JPS61211369A - Decorative/film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a multi-tone or multi-colored surface textured surface.
red) relates to a coating composition which is suitable for producing decorative coatings and, in particular, coatings on substrates when using a roll applicator.

Multitone or multicolored cosmetic coatings are known and can be produced in one or more separate steps. See, for example, U.S. Patent No. U, J 91,90 ft.

One type of multicolor ticket coating described in No. 321 is a dispersion or solution of a film-forming polymer and discrete emulsified droplets of optionally colored material. Manufactured from a composition consisting of: Dry on the substrate
Subsequently, the globules consisting of the droplets give irregular areas of the coating, which have a color tV different from the color of the pacgrain r coating imparted by the film-forming polymer. The droplets in this type of composition may contain, for example, a solution of nitrocellulose lacquer.

The main problem with such paints is that when the paint is applied to the substrate by a roll applicator, the pigments are mixed into small balls [g10b].
ules) tend to undergo shear deformation. This causes elongation, breaking and mixing of the globules, resulting in a most unattractive finish. Successful application of the paint by spraying is limited to spraying, and the resulting coating has a rough and unattractive lumpy texture due to drying globules.

Textured decorative coatings are also known and generally these coatings have some ability to mask small imperfections in the substrate as well as the satisfactory raised appearance that the coating imparts to the substrate. Therefore it is manufactured.

The present invention provides a decorative coating, suitable for example for walls or ceilings in a house, which coating has a multi-toned or multi-colored appearance ftVL and a surface that is more pleasant to the touch, for example with pronounced relief. It is textured in the sense that it has a surface that resembles the feel of Sue P leather rather than having a textured appearance.

According to the invention, there is provided a multi-tone or polychromatic surface-textured decorative coating on a substrate, the coating being distributed in an irregular pattern and in a coalesced dry coating comprising a film-forming polymer. Based on the total volume of the dry coating, hard spherical polymer beads embedded in In a decorative coating film containing j capacity: (a) hard polymer beads /, 2 to 3;
．． s However, up to 5% by weight of the individual polymer beads can have a diameter greater than the effective maximum diameter, based on the total amount of polymer beads: The dimensions are such that the 90 polymer beads have a diameter within the range of 066 to 3.0 ox (total average thickness of the combined dry coating); g (7% by weight is O
(d) a color tone between the coalesced dry coating and at least some of the hard polymeric beads; Alternatively, a multi-tone or multi-colored decorative coating is provided which is characterized by color contrast.

It is preferable that the cosmetic coating film is pleasant to the touch and has a fine texture (surface structure).

Preferably, the cosmetic coating has an appearance (sometimes referred to as a "clip") such that the perceived color density or hue changes depending on the angle from which the coating is viewed. This change in appearance occurs as the angle at which the coating is viewed changes, for example, by changing the viewing direction from an angular fart perpendicular to the coating to an angle nearly parallel to the coating. This change in appearance is usually most obvious when the light source is in front of the viewer, and weakest when the light source is behind the viewer.

According to the inventor's heading t', said cosmetic coating is dispersed in a liquid medium, preferably by means of a roll applicator.
A coating composition comprising a dispersion of a T-film cast polymer and hard spherical polymer beads, comprising: (a) hard polymer beads! , 2 to i, sx(
of the individual polymer beads, but with an effective maximum diameter that is within the total average thickness of the coalesced dry coating)! (b) The total dimensions of the polymeric beads may be less than or equal to the 9011 mm diameter of the beads.
(c) at least 400% by weight of the polymeric beads 0.
5 to 0 x (effective maximum diameter of the beads) and optionally (dl) said dispersion has a tonal or chromatic contrast with at least some of the rigid polymeric beads. , provided on a substrate by applying to the substrate a coating composition characterized in that it contains components other than hard polymeric beads, such as pigments, to give the dry coating to be produced. The liquid medium of the possible coating composition is preferably an aqueous medium.

Preferably, the film-forming polymer is a latex polymer.

The hard spherical polymer beads to be used in the coatings of the invention are preferably produced directly by polymerization methods, but may also be produced indirectly from ready-made polymers, for example by crushing. When the coating composition is made into an aqueous composition, an emulsion polymerization method or a suspension polymerization method is used for special kV.

Producing polymers by these methods, described further below, yields B/e that are substantially spherical while having a weight particle size distribution that approximates a Gaussian or normal distribution. It is therefore necessary to define the desired bead dimensions in the coatings of the present invention by the combination of bead dimensions obtained from these preferred polymerization methods. The dimensions are directly related to the thickness of the dried coating that embeds the beads.

In general, dry coatings conventionally produced from decorative coating compositions, such as those produced from emulsion paints on the walls or ceilings of houses, have a total average thickness in the range of 0 to 10μ. has. According to the inventor's nine headings,
The hard polymeric beads present in the coating and coating compositions of the present invention have, for most purposes, an effective maximum diameter of 1 and therefore 1. It should have an "effective maximum diameter" which is explicitly defined to be in the range x (minimum conventional coating thickness) to 3.sx (maximum conventional coating thickness), ie j4c,/7Jiμ.

This "maximum effective diameter" bead is the bead that has the optimum maximum bead size that will yield a particular coating for a given thickness of coalesced dry coating.

This is because using larger diameter beads will result in undesirable roughness of the coating surface.

Preferably the total average bonded coating thickness is in the range 3O-4Cjμ and the most preferred effective maximum diameter of the beads is then 90
~iroμ. Preferably, the beads have a diameter in the range of at least 30 to 1SQμ. Individual beads can have a diameter greater than the effective maximum diameter! It is contemplated that the normality of the bead diameter may be present at random below the multiple heredity, taking into account the Ussian distribution t-.

For example, to trace differences in appearance, it may be preferable to use a blend of one or more different bead samples produced separately and with different bead size distributions tV. For example, one bead sample can contain beads with one effective maximum diameter, 1, and another bead sample can contain beads with a lower effective maximum diameter.

Preferably at least some of the beads are colored and -poly(
In this case, preferably all of the beads are colored. Some of the beads may have seven colors (the term also includes white when white pigment is present), while other beads may have one or more different colors. The beads are colored during their formation, for example by using oil-soluble dyes or insoluble pigments. Dyed beads are usually bright, while pigmented beads are either bright or opaque, and these differences can result in perceived color differences.

A representative suspension polymerization process that can be used to prepare hard spherical polymer beads suitable for the decorative coatings of this invention is described in the following examples. Suspension polymerization is generally preferred over emulsion polymerization. These polymerization methods are commonly used. It may be advantageous for the beads to contain small pores when
A method for producing porous beads that can contain 4 pigments is described, for example, in British Patent No. 1. J J 2. It is described in the specification of U 69.

Pigments may be added at any suitable stage of the emulsion or suspension polymerization process to produce pigmented, non-porous polymer beads.

Suitable water-insoluble polymers from which the polymer beads can be formed include addition polymers such as polyethylene and polypropylene and polymers and copolymers of vinyl chloride, styrene, lower alkyl acrylates and methacrylates, double condensation polymers such as polyesters, polyamides, etc. and amine-formaldehyde 18': nine unsaturated polyester resins copolymerized with styrene. Mixtures of polymers may also be used.

When a latex polymer is present in the coating composition of the present invention to provide a coalesced coating in which solid polymer particles are embedded, coating compositions suitable for producing other types of decorative coatings may be used. It is generally similar to latex polymers used in commercial products, such as emulsion polymers.

Suitable latex polymers include vinyl esters and ethers, lower alkyl acrylates and methacrylates,
There are lower olefins, homo-12 polymers and co-12 polymers of vinyl halide monomers, and styrene-butadiene copolymers. Typical monomers include vinyl acetate, vinyl propionate, saturated tertiary monocarzenic acid [e.g.
The vinyl esters of "versatin" acid, commercially available from 5hall Chemicals, (meth)acrylic acid, methyl methacrylate, ethyl acrylate, coethylhexyl acrylate, vinyl chloride, and vinylidene chloride. Polymers other than latex polymers that can be used as film type W, injection polymers include polyesters, alkyl-P, polyurethanes, and non-latex-type addition polymers. These polymers can be present in the liquid medium as a solution or as a dispersion. Although aqueous media are generally preferred with a small amount of non-aqueous liquid present in some cases, non-aqueous media are also possible! ! It can also be used.

The final coated film of the coating layer may contain any of the substances conventionally used in coating layers, such as pigments, fillers, thickeners, structural modifiers, coagulating solvents, and surfactants. , dispersants and biocides? It can be modified by blending it into a film-type Sl injection polymer.

All the individual components of the coating composition are such that the properties of the hard polymer beads are such that the desired multitone or polychromatic coating layer is achieved according to the invention when applied by a preferred applicator of the type commonly referred to as a roll applicator. For example, color and dimensions?
Choose carefully.

Furthermore, it is necessary to achieve a flow characteristic for the coating composition that is suitable for the conditions to which it is to be applied and suitable for the substrate to which it is to be applied.

Generally, the total volume content of beads and any pigments and extenders present in a coating composition (and in any coating layer routinely prepared therefrom) is determined by the pigment volume! Expressed in relation to the volume of polymer present at any one time: i.e. expressed as the quotient of the total volume of beads, pigment and filler divided by the total volume of beads, pigment and filler. That is, the pigment volume concentration is in the range of 15 to 15. The capacity of beads is generally l! It is in the range of ~2S chi.

[ It is preferable to have a continuous multicolored appearance by containing 100% or more. Thus, for example, the aqueous polymer latex can be loaded with a white pigment so that the final coating is white, and the polymer beads can be dyed or pigmented with a contrasting color. Alternatively, a multi-toned appearance can be achieved without the use of different colors, for example by the presence or absence of white pigments in the coalesced coatings or beads: or alternatively with the coalesced coatings or beads. Beads may contain different shades of the same color.

The assembled bottom of the present invention? When applied to a substrate (with a roll applicator), it gives a coating with a unique appearance, and this coating layer' can be defined as a coating layer with areas of hard beads that can be resolved with the naked eye; It is not limited to. The above regions have different bead densities of 1! r and therefore have different colors or tonal densities.

Thus, the present invention also provides a decorative coating comprising applying a coating composition as described above to a substrate from a roll applicator. Applying the coating composition in 62 steps or more provides a method for obtaining the desired coating composition on the substrate, e.g. by applying a first coating IWl and, after this has dried, subsequently applying a λth coating layer. It is preferable to use a total coating of 1 liter (coating film).

Details of formulating coating compositions to provide cosmetic coatings of the present invention are provided in the following examples.

The present invention will be explained with reference to the following examples, in which parts and parts are by weight unless otherwise specified.

Example 1 Izu Preparation A Deionized water 3M 9B Poly(vinyl alcohol) (as 3M solution in water) jj7C
Hyroxyethyl cellulose (dissolved in water as fl-/j solution) tt
, tiB Penzoylnozo-oxide (containing 70% solids)
) l-OriF Polyester* (dissolved in styrene as a 970% solution by weight) 33.92
G 7 Atsutolets)' (Fat Red) Dye
0.2 /H styrene
3.67■ Diethylaniline 0
．． 90J Poly(beer alcohol) (dissolved in water as a 7t/j% solution)
Flopylene gellicol/maleic anhydride/phthalic anhydride-II J///r/
Prepared from 22 t) Items A, B and C of the above formulation are thoroughly mixed in a reaction vessel. Mix Items and E separately to form a solution. This solution is then first thoroughly mixed with item F and then item G.
and then thoroughly mixed with Item H. Item number, g, F, G
and H with rapid stirring for about 1 minute.

Transfer to the reaction vessel containing B and C and continue stirring.
+M@mJm1--1y4Wpss? ++, -”II1
++w-P- Samples are taken and the "effective maximum diameter" of the emulsion dispersed phase is measured by optical microscopy. coulter
Another measurement technique is to use a (Coulter) counter. Continue stirring until the desired "maximum effective diameter" is taken. Item I is then added and agitation is maintained for 1 minute at which time item Jt- is added and agitation t- is reduced to minimum. The temperature is raised to gj'C and maintained at the temperature tas°C for gj minutes after the resulting calorific value has finished.

The resulting slurry of red polymeric beads (solids content 4
9% by weight) have an "effective maximum diameter" (amd) of roμ (90% by weight of the beads have a diameter in the range 35 to toμ, and on the go weight of the beads s O% - r oμ
). Using a similar method, l15
Beads with an "effective maximum diameter" of μ are also manufactured.

Input Slurry of red beads from above (gOd solid content) B Ethylene glycol 1.93C
White Spirit 1. 3D
Biocides, surfactants o, abE Dispersants, antifoaming agents /, 1! F Titanium dioxide 21. lcoG filler 15, qrH acrylic latex (S solid content) 77.37I Oor t
077Mo = 7 0,345 Alkali-soluble thickener ([available commercially as PriIlnal Gito 2 kochi solids content) 0.1.0K
Antifoaming agent 0-12L
Structure modifier items A, B, C, D and g2 were added to the high speed disperser;
/ 00 Disperse with r, p, m. Add items F and G to the disperser and disperse by 00 r, p, ff+ - 90
Lasts for minutes. 3. 6 parts of water and 44 parts of antifoaming agent are added and the product is further dispersed in 100 (apom) for 5 minutes. Transfer to low speed mixer.Item 1-1.T.

Add J and Kt and stir for 30 minutes. Item Lt - then added.

The final product has a volume solids content of 55% and 60%
It has a weight solids content of The pigment volume concentration in the coalesced coating (PVC) (titanium dioxide + filler) (i.e. excluding the bead volume) is j7-. The bead volume concentration in the total composition is 33%.

Separate coating compositions are formed using dyed beads of effective maximum diameter (emd) of tOμ and l15μ, respectively. When these compositions are applied by roll to a non-absorbent substrate to give a dry coating of total average coating thickness gjμ, toμ
Both remdJ beads and ttsμ remdJ beads were found to produce coatings that were pleasant to the touch and had a satisfactory appearance.

Example 2 Effective Maximum - Rigid Polymer Satisfying Diameter to~yoμeNL and Other Defined Criteria for Dimensions? - Two combs of hair are each manufactured according to the procedure of $11ral, provided that one sample contains the same red dye and the other sample is colored with blue dye. A coating composition is prepared by the method of Example/(b) except that the slurry consists of 7.2 parts of red beads, 23.7 parts of blue, and 2 parts of beads.

The coating composition is applied to a non-absorbent substrate by a roll applicator to produce a dry coating with an overall average coating thickness of 100 yen, which has an attractive multicolored appearance and feel. It has a texture similar to suede grass.

Example 3 A coating composition containing dyed nine-red bead gold having an effective maximum diameter of 10 microns is prepared in the same manner as in Example 1, but
However, a high proportion (parts) of the structure modifier is used and sodium carboxymethyl cellulose (3.r parts) is used instead of the alkali-soluble thickener. When the resulting high-strength coating is applied to a substrate using a roll applicator, a coating having a total average thickness of 4 cOμ is produced which contains an attractive multicolored appearance and feel with an attractive suede grass-like texture.

The coating composition was similar to that prepared in Example 1(b) except that it contained hard polyurethane microspherical beads with a pigment formulation commercially available under the trade name Decosilk. A coating composition is produced.

These microspherical beads have an effective maximum diameter of 90μ and are believed to meet other dimensional criteria defined for useful beads.

After applying to a non-absorbent substrate using a roll applicator,
A coating of total average thickness≠σμ is produced which has an attractive multicolored appearance and an attractive suede-like feel to the touch.

Claims (1)

[Scope of Claims] 1. A decorative coating film with a multi-tone or multi-colored surface pattern on a substrate, which coating film is distributed in an irregular pattern and is composed of a film-forming polymer. A decorative coating film containing 15 to 95% by volume of hard spherical polymer beads embedded in the coating film, based on the total volume of the dry coating film, wherein: (a) the hard polymer beads are 1.2% by volume, based on the total volume of the dry coating film; to 3.5 x [total average thickness of the coalesced dry coating (this is defined as the quotient of the total weight of the coalesced coating per unit area divided by the density of the coalesced total coating) ], but up to 5% by weight of the individual polymer beads, based on the total weight of the polymer beads, may have a diameter greater than the effective maximum diameter; (b) a polymer; The total dimensions of the beads are 0.6 to 3.0 x (total average thickness of the combined dry coating) for 90% by weight of the beads.
(c) at least 40% by weight of the polymer beads have a diameter within the range of 0.5 to 1.0 x (the maximum effective diameter of the beads); (d) A multi-tone or polychromatic cosmetic coating characterized in that there is a tonal or chromatic contrast between the coalesced dry coating and at least some of the hard polymeric beads. 2. The cosmetic coating film according to claim 1, which is pleasant to the touch and has a fine texture. 3. The cosmetic according to claim 1 or 2, wherein the total average thickness of the coalesced coating is in the range of 30 to 45 μm, and the effective maximum diameter of the polymer beads is in the range of 90 to 150 μm. Paint film. 4. At least 40% by weight of the polymer beads are between 30 and 15
Cosmetic coating according to claim 3, having a diameter in the range of 0μ. 5. Contains 15 to 95% by volume, based on the total volume of the dry coating, of hard spherical polymer beads distributed in an irregular pattern and embedded in a coalesced dry coating of film-forming polymer. A coating composition suitable for application to a substrate by a roll applicator to produce a decorative coating comprising a film-forming polymer and a dispersion of hard spherical polymer beads dispersed in a liquid medium. In a coating composition consisting of (
a) The hard polymer beads have an effective maximum diameter in the range 1.2 to 3.5 x (total average thickness of the coalesced dry coating), but 5% by weight of the individual polymer beads. (b) The total dimensions of the polymer beads are such that 90% by weight of the beads are between 0.6 and 3.0 x (total average thickness of the coalesced dry coating). difference)
(c) at least 40% by weight of the polymer beads have a diameter within the range of 0.5 to 1.0 x (the maximum effective diameter of the beads); and optionally: (d) said dispersion contains hard polymeric beads, such as pigments, which provide tonal or chromatic contrast in the dry coating to be produced with at least some of the hard polymeric beads. A coating composition characterized by containing various components other than. 6. The coating composition according to claim 5, wherein the liquid medium is an aqueous medium. 7. The coating composition according to claim 6, wherein the film-forming polymer is a latex polymer. 8. The coating composition according to any one of claims 5 to 7, wherein the volume concentration of the pigment is in the range of 15 to 95%. 9. The coating composition according to any one of claims 5 to 8, wherein at least some of the polymer beads are colored. 10. The coating composition according to any one of claims 5 to 9, wherein the polymer beads are prepared by suspension polymerization.