JP2008169360A - Wipe-type gloss imparting agent and method for imparting gloss to article surface - Google Patents

Abstract

An object of the present invention is to provide a glossy surface of an article by a simple wiping operation without using a physical polishing process or a special processing apparatus, and the gloss obtained after the application is maintained over a long period of time and has excellent durability. A raised gloss imparting agent is provided.
The wipe-type gloss imparting agent of the present invention contains (A) an aqueous carbodiimide compound, (B) an aqueous liquid organic compound, (C) water or a mixed solvent of water and a hydrophilic organic solvent, The mass ratio [(A) :( B)] of the content of the component A) and the content of the component (B) is 8:92 to 92: 8.
[Selection figure] None

Description

  The present invention relates to a wipe-type gloss imparting agent that imparts gloss to the surface of an article, and a gloss imparting method.

  On the surface of automobile coatings, a myriad of small scratches occur due to the adhesion and friction of dirt components (dust, dust, carbon contaminants, animal contaminants, plant contaminants, brake dust, iron powder, etc.) that exist in nature. . Most of these small scratches are aggregates of small scratches having a depth of 0.50 μm or less, which cause the appearance of the surface of the coating to be whitened or cause a cloudy pattern on the surface. In addition, when the above-mentioned dirt component adheres firmly to the automobile coating film, the coating film may be chemically decomposed by the action of acid rain, sunlight, oxygen, or the like. When the coating film is damaged by such small scratches or chemical decomposition, the gloss of the coating film is remarkably lowered, and further, dirt components are easily accumulated.

Conventionally, automobile users have used automobile waxes for the purpose of beautifying the appearance of automobile coating (glossing) and protecting the appearance (protection by coating). Usually, automobile wax is composed of natural waxes such as carnauba wax or synthetic waxes, fats and oils, silicones and the like. The gloss is restored by filling these constituents with small scratches generated on the surface of the coating film (see Non-Patent Document 1, for example).
Further, as a method of restoring the gloss to the coating film and maintaining the gloss over a long period of time, for example, a step of cleaning the coating film to remove foreign matters such as dust, a step of polishing the coating film with a buff or the like, and removing a deteriorated part; A gloss restoration method comprising three steps of improving gloss using a surface protective polish is disclosed (for example, see Patent Document 1).
As a gloss restoration agent for the purpose of restoring gloss by a simpler operation, a gloss restoration agent is disclosed in which a photocurable resin is used as a coating agent, and an organopolysiloxane oil and water are added and emulsified and dispersed. (For example, refer to Patent Document 2). Such a gloss recovery agent forms a film that restores gloss by a photocuring reaction.
Further, as a method for imparting gloss by a simple operation, a gloss imparting method using a two-component solvent-based urethane resin as a gloss imparting agent is disclosed (for example, see Patent Document 3). Such a gloss imparting method is a method for imparting gloss by forming a film by a chemical reaction between a solvent-based main agent (acrylic resin) and a solvent-based curing agent (polyfunctional isocyanate).
“Auto Chemical” edited by Japan Auto Chemical Industry Association, 1991, p. 165-180 JP-A-9-187725 JP-A-9-137128 JP 2005-144229 A

However, in the method using the automotive wax described in Non-Patent Document 1, the gloss is not sustained for a long time because the wax dissolves with time. In addition, the surface of the paint film coated with automotive wax tends to adhere oleophilic soil components, or when rainwater remains on the paint film, water droplets generated by the water repellency of the wax cause a lens effect. There is a problem of damaging and deteriorating. For this reason, it has been difficult to maintain the appearance beautifying effect for a long period of time by ordinary care using wax for automobiles.
On the other hand, the gloss restoration method described in Patent Document 1 includes a step of physically polishing, and therefore, it takes a lot of time and labor. For example, in general, it takes about 4 hours to treat one used car over the entire surface, and several hours are required when mirror finishing is performed on the surface of the coating film to regain the same shine as a new car. In addition, the process of polishing the coating film with the buff and the like to remove the deteriorated portion is the same as the method in which a professional worker physically polishes the surface of the automobile coating film using a polishing device or the like at an automobile repair shop or the like. In addition, the smoothness of the coating film surface is greatly affected by the processing time of the polishing process and the skill level of the operator.
In the method using the gloss recovery agent described in Patent Literature 2, when the applied silicone acrylic photocurable resin is cured with natural light, it takes a long time to complete the curing after the application. Therefore, there is a possibility that scratches may occur while the coating strength is not sufficiently high. If a special light irradiation device having a specific light source is used, photocuring can be performed quickly, but in that case, it is difficult to obtain an excellent gloss recovery effect by a simple operation.
Although the gloss imparting method described in Patent Document 3 is simple in operation, it has a problem that the load on the environment is large because it contains a relatively large amount of solvent. For this reason, the above-described gloss imparting method requires special equipment. Further, since wiping is not performed like wax, there is a problem that, when a coating spot occurs, the coating spot remains and the appearance beautification is impaired.
The present invention has been made in view of the above-described problems of the prior art, and the surface of an article (in particular, the surface of an automobile coating film) can be obtained by a simple wiping operation without using a physical polishing process or a special processing apparatus. Furthermore, there is provided a wiping-type gloss imparting agent and a gloss imparting method which impart gloss to the coated film or the surface of the resin molded product), and the gloss obtained after the grant is long-lasting and excellent in durability. The purpose is to provide.

  As a result of intensive studies in order to solve the above problems, the present inventors have determined that the surface of an article (in particular, an automobile) using a wiping type gloss imparting agent containing a specific carbodiimide compound, a liquid organic compound, and a solvent. By forming a film on the surface of the coating film, and further on the surface of the coated product or the resin molded product), the surface of the article can be given a gloss, and the gloss obtained after the application can be maintained for a long time. I found it. Based on this knowledge, the following wiping-type gloss imparting agent and method for imparting gloss to the article surface were invented.

[1] (A) an aqueous carbodiimide compound, (B) an aqueous liquid organic compound, (C) water or a mixed solvent of water and a hydrophilic organic solvent, and the content of (A) component and (B) component The wipe-type gloss imparting agent, wherein the mass ratio [(A) :( B)] to the content is 8:92 to 92: 8.
[2] The wipe-type gloss imparting agent according to claim 1, wherein the (A) aqueous carbodiimide compound is a compound represented by the following general formula (1).

(In the formula, R ¹ and R ² each independently represent a divalent residue having 4 to 15 carbon atoms, excluding the isocyanate group of the diisocyanate compound, and R ³ and R ⁴ each independently represents the number of carbon atoms. 1 to 5 represents an alkoxy group or a hydroxy group, R ⁵ and R ⁶ each independently represents an alkylene group having 2 to 4 carbon atoms, and a and b are each independently any one of 1 to 30 Represents an integer, and n represents an integer of 1 to 10.)
[3] The wipe-type gloss according to [1] or [2], wherein the total content of the component (A) and the component (B) is 0.5 to 30% by mass. Giving agent.
[4] The wipe-type gloss imparting agent according to any one of [1] to [3], wherein the (B) aqueous liquid organic compound is a polyether-modified silicone.
[5] A coating step of coating the wipe-type gloss imparting agent according to any one of [1] to [4] on the surface of the article;
A method for imparting gloss to an article surface, comprising a step of wiping off an excessive wiping-type gloss imparting agent on the article surface after the coating step.
[6] The method for imparting luster to an article surface according to [5], wherein the process from the start of the coating process to the end of the wiping process is performed within an environment of 10 to 80 ° C. within 2 hours.

  According to the gloss imparting agent and the gloss imparting method of the present invention, the surface of an article (automobile coating) can be obtained by a simple operation without using a physical polishing process (polishing process) or a special processing apparatus (such as a dryer or a coating machine). Gloss can be imparted to the film, etc., and the film obtained after the gloss impartation can maintain the gloss over a long period of time. Therefore, general consumers can restore the gloss of automobile coatings and the like.

(Wipe-up gloss imparting agent)
The wipe-type gloss imparting agent (hereinafter abbreviated as gloss imparting agent) of the present invention comprises (A) an aqueous carbodiimide compound, (B) an aqueous liquid organic compound, and (C) water or water and a hydrophilic organic solvent. And a mixed solvent (hereinafter abbreviated as (C) solvent).

[(A) Aqueous carbodiimide compound]
(A) An aqueous carbodiimide compound is an aqueous (ie, soluble or dispersible in water) compound having a carbodiimide bond (—N═C═N—) in the molecule, and has a property of being uniformly compatible with water. It is.
(A) There is no restriction | limiting in particular in the molecular weight of an aqueous carbodiimide compound, Low molecular weight may be sufficient and high molecular weight may be sufficient, but when it becomes too high molecular weight, the viscosity of a gloss imparting agent will become high, and glossiness provision Therefore, the molecular weight is preferably 10,000 or less.

  Examples of the (A) aqueous carbodiimide compound include (i) a compound obtained by desulfurization reaction of thiourea using mercury (II) as a catalyst, (ii) a compound obtained by dehydration reaction of urea, (iii) Examples thereof include compounds obtained by decarboxylation condensation reaction and industrially compounds obtained by decarboxylation condensation reaction of diisocyanate compounds.

Examples of the diisocyanate compound in (iii) include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate; Aliphatic diisocyanates such as methylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate (hydrogenated xylylene diisocyanate), 4,4′-dicyclohexylmethane diisocyanate, etc. And diisocyanate compounds such as alicyclic diisocyanates. The
Among these diisocyanate compounds, 4,4′-dicyclohexylmethane diisocyanate (dicyclohexylmethane diisocyanate) can be suitably used because the storage stability of the gloss imparting agent and the workability at the time of gloss imparting are good.

The decarboxylation condensation reaction of the diisocyanate compound is carried out as necessary in a halogenated solvent having a boiling point of 80 ° C. or higher at atmospheric pressure or an alicyclic ether solvent having a boiling point of 80 ° C. or higher at atmospheric pressure. In the presence, it can be carried out at a temperature of 100 to 150 ° C. for 3 to 50 hours.
Examples of the halogen solvent having a boiling point of 80 ° C. or higher at atmospheric pressure include tetrachloroethylene, trichloroethylene, trichloroethane, tetrachloroethane, and the like. Examples of the alicyclic ether solvent having a boiling point of 80 ° C. or higher at atmospheric pressure include tetrahydrofuran, dioxane, tetrahydropyran and the like.
Examples of the catalyst for the decarboxylation condensation reaction include 3-methyl-1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phenyl-2-phospholene-1-oxide, and 1-ethyl-3- Methyl-2-phospholene-1-oxide and the like can be used. Among these, 3-methyl-1-phenyl-2-phospholene-1-oxide can be preferably used because of easy adjustment of the reaction.

The carbodiimide compound obtained by the decarboxylation condensation reaction of the diisocyanate compound has isocyanate groups at both ends. The isocyanate groups at both ends may be modified with one or both of an active hydrogen-containing compound having a hydrophilic segment and a low molecular weight polyol, and a hydrophilic segment and a hydroxyl group may be introduced into the (A) aqueous carbodiimide compound. If a hydrophilic segment and a hydroxyl group are introduced, water solubility can be improved.
Examples of the active hydrogen-containing compound having a hydrophilic segment include polyethylene glycol, propylene oxide-ethylene oxide copolymer, polyoxyethylene monoalkyl (for example, monomethyl) ether, and the like.
Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, butylene glycol and the like.

(A) Among the aqueous carbodiimide compounds, the compound represented by the general formula (1) is preferable because a glossy and glossy film can be formed more easily.
R ¹ and R ² in the compound represented by the general formula (1) each independently represent a divalent residue having 4 to 15 carbon atoms excluding the isocyanate group of the diisocyanate compound. Examples of the diisocyanate compound include those described above, and 4,4′-dicyclohexylmethane diisocyanate (dicyclohexylmethane diisocyanate) is particularly preferable.
R ³ and R ⁴ each independently represents an alkoxy group having 1 to 5 carbon atoms (that is, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a pentoxy group) or a hydroxy group. In particular, an alkoxy group having 1 to 3 carbon atoms is preferable because a gloss film having a high gloss can be formed more easily.
R ⁵ and R ⁶ each independently represents an alkylene group having 2 to 4 carbon atoms (that is, an ethylene group, a propylene group, or a butylene group). In particular, an alkylene group having 2 to 3 carbon atoms is preferable because a gloss film having a high gloss can be more easily formed.
a and b are each independently an integer of 1 to 30, preferably an integer of 1 to 15. When a and b exceed 30, it becomes difficult to manufacture.
n is an integer of 1 to 10, preferably an integer of 1 to 6. When n exceeds 10, it becomes difficult to manufacture.

  The compound represented by the general formula (1) is, for example, oligomerizing the diisocyanate compound by a decarboxylation condensation reaction, and then an active hydrogen-containing compound or a low molecular weight having the hydrophilic segment in the isocyanate groups at both ends of the oligomer. It is obtained by reacting a polyol compound.

[(B) Aqueous liquid organic compound]
(B) The aqueous liquid organic compound is a compound that is liquid at 20 ° C., has a boiling point at atmospheric pressure of more than 250 ° C., and has an aqueous property, that is, a property that is uniformly compatible with water.
(B) Specific examples of the aqueous liquid organic compound include glycerins such as glycerin, diglycerin, and triglycerin; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and propylene oxide-ethylene oxide copolymer; polyalkylene Nonionic surfactants such as glycol alkyl ether, polyalkylene glycol alkyl ester, and polyglycerin alkyl ester, and polyether-modified silicones such as polyoxyethylene-modified dimethyl silicone can be used.
Of these, polyether-modified silicones are preferably used because they have good sliding feeling and workability during wiping. As polyether-modified silicones, for example, SH-3746 manufactured by Toray Dow Corning Co., Ltd., KF-619 manufactured by Shin-Etsu Chemical Co., Ltd., and the like are commercially available.

  (B) As the aqueous liquid organic compound, those having a viscosity at 20 ° C. of 50,000 mPa · s or less can be preferably used. When the viscosity exceeds the above upper limit, the resistance at the time of wiping increases, and there is a possibility that a uniform glossy film cannot be formed.

[Content ratio of component A and component B]
In the gloss imparting agent, the mass ratio [(A) :( B)] of the content of the (A) aqueous carbodiimide compound and the content of the (B) aqueous liquid organic compound is 8:92 to 92: 8, 15: It is preferable that it is 85-85: 15. When the content of the (A) aqueous carbodiimide compound is less than the mass ratio of 8:92, the (A) aqueous carbodiimide compound is insufficient, the glossy coating becomes thin, and a sufficient gloss imparting effect cannot be obtained. Moreover, when (A) aqueous carbodiimide compound is made more than mass ratio 92: 8, content of (A) aqueous carbodiimide compound will become excess, the resistance at the time of wiping up will become large, and workability | operativity will fall.

  In the gloss imparting agent, the total content of the (A) aqueous carbodiimide compound and the (B) aqueous liquid organic compound is preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass. . When the total content of the (A) aqueous carbodiimide compound and the (B) aqueous liquid organic compound is less than 0.5% by mass, the glossy coating becomes thin, and a sufficient gloss imparting effect may not be obtained. Moreover, when the total amount of the content of the (A) aqueous carbodiimide compound and the (B) aqueous liquid organic compound exceeds 30% by mass, the amount applied on the surface of the article tends to be excessive, and wiping becomes difficult. In addition, paint spots such as streaks and sagging are likely to occur, and there is a risk of requiring effort for repair.

[(C) Solvent]
In the solvent (C), the compound used as the hydrophilic organic solvent is an aqueous liquid organic compound having a boiling point of 250 ° C. or less at atmospheric pressure.
(C) Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, and methyl butyl ketone; lower alcohols such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, and 2-propyl alcohol; ethylene glycol, propylene glycol Glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, a mixed solvent of water and a hydrophilic organic solvent such as glycol ethers such as diethylene glycol monoethyl ether, or water.
These hydrophilic organic solvents are appropriately used for adjusting the drying property and improving the wettability. Of these hydrophilic organic solvents, acetone, methyl ethyl ketone, and the like are preferably used because of excellent storage stability.

(C) It is preferable that content of a solvent is 70-99.5 mass%, and it is more preferable that it is 80-99 mass%. (C) When the content of the solvent is less than 70% by mass, the gloss-imparting agent may not be applied uniformly. When it exceeds 99.5 (upper limit) mass%, a glossy coating is formed from the gloss-imparting agent. In some cases, the gloss film becomes thin, and a sufficient gloss imparting effect may not be obtained.
In addition, the amount of the hydrophilic organic solvent in the solvent (C) is preferably an amount that is 20% by mass or less of the gloss imparting agent, and more preferably an amount that is 5% by mass or less. If the amount of the hydrophilic organic solvent exceeds 20% by mass, the drying property becomes too fast, resulting in uneven coating, and labor may be required for the wiping operation.

[Additive]
In the gloss imparting agent, additives can be blended within a range that does not impair the gloss imparting effect and durability. Additives used include silicone compounds, silica fine particles, fillers, resin components, crosslinking agents, surfactants, wettability improvers, antioxidants, UV absorbers, antiseptics, fungicides, dispersants, plastics Agents, fragrances and the like.

  Specific examples of the silicone compound include organomethoxy compounds such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and hydrolyzates or hydrolysis condensates thereof; methyltrimethoxysilane, ethyltrimethoxysilane, Methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxy Silane, pentyltrimethoxysilane, pentyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethyl Xysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, Silane coupling such as aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, isocyanatepropyltriethoxysilane, polyether-modified silane coupling agent And a hydrolyzate or hydrolysis condensate thereof.

As silica fine particles, for example, aqueous colloidal silica sold under the trade name Snowtex series (manufactured by Nissan Chemical Co., Ltd.), trade names MEK-ST, and IPA-ST (all manufactured by Nissan Chemical Co., Ltd.) are available. Examples thereof include solvent-based organosilica sols.
Examples of the filler include pigments, ceramics, and metal oxides.
Examples of the resin component include acrylate urethane resin, epoxy resin, polyester resin, acrylate resin, urethane resin, alkyd resin, alkyd melamine resin, and silicone resin.
Examples of the crosslinking agent include oxazoline compounds and ethyleneimine compounds.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

  Of these additives, the addition of a silicone compound is preferred because it can impart an antifouling function to the glossy film.

In the gloss imparting agent containing the (A) aqueous carbodiimide compound, (B) aqueous liquid organic compound, and (C) solvent, the (C) solvent is volatilized after coating, whereby the (A) aqueous carbodiimide compound is coated. A film can be formed. (A) The carbodiimide group of the aqueous carbodiimide compound easily reacts with a carboxy group, amino group, hydroxy group, alkoxy group, thiol group and the like at room temperature. Therefore, as the (C) solvent volatilizes, the reaction of the (A) aqueous carbodiimide compound proceeds to increase the molecular weight, and a highly glossy and durable coating can be formed.
Therefore, according to the gloss-imparting agent, the surface of the article (such as an automobile coating film) can be obtained by a simple operation without using a physical polishing process (polishing process) or a special processing apparatus (such as a dryer or a coating machine). Gloss can be imparted. Moreover, the resulting coating can maintain its gloss over a long period of time.

(Glossing method for article surface)
The gloss imparting method for the article surface of the present invention (hereinafter abbreviated as gloss imparting method) is a method including a coating step and a wiping step of the gloss imparting agent.

The coating process is a process of coating the gloss imparting agent on the surface of the article.
Here, the article surface is a surface of an object to which gloss is imparted, and examples thereof include a coating film surface of a coated product and a resin molded product surface. Specific examples of painted products include automobiles, bumpers for automobiles, automobile door mirror covers, motorcycles, train cars, aircraft, furniture, furniture, etc., which are coated on a base made of metal, synthetic resin, or wood Is mentioned. Examples of the resin molded product include a resin molded product colored with a pigment or the like.
Further, the surface of the article may be in a state after it has been used and has lost its gloss, or in a state of a new product.

As a means for applying the gloss-imparting agent to the surface of the article, for example, a spray, a cloth, a brush, a roller, or the like can be used. Among them, spray is preferable because it can more easily and reliably give gloss.
Further, a plurality of the above means may be used in combination.

The wiping process is a process of wiping off excess gloss-imparting agent on the article surface after the coating process.
Examples of methods for wiping off the gloss-imparting agent in the wiping process include mechanical buffing machines (air buffing machines, electric buffing machines, etc.) and manual wiping methods. It is preferable to wipe up with a hand using a lifting tool. The wiping tool is not particularly limited as long as it does not damage the surface of the article, and examples thereof include cloth, paper, sponge and the like. From the viewpoint of appearance beautification, it is preferable to use a microfiber cloth or paper having a smooth surface and fine eyes.
The number of times of wiping is appropriately selected according to the finished appearance, and may be once or twice or more.

In the wiping method, it is preferable to adjust the coating amount and the wiping amount of the gloss-imparting agent so that the film thickness of the glossy coating after the wiping step is in the range of 0.01 to 0.5 μm.
The reason why the glossy film thickness is in the above range is as follows. In other words, many of the factors that cause the loss of luster by whitening the appearance of paint films (particularly automobile paint films) and resin molded products, and causing cloudy patterns on the surface, It is an assembly of small scratches having a depth of 0.5 μm or less. Therefore, if a glossy film with a film thickness of 0.01 to 0.5 μm is formed, whitening and cloudy patterns can be eliminated and gloss can be imparted, the gloss can be restored to the original state, or the original state Better gloss can be obtained. If the thickness of the glossy coating is less than 0.01 μm, it is difficult to provide sufficient gloss. If the thickness of the glossy coating exceeds 0.5 μm, the thickness reaches the visible light region. , Coating spots such as interference fringes are likely to occur.

Here, the film thickness T (μm) of the glossy coating after the wiping process is as follows: coating amount A1 (g) of the gloss imparting agent, nonvolatile content F1 (%) of the gloss imparting agent, and density D1 (g of the gloss imparting agent) / Cm ³ ), the coated area S1 (m ² ), and the wiping rate W1 (%) can be substituted into the following formula (1) and calculated. The non-volatile content F1 (%) of the gloss imparting agent in the formula (1) is the mass after drying A3 (g) / mass before drying A2 (g) when the gloss imparting agent is dried at 105 ° C. for 3 hours × A value obtained from the equation of 100 is used.
T = [(A1 × F1) × (100−W1)] / (D1 × S1 × 10000) (1)
Therefore, in the present invention, it is preferable to adjust the coating amount of the gloss-imparting agent and the wiping rate so that the film thickness T of the gloss coating obtained by the above formula (1) satisfies the following formula (2). .
0.01 μm ≦ T ≦ 0.5 μm (2)

  The method for adjusting the coating amount of the gloss imparting agent is not particularly limited, and examples thereof include a method of appropriately selecting the concentration of the solvent (C) in the gloss imparting agent, the density of the gloss imparting agent, the coating area, and the like. .

The gloss-imparting method is preferably performed within a period of 2 hours in an environment at a temperature of 10 to 80 ° C., for 2 hours in an environment at a temperature of 10 to 50 ° C., from the start of the coating process to the end of the wiping process. Is more preferable. When temperature exceeds 80 degreeC, since reaction of (A) aqueous carbodiimide compound advances rapidly, and it will be high molecular weight in a short time, it exists in the tendency for workability | operativity to fall. When the temperature is less than 10 ° C., the volatilization rate of water or the hydrophilic organic solvent becomes slow, and the working efficiency tends to be lowered.
Moreover, when a coating process and a wiping process are performed over 2 hours, there exists a tendency for reaction of (A) aqueous | water-based carbodiimide compound to advance, and to wipe up easily. In addition, in the glossiness imparting method of the present invention, there is no problem in performing the wiping process immediately after the coating process, but the size of the coated surface is about 5 to 10 minutes from the aspect of management of the coating process. It is preferable to leave an interval.

  The relative humidity is preferably 20 to 90%. When the relative humidity exceeds 90%, the volatilization rate of the solvent (C) tends to be slow, and sufficient durability cannot be obtained in a short time. In order to make the relative humidity less than (lower limit)%, it is necessary to use a special device, which is not convenient.

  After the wiping step, it is preferably left at 10 to 80 ° C. for 10 minutes to 1 week. If left under such conditions, the effects of the present invention can be obtained easily and reliably.

In the gloss imparting method described above, the gloss imparting agent is applied to the surface of the article and wiped up, so that it is applied to the article surface (particularly, the surface of a paint film or resin molded article, and further the surface of an automobile paint film). Can give gloss. Moreover, the gloss film obtained after application lasts for a long time, and a gloss film having excellent durability can be formed by a simple operation.
Therefore, when the gloss applying method is applied to the surface of an article that has lost gloss, the gloss can be brought close to the original gloss. Further, when applied to the surface of a new article, the gloss is further improved, and a reduction in gloss can be prevented over a long period of time.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Hereinafter, a synthesis example of the aqueous carbodiimide compound used in Examples will be described.

(Synthesis Example 1)
A 1 L separable flask was charged with 280.7 g of 4,4′-dicyclohexylmethane diisocyanate and 1.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide as a catalyst, and reacted at 180 ° C. for 15 hours. An isocyanate-terminated dicyclohexylmethane carbodiimide (degree of polymerization = 4) was obtained. Next, 120.0 g of poly (ethylene oxide) monomethyl ether (degree of polymerization = about 12) and 19.3 g of propylene glycol monomethyl ether were added to the resulting isocyanate-terminated dicyclohexylmethane carbodiimide, and reacted at 150 ° C. for 5 hours. After the reaction, the reaction mixture was cooled to 80 ° C., and 578.5 g of distilled water was gradually added to obtain a light yellow transparent aqueous carbodiimide compound (A-1) (nonvolatile content: about 40% by mass).

(Synthesis Example 2)
Into a 1 L separable flask, 233.1 g of 4,4′-diphenylmethane diisocyanate and 1.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide as a catalyst were charged and reacted at 180 ° C. for 15 hours. Terminal diphenylmethane carbodiimide (degree of polymerization = 4) was obtained. Next, 182.7 g of poly (ethylene oxide) monomethyl ether (degree of polymerization = about 12) and 4.2 g of propylene glycol monomethyl ether were added to the resulting isocyanate-terminated diphenylmethane carbodiimide, and reacted at 150 ° C. for 5 hours. After the reaction, the reaction mixture was cooled to 80 ° C., and 578.5 g of distilled water was gradually added to obtain a light yellow transparent aqueous carbodiimide compound (A-2) (nonvolatile content: about 40% by mass).

(Synthesis Example 3)
A 1 L separable flask was charged with 236.8 g of hexamethylene diisocyanate and 1.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide as a catalyst, and reacted at 180 ° C. for 15 hours to give isocyanate-terminated hexamethylene carbodiimide. (Polymerization degree = 4) was obtained. Next, 157.9 g of poly (ethylene oxide) monomethyl ether (degree of polymerization = about 12) and 25.4 g of ethylene glycol monoethyl ether were added to the resulting isocyanate-terminated hexamethylenecarbodiimide, and the mixture was reacted at 150 ° C. for 5 hours. It was. After the reaction, the reaction mixture was cooled to 80 ° C., and 578.4 g of distilled water was gradually added to obtain a light yellow transparent aqueous carbodiimide compound (A-3) (nonvolatile content: about 40% by mass).

(Synthesis Example 4)
Into a 1 L separable flask was charged 194.8 g of tolylene diisocyanate and 1.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide as a catalyst and reacted at 180 ° C. for 10 hours to produce isocyanate-terminated tolylene carbodiimide. (Polymerization degree = 4) was obtained. Next, 219.4 g of poly (ethylene oxide) monomethyl ether (degree of polymerization = about 12) and 5.8 g of ethylene glycol monoisopropyl ether were added to the resulting isocyanate-terminated tolylene carbodiimide and reacted at 150 ° C. for 5 hours. . After the reaction, the reaction mixture was cooled to 80 ° C., and 578.5 g of distilled water was gradually added to obtain a light yellow transparent aqueous carbodiimide compound (A-4) (nonvolatile content: about 40% by mass).

(Synthesis Example 5)
A 1 L separable flask was charged with 216.3 g of xylylene diisocyanate and 1.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide as a catalyst, and reacted at 180 ° C. for 10 hours to produce isocyanate-terminated xylylene carbodiimide. (Polymerization degree = 4) was obtained. Next, 193.3 g of poly (ethylene oxide) monomethyl ether (polymerization degree = about 12) and 10.4 g of propylene glycol monomethyl ether were added to the resulting isocyanate-terminated xylylene carbodiimide, and reacted at 150 ° C. for 5 hours. After the reaction, the reaction mixture was cooled to 80 ° C., and 578.5 g of distilled water was gradually added to obtain a light yellow transparent aqueous carbodiimide compound (A-5) (nonvolatile content: about 40% by mass).

(Synthesis Example 6)
A 1 L separable flask was charged with 251.5 g of hydrogenated xylylene diisocyanate and 1.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide as a catalyst and reacted at 180 ° C. for 15 hours to produce isocyanate-terminated hydrogen. An added xylylene carbodiimide (degree of polymerization = 4) was obtained. Next, 145.2 g of poly (ethylene oxide) monomethyl ether (degree of polymerization = about 12) and 23.3 g of propylene glycol monomethyl ether were added to the resulting isocyanate-terminated hydrogenated xylylene carbodiimide and reacted at 150 ° C. for 5 hours. It was. After the reaction, the reaction mixture was cooled to 80 ° C., and 578.5 g of distilled water was gradually added to obtain a light yellow transparent aqueous carbodiimide compound (A-6) (nonvolatile content: about 40% by mass).

(Synthesis Example 7)
A 1 L separable flask was charged with 221.2 g of isophorone diisocyanate and 1.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide as a catalyst and reacted at 180 ° C. for 15 hours to give an isocyanate-terminated isophorone carbodiimide (polymerization). Degree = 4) was obtained. Subsequently, 194.5 g of poly (ethylene oxide) monomethyl ether (degree of polymerization = about 12) and 4.5 g of propylene glycol monomethyl ether were added to the resulting isocyanate-terminated isophorone carbodiimide, and the mixture was reacted at 150 ° C. for 5 hours. After the reaction, the mixture was cooled to 80 ° C., and 578.4 g of distilled water was gradually added to obtain a light yellow transparent aqueous carbodiimide compound (A-7) (nonvolatile content: about 40% by mass).

(Example 1)
3 g of the aqueous carbodiimide compound (A-1) of Synthesis Example 1 as the component (A) was added to 92 g of ion-exchanged water as the component (C), and the mixture was stirred and homogenized. Furthermore, 5 g of polyoxyethylene-modified dimethyl silicone (product name “SH-3746”, nonvolatile content: 100% by mass) manufactured by Toray Dow Corning Co., Ltd.) as component (B) is added, stirred and homogenized. A gloss imparting agent was prepared. The mass ratio [(A) :( B)] of the content of the component (A) and the content of the component (B) at this time is 19:81, and the content of the component (A) and the component (B) The total amount was 6.2% by weight in the gloss imparting agent.
Using this gloss-imparting agent, the coating film surface of a passenger car and the coating film surface of the painted plate, which are objects to be glossed, were applied as follows, and evaluated after wiping. The evaluation results are shown in Table 1.

In addition, the abbreviation in a table | surface represents the following compound.
SH-3746: Polyoxyethylene-modified dimethyl silicone (Toray Dow Corning Co., Ltd., nonvolatile content: 100%)
KF-619: polyoxyethyleneoxypropylene-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., nonvolatile content: 100%)
PR-3007: Propylene oxide-ethylene oxide copolymer (manufactured by ADEKA, nonvolatile content: 100%)
Softanol 70: secondary alcohol polyethylene oxide adduct (Nippon Shokubai Co., Ltd., nonvolatile content: 100%)
Snowtex 20: Aqueous colloidal silica (manufactured by Nissan Chemical Co., Ltd.)

<1. Evaluation by passenger car>
A coating film of a passenger car (trade name “Fit”, manufactured by Honda Motor Co., Ltd.) having a travel distance of 10,000 km was used as an object to be glossed. The coated surface of the object was washed with a commercially available detergent (trade name “Sunrex K” manufactured by Nikka Chemical Co., Ltd.) and dried. The glossiness (measurement angle 20 °) at this time was 75. Thereafter, the obtained gloss imparting agent was uniformly applied to the coating surface by spray spraying, and then wiped with a dry cloth (trade name “Microcloth” manufactured by Saito Shoten). At that time, from the start of coating to the end of wiping was performed in an environment of a temperature of 20 ° C. for 30 minutes.
Then, after leaving still at 20 degreeC for 30 minutes, it rinsed with running water, naturally dried, and formed the glossy film.
The workability at this time was evaluated as shown in (1) below. In addition, the gloss level of the coating film surface immediately after glossing (after glossing agent coating and wiping treatment) and after 6 months (after running a 6-month running test) are as follows: It was evaluated as follows. Furthermore, the coating film appearance was evaluated as shown in the following (3) on the coating film surface immediately after glossing and after 6 months. These evaluation results are shown in Table 1.

(1) Workability The workability (slip feeling) at the time of wiping after applying the gloss-imparting agent was evaluated in comparison with a commercially available wax (Carnauba wax, manufactured by Suaraster).
○: It had the same slipperiness as a commercially available wax.
Δ: There was some resistance to wiping, but wiping was possible.
X: There was resistance to wiping, and wiping was impossible.
(2) Glossiness Using a micro-TRI-gloss (manufactured by Gardner Co., Ltd.), the glossiness (measurement angle 20 °) of the coating surface was measured.
(3) Appearance of coating film The appearance of the coating film surface was visually judged according to the following criteria.
1: It was glossy and had a fleshiness.
2: The gloss was slightly weak and the surface of the coating film looked a little thin.
3: The gloss was low and the surface of the coating film was thin.
4: Paint spots occurred and the gloss was low.

<2. Evaluation with painted plate>
Cationic electrodeposition coating plate (Testpiece Co., Ltd., JIS G 3141 (SPCC SD)) for test, and intermediate coating (Kansai Paint Co., Ltd., trade name “HS60”) to a dry film thickness of 30 μm Air spray coating was performed, and baking was performed at 140 ° C. for 20 minutes. Subsequently, a blue pearl topcoat base coat (manufactured by Kansai Paint Co., Ltd., trade name “Magicron HM32-1, paint color symbol B-96P”) was applied by air spray so that the dry film thickness was 20 μm. Baked for a minute. Furthermore, a blue pearl top coat top coat paint (manufactured by Kansai Paint Co., Ltd., trade name “Luger Bake HK-4 Clear”) was air sprayed to a dry film thickness of 30 μm and baked at 140 ° C. for 20 minutes. A painted board was created. The resulting coated plate formed a uniform and glossy coating film, but after the small scratch was made with a rough compound (Cut 1-L 5967, manufactured by Sumitomo 3M Co., Ltd.), the compound component was N-hexane and acetone were wiped off in this order to obtain a coated plate having a glossiness (measurement angle of 20 °) of 70. This coated plate was used as an object to be given gloss.
The coated surface of the object is washed with a commercially available detergent (trade name “Sunrex K”, manufactured by Nikka Chemical Co., Ltd.), dried, and then given gloss to the coated surface. After about 0.5 cm ³ of the agent was uniformly applied by spraying, it was wiped with a dry cloth (Microfiber, manufactured by Saito Shoten, trade name “Microcloth”). At that time, from the start of coating to the end of wiping was performed in an environment of a temperature of 20 ° C. for 30 minutes.
Then, after leaving still at 20 degreeC for 30 minutes, it rinsed with running water, naturally dried, and formed the glossy film.
The workability at this time was evaluated in the same manner as (1) in the evaluation using the passenger car. Further, the glossiness was evaluated in the same manner as in (2) above for the coating film surface immediately after glossing (after glossing agent coating and wiping treatment) and after 500 hours of the weathering treatment described below. Further, the appearance of the coating film was evaluated in the same manner as in (3) above, immediately after the gloss application and the coating film surface after 500 hours of weathering treatment. These evaluation results are shown in Table 1.

[Weatherproof treatment]
Using a weather resistance tester (“Xenon Weather-O-Meter CI-4000” manufactured by Atlas Co., Ltd.), the treatment was performed for 500 hours. The treatment conditions were a black panel temperature of 63 ° C., a rain time of 12 minutes during a 2-hour cycle, and an irradiation time of 108 minutes.

<3. Glossy coating thickness>
The thickness of the glossy coating formed from the gloss-imparting agent is the change in the mass of the coated plate before and after applying the gloss-imparting agent when the coated plate is used as the object to be glossed. Post-mass (g) -mass before coating (g)], coating area, density of gloss imparting agent and wiping rate [wiping mass (g) × 100 / (mass after coating (g) -before coating From the mass (g))] (%), the following formula was used. The obtained values are shown in Table 1. Even when the object to be glossed was a passenger car, it was estimated that it was the same as the thickness of the glossy coating obtained by the process for the painted plate because it was treated in the same manner as the painted plate.
Coating film thickness (μm) = [mass after coating (g) −mass before coating (g)] / area (m ² ) / density of gloss imparting agent (g / cm ³ )
Glossy film thickness (μm) = Coating film thickness (μm) × Nonvolatile content of gloss imparting agent (%) × (1-Wipe rate (%) / 100) / 100
The non-volatile content of the gloss-imparting agent is calculated by the following formula using the gloss-imparting agent dried at 105 ° C. for 3 hours in a hot air dryer and using the mass (g) before drying and the mass (g) after drying of the gloss-imparting agent. did.
Nonvolatile content (%) = mass after drying (g) / mass before drying (g) × 100

(Examples 2 to 12)
A gloss-imparting agent was obtained in the same manner as in Example 1 except that the types and blending amounts of component (A), component (B), and component (C) were changed as shown in Table 1 or Table 2. And it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 1 or Table 2.

(Comparative Example 1)
Carnauba wax (manufactured by Shuaraster Co., Ltd.) was applied with a sponge to the paint film surface of the automobile and the paint film surface of the paint plate, which were the objects to be glossed in the same manner as in Example 1, and the cloth (Microfiber, manufactured by Saito Shoten, product) Wiped off with the name "Micro Cloth"). And it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 3.

In addition, the abbreviation in a table | surface represents the following compound.
Carnauba Wax: Shura Aster Carnauba Wax (made by Shuaraster)
Evaphanol HA-10: anionic urethane resin (manufactured by Nikka Chemical Co., Ltd., nonvolatile content: 40%)
Jonkrill 70: Anionic acrylate resin (manufactured by Johnson Polymer Co., Ltd., nonvolatile content: 30%)

(Comparative Examples 2 to 4)
A gloss-imparting agent was obtained in the same manner as in Example 1 except that the types (A), (B), (C), and other components, and the blending amounts thereof were changed as shown in Table 3. And it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 3.

According to the gloss imparting agents of Examples 1 to 12 containing (A) an aqueous carbodiimide compound, (B) an aqueous liquid organic compound, and (C) a solvent in a specific ratio, the gloss imparting agent has excellent glossiness and appearance. A glossy film having excellent durability could be formed. Moreover, it was excellent in workability and could easily form a glossy film. In particular, when polyether-modified silicones are used as the aqueous liquid organic compound (B), the effect is more exhibited.
On the other hand, the gloss imparting agent of Comparative Example 1 using carnauba wax was excellent in the glossiness after glossing and the coating film appearance, but lacked durability.
The gloss imparting agents of Comparative Examples 2 and 3 in which a urethane resin or an acrylate resin and a polyether-modified silicone are combined have low workability, and excellent glossiness and coating film appearance cannot be obtained.
Comparison in which the mass ratio [(A) :( B)] of the content of the (A) aqueous carbodiimide compound is (A) the content of the aqueous carbodiimide compound and the content of the (B) aqueous liquid organic compound is less than 8:92 With the gloss imparting agent of Example 4, excellent glossiness and coating film appearance could not be obtained.
Comparison in which the mass ratio [(A) :( B)] of the content of the (A) aqueous carbodiimide compound is (A) the content of the aqueous carbodiimide compound and the content of the (B) aqueous liquid organic compound is more than 92: 8 With the gloss imparting agent of Example 5, excellent glossiness and coating film appearance could not be obtained, and workability was also low.

Claims (6)

(A) an aqueous carbodiimide compound,
(B) an aqueous liquid organic compound,
(C) water or a mixed solvent of water and a hydrophilic organic solvent,
Containing
A wipe-type gloss imparting agent, wherein the mass ratio [(A) :( B)] of the content of the component (A) and the content of the component (B) is 8:92 to 92: 8. The wipe-type gloss imparting agent according to claim 1, wherein the (A) aqueous carbodiimide compound is a compound represented by the following general formula (1).

(In the formula, R ¹ and R ² each independently represent a divalent residue having 4 to 15 carbon atoms, excluding the isocyanate group of the diisocyanate compound, and R ³ and R ⁴ each independently represents the number of carbon atoms. 1 to 5 represents an alkoxy group or a hydroxy group, R ⁵ and R ⁶ each independently represents an alkylene group having 2 to 4 carbon atoms, and a and b are each independently any one of 1 to 30 Represents an integer, and n represents an integer of 1 to 10.)   The wipe-type gloss imparting agent according to claim 1 or 2, wherein the total content of the component (A) and the component (B) is 0.5 to 30% by mass.   The wipe-type gloss imparting agent according to any one of claims 1 to 3, wherein the (B) aqueous liquid organic compound is a polyether-modified silicone. A coating step of coating the wipe-type gloss imparting agent according to any one of claims 1 to 4 on the surface of the article;
A method for imparting gloss to an article surface, comprising a step of wiping off an excessive wiping-type gloss imparting agent on the article surface after the coating step.   The method for imparting luster to an article surface according to claim 5, wherein the process from the start of the coating process to the end of the wiping process is performed in an environment of 10 to 80 ° C within 2 hours.