JP2003212947A - Low temperature curing type coating composition with pleasant touch - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating film that gives pleasant feeling with slimy or moist touch, a coating composition to obtain the coating film and a polymeric fine particle which is mixed into the coating composition. <P>SOLUTION: The fine particle of a lanolin-adhered polyurethane resin is obtained by reacting at least one kind of a polyester resin or a polyether resin with a polyisocyanate having two or more isocyanato groups in the presence of a lanolin derivative in a poor solvent. The coating composition is characterized by containing (i) at least one binder resin selected from the group consisting of a polyester resin and a polyether resin, having a glass transition temperature of -30 to -70°C, a number-average molecular weight of 1,000 to 50,000 and a hydroxy value of 30 to 70 mgKOH/g resin, (ii) a polyisocyanate having two or more isocyanato groups, (iii) the fine particle of lanolin-adhering polyurethane resin and (iv) an organic solvent. A coated material is obtained by applying the coating composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to fine particles of polyurethane resin, a coating composition containing the particles having a pleasant touch, and a coated article obtained by coating the coating composition.

[0002]

2. Description of the Related Art Matte coating is generally applied to automobile interior parts such as an instrument panel in order to give a high-class feeling and a favorable feeling. In addition, matte paint may be applied to interior goods.

Conventional matting paints include silica, diatomaceous earth,
Inorganic fine powders such as alumina and calcium carbonate, and acrylic resin fine powders are used as matting agents. The coating film obtained with such a coating is hard and lacks elasticity as a coating film, and therefore lacks in "slick feeling" (moist feeling).

A matte coating film using a fine polyurethane resin powder as a matting agent has elasticity, but the surface of the coating film becomes uneven and rough and lacks surface smoothness.

As described above, the conventionally provided paints are
After all, a sufficient "slickness (moist feeling)" has not been obtained, and it is not sufficient as a tactile paint.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a coating film having a slimy feel (moisturizing feel) and a pleasant feel, and a coating composition for obtaining the coating film.

[0007]

[Means for Solving the Problems] Although it has been conventionally considered difficult to quantify tactile sensation, the concept of "soft value (S value)" for quantifying tactile sensation has recently been established [(Company ) Automotive Engineering Society, Academic Lecture Preprints, No.87-99, p19-22 (199
9), Kawazu Kenji et al .; SAE Technical Paper Series, 1362 (20
00-01), K. Kwazu et al.]. S value is dry and wet feeling, rough feeling,
It is a value obtained by using the four sensitivities of thermal sensation and softness.

Then, the feel of the coating film containing the inorganic fine powder and the acrylic resin fine powder was quantified by the S value,
It was found that the surface was hardened by the matting agent, lacked elasticity as a coating film, and was considerably poor in dry and wet feeling and soft feeling.
On the other hand, the coating film using the polyurethane fine powder is superior to the coating film containing the inorganic fine powder or the acrylic resin fine powder in terms of hardness and softness, but the dry and wet feeling is poor, and the "slick feeling" ( I found that it lacked "moist feeling".

The present inventor obtained by blending a polyurethane resin fine powder and lanolin in a coating composition in the course of various investigations in order to improve a dry and wet feeling and a soft and soft feeling and to give a "slimy feeling". The feel of the coating film was evaluated. Although the coating film had a slimy feel, it was inferior in beef tallow resistance, adhesion, recoat adhesion, moisture resistance and abrasion resistance.

As a result of further research, at least one selected from the group consisting of polyester resins and polyether resins and a polyisocyanate having two or more isocyanate groups were prepared in the presence of a lanolin derivative.
By using lanolin-adhered polyurethane resin fine particles, which can be obtained by reacting in a poor solvent, as a matting agent, a coating with a good feel that is excellent in "slickness" and excellent in beef tallow resistance, adhesion, recoat adhesion, etc. I found that I could get a membrane.

Further, the present inventor has examined the improvement of low temperature curability and pot life of such coating composition. In the curable resin composition, generally, in order to improve the curability, it is usually 0.1 to the total solid content of the coating composition.
About 5% by weight of a reaction accelerator is added, and in order to extend the pot life, a specified amount relative to the amount of the reaction accelerator normally used, generally, based on the total solid weight of the coating composition. A means of blending a reaction retarder in an amount of about 1% by weight has been adopted. With respect to the coating composition of the present invention, low-temperature curability could not be achieved by the conventional means, so an attempt was made to add a reaction accelerator in an amount larger than usual. In this case, a usual amount was added as a reaction retarder, but a long pot life was not obtained. In the process of further study, if a large amount of a reaction retarder is blended, the solubility of polyisocyanate is lowered, and it was thought that a coating composition having a long pot life could not be obtained, but it is surprising. In particular, as a result of trying to add a large amount of reaction retarder to a large amount of reaction accelerator, it was found that the polyisocyanate does not solidify and the contradictory effects of excellent low temperature curability and long pot life can be achieved at the same time. .

The present invention has been completed based on these findings.

That is, the present invention provides the invention according to the following items. Item 1 Lanolin-attached polyurethane resin fine particles, which consist of a lanolin derivative and polyurethane resin fine particles, and cannot remove (retain) the lanolin derivative even if washed with a good solvent for the lanolin derivative. Item 2 Consisting of a lanolin derivative and polyurethane resin fine particles, the lanolin derivative cannot be removed (retained) even if washed with a good solvent for the lanolin derivative, and the average particle size is 5 to 40 μm.
m is lanolin-adhered polyurethane resin fine particles. Item 3 It can be obtained by reacting at least one selected from the group consisting of polyester resins and polyether resins with a polyisocyanate having two or more isocyanate groups in the presence of a lanolin derivative in a poor solvent. Alternatively, the lanolin-adhered polyurethane resin fine particles according to item 2. Item 4 The amount of the lanolin derivative attached is at least one selected from the group consisting of polyester resins and polyether resins in the presence of the lanolin derivative and 2 or more isocyanate groups.
When a polyisocyanate having two or more polyisocyanates is reacted in a poor solvent, at least one selected from the group consisting of polyester resins and polyether resins in the absence of a lanolin derivative and a polyisocyanate having two or more isocyanate groups Compared to the case of reacting in a poor solvent,
Item 4. The lanolin-adhered polyurethane resin fine particles according to Item 3, which is in an amount such that the increase in the average particle size is 1 to 5 µm. Item 5. At least one selected from the group consisting of polyester resins and polyether resins and a polyisocyanate having two or more isocyanate groups are reacted in the presence of a lanolin derivative in a poor solvent. The method for producing lanolin-adhered polyurethane resin fine particles according to 1 or 2. Item 6 (i) Glass transition point is −30 to −70 ° C., number average molecular weight is 1,000 to 50,000, and hydroxyl value is 3
0 to 70 mgKOH / g resin, at least 1 selected from the group consisting of polyester resin and polyether resin
Coating composition containing two kinds of binder resin, (ii) polyisocyanate having two or more isocyanate groups, (iii) lanolin-adhered polyurethane resin fine particles according to item 1 or 2, and (iv) organic solvent . Item 7 The binder resin and the isocyanate group are 2
Item 7. The composition according to Item 6, wherein the lanolin-adhered polyurethane resin fine particles are contained in an amount of 5 to 20 parts by weight based on a total weight of 100 parts by weight of the polyisocyanate having one or more of them. Item 8 (v) further comprises a reaction accelerator and (vi) reaction retarder,
The content of the reaction accelerator is 0.2 to 2% by weight based on the total solid content of the composition, and the content of the reaction retarder is 5 to 15 weight based on the total solid content of the composition. %, The composition according to item 6, wherein Item 9 The binder resin has a glass transition point of −30 to −30.
-70 ° C and number average molecular weight of 1,000 to 250,000
00, having a hydroxyl value of 50 to 70 mgKOH / g resin and at least one selected from the group consisting of polyester resins and polyether resins, wherein the lanolin-adhered polyurethane resin fine particles are composed of lanolin derivatives and polyurethane resin fine particles. , The lanolin derivative could not be removed (retained) even after washing with a good solvent for the lanolin derivative, the average particle size was 5 to 40 μm, and the hydroxyl value was 50 to 200 mgK.
OH / g resin, and the mixing ratio of the binder resin (b) and the polyisocyanate (p) is b: p by weight.
= 80: 20 to 40:60, Item 8
The composition according to. Item 10 The reaction accelerator (x) and the reaction retarder (y)
The ratio of the compounding amount of x: y = 1: 20 to 1:
Item 7. The composition according to Item 8, which is 7.5. Item 11 The composition according to Item 8, wherein the reaction accelerator is a tin-based catalyst. Item 12 A coated article obtained by applying the coating composition according to Item 6 to an object to be coated.

Item 13 A coated article having a coating film having an S value of 0.51 to 1. Item 14 The coated article according to Item 13, wherein the coating film is a coating film obtained by applying the coating composition according to Item 6 to an object to be coated. Item 15. The method according to Item 5, wherein the lanolin derivative is a polyoxyalkylene (addition mole number 5 to 75) lanolin alcohol. Item 16. The poor solvent is at least one selected from the group consisting of xylene, toluene, mineral spirits, cyclohexane, and n-hexane.
The manufacturing method described in. Item 17. The method according to Item 5, wherein the reaction is performed in the presence of a carbodiimide reagent. Item 18. The method according to Item 5, wherein the reaction is carried out in the presence of an oil-modified alkyd resin and a salt of naphthenic acid. Item 19 Total weight of the binder resin and the polyisocyanate having two or more isocyanate groups is 100
Item 7. The lanolin-attached polyurethane resin fine particles are contained in an amount of 5 to 20 parts by weight, and the organic solvent is contained in an amount such that the solid content is 20 to 30% by weight, relative to parts by weight. Coating composition. Item 20 An automobile interior product obtained by applying the coating composition according to item 6 to an article to be coated. Item 21: The coating composition according to Item 8, wherein the amount of the reaction accelerator compounded is 0.4 to 2% by weight based on the total weight of the solid content of the composition. Item 22: The coating composition according to Item 8, wherein the compounding amount of the reaction retarder is 6 to 12% by weight based on the total solid weight of the composition. Item 23: The coating composition according to Item 11, wherein the tin-based catalyst is at least one selected from the group consisting of tin octylate, tin naphthenate, and dibutyltin dilaurate. Item 24: The coating composition according to Item 8, wherein the reaction retarder is at least one selected from the group consisting of ethyl acetoacetate, butyl acetoacetate, and acetylacetone. Item 25: The coating composition according to Item 8, wherein the blending amount of the polyurethane resin fine particles is 5 to 20 parts by weight based on 100 parts by weight of the total weight of the binder resin and the polyisocyanate.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

1 The lanolin-attached polyurethane resin of the present invention
Fine Particles The lanolin-adhered polyurethane resin fine particles of the present invention are lanolin-adhered polyurethane resin fine particles which are composed of a lanolin derivative and polyurethane resin fine particles and which are not removed by washing with a good solvent for the lanolin derivative (for example, xylene or toluene).

The lanolin-adhered polyurethane resin fine particles can be used, for example, by being blended with a coating composition. When the fine particles are added to the coating composition, the average particle size is 5 to 4
The thickness is preferably about 0 μm, more preferably about 5 to 35 μm, further preferably about 10 to 35 μm.

Further, in order to obtain excellent low temperature curability and long pot life for a coating composition containing the lanolin-adhered polyurethane resin fine particles, the following fine particles are generally preferred: Has a hydroxyl value of 5
0 ~ 200mgKOH / g resin, especially 50 ~ 150mgKOH
/ g resin and / or the width of the particle size distribution of the fine particles is narrow. For example, in the particle size distribution measurement by a laser diffraction type particle size distribution measuring device, the particle size is 20 to 30 μm.
90% or higher.

1-1 Lanolin attached polyurethane resin fine
Physical Properties of Particles The lanolin-adhered polyurethane resin fine particles of the present invention do not dissolve the polyurethane resin, but the lanolin derivative is not substantially removed by washing with a solvent that dissolves the lanolin or the lanolin derivative (that is, washing with xylene or toluene). The weight loss and particle size change of the lanolin-adhered polyurethane resin microparticles are not substantially before and after), so the details have not been fully elucidated, but the lanolin derivative is bound to the polyurethane resin surface through a covalent bond. Seem. The washing can be carried out by dispersing the lanolin-adhered polyurethane resin fine particles of the present invention in a good solvent for the lanolin derivative at about 15 to 40 ° C. and stirring for about 30 to 60 minutes.

The average particle diameter of the lanolin-adhered polyurethane resin fine particles is determined by a laser diffraction type particle size distribution measuring device [LA5
00 (manufactured by HORIBA, Ltd.)].

The amount of lanolin attached is determined by reacting at least one selected from the group consisting of polyester resins and polyether resins with a polyisocyanate having two or more isocyanate groups in the presence of a lanolin derivative in a poor solvent. In the same manner, the average particle size in the case of being in a poor solvent is at least one selected from the group consisting of polyester resin and polyether resin and polyisocyanate having two or more isocyanate groups except that the lanolin derivative is not present. The amount by which the increase in the average particle size is about 1 to 5 μm is preferable, and the amount by which the increase in the average particle size is about 1 to 3 μm is more preferable than the average particle size in the case of reaction.

That is, the amount of lanolin attached is such that when at least one selected from the group consisting of the above polyester resin and polyether resin is reacted with a polyisocyanate having two or more isocyanate groups in a poor solvent. The average particle diameter of the lanolin-attached polyurethane resin fine particles of the present invention obtained by reacting in the presence of the present invention is about 1 to 5 μm, as compared with the average particle diameter of the polyurethane resin fine particles obtained by the same reaction in the absence of lanolin.
In particular, the amount is about 1 to 3 μm.

1-2 Production Method The lanolin-adhered polyurethane resin fine particles can be produced, for example, as follows. That is, by reacting at least one selected from the group consisting of polyester resins and polyether resins with a polyisocyanate having two or more isocyanate groups in the presence of a lanolin derivative in a poor solvent, the lanolin of the present invention can be obtained. Adhesive polyurethane resin particles can be produced.

1-2-1 Lanolin Derivative Lanolin, which is a raw material for the lanolin derivative, is a kind of animal wax which is a wool fat produced as a by-product when wool is taken from raw sheep hair. Its chemical composition is not necessarily constant depending on the type and production area of sheep, weather conditions, etc., but its alcohol portion is dominated by aliphatic alcohols, cholesterols, triterpene alcohols, and the acid portion is normal fatty acid, isofatty acid, Antiiso-fatty acids and hydroxy fatty acids are said to occupy most. Thus, since lanolin is a mixture of many compounds, it usually has a paste form at room temperature and has a property of melting at several tens of degrees when heated, but it is essentially insoluble in water.

Various derivatives can be obtained by purifying such lanolin or adding chemical modification thereto. For example, alcohols and acid moieties obtained by hydrolyzing lanolin, which are fractionated and purified by solvent fractionation and the like, are examples of derivatives, but their hydrolyzates or lanolin itself are acetylated, alkoxylated, sulfonated, hydrogenated. A lanolin derivative is also a compound to which a chemical action such as oxidization, transesterification, or reduction is added.

In the present invention, any of these lanolin derivatives can be used. Among them, especially, those obtained by introducing alkylene oxide such as ethylene oxide or propylene oxide into lanolin and its derivative (=
Polyoxyalkylene lanolin alcohol; Usually, one having an addition mole number of ethylene oxide or propylene oxide of about 5 to 75, particularly about 10 to 30 is preferable. ), A salt introduced with a hydrophilic group such as a sulfate group or a phosphate group, and a salt thereof, and an alkali metal salt or ammonium salt of lanolin fatty acid.

The lanolin derivative may be a commercially available product, for example, the product names Bellpol A-20, Bellpol L-30, Bellpol L-50, Bellpol L-75 [all are
Manufactured by Nippon Seika Co., Ltd., etc.

The amount of the lanolin derivative used is usually about 5 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of at least one kind of polyester resin and polyether resin used for producing the polyurethane resin fine particles.
It is about part by weight.

1-2-2 Polyester Resin The polyester resin is obtained by subjecting a polybasic acid and a polyhydric alcohol to an esterification reaction by a usual method.

Polybasic acid has two carboxyl groups in one molecule.
Or more, especially 2 to 4 compounds, specifically, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, suberic acid,
Aliphatic polybasic acids such as pimelic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid; phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, tetrachlorophthalic acid, trimellitic acid, pyromellitic acid Aromatic polybasic acids such as acids; Hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hexahydrotrimellitic acid, methylhexahydroisophthalic acid, tetrahydrophthalic acid, tetrahydroisophthalic acid and other alicyclic polybasic acids Acid etc. are mentioned. The anhydrides of these polybasic acids can also be used in the present invention. Among these, terephthalic acid, adipic acid, maleic acid, maleic anhydride and phthalic anhydride are more preferable.

The polyhydric alcohol is a compound having two or more hydroxyl groups, particularly 2 to 4 hydroxyl groups in one molecule.
Ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, dipropylene glycol, butanediol, pentanediol, cyclohexanediol, neopentyl glycol, lactone-polyol adduct, glycerin, trimethylolpropane, trimethylolethane, pentol, water Aliphatic and alicyclic polyhydric alcohols such as added bisphenol A can be mentioned. Among these, ethylene glycol, glycerin and pentol are more preferable.

The polyester resin used for producing the lanolin-adhered polyurethane resin fine particles of the present invention can be obtained by subjecting the polybasic acid and the polyhydric alcohol as exemplified above to an esterification reaction by a usual method.

The molecular weight of the polyester resin is not particularly limited, but usually the number average molecular weight is 4,000.
0 to 40,000, preferably 15,000 to 3
The thing of about 10,000 is used.

The hydroxyl value of the polyester resin used in the production of the lanolin-adhered polyurethane resin fine particles of the present invention is not particularly limited, but is 20 to 80 mg.
About KOH / g resin is preferable, 40 ~ 70mgKOH / g resin
The degree is more preferable.

1-2-3 Polyether Resin As the polyether resin, polyethylene glycol,
Examples include polypropylene glycol and polyethylene-propylene glycol.

The polyether resin used for producing the lanolin-adhered polyurethane resin fine particles of the present invention can be obtained by polymerizing ethylene oxide, propylene oxide or the like as a raw material by a usual method. The molecular weight of the polyether resin is not particularly limited, but a number average molecular weight of about 4,000 to 40,000, preferably about 15,000 to 30,000 is usually used.

The hydroxyl value of the polyether resin used for producing the lanolin-adhered polyurethane resin fine particles of the present invention is not particularly limited, but is 20 to 80 mg.
About KOH / g resin is preferable, 40 ~ 70mgKOH / g resin
The degree is more preferable.

1-2-4 Two or more isocyanate groups
The polyisocyanate having 2 or more isocyanate groups is a compound having 2 or more, and especially 2 to 4 free isocyanate groups in one molecule. Specifically, aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as isophorone diisocyanate; Aromatic diisocyanates such as: triphenylmethane-4,4 ', 4 "-
Triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,
4'-dimethyldiphenylmethane-2,2 ', 5,5'
-Organic polyisocyanates such as polyisocyanates having three or more isocyanate groups such as tetraisocyanate.

In the polyisocyanate having two or more of these isocyanate groups, the isocyanate groups may be blocked with a blocking agent. Examples of the blocking agent include phenol type, lactam type, active methylene type, alcohol type, mercaptan type, acid amide type, imide type, amine type, imidazole type, urea type, carbamic acid ester type, imine type, oxime type, and sulfite type. Any blocking agent such as a salt type can be used. In particular, phenol-based, lactam-based, alcohol-based, and oxime-based blocking agents can be preferably used.

As the polyisocyanate having two or more isocyanate groups, various commercially available products can be used. For example, Vernock D-750, -800 and DN-95.
0, the same DN-970, the same DN-15-455 (these are all manufactured by Dainippon Ink and Chemicals, Inc., trade name), Desmodur L, the same N, the same HL, the same N3390 (these are all Sumitomo Bayer Urethanes). Company name, trade name), Takenate D
-102, -202, -110, -123N (all are manufactured by Takeda Pharmaceutical Co., Ltd., trade name), Coronate EH, L, HL, 203 (all manufactured by Nippon Polyurethane Industry Co., Ltd.) , Brand name), Duranate E-40
2-90T, 24A-90CX (manufactured by Asahi Kasei Corporation, trade name) and the like.

The amount of the polyisocyanate having two or more isocyanate groups used is usually M to 1.3M, 1.1M to 1.M with respect to at least one selected from the group consisting of polyester resins and polyether resins. 2M (M represents the amount of polyisocyanate in which the amount of isocyanate groups is stoichiometrically equivalent to the amount of hydroxyl groups in the resin).

That is, the amount of the polyisocyanate having two or more isocyanate groups used is at least 1 selected from the group consisting of polyester resins and polyether resins.
Generally, [amount (M) that provides an isocyanate group stoichiometrically equivalent to the hydroxyl group amount of the resin] to [an isocyanate group stoichiometrically equivalent to the hydroxyl group amount of the resin] with respect to the species. Such an amount (M) + M of about 30% (1.3M)], preferably [an amount (M) + M of 1 such that an isocyanate group stoichiometrically equivalent to the hydroxyl amount of the resin is obtained].
0% (about 1.1M)] to [amount (M) that gives an isocyanate group stoichiometrically equivalent to the amount of hydroxyl groups of the resin.
20% (1.2M) of + M].

1-2-5 Poor Solvent In the present specification, the poor solvent is a solvent which does not dissolve the obtained polyurethane resin fine particles and has a small ability to dissolve at least one of the polyester and polyether resins. Means a solvent having no reactivity with the polyisocyanate having two or more isocyanate groups. Examples of the poor solvent include aromatic hydrocarbons such as xylene and toluene; alicyclic hydrocarbons such as cyclohexane and ethylcyclohexane; saturated aliphatic hydrocarbons such as n-hexane; and mineral spirits.

The poor solvent is at least one selected from the group consisting of polyester resins and polyether resins.
It can be used in a proportion of usually about 500 to 1,000 parts by weight, preferably about 600 to 800 parts by weight, based on parts by weight.

1-2-6 Attachment Agent (Carbodiimide) When producing the polyurethane resin fine particles, an attachment agent may be used. Since the adhesion reagent reacts with a carboxyl group, a hydroxyl group, and an amino group, it acts as a medium during the reaction between the polyisocyanate having two or more isocyanate groups and the lanolin derivative, or when it is present in the reaction system, It is used for the purpose of working to narrow the intermolecular distance between the polyisocyanate having two or more and the lanolin derivative. As the adhesion reagent, N, N'-dicyclohexylcarbodiimide, carbodiimide reagents such as 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide are preferably exemplified, and particularly N, N'-
Dicyclohexylcarbodiimide is preferred.

When an adhesion reagent is used, its amount is usually 5 parts by weight per 100 parts by weight of at least one kind selected from the group consisting of polyester resins and polyether resins.
It is preferably about 30 to 30 parts by weight, particularly about 8 to 15 parts by weight.

1-2-7 Dispersion Aid A dispersion aid may be added to the reaction system. Examples of the dispersion aid include oil-modified alkyd resin, naphthenic acid salt, polycarboxylic acid, high molecular weight unsaturated ester, and silicone.

As the oil-modified alkyd resin, coconut oil-modified alkyd resin, castor oil-modified alkyd resin, rice bran oil-modified alkyd resin, tall oil-modified alkyd resin, linseed oil-modified alkyd resin, soybean oil-modified alkyd resin can be used. it can.

The oil-modified alkyd resin is a polyhydric alcohol component such as ethylene glycol, neopentyl glycol, propylene glycol, trimethylolpropane, hexanediol, glycerin, pentaerythritol, butanediol and isophthalic acid, terephthalic acid, adipic acid, sebacine. Acid, succinic acid, maleic acid or an acid component such as an anhydride thereof is polymerized by a conventional method,
Furthermore, it is modified with coconut oil, castor oil and the like.

The oil-modified alkyd resin used in the present invention is
A resin having an oil length of 10 to 50%, preferably 20 to 45% is desirable. Here, the oil length means the weight ratio (%) of the oil contained in the oil-modified alkyd resin. The oil-modified alkyd resin used in the present invention has a hydroxyl value of 50 to 160.
About mgKOH / g resin is preferable, 70 ~ 130mgKOH / gre
The degree of sin is more preferable, the acid value is preferably about 15 mgKOH / g resin or less, more preferably about 9 mgKOH / g resin or less.

Preferred examples of the salt of naphthenic acid include metal salts of naphthenic acid such as zinc naphthenate and iron naphthenate.

As the dispersion aid, these may be used alone or in combination of two or more kinds.

When a dispersion aid is used, the amount used is 5 to 30 with respect to 100 parts by weight of at least one selected from the group consisting of polyester resins and polyether resins.
It is about 10 parts by weight, preferably about 10 to 20 parts by weight.

The combination of two or more dispersing aids is preferably an oil-modified alkyd resin (particularly coconut oil-modified alkyd resin) and a salt of naphthenic acid, and an oil-modified alkyd resin (particularly coconut oil-modified alkyd resin). And a zinc naphthenate combination is more preferred.
In this case, the weight ratio is as follows: oil-modified alkyd resin (or coconut oil-modified alkyd resin): naphthenic acid salt (or zinc naphthenate) = 100: 1 to 1
About 00:20 is preferable, and 100: 3 to 100: 10.
A degree is preferable.

1-2-8 Reaction Catalyst A reaction catalyst is used in the reaction of at least one selected from the group consisting of polyester and polyether resins in the presence of a lanolin derivative with a polyisocyanate having two or more isocyanate groups. May be. Such catalysts include amines such as trimethylenebis (4-aminobenzoate), dimethylethanolamine, triethyleneamine, tetramethylpolymethylenediamine, tris (dimethylaminomethyl) phenol, tin octylate, tin naphthenate, Any of the salts commonly used for urethane reactions, such as metal salts such as cobalt naphthenate, zinc naphthenate, and dibutyltin dilaurate, bismuth higher carboxylate, can be used alone or in combination of two or more.

The amount of the catalyst used can be appropriately set according to the amount and type of the other raw materials, but is based on 100 parts by weight of at least one selected from the group consisting of polyester resins and polyether resins. Usually 0.0
It is about 1 to 5 parts by weight, preferably about 0.03 to 3 parts by weight, and more preferably about 0.07 to 2 parts by weight. Further, in order to obtain excellent low temperature curability and long pot life of the coating composition containing the fine particles, the amount of the catalyst used is at least one selected from the group consisting of polyester resin and polyether resin. Generally, about 0.02 to 5 parts by weight, preferably 0.1 to 100 parts by weight.
The amount is about 07 to 2 parts by weight, more preferably about 1 to 2 parts by weight.

1-2-9 Reaction Conditions In the production method of the present invention, for example, at least one selected from the group consisting of a lanolin derivative, a polyester resin and a polyether resin, and a polyisocyanate having two or more isocyanate groups, Furthermore, if necessary, add an adhesion reagent, etc. to the poor solvent,
About 70 to 100 ° C., preferably about 80 to 95 ° C., about 0.5 to 3 hours, preferably about 1 to 1.5 hours,
Continue the reaction with stirring.

Further, in order to obtain excellent low temperature curability and long pot life of the coating composition containing the fine particles, the reaction temperature is generally preferably about 90 to 95 ° C.

When a dispersion aid or a reaction catalyst is used, it may be added after the lanolin derivative, polyester or polyether resin is added to the poor solvent and sufficiently dispersed.

When the reaction is terminated, a reaction terminator such as propylene glycol monomethyl ether or propylene glycol butyl ether may be added to the reaction system. The amount of the reaction terminator added is at least one selected from the group consisting of polyester resins and polyether resins.
It is usually about 10 to 50 parts by weight, preferably about 20 to 40 parts by weight, relative to 00 parts by weight.

The reaction mixture containing the lanolin-attached polyurethane resin fine particles thus obtained may be used as it is for the preparation of the tactile coating composition of the present invention, or the reaction mixture containing the lanolin-attached polyurethane resin fine particles may be prepared by a conventional method, For example, in poor solvents such as those exemplified above (for example, aromatic hydrocarbons such as xylene and toluene; alicyclic hydrocarbons such as cyclohexane and ethylcyclohexane; mineral spirits; saturated aliphatic hydrocarbons such as n-hexane). It is also possible to obtain a lanolin-adhered polyurethane resin fine powder by diluting with water, isolating by filtering with a wire mesh of about 325 mesh and drying.

2. The touch-sensitive coating composition of the present invention The touch-sensitive coating composition of the present invention has (i) a glass transition point of −30.
To -70 ° C, and the number average molecular weight is 1,000 to 50,
000, hydroxyl value is 30 ~ 70mgKOH / g resin,
At least one binder resin selected from the group consisting of polyester resins and polyether resins, (ii) polyisocyanates having two or more isocyanate groups, (ii)
i) A coating composition comprising the lanolin-adhered polyurethane resin fine particles according to the present invention described in the above item 1 "Lanoline-adhered polyurethane resin fine particles according to the present invention" and (iv) an organic solvent.

2-1 Binder Resin The binder resin (i) of the coating composition of the present invention has a glass transition point of −30 to −70 ° C., a number average molecular weight of 1,000 to 50,000, and a hydroxyl group. Value is 30 ~ 7
0, and at least one resin selected from the group consisting of polyester resins and polyether resins is used.

The binder resin contained in the coating composition of the present invention has a glass transition point of about -30 to -70 ° C,
About -30 to -60 ° C is preferable, and about -30 to -50 ° C is more preferable.

The molecular weight of the binder resin is such that the number average molecular weight is about 1,000 to 50,000.
3,000 to 35,000 is preferable, and 3,000 to 3
About 10,000 is more preferable. Further, when trying to obtain excellent low temperature curability and long pot life for the coating composition of the present invention, the number average molecular weight of the binder resin is
Generally, it is preferably about 1,000 to 25,000, more preferably about 5,000 to 20,000, and even more preferably about 10,000 to 18,000.

When the molecular weight of the binder resin is within the above range, the resulting coating film is unlikely to change with time, which is preferable. Therefore, it is suitable for coating, for example, interior parts of automobiles, particularly instrument panels.

The hydroxyl value of the binder resin is
30 ~ 70mgKOH / g resin, 40 ~ 70mgKOH
/ g resin is preferable, and 45 to 70 mgKOH / g resin is more preferable. Further, in order to obtain excellent low temperature curability and long pot life of the coating composition of the present invention, the hydroxyl value of the binder resin is generally preferably about 50 to 70 mgKOH / g resin, ~
68mgKOH / g resin is more preferable, 58 ~ 65mgK
OH / g resin is more preferable.

The polyester resin is the above-mentioned 1-2.
2 It can be obtained by subjecting a polybasic acid and a polyhydric alcohol as exemplified in the section of "Polyester resin" to an esterification reaction by a usual method.

The polyester resin used as the binder resin is preferably a highly linear polyester resin.

Further, as such a polyether resin,
Polyethylene glycol, polypropylene glycol,
Examples thereof include polyethylene-propylene glycol. These are obtained by polymerizing ethylene oxide, propylene oxide, or the like as a raw material by a usual method so as to satisfy the requirements of the binder resin described above.

The content of the binder resin in the coating composition is usually about 20 to 80% by weight as the resin solid content,
It is preferably about 30 to 70% by weight.

2-2 Have two or more isocyanate groups
Polyisocyanate having two or more isocyanate groups
(ii) is used as a curing agent in the coating composition of the present invention.

As the polyisocyanate having two or more isocyanate groups, any of the polyisocyanates having two or more isocyanate groups exemplified in 1-2-4 "Polyisocyanate having two or more isocyanate groups" is exemplified. Can be used.

The amount of the curing agent used is usually such that the weight ratio to the solid content of the binder resin contained in the coating composition is binder resin (b): polyisocyanate (p) = 77: 23.
~ 45.5: 54.5, preferably 70: 30-4
The amount is about 6.5: 53.5.

When it is desired to obtain excellent low temperature curability and long pot life for the coating composition of the present invention,
The amount of the curing agent used is generally such that the weight ratio of the solid content of the binder resin contained in the coating composition to the binder resin (b): polyisocyanate (p) = 80: 20-4.
The amount is preferably about 0:60, 75: 25 ~
The amount is preferably about 50:50.

2-3 Lanolin-attached polyurethane resin
Particles As lanolin-adhered polyurethane resin particles (iii),
1 above "Polyurethane resin fine particles adhered with lanolin of the present invention"
The polyurethane resin fine particles according to the present invention described in the item 1) are blended.

The amount of the lanolin-adhered polyurethane resin fine particles to be added to the coating composition is usually 5 parts by weight based on 100 parts by weight of the binder resin and the polyisocyanate having two or more isocyanate groups. To about 30 parts by weight, preferably 5 to 2
It is about 0 parts by weight, more preferably about 5 to 15 parts by weight.

2-4 Reaction Accelerator and Reaction Retardant The coating composition of the present invention contains a reaction accelerator and a reaction retarder.
It can be blended in a predetermined ratio.

As the reaction accelerator which can be added to the coating composition of the present invention, a conventional reaction accelerator used for promoting the urethane reaction in the field of coating composition may be used. As such a reaction accelerator, tin-based reaction accelerators such as tin octylate, tin naphthenate and dibutyltin dilaurate are preferably used. These reaction accelerators can be used alone or in combination of two or more kinds.

Conventionally, when such a reaction accelerator is used,
Usually, it is used in an amount of about 0.1% by weight based on the total solid weight of the composition. However, in the present invention, the compounding amount of these reaction accelerators in the coating composition of the present invention is usually 0.2 with respect to the total solid content of the composition.
Is about 2 to 2% by weight, preferably about 0.4 to 2% by weight, and more preferably about 0.5 to 1.5% by weight.

As the reaction retarder that can be added to the coating composition of the present invention, those conventionally used as a reaction retarder in the urethane reaction in the field of coating compositions can be used. Such reaction retarder, ethyl acetoacetate, C ₁ ~ ₄ lower alkyl esters of acetoacetic acid such as acetoacetic acid butyl, acetyl acetone and the like.

Conventionally, when such a reaction retarder is used,
Usually, it is used in an amount of about 2% by weight based on the total solid content of the composition. However, when the reaction retarder is compounded in the coating composition of the present invention, the compounding amount is usually about 5 to 15% by weight, preferably 6% by weight based on the total solid content of the composition.
It is about 12 to 12% by weight, more preferably about 6 to 10% by weight.

The ratio of the compounding amount of the reaction accelerator (x) to the reaction retarding agent (y) is usually (x) :( y) = 1: 20 to 1: 7.
It is about 5, preferably about 1:15 to 1: 8, and more preferably about 1:12 to 1:10.

In general, a coating composition having excellent low temperature curability has a short pot life, but the coating composition of the present invention has an excellent low temperature curing property by blending a reaction accelerator and a reaction retarder in the above specified amounts. The two contradictory effects of gender and long pot life can be achieved at the same time.

2-5 Manufacture of Coating Composition The coating composition of the present invention may contain the same components as those contained in conventional coating compositions, as long as the desired effects of the present invention can be obtained. Good. For example, inorganic fine powders such as silica, diatomaceous earth, alumina and calcium carbonate, which have been conventionally used as matting agents, and acrylic resin fine powders may be blended as necessary.

The coating composition of the present invention comprises the polyurethane resin fine particles of the present invention, a binder resin, and an isocyanate group of 2
Using polyisocyanate having more than one and optionally other components, for example, reaction accelerator, reaction retarder, using an organic solvent as a solvent, according to a usual method,
The optimum viscosity for painting can be appropriately set.
For example, the solid content is about 20 to 30% by weight, and the viscosity value of FC (Ford Cup) No. 4 is about 12 to 14 s (2
It is preferable to adjust the temperature to be 0 ° C.). As the organic solvent, an organic solvent such as the poor solvent (for example, n-heptane, n-hexane, cyclohexane, benzene, toluene, xylene, etc.) described in the section 1-2-5 “Poor solvent” may be used. It is also possible to use an organic solvent other than the poor solvent. When the same solvent as the poor solvent used for producing the lanolin-adhered polyurethane resin fine particles to be blended in the coating composition is used as the organic solvent for preparing the coating composition, refer to 1-2 “Production method” above. It is convenient because the reaction mixture (suspension) containing the lanolin-adhered polyurethane resin fine particles obtained as described above can be used as it is.

When a specific amount of a reaction accelerator and a reaction retarder is added to the coating composition of the present invention, it has excellent low-temperature curability and can be cured by heating at 70 ° C. for about 5 minutes, which is similar to lacquer. It has a film forming property. Moreover, the pot life is long, for example, it reaches 2 to 4 hours at a temperature of 0 to 35 ° C. Thus, the coating composition of the present invention containing a specific amount of a reaction accelerator and a reaction retarder is a coating composition that simultaneously exhibits the contradictory effects of excellent low temperature curability and long pot life, and relates to coating film formation. It is preferable in terms of energy and line cost, and is very suitable for industrial use.

The pot life of the coating composition of the present invention containing a specific amount of the reaction accelerator and the reaction retarder is preferably 2 hours or more. The pot life is, for example, the time at which the viscosity increase measured by a Ford cup (Ford cup No. 4 at 20 ° C.) after preparing the coating composition is 2 seconds. If the increase in viscosity does not exceed 2 seconds in a Ford cup, it is not necessary to dilute with a solvent, and workability is excellent. The viscosity of the Ford cup immediately after preparation of the coating composition of the present invention is preferably about 12 to 14 s.
Even after exceeding, if it is not gelled, it can be used by diluting it to such an extent that it can be applied.

3 Article of the Present Invention The present invention was obtained according to the method described by Kenji Kawazu et al. In the Society of Automotive Engineers, Preprints for Academic Lectures, No.87-99, p19-22 (1999). A product (article) having a coating film having an S value of 0.51 to 1, preferably the coating composition of the present invention described in the above item 2 "Taste-sensitive coating composition of the present invention" on the surface of an object to be coated. Painted products (articles) are also included.

The above-mentioned coating composition of the present invention can be applied by a method which is usually used, for example, an air spray method, an airless spray method, a flow coater method or the like. The coating composition is usually at room temperature to 100.
At a temperature of about ℃, preferably about 75 ~ 90 ℃,
A coating film that is sufficiently cured and has a good tactile sensation is formed. When the coating composition of the present invention contains a reaction accelerator and a reaction retarder, it generally cures sufficiently at room temperature to about 90 ° C., preferably at about 65 to 75 ° C. It forms a good coating film. The coating amount of the favorable touch coating film can be appropriately set according to the application of the object to be coated, but usually the film thickness is about 10 to 70 μm (after curing), preferably 25 to
The amount is preferably about 45 μm (after curing). The curing time may be such that the coating film cures to a desired degree according to the set temperature. When the coating composition of the present invention contains a reaction accelerator and a reaction retarder, it has excellent low temperature curability, and therefore the time until curing is, for example, about 70 ° C. and about 5 minutes.

Examples of the article to be coated for forming the touch-sensitive coating film include automobile interior parts (for example, instrument panel (instrument panel), door trim, console panel, center cluster, switch panel, meter hood, shift knob) and the like. , Various kinds of plastic materials usually used for interior materials (wall materials, handrails, doorknobs, desk top plates and other interior materials), surface treatment, undercoating, intermediate coating, etc. Examples thereof include a composite member in which these materials are combined.

The plastic material is not particularly limited and may be selected from a wide range, and examples thereof include acrylonitrile-styrene-butadiene copolymer, polypropylene resin, thermoplastic polyolefin and the like.

The product (article) coated with the above-mentioned coating composition of the present invention has a coating film having a sufficiently rough feeling and warm and cold feeling.
Further, the coating film is excellent in dry and wet feeling and hard and soft feeling, and is a coating film having a sufficient slimy feeling and a favorable touch feeling. For example, the S value is 0.51 to 1. Further, since the above-mentioned coating composition contains the fine polyurethane resin particles of the present invention, the resulting coating film has excellent adhesion, recoat adhesion, and oil and fat stain resistance. Such products are particularly suitable for automobile interior parts such as automobile instrument panels and interior parts such as interior materials.

[0094]

EXAMPLES The present invention will be described in more detail with reference to the following examples and test examples.

Example 1 Polyurethane resin with lanolin attached
Production of fine particles First, polyester polyol [Desmon No. 2200;
Product name; Nippon Polyurethane Industry Co., Ltd.] 60 g and lanolin derivative [polyoxyethylene (20) lanolin alcohol; Bellpol A-20; Product name; Nissei Sangyo Co., Ltd.]
10 g together with 7.0 g of N, N-dicyclohexylcarbodiimide (adhesion reagent) in xylene (poor solvent, 445 g)
Pour in and coconut oil modified alkyd resin (oil length 33) [Teslac 2052-60; trade name; manufactured by Hitachi Chemical Polymer Co., Ltd.]
9.0 g and zinc naphthenate 0.56 g (both dispersion aids) were allowed to coexist and heated to 85 ° C. with stirring.

Next, 32.5 g of hexamethylene diisocyanate (Coronate HL; trade name; manufactured by Nippon Polyurethane Industry Co., Ltd.) and 50 mg of dibutyltin dilaurate (reaction catalyst) were added, and the mixture was suspended at 85 ° C. for 1 hour under non-uniform conditions. Suspension polymerization was performed.

After 1 hour, 20 g of propylene glycol monomethyl ether was added as a reaction terminator, and the mixture was stirred for about 10 minutes. Polyurethane resin fine particles in which about 3 μm of lanolin was attached to the surface of spherical polyurethane resin fine particles having an average particle diameter of about 30 μm. 650 g of suspension solution containing 260 g
Got The average particle diameter was measured by using a laser diffraction particle size distribution analyzer [LA500 (manufactured by Horiba, Ltd.)].

Even if the dried lanolin-adhered polyurethane resin fine particles were washed with xylene and toluene after filtering the suspension, the lanolin derivative could not be removed.

Reference Example 1 A suspension (solid content concentration 40%) containing 260 g of polyurethane resin fine particles was obtained in the same manner as in Example 1 except that the lanolin derivative was not added.

Examples 2 to 7 I-i) Preparation of coating composition A coating composition was prepared using the following components a) to e).

A) Binder resin glass transition point is −40 ° C., number average molecular weight is 3,000,
Linear polyester resin having a hydroxyl value of 40 mgKOH / g resin b) Polyisocyanate having two or more isocyanate groups (curing agent) Hexamethylene diisocyanate multimer (Duranate; E-402-90-T; Trade name; Asahi Kasei Corporation) C) Lanolin-adhered polyurethane resin fine particles obtained in Example 1 (polyurethane resin fine particles used were those contained in the suspension as they were) d) Organic solvent xylene e) Silica fine powder (silica fine particles) The powder is generally used as a delustering agent for paints, and the amount of the delustered delustered lanolin-adhered polyurethane resin particles of the present invention is supplemented to make each coating film have the same gloss. The coating compositions of Examples 2 to 7 were prepared by stirring and mixing the binder resin and the matting agent in 40 parts by weight of xylene according to the composition shown in Table 1, The coating composition was prepared by dispersing it in the suspension obtained in Example 1 so that the solid content of the coating composition was 25%. The curing agent was added to the composition just before coating.

Comparative Example 1 The procedure of Example 5 was repeated except that the suspension obtained in Reference Example 1 was used instead of the suspension obtained in Example 1.
A coating composition (solid content: 26% by weight) having the composition shown in Table 1 was prepared.

Comparative Example 2 A coating composition (solid content: 25% by weight) having the composition shown in Table 1 was prepared in the same manner as in Comparative Example 1 except that 40 parts by weight of xylene was further added to Bellpole A-20 which is a lanolin derivative. Prepared.

Comparative Example 3 As in Example 5, except that bellol A-20, which is a lanolin derivative, was further added to 40 parts by weight of xylene, and xylene itself was used instead of the suspension obtained in Example 1. A coating composition (solid content: 25% by weight) having the composition shown in Table 1 was prepared.

[0105]

[Table 1]

I-ii) The coating compositions of Coating Examples 2 to 7 and Comparative Examples 1 to 3 were applied to an acrylonitrile-styrene-butadiene copolymer so that the coating film thickness (after drying) was about 30 to 40 μm. A test piece was obtained by coating the substrate and drying at 80 ° C. for 30 minutes.

I-iii) Performance Evaluation (Adhesiveness) After the test piece obtained in I-ii) was left at room temperature for 48 hours, a cross -cut tape peeling test was performed to confirm the adhesiveness of the coating film. evaluated. In addition, place the test piece in a wet box (50 ° C,
It was left to stand for more than 95% RH) for 240 hours, and then a cross-cut tape peeling test was carried out to evaluate the adhesion of the coating film. The cross-cut tape peeling test was carried out by making 100 squares of 2 mm × 2 mm on the coating film by scratching with a cutter knife, applying a cellophane adhesive tape to the portion, and then peeling. The results are shown in Table 2.

[0108]

[Table 2]

(Tactile sensation) 48 hours after the test piece was dried, the tactile sensation was evaluated using the S value.

The respective values were obtained according to the measuring device and the correlation formula described in the Society of Automotive Engineers of Japan, Preprints for Academic Lectures, No. 87-99, p19-22 (1999).

[0111] In addition, such a reference value is a conventional lacquer paint coating film, a two-component urethane paint coating film (what is said to be soft) and natural leather that is excellent in touch, etc. are evaluated, and after making an S value distribution, It was set as an area with excellent tactile sensation.

The results are shown in Table 3.

[0113]

[Table 3]

(Beef tallow resistance) Beef tallow (reagent commonly used for beef tallow resistance test: manufactured by Kanto Kagaku Co., Ltd.) was applied to the surface of the coating film of the test piece at 2 g / 100 cm ^2, and the atmosphere was kept at 80 ° C. The test piece was left in an electric furnace without forced convection for 1 week. At that time, a flannel (a kind of cloth) was placed on the test piece in order to keep the volatilization amount of beef tallow constant.

After one week, the test piece was thoroughly washed with a small amount of a neutral detergent, and then a film peeling test with an adhesive tape (cellophane tape) and a dry cloth friction test with an abrasion tester were performed.

The peeling test was carried out by cross-cutting (making a cut mark on X) on the test surface of the test piece with a cutter knife, adhering a cellophane tape to that portion, and then peeling off the cellophane tape. .

On the other hand, in the dry cloth abrasion test, five layers of gauze were used as a friction element, and the friction element was subjected to a load of 40.0 on the surface of the test piece.
It was reciprocated 200 times at 9 kPa and a stroke of 100 mm. Evaluation Criteria: Peeling ◯: No peeling, ×: Peeling, dry cloth rubbing ◯: No exposure of base material, ×: Exposure of base material The results are shown in Table 4.

[0118]

[Table 4]

Beef tallow resistance is an index of oil and fat stain resistance,
When the "peeling" evaluation in Table 4 is ○, the adhesiveness is good enough to prevent adhesion inhibition due to natural oils and fats, and when the "dry cloth friction" is ○, the coating film does not swell due to natural oils and fats. The coating film has good barrier properties.

(Recoat Adhesion) The recoat adhesion of the test pieces obtained in the above I-ii) was evaluated according to the following method.

After the coated film was dried under the drying conditions shown in I-ii) above, immediately, and to confirm the change over time, left for 1 day, 3 days, 1 week, 10 days. After that, the same coating composition was applied onto each of the coating films, and the recoat adhesion was evaluated by a cross-cut tape peeling test. The cross-cut tape peeling test was carried out by making 100 squares of 2 mm × 2 mm on the coating film by scratching with a cutter knife, applying a cellophane adhesive tape to the portion, and then peeling. The results are shown in Table 5 below.

[0122]

[Table 5]

In Table 5, "○" means that there was no peeling between the coating film / recoat coating film immediately after drying and after aging, and the adhesiveness was satisfied, and "X" was applied immediately after or after aging. It means that peeling occurred in at least one cross-cut between the film / recoat coating film.

Example 8 Polyurethane resin with lanolin attached
Production of fine particles First, polyester polyol [Desmon No. 2200;
Product name; Nippon Polyurethane Industry Co., Ltd.] 60 g and lanolin derivative [polyoxyethylene (20) lanolin alcohol; Bellpol A-20; Product name; Nissei Sangyo Co., Ltd.]
10 g together with 7.0 g of N, N-dicyclohexylcarbodiimide (adhesion reagent) in xylene (poor solvent, 445 g)
Pour in and coconut oil modified alkyd resin (oil length 33) 9.
0 g and zinc naphthenate 0.56 g (both are dispersion aids)
Was coexisted and heated to 90 ° C. with stirring.

Next, 32.5 g of hexamethylene diisocyanate (Coronate HL; trade name; manufactured by Nippon Polyurethane Industry Co., Ltd.) and 55.3 mg of dibutyltin dilaurate (reaction catalyst) were added, and the mixture was heated at 90 ° C. for 90 minutes under non-uniform conditions. Suspension polymerization was carried out below.

After 1 hour, 20 g of propylene glycol monomethyl ether was added as a reaction terminator and the mixture was stirred for about 10 minutes. About 3 μm of lanolin adhered to the surface of spherical polyurethane resin fine particles having an average particle diameter of about 30 μm, and the hydroxyl value was increased. 650 g of a suspension containing 260 g of lanolin-adhered polyurethane resin fine particles having 150 mg KOH / g resin was obtained. The average particle diameter was measured by using a laser diffraction particle size distribution analyzer [LA500 (manufactured by Horiba, Ltd.)].

[0127] The lanolin derivative could not be removed even by washing the dried lanolin-adhered polyurethane resin fine particles with xylene and toluene after filtering the suspension.

Examples 9 to 15 II-i) Preparation of coating composition A coating composition was prepared using the following components a) to g).

A) Binder resin glass transition point is −40 ° C., number average molecular weight is 3,000,
Linear polyester resin having a hydroxyl value of 40 mgKOH / g resin and an elastic modulus of 30 MPa b) Polyisocyanate having two or more isocyanate groups (curing agent) Multimer of hexamethylene diisocyanate (Duranate; E-402-90-T; Product name; Asahi Kasei Kogyo Co., Ltd.) c) Lanolin-attached polyurethane resin fine particles obtained in Example 8 (The lanolin-attached polyurethane resin fine particles were used in the form of suspension as they were) d) Reaction accelerator dibutyl Chindilaurate e) Reaction delay agent butyl acetoacetate f) Organic solvent xylene g) Silica fine powder (Silica fine powder is generally used as a delustering agent for paints, and is insufficient even if lanolin-attached polyurethane resin particles are blended. The coating compositions of Examples 9 to 15 are listed in Table 6 to compensate for the degree of matting, and to mix the coatings so that each coating has the same gloss. The binder resin and the delusterant according to the composition shown in (4) are stirred and mixed in 40 parts by weight of xylene, and then dispersed in the suspension obtained in Example 8 so that the solid content of the coating composition is 25% by weight. A coating composition was prepared so that The curing agent, reaction accelerator and reaction retarder were added to the composition immediately before coating.

[0130]

[Table 6]

Pot life of coating composition The viscosity of the coating composition immediately after mixing the components (a) to (g) in predetermined amounts is measured, and then the lid is covered so that the solvent does not evaporate, and the temperature is set to 20 ° C.
The sample was allowed to stand in the atmosphere described in 1 above and viscosity was measured with time. The results are shown in Table 7 below.

[0132]

[Table 7]

The viscosity was measured with Ford cup No. 4,
The values in Table 7 are "seconds (s) / Ford Cup No.4 / 20
℃ ”is shown.

The coating compositions of the examples all had a pot life of 2 hours or more (the time from the viscosity immediately after preparation of the coating until the viscosity increased by 2 s).

Further, the coating compositions of Examples 9 to 15 were in a liquid state for up to 4 hours by adding a specific amount of the retarder and the accelerator, so that they could be coated by diluting.

II-ii) Coating The coating compositions of Examples 9 to 15 were applied to an acrylonitrile-styrene-butadiene copolymer substrate so that the coating film thickness (after drying) was about 30 to 40 μm, and 70 5 at ℃
It was dried for a minute to obtain a test piece.

II-iii) Evaluation of coating film performance (adhesiveness) After allowing the test piece obtained in II-ii) to stand at room temperature for 48 hours, a cross -cut tape peeling test was carried out, and the coating film Adhesion was evaluated. In addition, place the test piece in a wet box (50 ° C,
It was left to stand for more than 95% RH) for 240 hours, and then a cross-cut tape peeling test was carried out to evaluate the adhesion of the coating film. The cross-cut tape peeling test was carried out by making 100 squares of 2 mm × 2 mm on the coating film by scratching with a cutter knife, applying a cellophane adhesive tape to the portion, and then peeling. The results are shown in Table 8.

[0138]

[Table 8]

(Tactile sensation) 48 hours after the test piece was dried, the tactile sensation was evaluated using the S value.

The respective values were obtained according to the measuring device and the correlation formula described in the Society of Automotive Engineers of Japan, Preprints for Academic Lectures, No. 87-99, p19-22 (1999).

[0141] In addition, such a reference value was evaluated using conventional lacquer paint coatings, two-component urethane paint coatings (which are said to have a soft touch) and natural leather with excellent touch, and the S value distribution was calculated. After being manufactured, it was set as a region having excellent tactile sensation.

The results are shown in Table 9.

[0143]

[Table 9]

(Beef tallow resistance) Beef tallow (reagent commonly used for beef tallow resistance test: manufactured by Kanto Chemical Co., Inc.) on the coating film surface of the test piece
Was applied in an amount of ² g / 100 cm ² and the test piece was left in an electric furnace without forced convection at 80 ° C. for one week. At that time, a flannel (a kind of cloth) was placed on the test piece in order to keep the volatilization amount of beef tallow constant.

After one week, the test pieces were thoroughly washed with a small amount of a neutral detergent, and then a film peeling test with an adhesive tape (cellophane tape) and a dry cloth friction test with an abrasion tester were performed.

The peeling test was carried out by cross-cutting (making a cut mark on X) on the test surface of the test piece with a cutter knife, sticking a cellophane tape on that portion, and then peeling off the cellophane tape. .

On the other hand, in the dry cloth abrasion test, five layers of gauze were used as a friction element, and the friction element was subjected to a load of 40.0 on the surface of the test piece.
It was reciprocated 200 times at 9 kPa and a stroke of 100 mm. Evaluation criteria: Peeling ◯: No peeling, ×: Peeling, dry cloth rubbing ◯: No exposure of base material, ×: Exposure of base material The results are shown in Table 10.

[0148]

[Table 10]

Beef tallow resistance is an index of oil and fat stain resistance,
When the "peeling" evaluation in Table 10 is ○, the adhesion to the article is good enough to prevent adhesion inhibition by natural oils and fats, and when the "dry cloth friction" is ○, coating with natural oils and fats is performed. The film does not swell and the coating film has good barrier properties.

(Recoat Adhesion) The recoat adhesion of the test pieces obtained in the above II-ii) was evaluated according to the following method.

After drying the coated film under the drying conditions shown in II-ii), immediately after drying, and for confirming the change over time, left for 1 day, 3 days, 1 week, 10 days. After standing, the same coating composition was applied onto each of the coating films, and the recoat adhesion was evaluated by a cross-cut tape peeling test. The cross-cut tape peeling test uses a 100 mm grid of 2 mm x 2 mm on the coating film.
Each piece was scratched with a cutter knife, and a cellophane adhesive tape was attached to that portion, and then peeled off. The results are shown in Table 11 below.

[0152]

[Table 11]

In Table 11, "○" means that there was no peeling between the coating film / recoat coating film immediately after drying and after aging, and the adhesiveness was satisfied, and "x" means immediately after drying or after aging. It means that peeling occurred in at least one cross-cut between the coating film / recoat coating film.

[0154]

EFFECTS OF THE INVENTION The coating composition of the present invention satisfies the standard values of dry and wet feeling, soft feeling, rough feeling and warm and cool feeling, and shows an excellent S value, that is, an excellent touch feeling. Further, it has excellent adhesiveness and recoat adhesiveness, and also has excellent oil and fat stain resistance.

Further, the coating composition of the present invention containing a predetermined amount of the reaction accelerator and the reaction retarder is excellent in low-temperature curability and has a long pot life. Therefore, it is excellent in energy and line cost. And is very suitable for industrial use.

Continued front page    (72) Inventor Hiroyuki Arimoto             Ohashi, 40 Taiheidai, Shoo-cho, Katsuta-gun, Okayama Prefecture             Gaku Kogyo Co., Ltd. (72) Inventor Osamu Shoji             Ohashi, 40 Taiheidai, Shoo-cho, Katsuta-gun, Okayama Prefecture             Gaku Kogyo Co., Ltd. (72) Inventor Takayuki Kishimoto             Ohashi, 40 Taiheidai, Shoo-cho, Katsuta-gun, Okayama Prefecture             Gaku Kogyo Co., Ltd. (72) Inventor Kenji Kawazu             1 Toyota Town, Toyota City, Aichi Prefecture Toyota Auto             Car Co., Ltd. (72) Inventor Mika Kai             1 Toyota Town, Toyota City, Aichi Prefecture Toyota Auto             Car Co., Ltd. F-term (reference) 4J034 BA03 BA05 BA07 CA03 CA23                       CB02 CB07 DB03 DB07 DF01                       DF14 DF15 DF16 DF19 DF20                       DF21 DF22 DF27 DF29 DG03                       DG04 DG09 EA01 EA11 EA18                       HA01 HA06 HA07 HA08 HA09                       HC03 HC12 HC13 HC22 HC46                       HC52 HC61 HC64 HC67 HC71                       HC73 HD01 HD03 HD04 HD05                       HD06 HD07 HD08 HD09 HD12                       JA02 JA03 JA14 JA30 KA01                       KB02 KC17 KD02 KD12 KE02                       MA24 QA02 QA05 QA07 QC04                       QC05 RA05 RA07 RA12 SA02                 4J038 DF022 DG002 DG111 DG131                       GA03 JA34 JA47 JA56 JC39                       JC43 KA04 KA06 KA08 KA20                       MA13 MA14 NA06

Claims (12)

[Claims] 1. A lanolin-adhered polyurethane resin particle comprising a lanolin derivative and polyurethane resin particles, the lanolin derivative being unable to be removed by washing with a good solvent for the lanolin derivative. 2. A lanolin-adhered polyurethane resin fine particle comprising a lanolin derivative and polyurethane resin fine particles, wherein the lanolin derivative cannot be removed even by washing with a good solvent for the lanolin derivative, and the average particle diameter is 5 to 40 μm. 3. Obtained by reacting at least one selected from the group consisting of polyester resins and polyether resins with a polyisocyanate having two or more isocyanate groups in the presence of a lanolin derivative in a poor solvent. The lanolin-adhered polyurethane resin fine particles according to claim 1 or 2, which can be obtained. 4. The adhesion amount of the lanolin derivative is such that at least one selected from the group consisting of a polyester resin and a polyether resin reacts with a polyisocyanate having two or more isocyanate groups in the presence of the lanolin derivative in a poor solvent. In comparison with a case where at least one selected from the group consisting of polyester resin and polyether resin and polyisocyanate having two or more isocyanate groups are reacted in a poor solvent in the absence of a lanolin derivative, The lanolin-adhered polyurethane resin fine particles according to claim 3, wherein the amount of increase in average particle diameter is 1 to 5 µm. 5. A method comprising reacting at least one selected from the group consisting of polyester resins and polyether resins with a polyisocyanate having two or more isocyanate groups in the presence of a lanolin derivative in a poor solvent. The method for producing lanolin-adhered polyurethane resin fine particles according to claim 1 or 2. 6. (i) A glass transition point of −30 to −70 ° C., a number average molecular weight of 1,000 to 50,000, a hydroxyl value of 30 to 70 mgKOH / g resin, a polyester resin and a polyether. At least one binder resin selected from the group consisting of resins, (ii) polyisocyanate having two or more isocyanate groups, (iii) lanolin-attached polyurethane resin fine particles according to claim 1 or 2,
(iv) A coating composition containing an organic solvent. 7. The lanolin-attached polyurethane resin fine particles are contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of a total weight of the binder resin and the polyisocyanate having two or more isocyanate groups. Item 7. The composition according to Item 6. 8. The method further comprises (v) a reaction accelerator and (vi) a reaction retarder, wherein the amount of the reaction accelerator is 0.2 to 2% by weight based on the total solid content of the composition. The composition according to claim 6, wherein the compounding amount of the reaction retarder is 5 to 15% by weight based on the total solid content of the composition. 9. The binder resin has a glass transition point of −30 to −70 ° C. and a number average molecular weight of 1,000 to.
25,000 with a hydroxyl value of 50-70 mgKOH / g re
sin, which is at least one selected from the group consisting of polyester resins and polyether resins, wherein the lanolin-adhered polyurethane resin fine particles consist of lanolin derivatives and polyurethane resin fine particles, and the lanolin can be washed with a good solvent for the lanolin derivative. The derivative could not be removed, the average particle size was 5-40 μm, and the hydroxyl value was 50-200 mgKOH / g.
resin, and the compounding ratio of the binder resin (b) and the polyisocyanate (p) is b: p = 8 by weight ratio.
9. It is 0: 20-40: 60, It is characterized by the above-mentioned.
The composition according to. 10. The weight ratio of the reaction accelerator (x) and the reaction retarder (y) is x: y = 1: 2.
Composition according to claim 8, characterized in that it is between 0 and 1: 7.5. 11. The composition according to claim 8, wherein the reaction accelerator is a tin-based catalyst. 12. A coated article obtained by coating the article to be coated with the coating composition according to claim 6.