JP4379735B2 - Polyrotaxane-containing coating film repair wax - Google Patents

Description

The present invention relates to a coating film repairing wax containing a polyrotaxane, and more particularly to a coating film repairing wax which contains a predetermined polyrotaxane and hardly reduces the scratch resistance of the coating film.
The coating film repairing wax of the present invention is particularly suitably used for repairing automobile coatings.

  There are cases where coating film defects such as dust adhesion, sagging, repellency and scratches occur in the coating film. Conventionally, methods such as polishing repair, spot repair and recoating have been known as methods for correcting coating film defects. Yes.

Polishing repair is a method of removing dust with sandpaper, polishing with wax containing a compound to make fine scratches, and finally finishing with wax when small dust adheres (see, for example, Patent Document 1). ).
In addition, spot repair is performed for defects that cannot be repaired by polishing repairs such as repellency. After removing dust with sandpaper, a top coat for repair (generally a two-component urethane paint) is applied, dried and then compounded. It is a method of polishing with the contained wax and finally finishing with wax.
Further, the recoat repair is a method in which repellency or the like is generated on the entire painted surface, and is performed when there is a defect that cannot be repaired by polishing repair or spot repair.

As described above, polishing repair and spot repair, which are conventional coating film repair methods, are indispensable for polishing with wax containing a compound of fine particles, and the finish cannot be ensured without such a polishing process.
On the other hand, recently, development of a coating film having improved scratch resistance against scratches such as car wash scratches and scratches has been promoted (see, for example, Patent Document 2).
JP 10-165890 A JP 2003-320304 A

  However, such a coating film having good scratch resistance has a problem that it is practically difficult to repair by polishing since it is difficult to be damaged.

  The present invention has been made in view of such problems of the prior art, and an object of the present invention is to provide a coating film repairing wax capable of repairing a coating film having scratch resistance. Is to provide.

  In order to achieve the above object, the present inventors have made extensive studies focusing on filling the wound instead of erasing the scratch as in the past, and as a result, by blending a predetermined polyrotaxane, the above object is achieved. The inventors have found that this can be achieved and have completed the present invention.

That is, the coating film repairing wax of the present invention prevents the cyclic molecule from being detached by arranging the cyclic molecule, the linear molecule that includes the cyclic molecule in a skewered manner, and the both ends of the linear molecule. A coating film repairing wax containing a polyrotaxane having a blocking group
The polyrotaxane is a lipophilic polyrotaxane having a group in which polyethylene glycol monostearate is bonded via hexamethylene diisocyanate .

Moreover, the suitable form of the coating film repair wax of the present invention is characterized in that the linear molecule of the lipophilic polyrotaxane is polyethylene glycol and / or polycaprolactone .

Furthermore , in another preferred embodiment of the coating film repair wax of the present invention, the cyclic molecule is at least one cyclodextrin selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin. characterized in that there.

  According to the present invention, since a predetermined polyrotaxane is blended, it is possible to provide a coating film repairing wax capable of repairing a coating film having scratch resistance.

Hereinafter, the coating film repair wax of the present invention will be described in detail. In the present specification, “%” represents mass percentage unless otherwise specified.
As described above, the coating film repair wax of the present invention contains a predetermined polyrotaxane.
Here, the polyrotaxane has a cyclic molecule, a linear molecule that includes the cyclic molecule in a skewered manner, and a blocking group that is disposed at both ends of the linear molecule and prevents the cyclic molecule from being detached. A compound.
Coating repair wax of the present invention, among the above-described polyrotaxane is obtained by blending the Porirotakisa down lipophilic which function as a coating material.

First, the lipophilic polyrotaxane will be described.
This lipophilic polyrotaxane is one in which at least one of a linear molecule and a cyclic molecule in the above polyrotaxane has hydrophobicity, and functions as a curable or room temperature drying type solvent-based coating material.

Specifically, such a lipophilic polyrotaxane is, in principle, (i) a combination of a hydrophobic linear molecule and a hydrophilic cyclic molecule or a hydrophobic cyclic molecule, or (b) a hydrophilic However, it is sufficient that the polyrotaxane as a whole exhibits lipophilicity.
In order to impart hydrophobicity to the cyclic molecule, (1) all or part of the hydroxyl group of the cyclic molecule having a hydroxyl group may be modified with a hydrophobic modifying group, and (2) the linear molecule is hydrophobic. In order to impart the property, a specific linear molecule may be selected. In addition, (3) the whole polyrotaxane can be hydrophobized also by controlling the amount by which the linear molecule includes the cyclic molecule.

  On the other hand, the hydrophilic polyrotaxane is one in which at least one of a linear molecule and a cyclic molecule in the polyrotaxane has hydrophilicity, and functions as a curable or room temperature drying type water-based coating material.

Specifically, among the polyrotaxanes, such a hydrophilic polyrotaxane is, in principle, (c) a combination of a hydrophilic linear molecule and a hydrophilic cyclic molecule or a hydrophobic cyclic molecule, or (d) a hydrophobic However, it is sufficient that the polyrotaxane exhibits hydrophilicity as a whole.
In order to impart hydrophilicity to the cyclic molecule, (4) all or part of the hydroxyl group of the cyclic molecule having a hydroxyl group may be modified with a hydrophobic modifying group.

The above-described lipophilic polyrotaxane is soluble in an organic solvent, and the hydrophilic polyrotaxane is soluble in an aqueous solvent. Therefore, the above-described lipophilicity and hydrophilicity are imparted to a reaction field of an organic solvent or an aqueous solvent, typically a cross-linking, with respect to a polyrotaxane that has been hardly soluble or insoluble in an organic solvent or an aqueous solvent. It provides a place.
That is, the above-described lipophilic polyrotaxane and hydrophilic polyrotaxane can be said to have improved reactivity in which crosslinking with other polymers and modification with a modifying group can be easily performed in the presence of an organic solvent or an aqueous solvent.

FIG. 1 is a schematic diagram conceptually showing the basic structure of polyrotaxane.
In the figure, this polyrotaxane 5 has a linear molecule 6, a plurality of cyclic molecules 7, and blocking groups 8 arranged at both ends of the linear molecule 6, and the linear molecule 6 is cyclic. The cyclic molecule 7 is included through the opening of the molecule 7.
The polyrotaxane having such a structure is excellent in stretchability and viscoelasticity because the cyclic molecules 7 move freely along the straight-chain molecules 6 when an external force is applied (the pulley effect), and cracks and scratches. It has the outstanding characteristic that it is hard to produce.

In the present invention, (A) one or both of the cyclic molecule 7 and the linear molecule 6 are hydrophobic and exhibit lipophilicity as a whole. Typically, the cyclic molecule 7 has a hydroxyl group. Then, a polyrotaxane in which all or part of the hydroxyl groups of these cyclic molecules are modified with a hydrophobic modifying group, or a polyrotaxane having a hydrophobic linear molecule is blended.
In the coating film repairing wax, (B) a hydrophilic polyrotaxane having one or both of the cyclic molecule 7 and the linear molecule 6 having hydrophilicity and exhibiting hydrophilicity as a whole, typically a cyclic molecule. 7 has a hydroxyl group, all or some of the hydroxyl groups of these cyclic molecule is also possible to blend the polyrotaxane modified with hydrophilic modification groups, the properties of the wax coating film for repairing of interest (solid, It is also possible to use a lipophilic polyrotaxane and a hydrophilic polyrotaxane depending on the paste or liquid) and work efficiency .

Incidentally, when the coating film repair, when applying the coating for repair wax of the present invention containing a lipophilic Porirotakisa in to repair site, and coating resins and lipophilic Porirotakisa down a coating film forming component of the coating having a repair site It is presumed that both are cross-linked or pseudo-crosslinked, and the cross-linked product or pseudo-cross-linked product of both is formed at the repair site, and the repair is performed without reducing the scratch resistance.

FIG. 2 is a partial conceptual diagram conceptually showing a cross-linked structure between a lipophilic polyrotaxane (or hydrophilic polyrotaxane) and a coating resin.
In the figure, a crosslinked polyrotaxane 1 produced by crosslinking both has paint resins 3, 3 ′ and the lipophilic polyrotaxane (or hydrophilic polyrotaxane) 5. The crosslinked polyrotaxane 1 is bonded to the coating resin 3 and the coating resin 3 ′ through the cyclic molecules 7 through the crosslinking points 9.

When a deformation stress in the direction of arrow XX ′ in FIG. 2A is applied to the crosslinked polyrotaxane 1 having such a structure, the crosslinked polyrotaxane 1 is deformed as shown in FIG. 2B. The stress can be absorbed.
That is, as shown in FIG. 2 (B), the cyclic molecule 7 can move along the linear molecule 6 due to the pulley effect, so that the crosslinked polyrotaxane 1 can absorb the stress therein.
Therefore, the repaired site in which such a crosslinked polyrotaxane is formed has the property that it is excellent in stretchability and viscoelasticity, and is less prone to cracks and scratches.

On the other hand, even when the lipophilic polyrotaxane (or hydrophilic polyrotaxane) and the coating resin are not crosslinked, they approach each other and cause pseudo-crosslinking due to van der Waals force, etc. It is thought that it behaves as
Even in such a case, since at least the lipophilic polyrotaxane (or hydrophilic polyrotaxane) exhibits the pulley effect described above, the repaired part repaired with the coating film repairing wax of the present invention is elastic or viscoelastic as described above. It is excellent in that it has the property that cracks and scratches are difficult to occur.

Hereinafter, the lipophilic polyrotaxane used for the coating film repair wax of the present invention will be specifically described.
In the lipophilic polyrotaxane, the hydrophobic modifying group has a hydrophobic group or a hydrophobic group and a hydrophilic group, and may be hydrophobic as a whole.
Examples of the hydrophobic group include an alkyl group, a benzyl group (benzene ring) and a benzene derivative-containing group, an acyl group, a silyl group, a trityl group, a nitrate ester group, and a tosyl group.
Examples of the hydrophilic group include a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, an amino group (primary to tertiary), a quaternary ammonium base, and a hydroxyalkyl group.

The cyclic molecule in the lipophilic polyrotaxane is not particularly limited as long as it is included in a linear molecule and exhibits a pulley effect, and various cyclic substances can be mentioned. Many cyclic molecules have a hydroxyl group.
In addition, it is sufficient that the cyclic molecule is substantially cyclic, and it is not necessarily required to be completely closed like “C” shape.

Further, as the cyclic molecule, those having a reactive group are preferable, and this facilitates the binding with the above-described hydrophobic modifying group or the like.
Such a reactive group is a residue derived from a compound bonded to a hydroxyl group of a cyclic molecule, and examples thereof include a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, a thiol group, and an aldehyde group. However, it is not limited to these. In addition, as a reactive group, when forming the blocking group mentioned later (blocking reaction), the group which does not react with this blocking group is preferable.

The degree of modification of the cyclic molecule with the hydrophobic modifying group in the hydrophobic polyrotaxane used in the present invention is 0.02 or more when the maximum number of hydroxyl groups that the cyclic molecule can be modified is 1. Preferably, it is 0.04 or more, more preferably 0.06 or more.
If the modification degree is less than 0.02, the solubility in an organic solvent may not be sufficient, and insoluble matter may be generated.

  The maximum number of hydroxyl groups that can be modified in the cyclic molecule means the total number of hydroxyl groups that the cyclic molecule had before modification. The degree of modification is, in other words, the ratio of the number of modified hydroxyl groups to the total number of hydroxyl groups.

  Furthermore, when the polyrotaxane has a plurality of cyclic molecules, it is not necessary that all or a part of the hydroxyl groups of each cyclic molecule is modified with a hydrophobic modifying group. In other words, as long as the entire polyrotaxane exhibits hydrophobicity, there may be no problem even if a cyclic molecule having a hydroxyl group that is not modified by the hydrophobic modifying group is partially present.

As a method for introducing the hydrophobic modifying group, the following method can be employed.
As an example, cyclodextrin is used as a cyclic molecule of polyrotaxane, the hydroxyl group of the cyclodextrin is hydroxypropylated using propylene oxide, ε-caprolactone is added, and tin 2-ethylhexanoate is added. The modification rate can be arbitrarily controlled by changing the amount of ε-caprolactone added at this time.

In the lipophilic polyrotaxane, the number (inclusion amount) of the cyclic molecule included in the linear molecule is 0 when the maximum inclusion amount that the linear molecule can include the cyclic molecule is 1. 06-0.61 are preferable, and 0.11-0.22 are still more preferable. If the inclusion amount is 0.06 to 0.17, lipophilicity can be imparted to the target polyrotaxane separately from the modification of the cyclic molecule and the selection of the linear molecule described later.
If this ratio is less than 0.06, the pulley effect may be insufficient and the elongation of the repaired part may be reduced. If it exceeds 0.61, the cyclic molecules will be arranged too densely, the mobility of the cyclic molecules will decrease, the elongation rate of the coating film formed at the repair site will be insufficient, and the scratch resistance will tend to deteriorate. is there.

Further, the amount of inclusion of the cyclic molecule can be controlled as follows.
In the first method, DMF (dimethylformamide) is mixed with BOP reagent (benzotriazol-1-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate), HOBt, adamantaneamine, and diisopropylethylamine in this order. Add to make solution. On the other hand, a solution is obtained in which a clathrate complex in which a cyclic molecule is skewered into a linear molecule is dispersed in a DMF / DMSO (dimethyl sulfoxide) mixed solvent. By mixing these two and changing the mixing ratio of DMF / DMSO at this time, the inclusion amount of the cyclic molecule can be arbitrarily controlled. In addition, the higher the DMF / DMSO ratio, the greater the amount of inclusion of the cyclic molecule.

  Specific examples of the cyclic molecule include various cyclodextrins such as α-cyclodextrin (glucose number: 6), β-cyclodextrin (glucose number: 7), and γ-cyclodextrin (glucose number: 8). ), Dimethylcyclodextrin, glucosylcyclodextrin and derivatives or modified products thereof, and crown ethers, benzocrowns, dibenzocrowns, dicyclohexanocrowns and derivatives or modified products thereof.

The above-mentioned cyclic molecules such as cyclodextrin can be used alone or in combination of two or more.
Of the various cyclic molecules described above, α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are particularly preferable, and in particular, α-cyclodextrin is used from the viewpoint of inclusion. Is preferred.

On the other hand, the linear molecule may be substantially linear, and may have a branched chain as long as the cyclic molecule that is a rotor can be included so that it can rotate and exert a pulley effect. .
Further, although it is affected by the size of the cyclic molecule, its length is not particularly limited as long as the cyclic molecule can exert a pulley effect.

In addition, as a linear molecule, what has a reactive group in the both ends is preferable, and it becomes possible to react this with the said blocking group easily by this.
Such a reactive group can be appropriately changed according to the type of 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, and is a polyester such as polyalkylenes or polycaprolactone, a polyether such as polypropylene glycol or polyethylene glycol, polyisoprene, polybutadiene, polytetrahydrofuran, polydimethyl. Mention may be made of siloxane, polyethylene, polypropylene, polyamides, polyacryls and linear molecules having a benzene ring.
Among these linear molecules, polyethylene glycol and polycaprolactone are particularly preferable, and polyethylene glycol is preferably used from the viewpoint of solubility in water or solvent solvents.
If polycaprolactone is selected as the linear molecule, lipophilicity can be imparted to the polyrotaxane separately from the modification of the cyclic molecule and the control of the maximum inclusion amount.

In addition, the molecular weight of the linear molecule is preferably 1,000 to 100,000, and more preferably 10,000 to 50,000.
If the molecular weight of the linear molecule is less than 1,000, the pulley effect due to the cyclic molecule cannot be sufficiently obtained, and the scratch resistance may be deteriorated. When the molecular weight exceeds 100,000, the compatibility with the transparent resin is lowered, and the transparency may be lowered.
In addition, when polycaprolactone is selected as the linear molecule, if the molecular weight is 5,000 to 100,000, lipophilicity can be imparted to the polyrotaxane well.

On the other hand, the blocking group may be any group as long as it is arranged at both ends of the linear molecule as described above and can keep the cyclic molecule pierced by the linear molecule. It can be a group.
Examples of such a group include a group having “bulkiness” or a group having “ionicity”. Here, the “group” means various groups including a molecular group and a polymer group.

Examples of the group having “bulkyness” include a spherical shape and a side wall-shaped group.
In addition, the ionicity of the group having “ionicity” and the ionicity of the cyclic molecule interact with each other, for example, repelling each other, so that the cyclic molecule is skewed into a linear molecule. Can be held.

  Specific examples of such blocking groups include dinitrophenyl groups such as 2,4-dinitrophenyl group and 3,5-dinitrophenyl group, cyclodextrins, adamantane groups, trityl groups, fluoresceins and pyrenes. And derivatives or modified products thereof.

Here, an example of the manufacturing method of the lipophilic polyrotaxane used for this invention is demonstrated.
As mentioned above, the lipophilic polyrotaxane is
(1) mixing a cyclic molecule and a linear molecule, penetrating the opening of the cyclic molecule in a skewered manner with the linear molecule, and including the cyclic molecule in the linear molecule;
(2) a step of preparing both the ends of the obtained pseudopolyrotaxane (both ends of the linear molecule) with a blocking group so that the cyclic molecule is not detached from the skewered state;
(3) a step of modifying the hydroxyl group of the cyclic molecule of the obtained polyrotaxane with a hydrophobic modifying group,
Is obtained by processing.

  In the step (1), a lipophilic polyrotaxane can also be obtained by using a hydroxyl group of the cyclic molecule that has been modified with a hydrophobic modifying group in advance. In that case, the step (3) is performed. Can be omitted.

By this production method, as described above, a lipophilic polyrotaxane excellent in solubility in an organic solvent can be obtained.
The organic solvent is not particularly limited, but alcohols such as isopropyl alcohol and butyl alcohol, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, diethyl ether and dioxane. And ethers such as toluene and hydrocarbon solvents such as toluene and xylene. The lipophilic polyrotaxane exhibits good solubility even in a solvent in which two or more of these are mixed.

  The lipophilic polyrotaxane blended in the coating film repair wax crosslinks or pseudo-crosslinks with the coating film forming component of the coating film to be repaired, particularly the paint resin, as described above. The pseudo-crosslinked polyrotaxane is a composite of the coating resin and the polyrotaxane without impairing the physical properties of the lipophilic polyrotaxane and the coating resin to be crosslinked.

In general, a crosslinked polyrotaxane is obtained by (a) mixing a lipophilic polyrotaxane with another film-forming component, (b) physically and / or chemically crosslinking at least a part of the film-forming component, c) It is formed by bonding at least a part of the coating film-forming component and a lipophilic polyrotaxane via a cyclic molecule (curing reaction).
Moreover, these processes can be performed more smoothly by using a curing agent.

In the steps (b) and (c), it is preferable to perform chemical crosslinking. For example, the hydroxyl group of the lipophilic polyrotaxane as described above and the melamine resin, which is an example of the coating film forming component, form a urethane bond. By repeating the formation, a crosslinked polyrotaxane is obtained.
The mixing step (a) depends on the coating film forming component to be used, but can be carried out without a solvent or in a solvent. Further, the solvent can be removed by heat treatment or the like when forming the coating film.

In the present invention, the coating film repair wax of the present invention is applied to the repair site and heated as necessary to crosslink or coat the coating film forming component of the coating film to be repaired with the lipophilic polyrotaxane. A pseudo-crosslinked polyrotaxane can be produced.
At this time, a curing agent may be used, and the curing agent may be blended in advance with the coating film repairing wax. It is more convenient to handle in liquid form.

Specific examples of the curing agent include melamine resin, polyisocyanate compound, blocked isocyanate compound, cyanuric chloride, trimesoyl chloride, terephthaloyl chloride, epichlorohydrin, dibromobenzene, glutaraldehyde, phenylene diisocyanate, diisocyanate trilein. , Divinylsulfone, 1,1′-carbonyldiimidazole or alkoxysilanes. In the present invention, these can be used alone or in combination of two or more.
Moreover, the said hardening | curing agent can use the molecular weight below 2000, Preferably it is less than 1000, More preferably, it is less than 600, More preferably, it is less than 400.

Next , the hydrophilic polyrotaxane used for the coating film repair wax will be specifically described. In addition, about the matter which is not described, it is the same as the case of the above-mentioned lipophilic polyrotaxane.
In this hydrophilic polyrotaxane, the modifying group has a hydrophilic group or a hydrophilic group and a hydrophobic group, and may be hydrophilic as a whole. Such hydrophilic groups and hydrophobic groups are as described above.

The cyclic molecule is also as described above. Further, as the cyclic molecule, those having a reactive group are preferable, and this facilitates bonding with a hydrophilic modifying group or 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. In addition, as a reactive group, when forming the blocking group mentioned later (blocking reaction), the group which does not react with this blocking group is preferable.

In addition, the degree of modification of the cyclic molecule with the hydrophilic modifying group in the hydrophilic polyrotaxane is preferably 0.1 or more when the maximum number of hydroxyl groups that the cyclic molecule can be modified is 1, More preferably, it is more preferably 0.5 or more.
If the degree of modification is less than 0.1, the solubility in water or an aqueous solvent may not be sufficient, and insoluble bumps may be generated.

  Furthermore, when the polyrotaxane has a large number of cyclic molecules, it is not necessary that all or part of the hydroxyl groups of each cyclic molecule is modified with a hydrophilic group. In other words, as long as the entire polyrotaxane exhibits hydrophilicity, there may be no problem even if a cyclic molecule having a hydroxyl group that is not modified with a hydrophilic group is partially present.

Here, at least one hydrophilic group may be used, but it is desirable to have one hydrophilic group for one cyclic molecule, for example, one cyclodextrin ring.
Further, by introducing a hydrophilic group having a functional group, it becomes possible to improve the reactivity with other polymers.

  In addition, as a method for introducing a hydrophilic modification group into a cyclic molecule of polyrotaxane, for example, when cyclodextrin is used as the cyclic molecule, the hydroxy group of the cyclodextrin may be hydroxypropylated using propylene oxide. In this case, the degree of modification with the hydroxyalkyl group can be controlled by changing the amount of propylene oxide added.

In the hydrophilic polyrotaxane, the number (inclusion amount) of the cyclic molecules included in the linear molecule is 0 when the maximum inclusion amount that the linear molecule can include the cyclic molecule is 1. 06-0.61 are preferable, 0.11-0.48 are more preferable, and 0.24-0.41 are still more preferable.
If the inclusion amount is less than 0.06, the pulley effect may be insufficient, and the elongation of the coating film forming the repair site may be reduced. If it exceeds 0.61, the cyclic molecules are arranged too densely. This is because the mobility of the cyclic molecules is lowered, and similarly, the elongation rate of the coating film is insufficient and the scratch resistance tends to deteriorate.

  Such a linear molecule is not particularly limited, but polyethylene glycol is preferably used from the viewpoint of solubility in water or an aqueous solvent.

Further, the molecular weight of the linear molecule is preferably 1,000 to 40,000, preferably 10,000 to 40,000, and more preferably 20,000 to 35,000. preferable.
When the molecular weight of the linear molecule is less than 1,000, the pulley effect due to the cyclic molecule cannot be sufficiently obtained, the elongation rate of the coating film forming the repair site is lowered, and the scratch resistance is deteriorated, while the molecular weight is 40 If it exceeds 1,000, the solubility in the paint is lowered, and the appearance such as smoothness as a clear coating film tends to deteriorate due to the formation of a film on the surface.

Next, an example of a method for producing the hydrophilic polyrotaxane will be described.
As mentioned above, the hydrophilic polyrotaxane is
(1) mixing a cyclic molecule and a linear molecule, penetrating the opening of the cyclic molecule in a skewered manner with the linear molecule, and including the cyclic molecule in the linear molecule;
(2) a step of adjusting both ends of the obtained pseudopolyrotaxane (both ends of the linear molecule) with a blocking group so that the cyclic molecule is not detached from the skewered state;
(3) a step of modifying the hydroxyl group of the obtained polyrotaxane cyclic molecule with a hydrophilic modifying group,
Is obtained by processing.

  In the step (1), a hydrophilic polyrotaxane can also be obtained by using a hydroxyl group of the cyclic molecule that has been modified with a hydrophilic modifying group in advance. In that case, the step (3) is performed. Can be omitted.

In the present invention, the aqueous solvent means a solvent that interacts with water and has a strong affinity with water. Specifically, for example, isopropyl alcohol, butyl alcohol, ethylene glycol Alcohols such as cellosolve acetate, butyl cellosolve acetate, ether esters such as diethylene glycol monoethyl ether, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, etc. The hydrophilic polyrotaxane used in the present invention exhibits good solubility even in a solvent in which two or more of these are mixed.
Among these, alcohols are more preferable, and glycol ethers are more preferable. Even if an organic solvent such as toluene is slightly contained, it may be an aqueous solvent as long as it has a strong affinity with water as a whole.

  In addition, the hydrophilic polyrotaxane blended in the coating film repairing wax is crosslinked or pseudo-crosslinked with the coating film forming component of the coating film to be repaired, particularly the coating resin, in the same manner as the lipophilic polyrotaxane. The hydrophilic modifying group and other functional groups possessed by the hydrophilic polyrotaxane react with the coating film forming component to form a coating film having excellent scratch resistance and chipping resistance. In addition, cracks and the like hardly occur, and the weather resistance, stain resistance, adhesion and the like are excellent.

  In addition, as in the case of the lipophilic polyrotaxane, the crosslinked or pseudo-crosslinked polyrotaxane by the hydrophilic polyrotaxane can be used to form the coating film-forming component and the polyrotaxane without impairing the physical properties of the coating film-forming component to be crosslinked by the hydrophilic polyrotaxane. Can be said to be a complex. Therefore, as described below, by forming a crosslinked polyrotaxane in the repair 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, and a polymer type and the like can be selected. By doing, it can be set as the repair coating film which has desired mechanical strength.

Here, the crosslinking of the hydrophilic polyrotaxane will be described.
This crosslinked polyrotaxane is generally
(A) mixing a hydrophilic polyrotaxane with other 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 (curing reaction) at least a part of the coating film-forming component and a hydrophilic polyrotaxane via a cyclic molecule.

  In addition, since a hydrophilic polyrotaxane is soluble 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 perform chemical crosslinking. For example, this is a urethane bond between the hydroxyl group of the cyclic molecule of the hydrophilic polyrotaxane as described above and a melamine resin which is an example of a paint forming component. Is repeatedly formed to obtain a crosslinked polyrotaxane. 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 performed 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.

It should be noted that the hydrophilic polyrotaxane can be crosslinked or pseudo-crosslinked by applying the coating film repairing wax to the repair site, and the use and selection of the heating and curing agent are the same as in the case of the lipophilic polyrotaxane. .

Coating repair wax of the present invention, the lipophilic Porirotakisa emissions other than the above, including the wax component. Incidentally, the total content of the wax component and the lipophilic Porirotakisa down, i.e. the residue after coating to that the wax solids.
The mixing ratio of the lipophilic Porirotakisa down is preferably set to 1% to 30% relative to the wax solids.
When the lipophilic polyrotaxane is less than 1%, the pulley effect is reduced, the elongation of the repair coating film is lowered, and the scratch resistance may be lowered. When more than 30%, resulting a volume shrinkage by evaporation of the organic solvent include loss function repair site may be reduced.

The wax content is not particularly limited, and conventionally known natural and synthetic waxes can be exemplified, and examples thereof include carnauba wax, wood wax, beeswax and amide wax.
In the present invention, these waxes can be used alone or in combination of two or more.

The properties of the coating film repair wax of the present invention are not particularly limited, and may be any of solid, semi-solid, pasty and liquid forms.
In order to obtain a solid or semi-solid, the lipophilic polyrotaxane is preferably blended from the viewpoint of solubility in an organic solvent. For a paste or liquid, use either a lipophilic polyrotaxane or a hydrophilic polyrotaxane. Also good.
When producing a liquid wax, an organic solvent, an aqueous solvent, a conventionally known surfactant or other dispersant is used, and a water-in-oil type (W / O type) or an oil-in-water type (O / W type) is used. ) Emulsion may be formed.

Coating repaired subject to a coating film of repair wax of the present invention is not particularly limited, more lipophilic Porirotakisa emissions described in the cross-linking or pseudo cross-linked may such resins component (coating resin) The coating film containing is preferable, and the coating film repairing wax of the present invention is particularly suitable for repairing automobile coating films.

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.
Examples of the photocrosslinking group include cinnamic acid, coumarin, chalcone, anthracene, styrylpyridine, styrylpyridinium salt, and styrylquinoline salt.

Moreover, although the coating film in which 2 or more types of these resin components are mixed and used may be sufficient, it is desirable in this case that at least 1 type of resin component has couple | bonded with the polyrotaxane through the cyclic molecule.
Further, the 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, Polyolefin resins such as polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch and copolymers thereof, copolymer resins with polyethylene, polypropylene and other olefinic monomers, polyester resins, polyvinyl chloride resins , Polystyrene resins such as polystyrene and acrylonitrile-styrene copolymer resin, polymethyl methacrylate and (meth) acrylic Acrylic resins such as 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, polysiloxanes such as polydimethylsiloxane, polysulfones, List polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and their derivatives It can be.
As the derivatives, those having the above-mentioned hydroxyl group, amino group, carboxyl group, epoxy group, vinyl group, thiol group, photocrosslinking group, and groups related to these combinations are preferable.

In addition to the lipophilic polyrotaxane and the wax component, the coating film repairing wax of the present invention is blended with various additives, pigments, glittering materials, organic solvents or aqueous solvents, and any mixtures thereof. Can do.
In addition, about such various additives, a pigment, a luster material, etc., it is preferable to set it as the same component as the coating film of repair object from a viewpoint of repair, and it can change suitably according to repair object.
Therefore, the coating film repair wax of the present invention is a transparent wax when the coating film to be repaired is a transparent (including colored transparent) coating film, and when the coating film to be repaired is a colored coating film. It is desirable to use colored wax.

  Specific examples of the additive include a dispersant, an ultraviolet absorber, a light stabilizer, a surface conditioner, and a crack inhibitor.

Specific examples of the pigment include organic color pigments such as azo pigments, phthalocyanine pigments, and perylene pigments, and inorganic color pigments such as carbon black, titanium dioxide, and bengara.
Furthermore, specific examples of the brightening agent include aluminum pigments and mica pigments.

As described above, the coating film repair wax of the present invention is excellent in scratch resistance and chipping resistance, but there is no particular problem with respect to other characteristics such as weather resistance.
In addition, the coating film repair wax of the present invention can obtain the desired appearance with the same workability as the application of a normal repair wax.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.

[Formation of laminated coatings for repair]
The following operation was performed to form a laminated coating film to be repaired as shown in FIG.
In FIG. 3, the laminated coating film is formed by laminating an undercoat coating film layer 10, an intermediate coating film layer 20, and a clear coating film layer 30. The clear coating layer 30 is blended with a polyrotaxane having the following modifying group, which improves the scratch resistance.

(Synthesis of modified polyrotaxane)
According to the method of Zalipsky et al. (Zalipsky et al., Eur. Polym. J. 1989, 19, 1177-1183), PEG-monostearate (manufactured by TCI) was bound to toluene and then re-reacted with ether. Purified with crystals. After 15 g of the resulting isocyanateated PEG-monostearate was reacted with PR (polyrotaxane) (about 500 mg) dissolved in DMSO (dimethyl sulfoxide) overnight at room temperature, it was purified by reprecipitation with ether and dried to give a modified polyrotaxane. Obtained.

(Preparation of clear paint containing modifying group)
The polyrotaxane having a modifying group was dissolved with toluene so that its concentration became 10%. Bell coat no. The dissolved polyrotaxane was added to 6200 (trade name; acrylic / melamine curable clear coating) with stirring to obtain a clear coating containing polyrotaxane.

(Formation of laminated coating film)
A cationic electrodeposition coating (trade name “Power Top U600M”, a cation-type electrodeposition coating made by Nippon Paint Co., Ltd.) is applied to a 0.8 mm thick, 70 mm × 150 mm thick steel plate treated with zinc phosphate so that the dry film thickness becomes 20 μm. After electrodeposition coating, it was baked at 160 ° C. for 30 minutes.
Next, a gray intermediate coat (trade name: Hyepico No. 500) manufactured by Nippon Oil & Fats Co., Ltd. was applied to 30 μm and baked at 140 ° C. for 30 minutes.
Furthermore, Bell Coat No. 60 μl of silver metallic was applied with a thickness of 10 μm, a clear paint containing polyrotaxane was applied with a thickness of 30 μm by wet on wet, and baked at 140 ° C. for 30 minutes to obtain a multilayer coating film shown in FIG.

(Formation of repair site)
The clear coating layer of the laminated coating film obtained as described above was polished with # 1500 sandpaper to form a repair site, and the multilayer coating film having this repair site was subjected to the following performance evaluation.

(Examples 1-8)
As shown in Table 1, a predetermined polyrotaxane was dissolved with kerosene, and this specified amount was added to carnauba wax and mixed in a mortar to obtain a coating film repairing wax of each example.

(Comparative Example 1)
Except not using a predetermined polyrotaxane, the same operation as Examples 1-8 was repeated, and the coating film repair wax of this example was obtained.

[Performance evaluation]
The coating film repair waxes of Examples 1 to 8 and Comparative Example 1 obtained as described above were subjected to the following test.

(Degree of disappearance of scratches)
The repair wax of each example was applied to the clear coating layer (repair site) of the laminated coating film, and the degree of disappearance of the scratch was visually evaluated. The obtained results are also shown in Table 1. In addition, the meaning of the symbol in Table 1 is as follows.
○: Scratches are not noticeable.
Δ: Some scratches are visible.
X: Many scratches are visible.

(Car wash resistance)
The repaired laminated coating film was washed five times using a car wash machine, and the degree of damage was visually evaluated. In addition, the meaning of the symbol in Table 1 is as follows.
○: Scratches are not noticeable.
Δ: Some scratches are visible.
X: Many scratches are visible.

  As is apparent from the results in Table 1, according to the repair waxes of Examples 1 to 8 included in the scope of the present invention, the scratches on the coating film can be eliminated, and a good appearance and scratch resistance can be achieved. Can be provided at the same time.

It is a schematic diagram which shows notionally the basic structure of a polyrotaxane. It is a partial conceptual diagram which shows notionally the crosslinked structure of a polyrotaxane and resin. It is sectional drawing which shows an example of a laminated coating film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Crosslinked polyrotaxane 3 Transparent resin 3 'Transparent resin 5 Polyrotaxane 6 Linear molecule 7 Cyclic molecule 8 Blocking group 9 Crosslinking point 10 Undercoat coating layer 20 Intermediate coating layer 30 Clear coating layer

Claims (7)

A coating film containing a polyrotaxane having a cyclic molecule, a linear molecule that includes the cyclic molecule in a skewered manner, and a blocking group that is disposed at both ends of the linear molecule and prevents the cyclic molecule from detaching Repair wax,
A coating film repairing wax, wherein the polyrotaxane is a lipophilic polyrotaxane having a group in which polyethylene glycol monostearate is bonded via hexamethylene diisocyanate . The coating film repairing wax according to claim 1 , wherein the linear molecule of the lipophilic polyrotaxane is polyethylene glycol and / or polycaprolactone. The inclusion amount of the cyclic molecule of the lipophilic polyrotaxane is 0.06 to 0.61 when the maximum inclusion amount, which is the maximum amount that the linear molecule includes the cyclic molecule, is 1. The coating film repair wax according to claim 1 or 2 . The cyclic molecule, alpha-cyclodextrin, beta-cyclodextrin and any one of claims 1 to 3, wherein the γ- at least one cyclodextrin selected from the group consisting of cyclodextrin Coating film repair wax as described in 1. Said lipophilic Porirotakisa Nowa box solids relative to 30% by weight of the coating repair wax according to any one of claims 1 to 4, characterized in that a proportion. The coating film repairing wax according to any one of claims 1 to 5 , wherein the coating film repairing wax is solid, pasty or liquid. It is a transparent wax or a colored wax, The coating film repair wax according to any one of claims 1 to 6 .

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