than 2000, more preferably less than 1000, even more preferably less than 600, and even more preferably less than 400 can be used. The lower limit of the molecular weight of the curing agent is not particularly limited, but is preferably 150.

  The additive is not particularly limited, and additives usually used in water-based paints can be used in the same manner. Specifically, an ultraviolet absorber, a light stabilizer, a surface conditioner, a boiling inhibitor and the like can be mentioned.

  The pigment is not particularly limited, and pigments usually used in water-based paints can be used in the same manner. Specifically, organic color pigments such as azo pigments, phthalocyanine pigments, and perylene pigments, and inorganic color pigments such as carbon black, titanium dioxide, and bengara can be used.

  The brightening agent is not particularly limited, and brightening agents usually used in water-based paints can be used in the same manner. Specific examples include aluminum pigments and mica pigments, and examples of the solvent include water and the above-mentioned aqueous solvents such as alcohols and glycol ethers.

  When the modified polyrotaxane is mixed with the various coating materials described above, the modified polyrotaxane in a carboxylate-modified state may be blended as it is. However, it is desirable to blend the modified polyrotaxane in a state of being dispersed and diluted in advance in a solvent such as water or an aqueous solvent. Such a modified polyrotaxane solution may be prepared at the time of producing the paint, or may be prepared prior to the production of the paint.

  The water-based paint of the present invention can be a general clear paint, base coat paint or enamel paint. In the water-based paint of the present invention, a matte paint can be obtained by adding a matting agent such as silica or resin beads in addition to the above components.

  The present invention also provides an aqueous coating film formed using an aqueous coating material. As described above, since the water-based paint of the present invention uses a modified polyrotaxane, it is excellent in dispersibility in water or an aqueous solvent. For this reason, the aqueous coating film formed using the aqueous coating material of the present invention exhibits excellent smoothness. Polyrotaxane can exhibit excellent stretchability, viscoelasticity, and mechanical strength based on the pulley effect due to its structure, and this effect is maintained even with a modified polyrotaxane. For this reason, the water-based coating film formed using the water-based paint of the present invention can also exhibit excellent scratch resistance, chipping resistance, bird dropping resistance, and stretchability. Moreover, the water-based coating film of the present invention can also exhibit excellent base protection, removability, water resistance, moisture resistance, and acid resistance.

  Here, the application of the water-based coating film is not particularly limited, and may be used as any coating film such as an automobile or a building material. For example, in automotive applications, it can be applied to any coating film such as an undercoat coating film, a base coating film, a clear coating film, and a coating protective film. As described above, the aqueous coating film of the present invention is excellent in smoothness, scratch resistance, base protection, removability, water resistance, moisture resistance, acid resistance, bird dropping resistance, and stretchability. For this reason, the aqueous coating film of this invention can be conveniently used as a coating film arrange | positioned in the outermost layer of the coating film coat | covered with a to-be-coated article. The aqueous coating film of the present invention is excellent in smoothness, scratch resistance and water resistance. For this reason, the aqueous coating film of the present invention can be particularly suitably used as a clear coating film. Furthermore, the water-based coating film of the present invention is excellent in substrate protection, removability, acid resistance, bird dropping resistance, and stretchability. For this reason, the aqueous coating film of this invention can be used especially suitably as a coating protective film.

The method for forming the aqueous coating film of the present invention can be the same as the conventional method except that the aqueous coating material of the present invention is used. For example, in the case of a clear coating film, the water-based paint of the present invention is applied to various objects to be coated with various coating devices such as spray guns and brushes under the same workability as conventional paints. can do. Here, the material of the object to be coated is not particularly limited,
It is appropriately selected depending on the application. For example, metal materials such as iron, steel and aluminum, various organic materials such as polypropylene and polycarbonate, various inorganic materials such as quartz and ceramics (calcium carbide, etc.), wood materials, stone materials such as stone materials, bricks and blocks, leather Various coated objects made of materials can be used. After coating, the coating film can be solidified at room temperature or by baking to form a clear coating film. Although it does not specifically limit as a coating-film thickness at this time, It is desirable to apply so that it may become about 20-40 micrometers.

  Further, in the case of a paint protective film, the water-based paint of the present invention can be applied by adopting a known application method using a spray gun, a brush or the like as described above. After coating, the coating protective film can be formed by drying at room temperature or drying by heating to evaporate and solidify. Alternatively, the coating protective film is not limited to being formed by applying a water-based paint to the surface to be protected, but may be formed by previously forming a film shape on the surface to be protected. Although it does not specifically limit as thickness of a coating protective film, It is preferable to coat so that it may become about 100-1000 micrometers. More preferably, it is 500-1000 micrometers, Most preferably, it is 800-1000 micrometers. If it is less than 100 μm, the protective effect tends to be reduced. If it exceeds 1000 μm, it takes time to evaporate the water, and workability decreases. The coating film to be protected by the coating protective film is not particularly limited, and examples thereof include clear coating films such as acrylic melamine coating films and urethane coating films, and enamel coating films.

  The specific laminated structure of the aqueous coating film of the present invention is not particularly limited, and can be appropriately selected depending on the type of the coating film. For example, in the case of a clear coating film, it is also desirable to apply a base paint to an object to be coated and then apply the water-based paint of the present invention thereon, followed by baking, whereby the base coat film and the coating film are coated. Thus, a coating film having a two-layer structure is obtained. In addition, after applying an undercoat paint to an object to be coated and drying or baking at room temperature, the base paint and the paint of the present invention can be applied and baked in the same manner as described above. A three-layered coating film composed of an undercoat coating film, a base coating film and the coating film is formed on the surface. FIG. 3 is a cross-sectional view showing an example of such a three-layered laminated coating film. The laminated coating film shown in the figure includes an undercoat coating film 10 formed on an object to be coated and its It is composed of a base coat film 11 formed thereon and a clear film 12 made of the water-based film of the present invention thereon.

  Moreover, one Embodiment in case the water-system coating film of this invention is a coating protective film is shown in FIG. In FIG. 4, a laminated coating film comprising an undercoat coating film 20 and an enamel coating film 21 is formed on the surface of an object (not shown), and a water-based coating protective film 22 is further coated to protect the laminated coating film. Has been.

  Next, the coated article of the present invention will be described in detail.

  The coated article of the present invention comprises a water-based coating film comprising the above-described water-based paint of the present invention and an article to be coated, and the article is formed with a coating film comprising the water-based paint of the present invention. Needless to say, even if the above-described laminated coating film is provided and the laminated coating film is formed on the article, it is included in the scope of the present invention.

  The material of the object to be coated is as described above.

  In addition, specific examples of application of the object to be coated include automobile bodies that require scratch resistance, aluminum wheels that have been subjected to treatments such as plating, vapor deposition, and sputtering, door mirrors, and indoor and outdoor resin products. And wood products such as stairs, floors and furniture.

Painted articles obtained in this way include automobiles, motorcycles, bicycles, railways, other transport machinery, construction machinery, mobile phones, electrical appliances, optical equipment, furniture, building materials, musical instruments, bags, sports equipment, leisure goods, Kitchen supplies, pet supplies, stationery, etc.

  Hereinafter, the present invention will be described more specifically based on examples. The present invention is not limited to these examples.

Example 1
(1) Preparation of PEG-carboxylic acid by TEMPO oxidation of PEG As a linear molecule, 10 g of PEG (polyethylene glycol, molecular weight: 35,000), TEMPO (2,2,6,6-tetramethyl-piperidinyloxy) Radical) 100 mg and sodium bromide 1 g were dissolved in 100 mL of water, and 5 mL of a commercially available sodium hypochlorite aqueous solution (effective chlorine concentration 5%) was added thereto, followed by stirring at room temperature for 10 minutes. Subsequently, in order to decompose surplus sodium hypochlorite, ethanol was added in a range of up to 5 mL to terminate the reaction.

  Then, extraction with 50 mL of methylene chloride was repeated three times to extract components other than inorganic salts, and then the methylene chloride was distilled off with an evaporator and dissolved in 250 mL of warm ethanol, and then the freezer (−4 ° C. ) Overnight, only PEG-carboxylic acid was precipitated, collected and dried.

(2) Preparation of inclusion complex using PEG-carboxylic acid and α-CD 70 g of PEG-carboxylic acid prepared in the above (1) and 12 g of α-CD (cyclodextrin α) were prepared separately. After dissolving in 50 mL of warm water, both were mixed and shaken well. Next, this mixture was allowed to stand overnight in a refrigerator (4 ° C.), and the clathrate complex deposited in a cream form was recovered by freeze-drying.

(3) Blocking of inclusion complex using adamantaneamine and BOP reagent reaction Dissolve 0.13 g of adamantaneamine in 50 ml of dimethylformamide (DMF) at room temperature, and add the resulting inclusion complex quickly. Shaken. Subsequently, 0.38 g of BOP reagent (benzotriazol-1-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate) dissolved in DMF was further added and shaken well in the same manner. Further, a solution obtained by dissolving 0.14 ml of diisopropylethylamine in DMF was further added and shaken well in the same manner to obtain a reagent.

  Next, the reagent in the form of a slurry was allowed to stand overnight in a refrigerator (4 ° C.). Thereafter, 50 ml of a DMF / methanol mixed solvent (volume ratio 1/1) was added, mixed and centrifuged, and the supernatant was discarded. Further, the washing with the DMF / methanol mixed solution was repeated twice, and then the washing with 100 mL of methanol and centrifugation were repeated twice. The obtained precipitate was dried by vacuum drying and then dissolved in 50 mL of DMSO, and the obtained transparent solution was dropped into 700 mL of water to precipitate polyrotaxane. The precipitated polyrotaxane was collected by centrifugation and vacuum dried. Further, a cycle of dissolution in DMSO, precipitation in water, recovery, and drying was repeated twice to finally obtain a purified polyrotaxane. The inclusion amount of α-CD is 0.25.

(4) Hydroxypropylation of hydroxyl group of cyclodextrin 500 mg of the above prepared polyrotaxane was dissolved in 50 mL of 1 mol / L NaOH aqueous solution, 3.83 g (66 mmol) of propylene oxide was added, and the mixture was stirred overnight at room temperature in an argon atmosphere. . The solution was neutralized with a 1 mol / L HCl aqueous solution so as to have a pH of 7 to 8, dialyzed with a dialysis tube, freeze-dried and collected to obtain a hydroxypropylated polyrotaxane. The obtained hydroxypropylated polyrotaxane was identified by ¹ H-NMR and GPC, and confirmed to be a hydroxypropylated polyrotaxane having a desired structure.

(5) Modification of Modification Group of Hydroxypropylated Polyrotaxane 4.5 g of ε-caprolactone dried with molecular sieves was added to 1.0 g of the hydroxypropylated polyrotaxane prepared above, and the mixture was stirred for 30 minutes at room temperature and allowed to permeate. 0.16 g of tin 2-ethylhexanoate was added and reacted at 100 ° C. for 1 hour.

After completion of the reaction, the sample was dissolved in 50 mL of toluene, dropped into 450 mL of hexane which was stirred, precipitated, collected, and dried to obtain a modified polyrotaxane. The obtained modified polyrotaxane was identified by ¹ H-NMR and GPC, and confirmed to be a modified polyrotaxane having a desired structure. The obtained modified polyrotaxane was 4.5 times the weight added by the modifying group.

(6) Modification of carboxylate salt of modified polyrotaxane To 500 mg of the modified polyrotaxane prepared above, 20 mL of dehydrated toluene was added, and 0.40 g of succinic anhydride (20 mol% with respect to all hydroxyl groups of the polyrotaxane) was added, Stir for 24 hours. The pH after the reaction was 4-5. After removing 95% by volume of toluene with an evaporator, the solution was neutralized with 0.55 mL of triethylamine, confirmed to have a pH of 7-8, and then dried to obtain a modified polyrotaxane. The obtained modified polyrotaxane was identified by IR and GPC, and confirmed to be a modified polyrotaxane having a desired structure. In addition, the modification degree by the carboxylate of the modification group of the obtained modified polyrotaxane was 20%.

(7) Preparation of water-based paint First, 500 mg of the modified polyrotaxane obtained in (6) above is dispersed in distilled water so as to have a concentration of 10 (w / v), and polyoxyethylene octylphenyl ether is further used as a surfactant. (Wako Pure Chemical Industries, Ltd.) was added to a concentration of 1 (v / v)% and stirred well to obtain a modified polyrotaxane aqueous solution.

  Next, the modified polyrotaxane aqueous solution obtained above was added to a water-soluble alkyd resin (nonvolatile content: 42%, hydroxyl value: 100 KOH mg / g, acid value: 14 KOH mg / g) with stirring. HDI isocyanate (hexamethylene diisocyanate) (NCO: 8.2%) was added as a curing agent so that the ratio of the water-soluble alkyd resin to isocyanate was 133 / 2.17 (mass ratio). A modified polyrotaxane having a molecular weight of 35,000 for the linear molecule, an inclusion amount of 0.25, a weight 4.5 times the amount added by the modifying group, and a modification degree of the modifying group by the carboxylate of 20%. A water-based paint containing 50% by mass with respect to the coating film forming component was obtained.

(8) Formation of multilayer coating film A cationic electrodeposition paint (cation type electrodeposition paint manufactured by Nippon Paint Co., Ltd., trade name “Power Top U600M”) is applied to a 0.8 mm thick, 70 mm × 150 mm thick steel plate treated with zinc phosphate. Then, electrodeposition was applied so that the dry film thickness was 20 μm. Next, this electrodeposition coating film was baked at 160 ° C. for 30 minutes. Thereafter, a gray base paint (trade name “Hi-Epico No. 500”) manufactured by Nippon Oil & Fats Co., Ltd. was applied so that the dry film thickness was 30 μm, and baked at 140 ° C. for 30 minutes, whereby the base coat film was It formed on the electrodeposition coating film.

Next, Aqua BC-3 (3) metallic coating color manufactured by Nippon Oil & Fats Co., Ltd. is applied to a thickness of 10 μm, and the water-based paint obtained in (7) above is wet-on-wet so that the dry film thickness becomes 30 μm. And then baked at 140 ° C. for 30 minutes to form a clear coating.

(9) Formation of paint protective film Cationic electrodeposition paint (trade name “Power Top U600M”, a cation type electrodeposition paint manufactured by Nippon Paint Co., Ltd.) is applied to a 0.8 mm thick, 70 mm × 150 mm thick steel plate treated with zinc phosphate. After electrodeposition coating so that the dry film thickness was 20 μm, baking was performed at 160 ° C. for 30 minutes. Thereafter, the water-based paint obtained in the above (7) was applied so that the dry film thickness was 30 μm, and baked at 140 ° C. for 30 minutes.

(Examples 2-4, Comparative Examples 1-4)
Except for the specifications shown in Table 1, the same operations as in Examples 1 (1) to (7) were repeated, and the same operations as in Example 1 were performed to prepare a water-based paint. Moreover, except having used the water-system coating material obtained by each, the same operation as Example 1 (8) was repeated and the laminated coating film was formed. Further, a coating protective film was formed by repeating the same operation as in Example 1 (9) except that the water-based paint obtained in each case was used.

  Moreover, in Comparative Examples 1-3, (6) in Example 1 was not implemented. In Comparative Example 4, Examples 1 (5) and (6) were not performed.

  About the water-based paint obtained in each of the above examples and comparative examples, the dispersibility, the smoothness of the coating film by the paint, scratch resistance, water resistance, acid resistance, bird dropping resistance and stretchability are as follows. Evaluation was based on criteria. The results are shown in Table 1 below together with the characteristics of each paint.

(1) Dispersibility The white turbidity when each paint was applied to a glass plate (dry film thickness was 30 μm) was visually evaluated. The dispersibility was classified into the following three stages. ◯: No change, Δ: Some cloudiness, ×: Cloudiness and separation.

(2) Smoothness The degree of smoothness of each coating film was visually evaluated. In addition, smoothness was classified into the following three stages. ◯: Pretty smooth, Δ: Slightly uneven, X: Uneven.

(3) Scratch resistance For each coating film (size: 70 mm × 150 mm), a dustnel (friction cloth) was attached to a slider of an abrasion tester with a double-sided tape, and 50 under a load of 0.22 g / cm ^2. The sample was reciprocated once and evaluated for the presence or absence of scratches. In addition, smoothness was classified into the following three stages. ◯: Almost no scratches, Δ: Slightly scratched, X: There are many scratches that stand out.

(4) Water resistance Each coating film (size: 70 mm × 150 mm) was immersed in warm water at 40 ° C. for 240 hours. Thereafter, the degree of swelling of the surface of the coating film was visually evaluated. The water resistance was classified into the following three stages. ○: No abnormality, Δ: Slight swelling, ×: Clear swelling

(5) Acid resistance 2 mL of 1% sulfuric acid was dropped on each coating film (size: 70 mm × 150 mm) and left in a constant temperature bath at 40 ° C. for 24 hours. Thereafter, the coating film was peeled off, and the appearance of the coating film surface was visually evaluated. In addition, acid resistance was classified into the following three stages. ◯: No abnormality, Δ: Slight blotting, ×: Clear blotting

(6) Bird dropping resistance For each coating film (size: 70 mm × 150 mm), 2 mL of 10% albumin aqueous solution was dropped and left in a constant temperature bath at 40 ° C. for 24 hours. Thereafter, the coating film was peeled off, and the appearance of the coating film surface was visually evaluated. In addition, bird dropping resistance was classified into the following three stages. ◯: No abnormality, Δ: Slight blotting, ×: Clear blotting

(7) Stretchability Each coating film (size: 70 mm × 150 mm) was measured using TENSILON UTM-4-200 manufactured by Toyo Baldwin Co., Ltd. The film pulling speed was 4 mm / min. The stretchability was classified into the following three stages. ◯: Elongation rate 100% or more, Δ: Elongation rate 30 to less than 100%, X: Elongation rate 30% or less.

As is clear from the results in Table 1, the water-based paints of Examples 1 to 4 of the present invention exhibit good dispersibility by modifying the modifying group of the hydrophobic polyrotaxane with a carboxylate. In addition to the above-mentioned advantages, the coating film and the coating protective film formed using the water-based paints of Examples 1 to 4 of the present invention are scratch resistant and good appearance properties based on the pulley effect of the polyrotaxane, and the base protection. It is confirmed that the water resistance is exhibited together with the improvement of the property and the removability.

  On the other hand, in the coating film formed using the coating material of Comparative Examples 1 to 3 containing a hydrophobic polyrotaxane in which the modifying group is not modified to carboxylate, the dispersibility, smoothness, scratch resistance, stretchability, etc. are inferior. It has been found. In addition, the coating film formed using the coating material of Comparative Example 4 containing an unmodified hydrophilic polyrotaxane is excellent in dispersibility, smoothness, scratch resistance and stretchability, but is water resistant, acid resistant and bird droppings. It turned out to be inferior.

1 ... modified polyrotaxane,
2 ... cyclic molecule,
2a ... modifying group,
2b carboxylate,
3 ... linear molecule,
4. Blocking group,
6 ... cross-linked structure type modified polyrotaxane,
8 ... polymer,
10: Undercoat film,
11 ... Base coat film,
12. Clear film,
20: Undercoat film,
21 ... Enamel coating,
22 ... Water-based paint protective film.

Claims (11)

  A cyclic molecule having a modifying group and all or part of the modifying group is modified to a carboxylate; a linear molecule that includes the cyclic molecule in a skewered manner; and both ends of the linear molecule A water-based paint comprising a modified polyrotaxane having a blocking group that is disposed on the surface and prevents the elimination of the cyclic molecule. The carboxylate has the following formula (1):
However, R < ¹ >, R < ² > and R < ³ > represent each independently the hydrocarbon group which may have a hydrogen atom or a C1-C8 branched chain; R < ⁴ > is the hydroxyl group of a hydroxyalkyl group. Represents a modifying group modified with a lactone derivative,
The water-based paint according to claim 1, which has a group represented by: R ^1, R ² and R ³ are each independently a straight chain or branched chain alkyl group having a hydrogen atom or 1 to 4 carbon atoms, water-based paint according to claim 2. The cyclic molecule has a hydroxyl group,
The water-based paint according to any one of claims 1 to 3, wherein the modifying group is introduced into the cyclic molecule by reacting the hydroxyl group of the cyclic molecule with an alkylene oxide and then reacting with a lactone derivative.   The lactone derivative is at least one selected from the group consisting of ε-caprolactone, γ-butyrolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, and δ-valerolactone. The water-based paint according to claim 4.   The water-based paint according to any one of claims 1 to 5, further comprising a surfactant and a water-based solvent.   The water-based paint according to claim 6, wherein the surfactant is polyoxyethylene octylphenyl ether.   A water-based coating film characterized in that a layer made of the water-based paint according to any one of claims 1 to 7 is formed on an object to be coated.   The aqueous system according to claim 8, wherein the layer made of the aqueous paint according to any one of claims 1 to 7 is disposed on an outermost layer of a coating film formed on an object to be coated. Paint film.   The aqueous coating film according to claim 9 or 10, wherein the coating film is a clear coating film or a paint protective film.   A coated article comprising the water-based coating film according to claim 8 or 9, and an article to be coated.