JP3320769B2 - Painted material for design sticking - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a utility Naru designability sticking coating Sobutsu in the new.

More specifically, it comprises a specific polyurethane polyurea particle having a three-dimensional crosslinked structure and a binder resin as essential components, and is used especially for labels, emblems, stickers or stripe tapes. As marking material or coated paper,

[0003] Alternatively, as a building material or the like, a design which is extremely practical in the paint industry and printing ink industry, has excellent scratch resistance and secondary workability, and has both visual and tactile properties. The present invention relates to a coated product obtained by applying a paint resin composition for application which can form a functional coating film.

[0004]

2. Description of the Related Art Various decorative coating compositions for pasting applications have been known, but, among others, a matte coating film composed of various elastic or inelastic resin particles and a synthetic resin binder. Although it is well known and is used as a design imparting coating material, matte coating films using inelastic resin particles are particularly suitable for soft touch (soft touch) and scratch resistance. Inferior to

[0005] On the other hand, a coating film using elastic resin particles is superior to those of non-elastic resin particles in terms of touch and scratch resistance, but swells or dissolves with a solvent, and has durability against outdoor use. This is not enough.

However, in recent years, in order to improve these disadvantages, for example, JP-A-48-51949, JP-A-62-67003, JP-A-62-149333, or JP-A-63-58610. It has been reported that polyurethane polyurea particles formed by an interfacial polymerization reaction between a polyisocyanate and a polyamine as disclosed in US Pat.

[0007] However, in the particles obtained by such a method, the formation of the particles is carried out by a ureation reaction and, therefore, is limited to merely the formation of the outer wall of the particles. However, the particles have a hollow structure or a small pore (microvoid) structure, or if the pigment is to be included in the particles by such a method, the pigment is dispersed using isocyanates or isocyanate prepolymers. Therefore, water content in the pigment must be controlled, which is disadvantageous in many cases.

[0008] In particular, such microvoided particles have many uneven holes. Therefore, when a coating film is formed in combination with a synthetic resin binder, scratch resistance or scratch resistance (for nails). (It is difficult to scratch when rubbed) and the strength tends to be inferior.

It is known that the above-mentioned drawbacks such as scratch resistance can be improved by imparting strength to the synthetic resin binder itself to be combined with the elastic particles. For example, acrylic resin, polyester resin Specific urethane resins, such as melamine resins, phenol resins or epoxy resins, are known as this type of synthetic resin.

However, an elastic particle-containing coating film using such a resin as a binder component generally cannot improve both the scratch resistance and the soft feeling. It will be extremely limited in terms of the composition of the binder itself to express performance and the design of paints, so it can not cope with the diversification and individualization of designs in recent various products, There are fatal drawbacks.

[0011]

As described above, in the conventional design-imparting coating material, since the elastic resin particles in question do not have a sufficient three-dimensional cross-linking structure, they cannot swell in a solvent. It is easy and, furthermore, it is not preferable in terms of weather resistance, and because of the hollow structure, it is disadvantageous in terms of strength important for abrasion resistance. The major challenge remains that the power binder itself is to be extremely limited.

[0012] These problems have to be solved without being corrected, but the present invention seeks to fundamentally solve the various problems in the prior art as described above.

[0013] In view of the above, the present inventors have studied in order to obtain a paint resin composition for pasting, which has excellent design properties and a soft touch as a pollution-free paint, in response to the demands of the paint industry. Started.

[0014] Accordingly, the problem to be solved by the present invention is, at least in part, abrasion resistance, durability, and visual and tactile properties (hereinafter, both senses are also referred to as visual sensation). ) excellent like, moreover, may be applied to a wide variety of applications, is to provide a design property sticking painting articles multifunctional versatile.

[0015] That is, the problem to be solved by the present invention is to provide a coated product for design sticking having a design film having excellent scratch resistance and secondary workability and also having visual and tactile properties. To provide.

[0016]

To this end, the present inventors have conducted intensive studies with the aim of solving the problems to be solved by the invention as described above. As a result, the outer wall and the inner wall of the particles have become sufficiently large. The coating composition composed of a specific polyurethane polyurea particle having a three-dimensional cross-linked structure and a binder resin as described above, has abrasion resistance, durability and visual feeling. What is excellent is, of course,

In addition, various articles coated with such a decorative resin coating composition on metal materials and processed products thereof, plastic materials and processed products thereof, wood and processed products thereof, leathers and papers, etc. The present invention has been completed by finding that it is extremely useful.

That is, the present invention basically relates to a method in which a coating resin composition containing polyurethane polyurea particles having a three-dimensional crosslinked structure and a binder resin as essential film-forming components is applied to a substrate. Painted material, this painted
On one side other than the side, there is an adhesive or adhesive layer,
Furthermore, a design sticker with a release material as a protective layer on it
It is intended to provide a painted material for use . Also, the substrate
But each is characterized by a variety of articles such as a metallic material or a product, a plastic material or a product, timber and its products, leather acids or paper.

In particular, the polyurethane polyurea particles having a three-dimensional cross-linked structure are an organic phase in which isocyanate groups are blended in excess of hydroxyl groups, and the three-dimensional cross-linked structure is formed by a reaction. An organic phase that can be formed, an interfacial polymerization reaction between a polyamine having an equivalent amount or less with respect to an excess of isocyanate groups in the organic phase, and that obtained through a urethanation reaction inside the particles,

In addition, the particles contain and contain a pigment therein, and the particles have a specific film characteristic of 50 to 500 kgf / cm 2 as their initial elastic modulus. It is characterized by points.

Here, first, the polyurethane polyurea particles having three-dimensional crosslinks used in the present invention are obtained from, for example, a polyisocyanate compound, a polyhydroxy compound and a polyamine compound. As such a polyisocyanate compound, any of those known per se can be used.

Among them, only typical ones are exemplified. Tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane-4,
4'-diisocyanate, hydrogenated diphenylmethane-4,
4′-diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, 1,3-bis (α, α-dimethyl isocyanatomethyl) benzene, cyclohexyl-1 , 4-
Aliphatic, aromatic or cycloaliphatic di- or triisocyanate monomers, such as diisocyanate, oxadiazinetrione diisocyanate, isophorone diisocyanate or triphenylmethane diisocyanate;

Alternatively, various modified polyisocyanates such as tri- or higher functional polyisocyanurate-type polyisocyanate or burette-type polyisocyanate based on these various monomers;

Furthermore, at least one of the above-mentioned various monomers and modified polyisocyanates and one of various polyhydroxy compounds such as polyhydric alcohols, polyester polyols, polycarbonate polyols, polybutadiene polyols and polypentadiene polyols. Examples thereof include urethane-modified polyisocyanate prepolymers having an isocyanate group at a terminal obtained by the urethanization reaction described above, and these may be used alone or in combination of two or more.

In order for the obtained polyurethane polyol urea particles (hereinafter also referred to as polymer particles) to be particularly excellent in toughness, the number average molecular weight of the polyisocyanate compound should be within the range of 200 to 10,000. ,
Preferably, it falls within the range of 300 to 7,000, more preferably within the range of 500 to 5,000.

In the above-mentioned organic phase, the urethane-modified polyisocyanate compound obtained by the reaction of the polycaprolactone polyester polyol with the diisocyanate is contained in all polyisocyanate compounds in an amount of 10% by weight or more, preferably 20% by weight or more. If it is included, the toughness of the polymer particles is further improved.

In designing the polyisocyanate compound, the type of the isocyanate monomer unit should be limited to aliphatic and / or alicyclic type, especially in consideration of weather resistance and the like. The way is recommended.

On the other hand, the polyhydroxy compound as a component constituting the organic phase together with the polyisocyanate compound compensates for the lack of internal crosslinking due to the formation of the walls of the polymer particles, and further increases the mechanical strength of the particles. Although it is a very important component for improving the polyhydroxy compound, any of such polyhydroxy compounds which are known per se can be used.

[0029] Of those, if only typical ones are illustrated, they belong to any of the following groups. a) ethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butanediol,
1,3-butanediol, 1,5-pentanediol,
Neopentyl glycol, 1,6-hexanediol,
1,4-bis (hydroxytyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,
Polyhydric alcohols such as 3-pentanediol, glycerin, hexanetriol, tris (2-hydroxyethyl) isocyanurate or pentaerythritol;

B) polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene tetramethylene glycol, polyoxypropylene tetramethylene glycol or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol;

C) Ring-opening polymerization of various polyhydric alcohols as described above with ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether. The resulting modified polyether polyols;

D) Polyester polyols obtained by co-condensing at least one of the various polyhydric alcohols listed above with polycarboxylic acids. If only typical examples of polycarboxylic acids mentioned here are given, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citracone Acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2,2
Examples thereof include 4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, and 2,5,7-naphthalenetricarboxylic acid.

E) a polycondensation reaction between at least one of the above-mentioned various polyhydric alcohols and various lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. Lactone-based polyester polyols obtained, or lactone-modified polyester polyols obtained by polycondensation reaction of various polyhydric alcohols and polycarboxylic acids with various lactones as described above, respectively, as described above Kind;

F) Various epoxies such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, and glycidyl esters of monobasic and / or polybasic acids. Compounds, at the time of the preparation of the polyester polyol, at least one, epoxy-modified polyester polyols obtained in combination; further,

G) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative or hydroxyl group-containing acrylic copolymer.

The polyhydroxy compounds as shown in (a) to (g) may be used alone or in combination of two or more, but the number average molecular weight is preferably 200 to 10 000, preferably 3
Within the range of 00 to 7,000, more preferably 50
It is preferable that the amount falls within the range of 0 to 5,000 for sufficient crosslinking inside the polymer particles.

In order to obtain tough polymer particles, it is preferable to use a polyester polyol.
It is desirable to use lactone-based polyester polyols obtained by a polycondensation reaction with a lactone such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone.

In the present invention, the ratio of the isocyanate group equivalent of the polyisocyanate compound to the hydroxyl group equivalent of the polyhydroxy compound is 1: 0.1 to 1: 0.
9, more preferably 1: 0.1 to 1: 0.8, and more preferably 1: 0.1 to 1: 0.8.
These two components are mixed so as to be in the range of 0.7,
In addition, the composition ratio should be such that the mixture of the two components itself can be three-dimensionally crosslinked.

That is, when these mixtures are completely urethanized, it is necessary to make the mixture into a gel so that fluidity cannot be obtained even by heating or diluting the true solvent.

The above two conditions for designing the organic phase are indispensable conditions for obtaining an internal crosslinked state which cannot be obtained only by the interfacial polymerization reaction by the addition of a polyamine compound described later. It is one of the typical requirements.

In this case, in order to make the interfacial polymerization effective and effective, an excess of isocyanate groups in the above-mentioned range is necessary, and such a range is set so that the outer wall of the particles is formed quickly. It is.

In the present invention, the urethanization reaction in the particles is three-dimensionally advanced, so that the toughness and solvent resistance of the whole particles, which could not be obtained by the prior art, are improved. Is planned.

In designing such a three-dimensional urethanization reaction inside the polymer particles, a polyisocyanate compound and / or a polyhydroxy compound having three or more functional groups are combined with the polyisocyanate compound and the polyhydroxy compound contained in the organic phase. By adding 0.1 mol% or more, preferably 0.2 mol% or more, more preferably 0.3 mol% or more in the total amount, a good three-dimensional cross-linked state inside the particles can be obtained.

As the polyisocyanate groups in the organic phase are consumed with the progress of the interfacial polymerization reaction with the polyamine described below, the equivalent ratio between the isocyanate groups and the hydroxyl groups in the polymer particles approaches, and the inside of the polymer particles is reduced. Of the polyurethane polyurea particles used in the present invention, such as toughness and durability, are further improved.

As the pigment to be included in the present invention, known and commonly used organic pigments, inorganic pigments, extenders and the like are used. Are insoluble azo pigments such as Benzidine Yellow, Hansa Yellow or Lake Red 4R; soluble azo pigments such as Lake Red C, Carmine 6B or Bordeaux 10;

Copper phthalocyanine pigments such as phthalocyanine blue or phthalocyanine green; basic dyeing lakes such as rhodamine lake or methyl violet lake; acid dyeing lakes such as quinoline lake or fast sky blue; mordant pigments such as alizarin lake;

Vast dye-based pigments such as anthraquinone-based or thioindigo-based or perinone-based pigments; Synchasia Red B
Oxazine pigments such as oxazine violet; condensed azo pigments such as chromophtal; and inorganic pigments such as chromate salts such as graphite, zinc chromate or molybdate orange;

Ferrocyan compounds such as navy blue; metal oxides such as titanium white, zinc white, mapico yellow, iron black, red iron or chromium oxide green; cadmium yellow;
Sulfide selenides such as cadmium red or mercury sulfide; sulfates such as barium sulfate or lead sulfate; silicates such as calcium silicate or ultramarine; carbonates such as calcium carbonate or magnesium carbonate; cobalt violet or manganese purple. Phosphate; aluminum powder,
Metal powders such as gold powder, silver powder or brass powder; or pearl pigments,

As extenders, precipitated barium sulfate,
Barium carbonate, powder, gypsum, alumina white, clay,
Silica, silica white, talc, calcium silicate or precipitated magnesium carbonate and the like, and carbon black and the like that do not belong to both inorganic pigments and organic pigments, of course,
Can be used.

These pigments are kneaded uniformly with one or more of the above-mentioned polyhydroxy compounds in advance and used as a mill base. If necessary, the pigments may be chemically mixed before being used or during kneading. Surface treatment, kneading and mixing of two or more kinds of pigments, or combined use of additives such as a pigment dispersant and a color separation preventing agent which are well-known and commonly used in the paint industry and the printing ink industry are also possible.

The kneading is carried out using a well-known and conventional dispersing machine such as a ball mill, a pebble mill, a sand mill, an attritor, a roll mill, a high-speed impeller disperser or a high-speed stone mill. The viscosity of the kneading system may be adjusted by adding an active organic solvent.

Suitable organic solvents include aromatic or aliphatic hydrocarbons, esters, ethers, and ketones. Among them, benzene, toluene, xylene,
Suitable are cyclohexane, methylcyclohexane, diphenyl ether or mineral spirit.

The ratio of the resin to the pigment in the mill-base kneading step is 1 to 900 parts by weight, preferably 2 to 800 parts by weight, particularly preferably 5 to 500 parts by weight, based on 100 parts by weight of the resin solids. It is appropriate within a certain range.

The mill base thus obtained and the polyhydroxy compound or polyisocyanate compound are blended in the above-described various ranges and uniformly mixed to form the hydrophobic organic phase (1). Phase (1)
The ratio of the pigment contained therein is 1% of the total resin solids.
0.5 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 2 to 100 parts by weight, per 100 parts by weight.
A range of parts by weight is appropriate.

The hydrophobic organic phase (1) is finely dispersed in the aqueous phase (2), and the polyamine compound is added in an amount of 0.1 equivalent per equivalent of excess isocyanate groups contained in the organic phase.
Preferably, 0.3- so that it becomes 2-1.0 equivalent.
More preferably, 0.4 to 0.4 equivalent.
By adding so as to be 0.9 equivalent, performing a ureation reaction at the particle interface, and performing a urethanation reaction inside the polymer particles, extremely tough, pigmented polyurethane polyurea particles can be obtained. .

Suitable polyamine compounds for use in the present invention are known and commonly used diamines, polyamines or mixtures thereof. Of these, 1,2-ethylenediamine and bis- (3-aminopropyl) -amine, hydrazine, hydrazine-2-ethanol, bis- (2-methylaminoethyl) -methylamine, 1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-hydroxy Ethyl ethylenediamine, N-methyl-bis-
(3-aminopropyl) -amine, tetraethylenediamine, hexamethylenediamine, 1-aminoethyl-
1,2-ethylenediamine, bis- (N, N′-aminoethyl) -1,2-ethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, phenylenediamine, toluylenediamine,
2,4,6-triaminotoluenetrihydrochloride, 1,3,8-triaminonaphthalene, isophoronediamine, xylylenediamine, hydrogenated xylylenediamine, 4,4′-diaminodiphenylmethane or hydrogenated 4,4 ′ -Diaminodiphenylmethane,

Alternatively, derivatives of these polyamine monomers may be mentioned, but from the viewpoint of weather resistance, use of aliphatic and / or alicyclic compounds is preferred. In the present invention, the organic phase dispersed in the aqueous phase is itself non-reactive, and reduces the viscosity of the hydrophobic organic solvent by adding the organic solvent as necessary, and disperses the organic solvent in the aqueous phase. Performance can be improved.

In this case, the amount of the organic solvent is 50% by weight or less, preferably 40% by weight or less in the total organic phase.
More preferably, the amount is 30% by weight or less.

Suitable organic solvents include aromatic or aliphatic hydrocarbons, esters, ethers, and ketones. Among them, benzene, toluene, xylene,
Suitable are cyclohexane, methylcyclohexane, diphenyl ether or mineral spirit.

These organic solvents may be distilled off during the formation of the polymer particles or after the formation of the polymer particles by a treatment such as heating or depressurization, if necessary. The aqueous phase in which the organic phase is dispersed is polyvinyl alcohol, hydroxyalkyl cellulose, carboxyalkyl cellulose,
One or more selected from various protective colloids such as gum arabic, polyacrylate, polyacrylamide, polyvinylpyrrolidone, and ethylene-maleic anhydride copolymer are contained in an amount of 0.2 to 20% by weight.

The aqueous phase may contain 0.2 to 10% by weight of a nonionic, anionic or cationic surfactant. In the present invention,
Although it is characterized by aggressive urethanization reaction inside the polymer particles, as is well known, the urethanization reaction between a hydroxyl group and an isocyanate group is particularly effective when the isocyanate group is aliphatic or alicyclic. When based on the formula system, the rate tends to be slower than the ureation reaction with an amino group.

As is well known, the reactivity between water and an isocyanate is extremely slow as compared with the reactivity with a hydroxyl group, and the penetration of water into the interior of the particles is caused by the isolation effect of the outer wall formed by the addition of the polyamine compound. From the negligible point, the purpose of the present invention is to achieve the urethanization reaction in the particles by raising the reaction temperature and taking time, while achieving the object of the present invention.

The present inventors have conducted various studies to improve the above reaction conditions. As a result, cobalt naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tetra-n-butyltin, tri-n-butyltin, n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, tin octenoate or potassium oleate;

For the hydrophobic organic phase, 5-10,00
It has been found that by adding at 0 ppm, preferably within the range of 10 to 5,000 ppm, tough crosslinked polymer particles are formed in a very short time.

These organometallic catalysts promote the reaction between isocyanate groups and hydroxyl groups extremely effectively. The addition of the above-mentioned organometallic catalyst to the organic phase prior to water dispersion (fine dispersion) increases the viscosity of the organic phase and decreases the dispersibility in the aqueous phase. Is not practical, and the addition of the organometallic catalyst after the addition of the polyamine is difficult due to the state in which the outer wall of the polymer particles is being formed. Since it is difficult to be taken in, and the effect of accelerating the urethanization reaction inside the polymer particles tends to be reduced, the timing of addition of the organometallic catalyst is determined by dispersing an organic phase in an aqueous phase. The most suitable time is during the conversion step or between the dispersing step and the middle of the step of adding the polyamine.

Next, as the binder resin, any resin capable of forming a coating film may be basically used. Therefore, any binder resin may be used. If it is limited to, polyurethane resin, acrylic resin, alkyd resin, polyester resin,
Various synthetic resins such as melamine resin, urea resin, epoxy resin, polyamide resin, vinyl acetate resin, vinyl chloride resin or fluorine resin;

Alternatively, various kinds of rubbers such as natural rubber or synthetic rubber, and various kinds of natural high molecular compounds such as cellulose may be used alone or in combination of two or more. Of course.

As a method of preparing the paint composition for decorative application, it is recommended that a binder resin whose particle size has been adjusted and polymer particles be blended in advance.

The mixing ratio of the polyurethane polyurea particles having a three-dimensional crosslinked structure and the binder resin is such that the weight ratio of the solid content of the binder resin / polymer particles is 20/8.
A range from 0 to 80/20 is appropriate.

[0070] Thus obtained, for sticking the design of the present invention
The coating composition used for the coated product is, if necessary, diluted with a solvent or water that can be diluted with the binder resin therein, and brush-coated, roll-coated, flow-coated, spray-coated or dip-coated. Can be applied to various substrates by various known and commonly used coating methods.

That is, the composition of the present invention obtained as described above includes, for example, ABS resin, AS resin, polyester resin, polyphenylene oxide resin, polyurethane resin, polycarbonate resin, polyamide resin (especially nylon), PS Resin, polypropylene resin,
Various plastics such as acrylic resin, vinyl chloride resin or epoxy resin;

Various metal materials such as steel plate, galvanized steel plate, galvanized steel plate, tin plate, copper plate, aluminum plate and zinc plate; various wood materials such as rosewood, ebony, rosewood, teak, oak, oak, cherry blossom or lauan Various types of paper, such as fine paper, coated paper, kraft paper or roll paper;
Alternatively, it is applied to various kinds of leathers such as natural leather or synthetic leather such as urethane, nylon or vinyl chloride, etc., and applied, and has a layer of an adhesive or an adhesive on a surface different from these painted surfaces. Further, a coated article having a release material is provided as a protective layer on the layer.

As the above-mentioned pressure-sensitive adhesive or adhesive used in the present invention, various general-purpose pressure-sensitive adhesives such as acrylic, rubber, urethane, silicone, polyester or epoxy, or Vinyl acetate, urethane, epoxy or glue
Various general-purpose adhesives are particularly typical.

Further, as the release material used in the present invention, various general-purpose materials such as siliconized paper, film or release paper are particularly typical examples.

[0075]

Next, the present invention will be described more specifically with reference examples, examples and comparative examples. In the following, all parts and percentages are by weight unless otherwise specified.

The following is a description of each raw material component used in advance. Among them, first, the polyisocyanate compound is as follows.

That is, "Barnock DN-950"
A solid content of [hexamethylene diisocyanate adduct type polyisocyanate compound manufactured by Dainippon Ink and Chemicals, Inc .; number average molecular weight = 640, isocyanate group content = 16.8% in terms of solid content] was used. , Which is abbreviated as PI-1.

"Bernock DN-980S" (isocyanurate type polyisocyanate compound obtained by using hexamethylene diisocyanate manufactured by Dojo Co .; isocyanate group content = 21.0%);
Abbreviated as -2.

Further, 1,000 parts of a polycaprolactone polyester triol having a hydroxyl value of 168.5 obtained by a polycondensation reaction of trimethylolpropane and ε-caprolactone, and 666 parts of isophorone diisocyanate were subjected to a urethanization reaction. Although a polyisocyanate compound having an isocyanate group content of 7.5% obtained by the above method was also used, this is hereinafter abbreviated as PI-3.

Further, hydrogenated 4,4'-diphenylmethane diisocyanate or 1,6-hexamethylene diisocyanate was also used.
Or abbreviated as HDI.

Next, as the polyhydroxy compound,
It looks like this: That is, a polyester polyol having a hydroxyl value of 187 obtained by co-condensation of neopentyl glycol and adipic acid was used. Hereinafter, this is abbreviated as PO-1.

Further, a polycaprolactone polyester diol having a hydroxyl value of 187 obtained by a polycondensation reaction of neopentyl glycol and ε-caprolactone was also used. Hereinafter, this is abbreviated as PO-2.

Further, a polycaprolactone polyester polyol having a hydroxyl value of 168.5 obtained by a polycondensation reaction between trimethylolpropane and ε-caprolactone was also used. Hereinafter, this is abbreviated as PO-3.

Further, trimethylolpropane and ε
A hydroxyl value of 112.2 and a number average molecular weight of 1,50, obtained by a polycondensation reaction with caprolactone;
A polycaprolactone polyester triol of 0 was also used, and is hereinafter abbreviated as PO-4.

Further, the polyamine is as follows. That is, although ethylenediamine was used,
Hereinafter, this is abbreviated as EDA. In addition, 1,6-hexamethylenediamine was also used.
Abbreviated.

Further, although isophoronediamine was used, it will be abbreviated as IPDA hereinafter. Reference Example 1 (Preparation Example of Polyurethane Polyurea Particles) In a 1-liter flask, 0.1% of "PVA-217" (partially saponified product of polyvinyl alcohol manufactured by Kuraray Co., Ltd.) was added.
While 300 parts of a 2% aqueous solution was put into the aqueous phase, 55.7 parts of PI-1 and 9.9 of HDI were placed in another container.
3 parts and 30 parts of PO-1 were mixed to obtain an organic phase.

At 20 ° C., using a homomixer,
7,000 to 7,500 rpm. Then, while stirring the aqueous phase, an organic phase prepared in advance was charged therein and stirred for 1 minute to obtain a dispersion.

Next, the dispersion was transferred to another flask, and the dispersion was stirred at 200 rpm with a paddle type stirring blade. N-butyltin dilaurate (DBTDL)
Was added and 2 minutes later 21.7 parts of a 50% aqueous solution of HMDA were also added.

After maintaining at room temperature (about 25 ° C.) for 2 hours, the temperature is raised to 50 ° C., and the same temperature is maintained for 1 hour and further 8 hours.
The reaction was maintained at 0 ° C. for 2 hours to continue the reaction, and a suspension of the desired polyurethane polyurea particles was obtained.

The average particle size of the particles is 30 microns (μ
m). In addition, these particles are extremely stable without swelling and dissolving in acetone, ethyl acetate, xylene, or the like, and furthermore, the particles may be sufficiently filled inside with a polymer. As a result of observation with an electron microscope, it was confirmed.

Reference Example 2 (Preparation Example of Polyurethane Polyurea Particles Containing Pigment) First, 80 parts of PO-2, "Fast-gen Super Red"
2093 of "7093Y" (a quinacridone-based organic pigment manufactured by Dainippon Ink and Chemicals, Inc.) and 25 parts of toluene were mixed and dispersed with a sand grinder for 1 hour to obtain a red mill base. Hereafter, this is called MB
Abbreviated as -1.

Next, “PVA” was placed in a 1-liter flask.
-217 ", 300 parts of a 0.2% aqueous solution,
At 7,000 to 7,000 using a homomixer.
500 rpm. In a separate container, 37.5 parts of MB-1, 16 parts of PO-1, PI
An organic phase prepared by mixing 30 parts of -1 and 20 parts of HDI was added, and 0.2 part of DBTDL was further added, followed by stirring for 1 minute to obtain a dispersion.

Thereafter, the dispersion was transferred to another flask, and the dispersion was stirred at 200 rpm with a paddle type stirring blade. While stirring with, 22.3 parts of a 25% aqueous solution of EDA was added.

After maintaining at room temperature (about 25 ° C.) for 2 hours, the temperature was raised to 50 ° C., and the same temperature was maintained for 1 hour,
The reaction was continued at 80 ° C. for 2 hours to obtain the desired suspension of the pigmented, red polyurethane polyurea particles.

The average particle size of the polymer particles obtained here was 37 μm. Further, these particles did not swell and dissolve in acetone, and therefore, no outflow of the red pigment was observed in acetone.

Reference Example 3 (Preparation Example of Pigment-Containing Polyurethane Polyurea Particles) First, 80 parts of PO-2 and "carbon black CF-
9 "[Mitsubishi Chemical Co., Ltd.] 20 parts and toluene 2
Five parts were mixed and dispersed with a sand grinder for 1 hour to obtain a black mill base. Hereinafter, this is abbreviated as MB-2.

Next, “PVA” was placed in a 1-liter flask.
-217 "in a 0.2% aqueous solution.
At 7,000 to 7,000 using a homomixer.
500 rpm. In a separate container, 37.5 parts of MB-2, 16 parts of PO-1, PI
An organic phase prepared by mixing 30 parts of -1 and 20 parts of HDI was added, and 0.2 part of DBTDL was further added, followed by stirring for 1 minute to obtain a dispersion.

Thereafter, the dispersion was transferred to another flask, and the suspension was stirred at 200 rpm with a paddle type stirring blade. While stirring with, 22.3 parts of a 25% aqueous solution of EDA was added.

After maintaining at room temperature (about 25 ° C.) for 2 hours, the temperature was raised to 50 ° C., and the same temperature was maintained for 1 hour,
The reaction was continued at 80 ° C. for 2 hours to obtain the desired suspension of the pigmented, black polyurethane polyurea particles.

The average particle size of the polymer particles obtained here was 13 μm.

Examples 1 to 5 According to the combinations shown in Table 1, 20 parts of polymer particles, 20 parts of a binder resin, 0.2 parts of a silicone-based leveling agent, and a polyamide-based settling inhibitor And xylene / n-butyl acetate = 50/50
(Weight ratio) of 60 parts of the mixture was uniformly mixed to obtain various target decorative paint resin compositions having a PWC (pigment weight concentration) of 50%.

Comparative Examples 1 to 5 According to the combinations shown in Table 1, 2
0 parts, 20 parts of a binder resin, 0.2 parts of a silicone-based leveling agent, 0.4 parts of a polyamide-based precipitation inhibitor, and xylene / n-butyl acetate = 50/50 (weight ratio)
And 60 parts of the mixture,
Was 50%, and various control coating resin compositions for application were obtained.

[0103]

[Table 1]

[0104]

[Table 2]

The various coating resin compositions for application obtained in each of the examples and comparative examples were separately applied to an iron plate or an ABS plate, respectively, so that the dry film thickness became 50 μm. Dry curing was performed for 30 minutes.

Then, after leaving at room temperature for one week, various coating film performances were evaluated. The results are summarized in Table 2. The evaluation of these various performances was performed in the following manner.

Appearance: Specular gloss at 60 ° was measured with a gloss meter, and the matte state of the coated surface was visually determined. ◎: The gloss is 2 or less, and the coated surface is uniform and completely matte.…: The gloss is 2 or less, uneven gloss of the coated surface is recognized. ×: The gloss is 2 or less.

Tactile sensation: Touching with a hand was performed to determine the degree of soft touch. ◎: Very soft feeling ○: Pretty soft feeling ×: Hard and rigid feeling

Roughness ◎: Extremely soft and low roughness ○: Extremely soft and roughnessy ×: Hard and rigid, no roughness

Scratch resistance: # 000 steel wool for 30
One hour after rubbing with a contact pressure of g / cm @ 2, the state of the coated surface was visually determined. ◎… No trace at all ○… Some traces × …… Clearly scratched

Flexibility: The painted tin plate was bent by 180 degrees (2 mmφ), and the condition of the painted surface was visually judged. (Compliant with JIS K-5400.)…: No change was observed at all ×: Cracks occurred in the bent portion

Solvent resistance: A glass cap containing acetone was always placed on the coated surface so that the acetone was hung on the coated surface, and after standing for 24 hours, the state of the coated surface was visually determined. . ◎: no change was observed x: coating film dissolved

[0113]

[Table 3]

Examples 6 to 8 As a substrate, a 0.1 mm-thick polyester sheet, vinyl chloride sheet or coated paper having a pressure-sensitive adhesive or an adhesive on one side and a release material as a protective layer, respectively, was used. If necessary, these base materials were pre-treated, and the paint resin composition for decorative application obtained in Example 1 was applied so that the dry film thickness became 50 µm.

Next, each of the coated articles thus obtained was allowed to stand at room temperature for one week, and then the performance of various coating films was evaluated in the same manner as in Examples 1 to 5. The results are summarized in Table 3.

[0116]

[Table 4]

[0117]

As described above, the decorative paste application product of the present invention comprises a polyurethane resin containing a three-dimensionally cross-linked polyurethane resin and a binder resin. To
It contains as an essential film-forming component, and all of the coated products form a highly matte, high-grade matte coating film from where the polymer particles protrude to the particle surface. It can also be done.

[0118] In addition, the polymer particles themselves, since those having a three-dimensional crosslinked structure, design properties sticking coating Sobutsu of the present invention, solvent resistance, abrasion resistance, scratch resistance, It has a coating film that has the effect of being excellent in scratch resistance and durability, etc., and in particular, by limiting the coating film performance of the binder resin, such a coating film whose characteristic effect is further enhanced And a coating film having excellent soft touch (soft touch).

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C09J 7/02 C09J 7/02 B // C08G 18/09 C08G 18/65 Z 18/65 18/08 (72) Inventor Shigeo Yukawa Wakayama 620-5 Kokura, Wakayama (56) References JP-A-3-139582 (JP, A) JP-A-2-4869 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 175/04 C09D 175/06 C09D 5/28 C09D 161/28 C09J 7/02

Claims (5)

(57) [Claims] 1. A coating in which a coating resin composition containing polyurethane polyurea particles having a three-dimensional crosslinked structure and a binder resin as essential film-forming components is applied to a substrate.
Object, on one side other than the painted side,
With an adhesive or adhesive layer and a protective layer on it
Coating for decorative application, characterized by having a release material
Thing . 2. The base material is a metal material or a plastic material.
The coated product for design sticking according to claim 1, which is a material, wood, leather or paper . 3. The polyurethane polyurea particles having a three-dimensional cross-linked structure are converted into an organic phase in which a polyisocyanate compound having a stoichiometric excess of isocyanate groups and a polyhydroxy compound are mixed. Moreover, an interfacial polymerization reaction between an organic phase capable of forming a three-dimensional crosslinked structure by reaction and a polyamine compound having an equivalent weight or less with respect to a stoichiometric excess of isocyanate groups in the organic phase, The coated product for decorative application according to claim 1 or 2 , which is a polyurethane polyurea particle obtained through a urethanization reaction in (1). 4. A mixture of a polyisocyanate compound containing a pigment and having a stoichiometric excess of isocyanate groups and a polyhydroxy compound, wherein the polyurethane polyurea particles having a three-dimensional crosslinked structure contain a pigment. And an organic phase capable of forming a three-dimensional crosslinked structure by reaction, and a polyamine compound having an equivalent weight or less with respect to a stoichiometric excess of isocyanate groups in the organic phase. The coated article for decorative application according to claim 1 or 2 , which is a pigmented polyurethane polyurea particle obtained through an interfacial polymerization reaction of the above and a urethanization reaction inside the particle. 5. The method according to claim 1, wherein the binder resin is 50 to 500 k.
having an initial elastic modulus within a range of gf / cm ^2.
The coated product for design sticking according to claim 1 or 2 .