JP2968620B2 - Composite resin particles and coating composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite resin particle comprising a collagen particle which is a natural protein compound and a resin,
And a coating composition using the particles.

[0002]

2. Description of the Related Art In recent years, coating compositions for imparting a unique tactile sensation to coated substrates have been used in household goods, automobile interior parts, OA equipment,
It is used in various fields such as building materials and electrical products. The feature of these coating compositions is a unique feel when touching various painted products, and a special touch is imparted by blending resin particles colored as an extender pigment with a paint binder resin, A soft touch is expressed by blending extenders such as silica and talc with a paint binder resin having soft rubber elasticity.

[0003] Further, there has been proposed a coating composition exhibiting a leather-like touch in which natural polymer compound particles derived from proteins such as collagen and chitosan and polysaccharides are blended with a binder.

[0004]

However, in such a conventional coating composition, for example, in the case of a coating composition obtained by blending a resin binder or an extender such as silica with a paint binder resin. However, it has not been possible to obtain a coating composition having a moist, real leather-like feel.

[0005] Therefore, attempts have been made to obtain a coating composition closer to real leather by blending collagen particles obtained by crushing and purifying natural leather into a paint.
However, in this method, although a moist leather-like texture excellent in water absorption and release properties is obtained, a soft touch cannot be obtained because the collagen particles are hard, and collagen particles are not absorbed or released due to water absorption and release. There are problems such as a decrease in adhesion to a coating substrate due to a change in volume.

Accordingly, the present invention has moist, and with obtaining the coating composition capable of suppressing a decrease in the adhesion to coating Somotozai simultaneously to have the texture of leather-like soft texture, hardness and particle size It is an object of the present invention to obtain collagen-containing composite resin particles capable of controlling the uniformity of the composition.

[0007]

Since the present invention SUMMARY OF THE INVENTION The to solve the above problems, wraps a portion of a resin having a crosslinked structure particles of collagen, a natural protein compound, or <br/> wrapped partially divided portion exposed is intended to provide a new composite resin particles you (hereinafter referred to as collagen composite resin particles), also there is provided a coating composition of the present collagen composite resin particles are contained in the binder resin.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention focuses on the change in volume of a substance obtained by processing collagen, which is a natural protein compound into powder or particles, due to the water absorption and release properties of the substance. This has been achieved as a result of studying the use of resin particles as an extender or the like of a coating composition.

[0009] The main components of the collagen composite resin particles of the present invention are a resin and collagen particles.
Various resins such as an acrylic resin, an epoxy resin, a polyester resin, a urethane resin, and a polyolefin resin can be considered. The selection is made based on the affinity with the binder resin used in the coating composition.

However, when a coating composition is prepared using such collagen composite resin particles and a resin, it is necessary to obtain a tactile sensation closer to that of real leather and to suppress a decrease in adhesion to a coating substrate. Preferably, the mechanical properties of the resin used for the collagen composite resin particles are soft resins having rubber elasticity, and since the coating composition generally contains an organic solvent component, the resin used for the collagen composite resin particles is It is desirable to have a crosslinked structure.

The collagen used in the present invention also includes collagen that has been chemically treated to improve heat resistance and chemical resistance, and collagen particles that have been dyed. The above is the main component of the collagen composite particles, but collagen composite resin particles combined with a coloring pigment for coloring the collagen composite resin particles, and various stabilizers for the purpose of improving heat stability, light stability, etc. Collagen composite resin particles to which is added.

The collagen composite resin particles of the present invention are prepared by synthesizing resin particles in advance and then mechanically embedding or fusing collagen fine powder, or by suspending a mixture of resin monomer or oligomer and collagen fine powder. It is obtained by polymerizing by a turbid polymerization method or the like.

In this case, when the collagen composite resin particles are spherical, the size of the collagen composite resin particles is preferably within a range of 100 μm or less.
In cases other than spherical, those having an average major axis of 100 μm or less are suitable. The reason is that when collagen composite particles having an average particle diameter or an average major axis of 100 μm or more are applied to artificial leather or a coating composition, problems such as roughening of the finished surface of the coating occur, which is not preferable. When the size of the collagen composite resin particles is within this range, when the resin used together with the collagen particles has rubber elasticity, the resin having rubber elasticity effectively absorbs the volume change due to the absorption and release of moisture of the collagen particles. Therefore, the decrease in the adhesive force of the coating composition containing the collagen composite resin particles to the coating substrate is effectively suppressed, which is preferable.

As the binder resin of the coating composition used together with the above-mentioned collagen composite resin particles, there may be mentioned resins used in various fields. For example,
Acrylic resin, urethane resin, epoxy resin, alkyd resin, polyamide resin, organosiloxane resin, polyester resin and the like can be exemplified. These resins are selected according to the environment in which the coating composition is used and the coating substrate, and are not particularly limited. Also,
It may be used together with commonly used extender pigments, coloring pigments, resin particles, antiwear agents, ultraviolet absorbers and the like.

In the coating composition of the present invention, the collagen composite resin particles obtained as described above are used as an extender of the coating composition or as a coloring pigment when colored, and the mechanical properties of the cured film are broken. Strength of 20 to 500 kg / cm ² and maximum elongation of 20
% Of the binder resin having a rubber elasticity of not less than 0.1%, the binder resin further absorbs the volume change of the collagen particles due to the absorption and release of water, so that the adhesion to the coating substrate is reduced. At the same time, a leather-like coating composition having a moist and soft touch can be obtained.

Here, the breaking strength of the cured film is 20 k
The use of a binder resin of not more than g / cm ² is not preferable because the coating film of the coating composition tends to become brittle. The breaking strength of the cured film is 500 kg / cm ²
When the above binder resin is used, it is difficult to obtain a good touch because the coating film of the coating composition tends to be hard. On the other hand, if a resin having soft mechanical properties with rubber elasticity is selected as the resin of the collagen composite resin particles,
Further, it is possible to obtain a coating composition which has a good touch feeling and at the same time does not reduce the adhesive force to the coating substrate.

Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited thereto.

Example 1 Plaxel 220AL (polycaprolactone diol manufactured by Daicel Chemical Industries, Ltd.) 50 parts by weight, Plaxel 30
3 (Caprolactone triol manufactured by Daicel Chemical Industries, Ltd.), 10 parts by weight of CX-285 (collagen powder manufactured by Showa Denko KK) and 5 parts by weight of carbon black together with 25 parts by weight of methyl ethyl ketone in a paint shaker To obtain 100 parts by weight of a paste containing collagen.

To 100 parts by weight of this paste, 20 parts by weight of Desmodur W (a diisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) and 10 parts by weight of Coronate EH (an isocyanate oligomer manufactured by Nippon Polyurethane Co., Ltd.) were added and sufficiently stirred. Then, 500 ml of a 1% carboxymethylcellulose aqueous solution is put into a 1 L separable flask equipped with a thermometer and a stirrer, and 100 g of this isocyanate-containing paste is stirred while high-speed stirring is performed.
Was gradually added and stirring was continued for 30 minutes.

After that, while continuing stirring, 8 hours
When the temperature was raised to 0 ° C. and stirring was further continued for 24 hours,
80 g of black urethane particles containing collagen particles and having a particle diameter of 200 μm were obtained. After the black urethane particles enclosing the collagen particles or partially enclosing them and partially exposed are washed with water and dried,
The particles were classified to not more than μm to obtain collagen composite resin particles.

Example 2 50 parts by weight of PLACCEL 220AL (polycaprolactone diol manufactured by Daicel Chemical Industries, Ltd.), PLAXEL 30
3 (Caprolactone triol manufactured by Daicel Chemical Industries, Ltd.) was dispersed in a mixture of 10 parts by weight of carbon black and 35 parts by weight of methyl ethyl ketone with a paint shaker to obtain 100 parts by weight of a paste.

To 100 parts by weight of this paste, 20 parts by weight of Desmodur W (a diisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) and 10 parts by weight of Coronate EH (an isocyanate oligomer manufactured by Nippon Polyurethane Co., Ltd.) were added and sufficiently stirred. Then, 500 ml of a 1% carboxymethylcellulose aqueous solution was put into a 1 L separable flask equipped with a thermometer and a stirrer, and 100 g of this isocyanate-containing paste was gradually added thereto while stirring at a high speed, and stirring was continued for 30 minutes. While stirring was continued, 10 g of CX-280 (collagen powder manufactured by Showa Denko KK) was gradually added to the dispersion medium.

Thereafter, the temperature was raised to 80 ° C. in one hour,
When stirring was continued for 4 hours, 80 g of black urethane resin particles coated with collagen particles and having a particle diameter of 5 to 200 μm were obtained. After the black urethane resin particles were washed with water and dried, they were classified to 100 μm or less to obtain collagen composite resin particles.

Example 3 Number average molecular weight: 3000, hydroxyl value: 112 mg KOH / g
30 parts by weight of toluene to 40 parts by weight of a polyester resin,
25 parts by weight of ethyl acetate and 5 parts by weight of carbon black were added, and the mixture was dispersed with a paint shaker to obtain a paste. To 50 parts by weight of the paste, 20 parts by weight of the collagen composite resin particles obtained in Example 1, 1 part by weight of Mizukasil P-801 (hydrous silicate of fine powder manufactured by Mizusawa Chemical Industry Co., Ltd.), and 0.01 part by weight of dibutyltin dilaurate were added. Thus, a coating composition was obtained. In addition, there was almost no decrease in adhesion to the coating substrate.

To 100 parts by weight of the coating composition, 8 parts by weight of Sumidur N-75 (isocyanate oligomer manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added, and the mixture was sufficiently stirred. The composition was mixed with 10 parts by weight of cellosolve acetate and toluene. When diluted with an organic solvent consisting of 10 parts by weight, 10 parts by weight of ethyl acetate, and 10 parts by weight of methyl isobutyl ketone,
Ford Cup # 4 exhibited a viscosity of 15 seconds (25 ° C). This coating composition is spray-coated on an ABS substrate, and 8
After drying at 0 ° C. for 30 minutes, a coating film having a moist leather-like touch was obtained.

Example 4 To 100 parts by weight of R-960 (water-based urethane emulsion manufactured by Polyvinyl Chemical Co., Ltd.), 50 parts by weight of the collagen composite resin particles obtained in Example 2 were added to 100 parts by weight of water using a paint shaker. The dispersed paste was added to obtain an emulsion coating composition. This paint was diluted with water, spray-coated on an ABS substrate, and dried at 80 ° C. for 30 minutes to obtain a coated film having a smooth leather-like touch.

[0027]

As described above, according to the present invention, collagen composite resin particles containing natural microparticles of a collagen, which is a natural protein compound, are encapsulated in a resin, or partially encapsulated and partially exposed, or coated with a resin. Since the hardness of the collagen composite resin particles can be controlled by the resin, it is possible to soften the collagen composite resin particles. Conventional collagen powders have a wide range of particle diameters. Since the particle size can be made uniform and controlled at the same time, its application range has been expanded. In addition, the coating composition containing the collagen composite resin particles can form a coating film having a smooth and soft leather-like touch, and the collagen composite resin particles absorb the volume change due to moisture absorption and release of the collagen particles. Therefore, a decrease in the adhesive force of the coating composition to the coating substrate can be suppressed.

Claims (5)

(57) [Claims] 1. Composite resin particles, wherein collagen particles, which are natural protein compounds, are wrapped with a resin having a crosslinked structure . 2. A wrapping part minute resin having a crosslinked structure particles of collagen, a natural protein compound, and
Composite resin particles characterized by having a structure exposed portion of a resin having the crosslinked structure. 3. A resin having a crosslinked structure, also claim 1 characterized in that it is a soft resin having rubber elasticity
Is the composite resin particle according to claim 2 . Wherein said composite one or more of the composite resin particles of the resin particles, the coating composition characterized in that it uses in conjunction with resin as a binder according to any one of claims 1 to 3. 5. The breaking strength in the properties of the film after curing 20~500kg / cm2, and the maximum elongation of 20% or more, and a binder resin comprising a soft resin having rubber elasticity, claims 1 to Item 4. A coating composition having a leather-like finger touch using at least one kind of the composite resin particles according to Item 3 .