KR20050019115A - Printing and coating compositions containing expandable polystyrene - Google Patents

Abstract

The present invention applies a printing or coating composition comprising a film-forming polymer binder, a solvent, thermally expandable polymer particles, and, if necessary, other general additives to a substrate by printing or coating, and heat treating the printed or coated substrate. A method of producing raised tissue on a substrate is provided, including the use of expandable polymer particles as colored or colorless expandable polystyrene microbeads of 0.1 mm to 5 mm in diameter in the unfoamed state.

Description

Printing Compositions and Coating Compositions Containing Expandable Polystyrene {PRINTING AND COATING COMPOSITIONS CONTAINING EXPANDABLE POLYSTYRENE}

FIELD OF THE INVENTION The present invention relates to printing compositions and coating compositions comprising expandable polystyrene and also to methods of producing raised textures on a substrate.

It is known that heat-expandable polymer particles can be used in printing or coating compositions for producing raised tissue on a printed or coated substrate.

U.S. Patent 4,194,026 discloses a crosslinkable foamed elastomeric emulsion comprising up to 20% by weight of thermally expandable polymer particles evenly applied to the polyurethane foam component, and heating the emulsion to foam the polymer particles and dry the elastomer emulsion and A method of making organized flexible foam coatings for sound insulation walls and sound insulation ceilings is disclosed by crosslinking to produce an organized elastomeric coating.

Japanese Patent 54137067 relates to the production of a decorative material by printing the material with an ink comprising foamable polymer particles. The particles are mixed with a binder, applied by printing and foamed at about 150 ° C. Wallpaper is referred to as the material to be printed.

Japanese Patent 53115779 relates to coated polyurethane foams and their preparation. To this end, an elastomeric emulsion comprising foamable polymer particles is spread over the polyurethane foam, and the foam is dried and heated. Foaming of the particles forms a textured surface.

Japanese Patent 11105399 relates to a foaming ink for producing a foamed image comprising a photoactive material and thermally expandable microcapsules. The ink is applied by screen printing and subsequently exposed to light.

U.S. Patent 4,006,273 discloses a method of making a water resistant foam formed print on a fibrous substrate, wherein the method comprises a crosslinkable film forming polymer binder, a solvent, and 1% by weight of thermoplastic and thermally expandable microcapsules having a diameter of 0.5 m to 300 m A printing composition comprising from about 45 wt% is applied over the substrate and the resulting coated substrate is dried and heated to produce a raised textured surface. Polymeric materials mentioned for thermally foamed microcapsules include polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, copolymers of acrylonitrile and methyl acrylate, and copolymers of methacrylonitrile and methyl acrylate. Copolymers.

It is an object of the present invention to further provide a printing or coating composition for fiber printing and fiber coating.

The inventors have found that this object can be achieved by a method of producing raised tissue on a substrate, in which printing or coating comprising a film forming polymer binder, thermally expandable polymer particles, and other common additives, if necessary Applying the composition to the substrate by printing or coating, heat treating the printed or coated substrate, and using the expandable polymer particles which are colored or colorless expandable polystyrene beads having a diameter of 0.1 mm to 5 mm in the unfoamed state. Include.

Preferred expandable polystyrene particles are those having an unfoamed diameter of 0.4 mm to 2 mm. Examples of its preparation are described in H. Gausepohl and R. Gellert (editors), Polystyrol (Polystyrene), Becker / Braun Kunststoff Handbuch (Plastics Handbook), Hanser Verlag.

Polystyrene is readily available, inexpensive, and readily foamable.

The printing or coating composition may be applied onto the substrate by conventional fiber printing methods, coating methods, or foam coating methods.

Examples of suitable fiber printing methods are flat-bed printing, rotary printing, and specialty printing methods.

Suitable coating compositions can be used in paste form or in foamed form, which forms are known as paste compounds or foam compounds. Examples of methods for applying the composition to substrates include air-knife coatings, doctor-and-slot coatings, knife-over-blanket coatings, rotating screens, transfer systems, Face padding devices, and horizontal pad-mangle systems. It is also possible to use suitable coating compositions in liquid form and apply the compositions onto substrates.

Suitable substrates are fibrous or nonfibrous substrates.

Examples of fiber substrates are any type of woven, knitted and nonwoven fabrics made of cotton, viscose, linen, wool, polyester, polyamide, acetate, triacetate or other synthetic fibers. Examples of nonfibrous substrates are paper, cardboard, leather, plastic and wood.

Preferred substrates are fiber substrates.

The printed or coated substrate is then heat treated. During the heat treatment, water evaporates, the coating crosslinks if necessary, and the expandable polystyrene microbeads foam to form foam beads to form a raised textured surface on the fibrous substrate. The heat treatment is usually performed at a temperature of 70 ° C. to 140 ° C. for 20 seconds to 20 minutes. When the heat treatment is performed at a relatively high temperature, for example from 120 ° C. to 200 ° C., the foamed polystyrene particles may melt, forming a speck of molten polystyrene on the fiber substrate.

In addition, the present invention

(a) 1% to 99.9% by weight of the aqueous dispersion of the film-forming polymer binder, preferably 8% to 80% by weight,

(b) 0.1% to 99% by weight, preferably 5% to 25% by weight of white or colored thermally expandable polystyrene particles having a diameter of 0.1 mm to 5 mm in the unfoamed state,

(c) 0% to 98.9% by weight of water added, preferably 0% to 87% by weight,

(d) 0 wt% to 98.9 wt%, preferably 0 wt% to 20 wt%, of common additives such as antifoams, emulsifiers, thickeners, crosslinkers, colorants, pigment dispersion formulations, fillers, and fastness improvers

It provides a printing composition and a coating composition for foam coating comprising a printing.

Examples of common aqueous dispersions of film-forming polymer binders are aqueous dispersions of acrylates, aqueous dispersions of butadiene, aqueous dispersions of vinyl acetate or aqueous dispersions of polyurethanes, and aqueous dispersions of copolymers of these monomers. The solids content of the aqueous dispersion is preferably 35% to 60% by weight. In addition to the water already present in the aqueous dispersions used, the printing compositions and coating compositions may comprise added water.

Examples of common crosslinkers are urea-formaldehyde addition products and melamine-formaldehyde addition products. Another common crosslinker is polyisocyanate.

An example of a general fastness enhancer is Luprimol®. SIG and Luprimol® Silicone oils such as SE (polysiloxanes).

Examples of common colorants (dyes and pigments) are Helizarin® pigment preparations.

Suitable emulsifiers are nonionic or anionic surfactants such as Luprintol® PE New.

The printing composition and coating composition of the present invention can create a three-dimensional structure on a fibrous substrate. Fiber printing can be used to apply the structure in decorative designs. It is also possible to use uncolored or colored expandable polystyrene particles or to color the coating paste or coating solution. Therefore, various design effects can be obtained. Depending on the heat treatment used, the form in which the polystyrene particles are fixed to the fibers is in the form of foamed foam beads or in the form of molten polystyrene specks. The water resistance of prints and coatings is very good.

The present invention also provides the use of thermally expandable polystyrene particles having a diameter of 0.1 mm to 5 mm in the unfoamed state as an additive to a printing or coating composition for a fibrous substrate.

Preferred printing compositions A-J for fiber printing are listed as follows, for example.

Preferred composition A is

Film-forming polymer binders, dispersions of acrylates, dispersions of butadiene, dispersions of vinylacetate or dispersions of polyurethane (e.g., Helizarin® Binder TX 4574) with a solids content of 10% to 70% by weight. Weight percent to 99.9 weight percent, especially 4 weight percent to 90 weight percent,

0.1% to 99% by weight, in particular 5% to 25% by weight, of white or colored polystyrene particles having a particle size of 0.1 mm to 5 mm (eg Styropor® P656),

0% to 98.9% by weight of water added, in particular 0% to 87% by weight,

0% to 1% by weight of silicone-free defoamer or silicone-containing defoamer,

As an emulsifier compound, 0% to 6% by weight, in particular 0.5% to 4.5% by weight, of mixtures of nonionic surfactants, methoxylated melamines, and silicone oils (e.g., Luprintol® MCL), and

0% to 6% by weight of polyacrylate (e.g. Lutexal® HIT) as a thickener, in particular 0% to 4.5% by weight

It includes.

Preferred further compositions B are

As film-forming polymer binders, 1% to 99.9% by weight, in particular 8% by weight of acrylate, dispersion of butadiene, dispersion of vinyl acetate or dispersion of polyurethane (e.g. Helizarin® Binder TX 4574) To 80% by weight,

0.1% to 99% by weight, in particular 5% to 25% by weight, of white or colored polystyrene particles having a particle size of 0.1 mm to 5 mm (eg Styropor® P656),

0% to 98.8% by weight of water added, in particular 0% to 87% by weight,

0% to 1% by weight of silicone-free defoamer or silicone-containing defoamer,

Nonionic or anionic surfactants as emulsifiers (e.g. Luprintol®) PE New) 0.1% to 2% by weight, in particular 0.3% to 1.5% by weight,

0% to 4% by weight of urea-formaldehyde addition product or melamine-formaldehyde addition product (eg Helizarin® fixer LF) as crosslinking agent, in particular 0% to 2.5% by weight,

As a fastness improver, polysiloxane (for example Luprimol® SE) 0% to 3% by weight, in particular 0% to 1.5% by weight,

0% to 6% by weight of polyacrylate (e.g. Lutexal® HIT) as a thickener, in particular 0% to 4.5% by weight

It includes.

Preferred further compositions C

As film-forming polymer binders, 1% to 99.9% by weight, in particular 8% by weight of acrylate, dispersion of butadiene, dispersion of vinyl acetate or dispersion of polyurethane (e.g. Helizarin® Binder TX 4574) To 80% by weight,

0.1% to 99% by weight, in particular 5% to 25% by weight, of white or colored polystyrene particles having a particle size of 0.1 mm to 5 mm (eg Styropor® P656),

0% to 98.9% by weight of water added, in particular 0% to 87% by weight,

0% to 1% by weight of silicone-free defoamer or silicone-containing defoamer,

As an emulsifier compound, 0% to 6% by weight, in particular 0.5% to 4.5% by weight, of mixtures of nonionic surfactants, methoxylated melamines, and silicone oils (e.g., Luprintol® MCL), and

As a fastness improver, polysiloxane (for example Luprimol® SE) 0% to 3% by weight, in particular 0% to 1.5% by weight,

Polyisocyanates as crosslinkers (e.g., Astazin®) hardener CN) 0% to 10%, in particular 0% to 8.5%, and

0% to 6% by weight of polyacrylate (e.g. Lutexal® HIT) as a thickener, in particular 0% to 4.5% by weight

It includes.

Preferred further compositions D are

As film-forming polymer binders, 1% to 99.9% by weight, in particular 8% by weight of acrylate, dispersion of butadiene, dispersion of vinyl acetate or dispersion of polyurethane (e.g. Helizarin® Binder TX 4574) To 80% by weight,

0.1% to 99% by weight, in particular 5% to 25% by weight, of white or colored polystyrene particles having a particle size of 0.1 mm to 5 mm (eg Styropor® P656),

0% to 98.9% by weight of water added, in particular 0% to 87% by weight,

0% to 1% by weight of silicone-free antifoaming agent or silicone-containing antifoaming agent,

Nonionic or anionic surfactants as emulsifiers (e.g. Luprintol®) PE New) 0% to 2% by weight, in particular 0.3% to 1.5% by weight,

As a fastness improver, polysiloxane (for example Luprimol® SE) 0% to 3% by weight, in particular 0% to 1.5% by weight,

Polyisocyanates as crosslinkers (e.g., Astazin®) hardener CN) 0% to 10% by weight, in particular 0% to 8.5% by weight,

0% to 6% by weight of polyacrylate (e.g. Lutexal® HIT) as a thickener, in particular 0% to 4.5% by weight

It includes.

Preferred further compositions E are

As film-forming polymer binders, 1% to 99.9% by weight, in particular 8% by weight of acrylate, dispersion of butadiene, dispersion of vinyl acetate or dispersion of polyurethane (e.g. Helizarin® Binder TX 4574) To 80% by weight,

0.1% to 99% by weight, in particular 5% to 25% by weight, of white or colored polystyrene particles having a particle size of 0.1 mm to 5 mm (eg Styropor® P656),

0% to 98.9% by weight of water added, in particular 0% to 87% by weight,

0% to 1% by weight of silicone-free antifoaming agent or silicone-containing antifoaming agent,

As an emulsifier compound, 0% to 6% by weight, in particular 0.5% to 4.5% by weight, of mixtures of nonionic surfactants, methoxylated melamines, and silicone oils (e.g., Luprintol® MCL), and

0 to 70 weight percent, especially 0 to 10 weight percent of a pigment preparation (e.g., Helizarin® pigment),

0% to 6% by weight of polyacrylate (e.g. Lutexal® HIT) as a thickener, in particular 0% to 4.5% by weight

It includes.

Preferred further compositions F are

As film-forming polymer binders, 1% to 99.9% by weight, in particular 8% by weight of acrylate, dispersion of butadiene, dispersion of vinyl acetate or dispersion of polyurethane (e.g. Helizarin® Binder TX 4574) To 80% by weight,

0.1% to 99% by weight of white or colored polystyrene particles (eg Styropor® P656) having a particle size of 0.1 mm to 5 mm, in particular 0% to 87% by weight,

0% to 98.9% by weight of water added, in particular 0% to 87% by weight,

0% to 1% by weight of silicone-free antifoaming agent or silicone-containing antifoaming agent,

Nonionic or anionic surfactants as emulsifiers (e.g. Luprintol®) PE New) 0% to 2% by weight, in particular 0.3% to 1.5% by weight,

0% to 4% by weight of urea-formaldehyde addition product or melamine-formaldehyde addition product (eg Helizarin® fixer LF) as crosslinking agent, in particular 0% to 2.5% by weight,

As a fastness improver, polysiloxane (for example Luprimol® SE) 0% to 3% by weight, in particular 0% to 1.5% by weight,

0 to 70 weight percent, especially 0 to 10 weight percent of a pigment preparation (e.g., Helizarin® pigment),

0% to 6% by weight of polyacrylate (e.g. Lutexal® HIT) as a thickener, in particular 0% to 4.5% by weight

It includes.

Preferred further compositions G are

As film-forming polymer binders, 1% to 99% by weight, in particular 8% by weight, of dispersions of acrylate, dispersions of butadiene, dispersions of vinylacetate or dispersions of polyurethane (e.g. Helizarin® Binder TX 4574) To 80% by weight,

0.1% to 99% by weight, in particular 5% to 25% by weight, of white or colored polystyrene particles having a particle size of 0.1 mm to 5 mm (eg Styropor® P656),

0% to 98.9% by weight of water added, in particular 0% to 87% by weight,

0% to 1% by weight of silicone-free antifoaming agent or silicone-containing antifoaming agent,

As emulsifier compounds, 0% to 6% by weight, in particular 0.5% to 4.5% by weight, of mixtures of nonionic surfactants, methoxylated melamines and silicone oils (e.g. Luprintol® MCL),

As a fastness improver, polysiloxane (for example Luprimol® SE) 0% to 3% by weight, in particular 0% to 1.5% by weight,

Polyisocyanates as crosslinkers (e.g., Astazin®) hardener CN) 0% to 10% by weight, in particular 0% to 8.5% by weight,

0 to 70 weight percent, especially 0 to 10 weight percent of a pigment preparation (e.g., Helizarin® pigment),

0% to 6% by weight of polyacrylate (e.g. Lutexal® HIT) as a thickener, in particular 0% to 4.5% by weight

It includes.

Preferred further compositions H are

As film-forming polymer binders, 1% to 99.9% by weight, in particular 8% by weight of acrylate, dispersion of butadiene, dispersion of vinyl acetate or dispersion of polyurethane (e.g. Helizarin® Binder TX 4574) To 80 weight percent,

0.1% to 99% by weight, in particular 5% to 25% by weight, of white or colored polystyrene particles having a particle size of 0.1 mm to 5 mm (eg Styropor® P656),

0% to 98.9% by weight of water added, in particular 0% to 87% by weight,

0% to 1% by weight of silicone-free antifoaming agent or silicone-containing antifoaming agent,

Nonionic or anionic surfactants as emulsifiers (e.g. Luprintol®) PE New) 0.1% to 2% by weight, in particular 0.3% to 1.5% by weight,

0 to 3 weight percent of polysiloxanes (for example Luprimol® SE) as fastness enhancers, in particular 0.3 to 1.5 weight percent,

Polyisocyanates as crosslinkers (e.g., Astazin®) hardener CN) 0% to 10% by weight, in particular 0% to 8.5% by weight,

0 to 70 weight percent, especially 0 to 10 weight percent of a pigment preparation (e.g., Helizarin® pigment),

0% to 6% by weight of polyacrylate (e.g. Lutexal® HIT) as a thickener, in particular 0% to 4.5% by weight

It includes.

Preferred coating compositions I and J for foam coating are listed, for example, as follows.

Preferred composition I is

As film-forming polymer binders, 1% to 99.9% by weight, in particular of dispersions of acrylate, dispersions of butadiene, dispersions of vinylacetate or dispersions of polyurethane (for example, Helizarin® Binder TX 4624 or TX 4574), in particular 8% to 80% by weight,

0.1% to 99% by weight, in particular 5% to 25% by weight, of white or colored polystyrene particles having a particle size of 0.1 mm to 5 mm (eg Styropor® P656),

0% to 98.8% by weight of water added, in particular 0% to 87% by weight,

0% to 1% by weight of aqueous ammonia of 25% by weight, in particular 0% to 0.5% by weight,

0% to 2% by weight, in particular 0% to 1% by weight of the urea-formaldehyde addition product or melamine-formaldehyde addition product (eg Saduren® 163) as a crosslinking agent,

0% to 1% by weight of polyphosphate, sodium polyacrylate or ammonium polyacrylate (e.g. Pigmentverteiler® A), in particular 0% to 0.5% by weight,

Magnesium silicate or aluminum silicate (e.g., Talkum® IT Star 20) as a filler 0% to 30% by weight, in particular 0% to 15% by weight,

0 to 5 weight percent, especially 0 to 3 weight percent of fatty esters, potassium stearate, or ammonium stearate (e.g. C & S-Stabsol®) as foam stabilizers,

0% to 30% by weight of polyacrylate as a thickener (eg Latekoll® D or Lutexal HIT)

It includes.

The pH of composition I is especially 9 to 9.5. The viscosity of composition I is preferably in the range of 20 dPa x s to 45 dPa x s as measured using Haake VT02, spindle 1.

Another preferred composition J is

As film-forming polymer binders, 1% to 99.9% by weight, in particular of dispersions of acrylate, dispersions of butadiene, dispersions of vinylacetate or dispersions of polyurethane (for example, Helizarin® Binder TX 4624 or TX 4574), in particular 8% to 80% by weight,

0.1% to 99% by weight, in particular 5% to 25% by weight, of white or colored polystyrene particles having a particle size of 0.1 mm to 5 mm (eg Styropor® P656),

0% to 98.9% by weight of water added, in particular 0% to 87% by weight,

0% to 1% by weight of aqueous ammonia of 25% by weight, in particular 0% to 0.5% by weight,

0% to 2% by weight, in particular 0% to 1% by weight of the urea-formaldehyde addition product or melamine-formaldehyde addition product (eg Saduren® 163) as a crosslinking agent,

0% to 1% by weight of polyphosphate, sodium polyacrylate or ammonium polyacrylate (e.g. Pigmentverteiler® A), in particular 0% to 0.5% by weight,

Magnesium silicate or aluminum silicate (e.g., Talkum® IT Star 20) as a filler 0% to 30% by weight, in particular 0% to 15% by weight,

0 to 70 weight percent, especially 0 to 10 weight percent of a pigment preparation (e.g., Helizarin® pigment),

0 to 5 weight percent, especially 0 to 3 weight percent of fatty esters, potassium stearate, or ammonium stearate (e.g. C & S-Stabsol®) as foam stabilizers,

0 to 30 weight percent polyacrylate (e.g. Latekoll D) as thickener

It includes.

The pH of composition J is especially 9 to 9.5. The viscosity of the composition J is preferably in the range of 20 dPa x s to 45 dPa x s as measured using Haake VT02, spindle 1, with a foam density of 200 g / l to 600 g / l. Composition J is preferably applied by a doctor system, for example dried at 100 ° C. and foamed at 130 ° C. for 1 minute.

The invention also provides the use of printing compositions and coating compositions for printing or coating fibrous substrates.

Claims (6)

A printing or coating composition comprising a film-forming polymeric binder, a solvent, thermally expandable polymer particles, and, if necessary, other common additives, is applied to the substrate by printing or coating, the printed or coated substrate is heat treated, and non-foamed. A method for producing raised tissue on a substrate, including the use of expandable polymer particles as colored or colorless expandable polystyrene microbeads having a diameter of 0.1 mm to 5 mm in a closed state. The method of claim 1 wherein the substrate is a fiber substrate. (a) 1% to 99.9% by weight of the aqueous dispersion of the film-forming polymer binder, (b) 0.1% to 99% by weight of thermally expandable polystyrene particles having a diameter of 0.1 mm to 5 mm in the unfoamed state, (c) 0% to 98.9% by weight of added water, (d) 0 to 98.9 weight percent of general additives such as antifoams, emulsifiers, thickeners, crosslinkers, colorants, pigment dispersers, dispersing agents, and fillers Coating composition for printing or foam coating for fiber printing comprising a. The aqueous dispersion of the film-forming polymer binder according to claim 3, which is an aqueous dispersion of acrylate, an aqueous dispersion of butadiene, an aqueous dispersion of vinyl acetate or an aqueous dispersion of polyurethane, or an aqueous dispersion of a copolymer of these mentioned monomers. Printing or coating composition. Use of thermally expandable polystyrene particles having a diameter of 0.1 mm to 5 mm in the foamed state as an additive to a printing or coating composition for a fibrous substrate. Use of the printing or coating composition according to claim 3 or 4 for printing or coating a fibrous substrate.