JPH05302062A - Coating resin composition for decorative sticker and article coated therewith - Google Patents

Abstract

PURPOSE:To provide the title compsn. capable of forming a decorative coating film which is excellent in scratch resistance and fabricability and has both a good appearance and a good touch by compounding a particulate three- dimensionally cross-linked polyurethane-polyurea and a binder resin. CONSTITUTION:The title compsn. contains as the essential components a particulate three-dimensionally cross-linked polyurethane-polyurea (e.g. one obtd. from a polyisocyanate compd., a polyhydroxyl compd., and a polyamine compd.) and a binder resin (e.g. a polyesterurethane resin). The compsn. forms a coating film contg. polymer particles projecting from the surface and thus imparts an excellent matte finish with a high-quality appearance to an article coated with the compsn. The coating film is excellent in solvent, abrasion, mar, and scratch resistance and in durability, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful paint resin composition for decorative sticking and its coated product.

More specifically, it is used for a label, an emblem, a sticker or a striped tape, which comprises specific polyurethane polyurea particles having a three-dimensional crosslinked structure and a binder resin as essential components. As a marking material or coated paper,

[0003] Alternatively, as a construction material, etc., in the field of paint industry and printing ink industry, it is extremely practical and has excellent scratch resistance and secondary processability, and also has visual and tactile properties. TECHNICAL FIELD The present invention relates to a coating resin composition for sticking capable of forming a hydrophilic coating film and a coated product thereof.

[0004]

2. Description of the Related Art Up to now, various design coating compositions for laminating have been known, but above all, a matte coating film comprising various elastic or inelastic resin particles and a synthetic resin binder. Although it is well known that it has been used as a design-imparting coating material, matte coatings using non-elastic resin particles are especially suitable for soft feeling (soft touch) and scratch resistance. Inferior to

On the other hand, the coating film using the elastic resin particles is superior to those of the non-elastic resin particles in terms of touch and scratch resistance, but it swells or dissolves in a solvent and has outdoor durability. In terms of, it cannot be said to be sufficient.

In recent years, however, in order to improve these various drawbacks, for example, JP-A-48-51949, JP-A-62-67003, JP-A-62-149333 or JP-A-63-58610 is used. It has been reported that polyurethane polyurea particles formed by an interfacial polymerization reaction of polyisocyanate and polyamine, as disclosed in, for example, are used.

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

[0008] In particular, since such particles having a microvoid structure have many non-uniform holes, when they are used in combination with a synthetic resin binder to form a coating film, they have scratch resistance or scratch resistance (with nails). It is difficult to make scratches when rubbed), and it tends to be inferior in strength.

By the way, it is known that the above-mentioned defects 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 and polyester resin. Specific urethane resins such as melamine resin, phenol resin, and epoxy resin are known as this type of synthetic resin.

However, an elastic particle-containing coating film using these resins as a binder component generally cannot improve both the scratch resistance and the soft feeling, which is why such various coatings are used. It will be extremely limited in terms of the composition of the binder itself for expressing the performance and the design of the paint, and thus it will not be possible to cope with the recent diversification of designs and individualization of various products. So to speak, it has a fatal drawback.

[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 crosslinked structure, they swell in the solvent. In addition, it is easy and is not preferable in terms of weather resistance. Further, since it has a hollow structure, it is also disadvantageous in strength, which is important for scratch resistance. The major problem remains that the binder itself, which should be, will be extremely limited.

Although these problems are urgent and need to be solved, the present invention intends to solve the various problems in the prior art as described above.

Accordingly, the inventors of the present invention have conducted research in order to obtain a paint resin composition for sticking, which has excellent designability and soft feel, as a pollution-free paint, in accordance with the needs of the paint industry. Started.

Therefore, the problem to be solved by the present invention depends, in particular, on scratch resistance, durability, and visual and tactile properties (hereinafter, both senses are also referred to as visual and tactile sensation). (EN) It is intended to provide a versatile and multifunctional coating composition for decorative sticking, which is excellent in the above, and can be applied to a wide range of applications, and a coated article thereof.

That is, the problem to be solved by the present invention is to provide a designable coating which has excellent scratch resistance and secondary workability and can form a designable coating having both visual and tactile properties. A coating resin composition is provided.

[0016]

Therefore, as a result of intensive studies, the inventors of the present invention have focused their attention on the problems to be solved by the invention as described above, and as a result, have found that the outer wall and the inner wall of the particles are sufficiently large. The coating composition composed of specific polyurethane polyurea particles having a three-dimensional cross-linking structure and a binder resin has excellent scratch resistance, durability and visual sensation. Being excellent is, of course,

[0017] In addition, various kinds of articles in which such a coating resin composition for decorative sticking is applied to metal materials and processed products thereof, plastic materials and processed products thereof, wood and processed products thereof, leather and papers, etc. The present invention has been completed by discovering that it is extremely useful.

That is, the present invention basically comprises a coating resin composition for decorative sticking, which comprises polyurethane polyurea particles having a three-dimensional crosslinked structure and a binder resin as essential film-forming components. And further coated with a designable sticking resin composition having such a specific composition, respectively, a metal material or a product thereof, a plastic material or a product thereof, wood and a product thereof, It intends to provide various articles such as leather and paper.

In particular, the polyurethane polyurea particles having the three-dimensional crosslinked structure are an organic phase formed by blending so that the isocyanate groups are in excess of the hydroxyl groups, and the three-dimensional crosslinked structure is formed by the reaction. An organic phase that can be formed and an interfacial polymerization reaction between an equivalent amount or less of a polyamine with respect to an excess isocyanate group in the organic phase, and a urethanization reaction inside the particles,

Further, the particles contain a pigment inside and are encapsulated therein, and further, the particles have a specific film property of 50 to 500 kgf / cm 2 as an initial elastic modulus. It features points.

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.

Of these, only typical ones will be 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-dimethylisocyanate methyl) 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 polyisocyanates or burette type polyisocyanates based on these various monomers;

Further, at least one of the various monomers and modified polyisocyanates listed above and one of various polyhydroxy compounds such as polyhydric alcohol, polyester polyol, polycarbonate polyol, polybutadiene polyol or polypentadiene polyol. Examples thereof include urethane-modified polyisocyanate prepolymers having an isocyanate group at the end, which are obtained by the urethanization reaction with the above, and these may be used alone or in combination of two or more kinds.

In order that the obtained polyurethane polyol urea particles (hereinafter, also referred to as polymer particles) are particularly excellent in toughness, the number average molecular weight of the polyisocyanate compound is in the range of 200 to 10,000. ,
It is desirable that it is in the range of 300 to 7,000, and more preferably in the range of 500 to 5,000.

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

In designing the polyisocyanate compound, the type of the isocyanate monomer units should be limited to aliphatic and / or alicyclic systems, particularly when weather resistance is taken into consideration. The method 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 cross-linking due to the formation of the wall portion of the polymer particles, and further improves the mechanical strength of the particles. As the polyhydroxy compound, any of those known per se can be used, though it is an extremely important component for improving.

Of these, only typical ones will be exemplified and 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 pentaerythryl.

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

C) by ring-opening polymerization of various polyhydric alcohols such as those listed above with ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether. Modified polyether polyols obtained;

D) Polyester polyols obtained by cocondensation of at least one of the various polyhydric alcohols listed above with polyhydric carboxylic acids. To give only representative polyvalent carboxylic acids mentioned here, 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,
4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid.

E) by polycondensation reaction of at least one of various polyhydric alcohols as listed above with various lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. The lactone-based polyester polyols obtained, or a lactone-modified polyester polyol obtained by a polycondensation reaction of each of the above-mentioned various polyhydric alcohols and polycarboxylic acids with each of the above-mentioned various lactones. 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, or glycidyl esters of monobasic and / or polybasic acids. Epoxy-modified polyester polyols obtained by using at least one compound in combination during the preparation of the polyester polyol;

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.

Of course, the polyhydroxy compounds shown in (a) to (g) may be used alone or in combination of two or more, but the number average molecular weight thereof is from 200 to 10. Within a range of 3,000, preferably 3
Within the range of 00 to 7,000, more preferably 50
It is preferable that it is 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 polyester polyol. Among them,
It is desirable to use lactone-based polyester polyols obtained by polycondensation reaction with lactones 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 range, preferably 1: 0.1 to 1: 0.8, more preferably 1: 0.1 to 1:
Mix these two components so that the range is 0.7,
In addition, the composition ratio should be such that the mixture of both components itself can be three-dimensionally crosslinked.

That is, when these mixtures are completely urethanized, it is necessary to make the composition into a gel, which does not have fluidity even when heated or diluted with a true solvent.

The above-mentioned two conditions for designing the organic phase are essential conditions for obtaining an internal cross-linking state which cannot be obtained only by the interfacial polymerization reaction by adding the polyamine compound described later, and are the basis of the present invention. Is one of the basic requirements.

At this time, in order to reasonably and effectively effect the interfacial polymerization, 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 particle is promptly formed. Is.

Further, in the present invention, the urethanization reaction within the particles is three-dimensionally proceeded to improve the toughness and solvent resistance of the whole particles which could not be obtained by the prior art. Is being pursued.

In designing such a three-dimensional urethanization reaction inside the polymer particles, a polyisocyanate compound and / or a polyhydroxy compound having a functionality of 3 or more are contained in the organic phase. By containing 0.1 mol% or more, preferably 0.2 mol% or more, and more preferably 0.3 mol% or more in the total amount, a good three-dimensional crosslinked state inside the particles can be obtained.

As the polyisocyanate group in the organic phase is consumed with the progress of the interfacial polymerization reaction with the polyamine described below, the equivalence ratio of the isocyanate group and the hydroxyl group in the polymer particle approaches, and the inside of the polymer particle The crosslink density of the polyurethane polyurea particles further increases with the progress of the urethanization reaction, and various properties such as toughness and durability of the polyurethane polyurea particles used in the present invention are further improved.

As the pigment to be included in the present invention, known and commonly used organic pigments, inorganic pigments and extender pigments are used. Of these, only typical ones are listed as organic pigments. Are insoluble azo pigments such as Benzidin 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 dyed lakes such as rhodamine lake or methyl violet lake; acid dyed lakes such as quinoline lake or fast sky blue; mordant pigments such as alizarin lake;

Anthraquinone-based pigments such as thioindigo-based or perinone-based vat dyes; Shincasia Red B
Examples thereof include quinacridone-based pigments, such as dioxazine violet, dioxazine-based pigments such as chromophthal, and condensed azo pigments such as chromophtale. As inorganic pigments, yellow lead, zinc chromate, or chromate salts such as molybdate orange;

Ferrocyan compounds such as navy blue; metal oxides such as titanium white, zinc white, mapico yellow, iron black, red iron oxide or chrome 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 Blue; Carbonates such as Calcium Carbonate or Magnesium Carbonate; Cobalt Violet or Manganese Purple Phosphate; aluminum powder,
Metal powder such as gold powder, silver powder or brass powder; or pearl pigment,

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

These pigments are preliminarily uniformly kneaded together with one or more of the above-mentioned polyhydroxy compounds to be used as a mill base. If necessary, the pigments may be chemically mixed before or during use. It is also possible to carry out a surface treatment, to combine two or more kinds of pigments in kneading, or to use additives commonly used in the paint industry, the printing ink industry, etc., such as pigment dispersants and color separation inhibitors.

The kneading is carried out by using a known and commonly used disperser 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. It is also possible to adjust the viscosity of the kneading system by adding active organic solvents.

Suitable organic solvents are aromatic or aliphatic hydrocarbons, esters, ethers and ketones, among which benzene, toluene, xylene,
Cyclohexane, methylcyclohexane, diphenyl ether or mineral spirits are suitable.

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 solid content. It is appropriate within the range.

The mill base thus obtained and a polyhydroxy compound or a polyisocyanate compound are blended in various ranges as described above and uniformly mixed to obtain a hydrophobic organic phase (1). Phase (1)
The ratio of the pigment contained in the resin is 1 of the total solid content of the resin.
0.5 to 200 parts by weight, preferably 1 to 150 parts by weight, and more preferably 2 to 100 parts by weight with respect to 00 parts by weight.
The appropriate range is parts by weight.

The hydrophobic organic phase (1) was finely dispersed in the aqueous phase (2), and the polyamine compound was added in an amount of 0.1% to 1 equivalent of excess isocyanate groups contained in the organic phase.
2 to 1.0 equivalent, preferably 0.3 to
It is more preferably from 0.4 to 1.0 equivalent.
By adding so as to have an amount of 0.9 equivalents to carry out the urethanization reaction at the particle interface and to carry out the urethanization reaction inside the polymer particles, extremely strong pigmented polyurethane polyurea particles can be obtained. .

Suitable polyamine compounds to be used in the present invention are known and conventional diamines, polyamines and mixtures thereof. Among them, only typical ones are 1,2-ethylenediamine and bis-diamine. (3-Aminopropyl) -amine, hydrazine, hydrazine-2-ethanol, bis- (2-methylaminoethyl) -methylamine, 1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-hydroxy. Ethylethylenediamine, 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-Triaminotoluenthi hydrochloride, 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 desirable. In the present invention, the organic phase dispersed in the aqueous phase is itself non-reactive, and the viscosity of this hydrophobic organic solvent is added as necessary to reduce the viscosity, and dispersed in the aqueous phase. It is possible to improve the sex.

The amount of organic solvent in this case is 50% by weight or less, preferably 40% by weight or less, based on the total organic phase.
More preferably, an amount of 30% by weight or less is suitable.

Suitable organic solvents are aromatic or aliphatic hydrocarbons, esters, ethers and ketones, among which benzene, toluene, xylene,
Cyclohexane, methylcyclohexane, diphenyl ether or mineral spirits are suitable.

If necessary, 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 reduced pressure. The aqueous phase in which the organic phase is dispersed is polyvinyl alcohol, hydroxyalkyl cellulose, carboxyalkyl cellulose,
One or more kinds 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 various nonionic, anionic or cationic surfactants. In the present invention,
The inside of the polymer particles is characterized by positively reacting with a urethane, but as is well known, the urethane-forming reaction between a hydroxyl group and an isocyanate group is particularly advantageous when the isocyanate group is an aliphatic group or an alicyclic group. 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 isocyanate is extremely slow as compared with the reactivity with hydroxyl groups, and the permeation effect of the outer wall formed by the addition of the polyamine compound causes the permeation of water into the inside of the particles. The object of the present invention is to achieve the urethanization reaction in the particles by increasing the reaction temperature and taking time from a negligible place,

As a result of repeated studies aimed at improving the above reaction conditions, the present inventors have found that cobalt naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tetra-n-butyltin, tri- One or more of various organometallic catalysts such as n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, tin octenoate or potassium oleate,

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

These organometallic catalysts can very effectively accelerate the reaction between the isocyanate group and the hydroxyl group. Adding the above-mentioned organometallic catalyst to the organic phase prior to water dispersion (fine dispersion) increases the viscosity of the organic phase and reduces the dispersibility in the water phase. However, the addition of the organometallic catalyst after the addition of the polyamine is not practical because the outer wall of the polymer particles is being formed, so that the organometallic catalyst is added to the inside of the polymer particles. Since it becomes difficult to be taken in, and by extension, the effect of accelerating the urethanization reaction inside the polymer particles tends to be reduced, the timing for adding the organometallic catalyst is to disperse the organic phase in the aqueous phase. Most suitable is during the polymerization step or between the dispersion step and the middle of the step of adding the polyamine.

Next, as the above-mentioned binder resin, basically any binder resin may be used so long as it can form a coating film, and therefore any one may be used, but among them, only typical ones are exemplified. If you keep it, 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 rubbers such as natural rubber and synthetic rubber, and further various natural polymer compounds such as cellulose may be used alone or in combination of two or more kinds. Of course.

As a method of preparing the coating composition for decorative sticking, a method of blending a binder resin having a particle size adjusted in advance with polymer particles is recommended.

As for the mixing ratio of the polyurethane polyurea particles having a three-dimensional crosslinked structure and the binder resin, the solid content weight ratio of binder resin / polymer particles is 20/8.
The range of 0 to 80/20 is suitable.

The thus obtained coating composition for decorative sticking according to the present invention is diluted with a solvent capable of diluting the binder resin among them, water or the like, if necessary, and then applied with a brush, a roll coater or a flower. Coating can be carried out on various substrates by various known and commonly used coating methods such as coater, spray coating or dip coating.

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

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

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

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

[0075]

EXAMPLES Next, the present invention will be explained more concretely by reference examples, examples and comparative examples. In the following, all parts and% are based on weight unless otherwise specified.

The respective raw material components used will be described below in advance. Among them, the polyisocyanate compound is as follows.

That is, "Bernock DN-950"
The solid content of [hexamethylene diisocyanate / adduct type polyisocyanate compound; manufactured by Dainippon Ink and Chemicals, Inc .; number average molecular weight = 640, solid content conversion isocyanate group content = 16.8%] was used. , Abbreviated as PI-1.

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

Further, 1,000 parts of polycaprolactone polyester triol having a hydroxyl value of 168.5 and 666 parts of isophorone diisocyanate obtained by polycondensation reaction of trimethylolpropane and ε-caprolactone are subjected to urethanization reaction. A polyisocyanate compound having an isocyanate group content of 7.5%, which was obtained as described above, was also used, but 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.

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

A polycaprolactone polyester diol having a hydroxyl value of 187, which is obtained by a polycondensation reaction of neopentyl glycol and ε-caprolactone, was also used, which will be abbreviated as PO-2 hereinafter.

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

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

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

Further, isophoronediamine was also used, but hereinafter this will be abbreviated as IPDA. Reference Example 1 (Preparation Example of Polyurethane Polyurea Particles) A 1 liter flask was charged with 0.5 parts of "PVA-217" (partial saponification product of polyvinyl alcohol manufactured by Kuraray Co., Ltd.).
While adding 300 parts of a 2% aqueous solution to make this an aqueous phase, in a separate container, 55.7 parts of PI-1 and 9.
3 parts and 30 parts of PO-1 were mixed together to form 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 the mixture was stirred for 1 minute to obtain a dispersion liquid.

Then, this dispersion was transferred to another flask, and was rotated at 200 rpm by a paddler type stirring blade. Di-n-butyltin dilaurate (DBTDL) with stirring
Was added, and 2 minutes later, 21.7 parts of a 50% aqueous solution of HMDA was also added.

After being kept at room temperature (about 25 ° C.) for 2 hours, the temperature was raised to 50 ° C. and the temperature was kept at the same temperature for 1 hour.
The reaction was continued by holding it at 0 ° C. for 2 hours to obtain a desired suspension of polyurethane polyurea particles.

The average particle size of this particle is 30 microns (μ
m). Further, the particles are extremely stable without swelling and dissolving in acetone, ethyl acetate, xylene or the like, and further, the particles may be fully filled with a polymer inside. It was confirmed as a result of observation with an electron microscope.

Reference Example 2 (Preparation Example of Polyurethane Polyurea Particles Containing Pigment) First, 80 parts of PO-2, “Fast-ogen Super Red” was used.
7093Y "[quinacridone 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. Below, this is MB
It is abbreviated as -1.

Then, the PVA was added to a 1 liter flask.
-300 "of 0.2% aqueous solution of" -217 ",
At 7,000, using a homomixer,
500 rpm. While agitating with, here, in a separate container, 37.5 parts of MB-1, 16 parts of PO-1, PI
The organic phase prepared by mixing 30 parts of -1 and 20 parts of HDI was added, further 0.2 part of DBTDL was added, and the mixture was stirred for 1 minute to obtain a dispersion liquid.

After that, this dispersion was transferred to another flask, and was stirred at 200 rpm with a paddler type stirring blade. With stirring at 22.3 parts of a 25% aqueous solution of EDA was added.

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

The average particle size of the polymer particles obtained here was 37 μm. Further, the particles did not swell and dissolve in acetone, and therefore, outflow of the red pigment was not observed in acetone.

Reference Example 3 (Preparation Example of Polyurethane Polyurea Particles Containing Pigment) First, 80 parts of PO-2, “carbon black CF-
9 "(manufactured by Mitsubishi Kasei) and 2 parts of toluene
5 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.

Then, the PVA was added to a 1 liter flask.
-217 "was charged with 400 parts of a 0.2% aqueous solution, and 20
At 7,000, using a homomixer,
500 rpm. While agitating with, here, in a separate container, 37.5 parts of MB-2, 16 parts of PO-1, PI
The organic phase prepared by mixing 30 parts of -1 and 20 parts of HDI was added, 0.2 parts of DBTDL was further added, and the mixture was stirred for 1 minute to obtain a dispersion liquid.

Then, this dispersion was transferred to another flask, and the speed was adjusted to 200 rpm with a paddler type stirring blade. With stirring at 22.3 parts of a 25% aqueous solution of EDA was added.

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

The polymer particles obtained here had an average particle diameter of 13 μm.

Examples 1-5 According to the combinations as shown in Table 1, 20 parts of polymer particles, 20 parts of binder resin, 0.2 part of silicone leveling agent and polyamide anti-precipitation agent. 0.4 part of xylene / n-butyl acetate = 50/50
60 parts of the mixture (weight ratio) was uniformly mixed to obtain various intended coating resin compositions for sticking to a design having a PWC (pigment weight concentration) of 50%.

Comparative Examples 1-5 According to the combinations as shown in Table 1, 2 of pigments were prepared.
0 part, 20 parts of binder resin, 0.2 part of silicone leveling agent, 0.4 part of polyamide precipitation inhibitor, xylene / n-butyl acetate = 50/50 (weight ratio)
PWC with 60 parts of the mixture
Various coating resin compositions for sticking having 50% were obtained.

[0103]

[Table 1]

[0104]

[Table 2]

The various kinds of coating resin compositions for sticking obtained in each of the examples and the comparative examples were individually coated on an iron plate or an ABS plate so that the dry film thickness was 50 μm, and at 60 ° C. It was dried and cured for 30 minutes.

Next, the coating films were left at room temperature for 1 week, and then the coating film performances were evaluated. The results are collectively shown in Table 2. The evaluation of these various performances was performed in the following manner.

Appearance: The specular gloss of 60 degrees 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 coating surface is uniform and completely matte. ○: The gloss is 2 or less, and the coating surface has uneven gloss. ×: The gloss is 2 or less.

Tactile sensation: It was judged by the degree of soft feeling when touched by hand. ◎… Extremely soft feeling ○… Quite soft feeling ×… Hard and rigid feeling

Graininess ◎ ・ ・ ・ Extremely soft and less gritty ○ ・ ・ ・ Extremely soft and gritty × ・ ・ ・ Hard and rigid, no grittyness

Scratch resistance: # 000 steel wool 30
The surface was rubbed with a surface pressure of g / cm @ 2, and 1 hour later, the condition of the coated surface was visually evaluated. ◎ ... No traces are marked ○ ... Slight marks are marked × ... Scratches remain clearly

Flexibility: The coated tin plate was bent by 180 degrees (2 mmφ) and the state of the coated surface was visually judged. (Compliant with JIS K-5400.) ⊙: No change is observed ×: Cracks are generated in the bent portion

Solvent resistance: A glass cap containing acetone was always placed on the coated surface so that the acetone would hang on the coated surface, and after leaving it for 24 hours, the state of the coated surface was visually judged. . ⊚: No change was observed ×: The coating film dissolved

[0113]

[Table 3]

Examples 6 to 8 A 0.1 mm thick polyester sheet, vinyl chloride sheet or coated paper having a pressure sensitive adhesive or adhesive on one side and a release material as a protective layer was used as the substrate, If necessary, these substrates were pretreated, and then the coating resin composition for decorative sticking obtained in Example 1 was applied so that the dry film thickness was 50 μm.

Then, each of the coated articles thus obtained was allowed to stand at room temperature for one week, and various coating film performances were evaluated in the same manner as in Examples 1-5. The results are collectively shown in Table 3.

[0116]

[Table 4]

[0117]

EFFECTS OF THE INVENTION As described above, the decorative coating resin composition of the present invention, its coated product, and its coated product are
Polyurethane polyurea particles having a three-dimensional crosslinked structure,
In particular, any article coated with the binder resin has an extremely high-grade feeling because the polymer particles are in a state of protruding onto the surface of the particles. It can also be made with a high degree of matte coating formed.

In addition, since the polymer particles themselves have a three-dimensional crosslinked structure, the resin composition for coating composition for decorative use of the present invention and the coated product thereof have solvent resistance and abrasion resistance. It is possible to form a coating film having excellent effects such as scratch resistance, scratch resistance, and durability. Particularly, by limiting the coating film performance of the binder resin, such a characteristic It is possible to form a coating film having an enhanced effect, and moreover, it is possible to form a coating film excellent in soft feeling (soft touch).

Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 175/06 C09J 7/02 JJH 6770-4J // C08G 18/08 NFQ 8620-4J 18/65 NEV 8620- 4J (72) Inventor Shigeo Yukawa 620-5 Ogura, Wakayama City, Wakayama Prefecture

Claims (9)

[Claims] 1. A paint resin composition for decorative sticking, comprising polyurethane polyurea particles having a three-dimensional crosslinked structure and a binder resin as essential film-forming components. 2. A polyurethane polyurea particle having a three-dimensional crosslinked structure, and a binder resin, which are obtained by using a coating composition containing the binder resin as an essential film-forming component. Painted product for designing. 3. A polyurethane polyurea particle having a three-dimensional cross-linking structure as described above, which is made into an organic phase in which a polyisocyanate compound in which an isocyanate group is stoichiometrically excessive and a polyhydroxy compound are mixed, Moreover,
Interfacial polymerization reaction between an organic phase capable of forming a three-dimensional crosslinked structure by a reaction and a polyamine compound having an equivalent amount or less with respect to a stoichiometrically excess isocyanate group in the organic phase, and urethane inside the particle The paint resin composition for decorative sticking according to claim 1, which is a polyurethane polyurea particle obtained through a chemical reaction. 4. The above-mentioned polyurethane polyurea particles having a three-dimensional crosslinked structure are made into an organic phase which is a mixture of a polyisocyanate compound and a polyhydroxy compound in which an isocyanate group is stoichiometrically excessive, Moreover,
Interfacial polymerization reaction between an organic phase capable of forming a three-dimensional crosslinked structure by a reaction and a polyamine compound having an equivalent amount or less with respect to a stoichiometrically excess isocyanate group in the organic phase, and urethane inside the particle The coated product for decorative sticking according to claim 2, which is a polyurethane polyurea particle obtained through a chemical reaction. 5. A mixture of a polyisocyanate compound in which the above-mentioned polyurethane polyurea particles having a three-dimensional cross-linking structure contains a pigment and a stoichiometrically excess isocyanate group is mixed with a polyhydroxy compound. Between the organic phase capable of forming a three-dimensional crosslinked structure by a reaction and a polyamine compound having an equivalent amount or less with respect to a stoichiometrically excess isocyanate group in the organic phase. The paint resin composition for decorative patch according to claim 1, which is a pigmented polyurethane polyurea particle obtained through the interfacial polymerization reaction of 1) and the urethanization reaction inside the particle. 6. A mixture of a polyisocyanate compound in which the above-mentioned polyurethane polyurea particles having a three-dimensional cross-linking structure contains a pigment and a stoichiometrically excess isocyanate group is mixed with a polyhydroxy compound. Between the organic phase capable of forming a three-dimensional crosslinked structure by a reaction and a polyamine compound having an equivalent amount or less with respect to a stoichiometrically excess isocyanate group in the organic phase. 3. The coated product for decorative sticking according to claim 2, which is a pigmented polyurethane polyurea particle obtained through the interfacial polymerization reaction and the urethanization reaction inside the particle. 7. The binder resin is 50-50,00.
The paint resin composition for decorative sticking according to claim 1, which has an initial elastic modulus within a range of 0 kgf / cm 2. 8. The binder resin is 50-50,00.
The coated product for decorative sticking according to claim 2, which has an initial elastic modulus within a range of 0 kgf / cm 2. 9. A metal material, plastic material, wood, leather or paper coated with the coating composition for decorative sticking according to claim 1, 3, 5 or 7. On one surface different from the surface, has a pressure-sensitive adhesive or an adhesive layer, and further has a release material as a protective layer thereon,
The coated article for designing according to claim 2, 4, 6 or 8.