JP4376847B2 - Room temperature dry water-based soft-feel paint - Google Patents

Description

The present invention relates to a soft feel paint that can give a soft feeling to products that are frequently touched, such as resin molded products and furniture, and more particularly, it contains a hydrophilic polyrotaxane and has high productivity. In addition, the present invention relates to a room-temperature dry-curing water-based soft-feel paint that can provide a coating film with an excellent soft feeling.

For example, products that are frequently touched by human hands, such as automobile interior parts such as power window finishers and audio switches, or eyeglass cases, are given a soft feeling by surface treatment.
For such surface treatment, soft feel paint is often used in European vehicles, and recently, the application of such soft feel paint is also increasing in Japan.

For such a soft feel paint, a reactive curable paint such as a two-component urethane paint is mainly used, and there are a solvent-based paint and a water-based paint (for example, see Patent Document 1).
Japanese Patent Laid-Open No. 2-174976

  However, when forming a coating film with such a soft feel paint, adhesion is improved by applying a primer so that scratches caused by rubbing on nails, rings, etc., and peeling due to sweat or cosmetics do not occur. Such as increasing the film thickness of soft feel paint, increasing the baking temperature, or increasing the baking time, and so on. There is a problem that the cost is reduced and the cost is increased.

The present invention has been made in view of the above-described problems in the conventional soft feel paint, and the object thereof is to produce a product without requiring undercoating or baking at a high temperature for a long time. An object of the present invention is to provide a room-temperature dry-type water-based soft-feel paint capable of obtaining a soft-feel coating film without lowering the temperature.

  As a result of repeating earnest studies to solve the above problems, the present inventors focused on excellent stretchability, viscoelasticity, and mechanical strength based on the pulley effect of polyrotaxane. For example, all of the hydroxyl groups possessed by the cyclic molecules of polyrotaxane Alternatively, by imparting hydrophilicity by modifying a part with a hydrophilic modifying group, etc., it is possible to modify insoluble polyrotaxane into room temperature drying type polyrotaxane that dissolves in water, and such polyrotaxane is applied to paints As a result, the inventors have found that the above object can be achieved and have completed the present invention.

The present invention is based on the above knowledge, and the room-temperature-drying water-based soft-feel paint of the present invention comprises a cyclic molecule, a linear molecule that includes the cyclic molecule in a skewered manner, and the linear molecule. A blocking group disposed at both ends to prevent the elimination of the cyclic molecule, and at least one of the linear molecule and the cyclic molecule is a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, 1 to 3 amino groups, quaternary ammonium bases, and hydrophilic polyrotaxanes having at least one hydrophilic group selected from the group consisting of hydroxyalkyl groups, or at least one of the linear and cyclic molecules as a whole A hydrophilic modification group, the hydrophilic modification group has the hydrophilic group and the hydrophobic group, and the hydrophobic group is an alkyl group, a benzyl group, a benzene derivative-containing group, an acyl group, a silyl group; Trityl group, and a hydrophilic polyrotaxane is at least one group selected from the group consisting of nitrate ester groups and tosyl groups, characterized in that it contains an acrylic aqueous lacquers and / or cellulose aqueous lacquers.

  According to the present invention, the polyrotaxane having the above properties is imparted with hydrophilicity, and the hydrophilic polyrotaxane modified to be water-soluble is used as a coating material. The soft feeling of the coating film made of paint can be greatly improved.

  Hereinafter, the hydrophilic polyrotaxane used in the present invention and the room temperature dry water-based soft feel paint of the present invention using such a hydrophilic polyrotaxane as a material will be described in more detail. In the present specification, “%” means mass percentage unless otherwise specified.

As described above, the room temperature dry type water-based soft feel paint of the present invention has one or both of linear molecules and cyclic molecules having a predetermined hydrophilic group or a hydrophilic group and a hydrophobic group as a whole and hydrophilic. And a hydrophilic polyrotaxane modified to a room temperature drying type that dissolves in water and an acrylic aqueous lacquer or a cellulose aqueous lacquer .

  FIG. 1 is a schematic diagram conceptually showing the basic structure of a polyrotaxane. The polyrotaxane 1 has a linear molecule 3 penetrating through openings of a large number of cyclic molecules 2, and this linear shape. A blocking group 4 is bonded to both ends of the molecule 3 to prevent the cyclic molecule 2 from detaching from the linear molecule 3, and as described above, when an external stress is applied, the cyclic molecule 2 Since the molecule 2 freely moves along the straight-chain molecule 3 (pulley effect), it has excellent properties such as excellent elasticity and viscoelasticity, high flexibility, and resistance to cracks and scratches.

In the present invention, one or both of the cyclic molecule 2 and the linear molecule 3 are hydrophilic, and are hydrophilic as a whole. Typically, as shown in the figure, the cyclic molecule 2 Has a hydroxyl group, and a hydrophilic polyrotaxane in which all or part of the hydroxyl groups of these cyclic molecules are modified with the hydrophilic modifying group 2a is used, and the polyrotaxane is soluble in water or an aqueous solvent described later. Therefore, it can be blended as a component of the water-based paint.
When such a hydrophilic polyrotaxane and another polymer are mixed, pseudo-crosslinking due to van der Waals force or the like occurs, and both are considered to behave as a composition or a compound. In this case, it is considered that at least the polyrotaxane exhibits the pulley effect described above.

In the present invention, examples of the modifying group exhibiting hydrophilicity include a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, a first to third amino group, a quaternary ammonium base, and a hydroxyalkyl group. Can be mentioned.

  Further, as the hydrophilic polyrotaxane used in the present invention, as long as it exhibits hydrophilicity as a whole, the hydroxyl group of the cyclic molecule may be partially modified by a hydrophobic modifying group. Examples of the 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.

The cyclic molecule in the hydrophilic polyrotaxane is not particularly limited as long as it is included in the linear molecule as described above and exhibits a pulley effect, and various cyclic substances can be exemplified. 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 bonding with the hydrophilic modification group described above.
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 modification group in the hydrophilic polyrotaxane used in the present invention is 0.1 or more when the maximum number of hydroxyl groups that the cyclic molecule can be modified is 1. Preferably, it is 0.3 or more, more preferably 0.5 or more.
That is, if the modification degree is less than 0.1, the solubility in water or an aqueous solvent may not be sufficient, and insoluble material (protrusion derived from adhesion of foreign 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 large number of cyclic molecules, it is not necessary that all or part of the hydroxyl groups of each of the cyclic molecules is modified with a hydrophilic modifying group. In other words, as long as the polyrotaxane as a whole exhibits hydrophilicity, there is no problem even if a cyclic molecule having a hydroxyl group that is not modified by the hydrophilic modification group is partially present.

  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.
That is, if the ratio is less than 0.06, the pulley effect may be insufficient and the coating film elongation may be reduced. If the ratio exceeds 0.61, the cyclic molecules are arranged too closely and the cyclic molecules are movable. This is due to the tendency that the elongation of the coating film is insufficient and the softness of the coating film cannot be sufficiently produced.

  The inclusion amount of the cyclic molecules is, for example, DMF (dimethylformamide), BOP reagent (benzotriazol-1-yl-oxy-tris (dimethylamino) phosphonium / hexafluorophosphate), HOBt (1-hydroxybenzoate). Triazole), adamantaneamine, and diisopropylethylamine are dissolved in this order in a mixed solvent of dimethylformamide and dimethylsulfoxide (DMSO), and an inclusion complex in which cyclic molecules are skewed into linear molecules is dispersed in advance. When the polyrotaxane is synthesized by adding the dispersed liquid, it can be controlled by changing the mixing ratio of the mixed solution, and the higher the DMF / DMSO ratio, the larger the inclusion amount of the cyclic molecules be able to.

  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 having a polyalkylene, polycaprolactone, or the like, a polyether such as polyethylene glycol, a polyamide, a polyacryl, or a linear chain having a benzene ring. Can be mentioned.
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 an aqueous solvent.

The molecular weight of the linear molecule is preferably 1,000 to 100,000, preferably 10,000 to 60,000, and more preferably 30,000 to 50,000. preferable.
That is, when the molecular weight of the linear molecule is less than 1,000, the pulley effect due to the cyclic molecule is not sufficiently obtained, the elongation rate of the coating film is lowered, and the desired soft feeling cannot be given to the coating film, When the molecular weight exceeds 100,000, the paintability deteriorates and the paint appearance such as smoothness tends to deteriorate.

Next, as long as the blocking group is a group which is disposed at both ends of the linear molecule as described above and can maintain the state in which the cyclic molecule is 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.

Next, the manufacturing method of the hydrophilic polyrotaxane used for this invention is demonstrated.
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 cyclic molecule of the obtained polyrotaxane 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 a cyclic molecule that has been modified with a hydrophilic modifying group in advance. In that case, the step (3) is performed. Can be omitted.

  By the above production method, a hydrophilic polyrotaxane excellent in solubility in water or an aqueous solvent as described above can be obtained.

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 the present invention, the hydrophilic polyrotaxane may be cross-linked or pseudo-cross-linked as long as it is soluble in water or the above-mentioned aqueous solvent. It can be used instead of or in combination with the active polyrotaxane.
Examples of such a hydrophilic cross-linked polyrotaxane include a hydrophilic polyrotaxane crosslinked with a relatively low molecular weight polymer, typically a polymer having a molecular weight of about several thousand.

The room temperature dry-type water-based soft-feel paint of the present invention contains the above-mentioned hydrophilic polyrotaxane, and the content at this time is 30 to 80% by mass ratio with respect to the coating film forming component (solid content). It is possible to make the range, and it is more preferable that the range be 40 to 80%, and more preferably 50 to 70%.
That is, when the content of the hydrophilic polyrotaxane with respect to the coating film forming component is less than 30%, the pulley effect by the polyrotaxane cannot be sufficiently obtained, the elongation rate of the coating film is lowered, and the softness of the coating film is reduced. When it exceeds 80%, the coating film may have a sticky feeling.

The room-temperature dry water-based soft feel paint of the present invention blends the above hydrophilic polyrotaxane into an existing room-temperature dry-type water-based paint such as an acrylic water-based lacquer or a cellulosic water-based lacquer so that the content is desirably the above. Can be obtained.
In other words, the hydrophilic polyrotaxane can be obtained by blending and mixing at least one selected from the group consisting of an additive, a pigment and a brightening agent, a solvent, and a resin component based on a conventional method. .

Here, examples of the resin component include a urethane resin, a cellulose resin, an acrylic resin, and a polyolefin resin. Examples of the additive include an ultraviolet absorber, a light stabilizer, a surface conditioner, and an anti-boiling agent. it can.
As the pigment, organic color pigments such as azo pigments, phthalocyanine pigments, perylene pigments, and inorganic color pigments such as carbon black, titanium dioxide, and bengara can be used.

  Examples of the brightening agent 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.

  In addition, when mixing the hydrophilic polyrotaxane with the various coating materials described above, the polyrotaxane in a state of imparting hydrophilicity can be blended as it is, but the hydrophilic polyrotaxane is previously dissolved in a solvent such as water or an aqueous solvent. It is desirable to mix in a diluted state. Such a polyrotaxane solution may be prepared at the time of producing the paint or may be prepared prior to the production of the paint.

The room-temperature dry type water-based soft feel paint of the present invention can be a transparent, translucent or matte clear paint.
At this time, an organic or inorganic pigment or dye may be added to obtain a translucent clear paint. Further, in order to obtain a matte clear paint, it is necessary to add a matting agent such as silica or resin beads.

  Moreover, the room temperature dry type water-based soft feel paint of the present invention can exhibit the performance as an enamel paint by adding an organic / inorganic pigment, and can be a soft feel type enamel paint.

  The room temperature dry-type water-based soft-feel paint of the present invention is a metal material such as iron, steel, and aluminum, a resin material, and a woody material, with various work equipment such as a spray gun, under the same workability as a conventional paint. It can be applied to a variety of objects made of materials, stone materials such as stone, bricks, blocks, and leather materials, leather materials, etc., and by drying and solidifying at room temperature, a base coat film or enamel coating with a soft feeling can be applied. Films and clear coatings can be formed. Although it does not specifically limit as coating film thickness at this time, It is desirable to apply so that it may become about 30-50 micrometers.

  As a specific coating film structure including a soft feel coating film comprising the room temperature dry type water based soft feel paint of the present invention, a base paint is applied to the surface of an object to be coated, and the room temperature dry type water based soft feel paint of the present invention is further applied. It can be obtained by applying a transparent, translucent or matte clear paint comprising, and then drying at room temperature.

  Prior to the application of the base paint, an undercoat paint is applied and baked or dried at room temperature, and then the base paint and the clear paint are applied as described above and dried at room temperature. As shown in FIG. 2, a three-layered laminated coating film having a clear coating film 12 composed of the undercoat coating film 10, the basecoat coating film 11, and the room temperature drying type water-based soft-feel coating material of the present invention is obtained.

Further, an undercoat paint may be applied to an object to be coated, and then coated with an enamel paint composed of the room temperature dry type water-based soft feel paint of the present invention and dried at room temperature, thereby, as shown in FIG. A laminated coating film having a two-layer structure consisting of the undercoating film 10 and the enamel coating film 13 made of the room temperature dry-type water-based soft-feel paint of the present invention is obtained.
At this time, depending on the article to be coated, it is possible to omit the formation of the coating film by the undercoat paint.

  Furthermore, the room temperature dry type water-based soft feel paint of the present invention is applied to the object to be coated as an undercoat paint, and this is coated with a top coat paint and baked or dried at room temperature, and then an enamel paint film or a base + clear paint film. May be formed.

  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: 1,000), 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 Hot water at 70 ° C. prepared separately from 3 g of PEG-carboxylic acid prepared in (1) and 12 g of α-CD (cyclodextrin). After dissolving in 50 mL and mixing well, the mixture was allowed to stand overnight in a refrigerator (4 ° C.), and the clathrate complex deposited in a cream form was lyophilized and recovered.

(3) Reduction of α-CD and blockage of inclusion complex using adamantaneamine and BOP reagent reaction system 14 g of inclusion complex prepared according to (2) above was mixed with dimethylformamide / dimethylsulfoxide (DMF / DMSO) mixed solvent ( (Volume ratio 90/10) was dispersed in 20 mL.
On the other hand, 10 mL of DMF (dimethylformamide) at room temperature, 3 g of BOP reagent (benzotriazol-1-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate), 1 g of HOBt (1-hydroxybenzotriazole), adamantaneamine 1.4 g and 1.25 mL of diisopropylethylamine are dissolved in this order, this solution is added to the dispersion prepared above, and the mixture is quickly shaken and the slurry sample is placed in a refrigerator (4 ° C.). Left overnight.
After allowing to stand overnight, 50 mL of a DMF / methanol mixed solvent (volume ratio 1/1) was added, mixed, centrifuged, and the supernatant was discarded. After washing with the above DMF / methanol mixed solution was repeated twice, washing with 100 mL of methanol was further repeated twice by the same centrifugation.
The obtained precipitate is dried by vacuum drying and then dissolved in 50 mL of DMSO (dimethyl sulfoxide). The obtained transparent solution is dropped into 700 mL of water to precipitate polyrotaxane, and the precipitated polyrotaxane is centrifuged. Collected and vacuum dried or lyophilized. The cycle of dissolution in DMSO, precipitation in water, recovery, and drying was repeated twice to finally obtain a purified polyrotaxane.

(4) Hydroxypropylation of hydroxyl group of cyclodextrin 500 mg of the polyrotaxane prepared as described above was dissolved in 50 mL of 1 mol / L NaOH aqueous solution, 21.1 g (330 mmol) of propylene oxide was added, and the mixture was stirred overnight at room temperature in an argon atmosphere. did. And after neutralizing with 1 mol / L HCl aqueous solution and dialyzing with a dialysis tube, it recovered by freeze-drying and obtained the hydrophilic polyrotaxane.
The obtained hydrophilic polyrotaxane was identified by ¹ H-NMR and GPC, and confirmed to be the desired polyrotaxane. The inclusion amount of α-CD was 0.35, and the modification degree with the hydrophilic modifying group was 0.5.

(5) Preparation of paint A solution in which 10% of the hydrophilic polyrotaxane obtained above was dissolved in distilled water in a resin solution in which CMCAB-641-0.5 manufactured by EASTMAN CHEMICAL was dissolved to 20% was prepared. A hydrophilic polyrotaxane having a linear molecular molecular weight of 1,000, an inclusion amount of 0.35, and a degree of modification with a hydrophilic modifying group of 0.5 is added to the coating film-forming component with stirring while stirring. The room temperature dry type water-based soft feel enamel paint of this example contained.
The resin solution is prepared by pouring a water / amine mixed solution (water 498.09 g / dimethylaminoethanol 1.91 g) into a solution obtained by adding 200 g CMCAB to 300 g buticerorubu (ethylene glycol monobutyl ether) with stirring. It was prepared by.

(6) Formation of Laminated Coating Film 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. After electrodeposition coating so that the dry film thickness was 20 μm, baking was performed at 160 ° C. for 30 minutes.
Next, a base coat film was formed by applying a gray base paint (trade name “Hi-Epico No. 500”) manufactured by NOF Corporation to a dry film thickness of 30 μm and baking at 140 ° C. for 30 minutes. .
Then, the room temperature dry water-based soft-feel enamel paint obtained in each of the above examples and comparative examples was applied to a dry film thickness of 30 μm and dried at room temperature for 1 hour to form a soft-feel enamel coating film. did.

(Examples 2 to 12, Comparative Example 1)
A laminated coating film was formed by repeating the same operation as in Example 1 except that the specifications shown in Table 1 were adopted.

  About the coating film by the room temperature dry type water-based soft feel enamel paint obtained in each of the above Examples and Comparative Examples, the soft feeling, tackiness and smoothness were evaluated based on the following criteria. The results are shown in Table 1 together with the specifications of each paint.

(1) Soft feeling The touch of each paint film was evaluated.
○: Very soft feeling △: Some soft feeling ×: No soft feeling at all

(2) Adhesiveness When two coated plates were overlapped and only one coated plate was held, it was determined whether or not the other coated plate fell.
○: Drops immediately △: Drops after a while ×: Does not drop at all

(3) Smoothness The degree of smoothness of the coating film was visually evaluated.
◯: Pretty smooth △: Slightly uneven ×: Uneven

As is apparent from the results in Table 1, the coating films of the room temperature dry-type water-based soft-feel enamel paints of Examples 1 to 8 of the present invention have a soft appearance based on the pulley effect of the polyrotaxane and a good paint appearance (smoothness). ).
In addition, in Examples 9 to 12, a tendency to be somewhat inferior in some performances was recognized due to the deviation from the preferred range in the molecular weight of the linear molecule and the content of the hydrophilic polyrotaxane, but it can be used as a whole. Judged to be at level.

  On the other hand, it was found that the coating film made of the paint of Comparative Example 1 containing only PEG (polyethylene glycol) and no polyrotaxane was inferior in soft feeling.

It is a schematic diagram which shows notionally the basic structure of the polyrotaxane used for this invention. It is a schematic sectional drawing which shows the structural example of the laminated coating film using the soft feel coating material of this invention. It is a schematic sectional drawing which shows the other structural example of the laminated coating film using the soft feel coating material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polyrotaxane 2 Cyclic molecule 2a Hydrophilic modification group 3 Linear molecule 4 Blocking group 10 Undercoat coating 11 Base coat coating 12 Clear coating (soft-feel coating)
13 Enamel coating (soft-feel coating)

Claims (10)

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 to prevent the cyclic molecule from being removed. At least one of the molecule and the cyclic molecule is at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, a primary to tertiary amino group, a quaternary ammonium base, and a hydroxyalkyl group. A room-temperature dry-type water-based soft-feel paint containing a hydrophilic polyrotaxane having a kind of hydrophilic group and an acrylic water-based lacquer and / or a cellulosic water-based lacquer . The room-temperature-drying water-based soft feel paint according to claim 1, wherein the cyclic molecule has a hydroxyl group, and all or part of the hydroxyl group is modified with the hydrophilic group . The room-temperature-drying water-based soft-feel paint according to claim 2, wherein when the maximum number of hydroxyl groups of the cyclic molecule that can be modified is 1, the degree of modification of the cyclic molecule with a hydrophilic group is 0.1 or more. The inclusion amount of the cyclic molecule is 0.06 to 0.61 when the maximum inclusion amount that the linear molecule can include the cyclic molecule is 1. The room temperature dry-type water-based soft feel paint according to any one of the items. The cyclic molecule α- cyclodextrin, in any one of claims 1-4, characterized in that at least one cyclodextrin selected from the group consisting of β- cyclodextrin and γ- cyclodextrin The room temperature dry-type water-based soft feel paint described . 6. The room temperature dry aqueous soft feel paint according to claim 1 , wherein the content of the hydrophilic polyrotaxane relative to the coating film forming component is 30 to 80% by mass ratio. The room temperature drying according to any one of claims 1 to 6 , wherein the solvent is mixed with at least one selected from the group consisting of an additive, a pigment, and a brightening agent, a solvent, and a resin component. Type water-based soft-feel paint . The room-temperature drying water-based soft-feel paint according to any one of claims 1 to 7 , which is a clear, translucent or matte clear paint . It is an enamel paint, The room temperature dry-type water-based soft feel paint of any one of Claims 1-7 characterized by the above-mentioned. 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 to prevent the cyclic molecule from being removed. At least one of the molecule and the cyclic molecule has a hydrophilic modifying group as a whole, the hydrophilic modifying group has a hydrophilic group and a hydrophobic group, and the hydrophilic group is a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphorus group. And at least one group selected from the group consisting of acid ester groups, primary to tertiary amino groups, quaternary ammonium bases and hydroxyalkyl groups, wherein the hydrophobic group is an alkyl group, a benzyl group, a benzene derivative-containing group , acyl group, silyl group, trityl group, and a hydrophilic polyrotaxane is at least one group selected from the group consisting of nitrate ester groups and tosyl groups, aqueous acrylic lacquer and / or cellulose Air drying aqueous soft feel coating material characterized by containing the system aqueous lacquers.

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