10.1515 - PSR 2015 0003

DE GRUYTER Physical Sciences Reviews.
2016; 20150003
Boh Podgornik Bojana1 / Starešinič Marica1
Microencapsulation technology and applications

in added-value functional textiles
1 University of Ljubljana, Faculty of Natural Sciences and Engineering, Department of textiles Ljubljana, Slovenia, E-mail:
bojana.boh@ntf.uni-lj.si, marica.staresinic@a.ntf.uni-lj.si
DOI: 10.1515/psr-2015-0003
1 Introduction
1.1 Research and development trends
Microencapsulation is a knowledge-intensive and dynamic research field with an increasing growth of publi-
cations. Trends in patent vs. non-patent literature on microencapsulation illustrate the growth of basic research
(scientific articles), as well as the fast growth of industrial research, represented in waves of patented inventions
(Figure 1).
Figure 1: Trends in scientific articles vs. patent documents on microencapsulation. Web of Science [1], advanced search:
Automatically generated rough PDF by ProofCheck from River Valley Technologies Ltd
TS = (microcapsule* OR microencapsulat* ) AND TS = (textile* OR cloth OR fabric OR garment* ). Espacenet [2], advanced
search: Title or abstract: (microcapsule* OR microencapsulat* ) AND (textile* OR cloth OR fabric OR garment* ).
Among numerous possible applications fields, microencapsulation offers many opportunities to improve
the properties of textiles or to give them new functions.
A bibliometric analysis of scientific articles in the Web of Science [1], and patents in the Espacenet database
[2] reveals that the first ideas of applying microcapsules in textiles emerged in the early 1970s, and that the
majority of publications on microencapsulation for textile applications remain patents (Figure 2). This empha-
sises the importance of industrial property rights, and the strong participation of industrial research in the
development of added-value functional textiles, invented with microencapsulated active ingredients.
Boh Podgornik Bojana is the corresponding author.

© 2016 Walter de Gruyter GmbH, Berlin/Boston.
This content is free.
1
Bojana and Marica DE GRUYTER
Figure 2: Trends in scientific articles vs. patent documents on microencapsulation for textiles. Web of Science [1], ad-
vanced search: TS = (microcapsule* OR microencapsulat* ) AND TS = (textile* OR cloth OR fabric OR garment* ). Es-
pacenet [2], advanced search: Title or abstract: (microcapsule* OR microencapsulat* ) AND (textile* OR cloth OR fabric
OR garment* ).
2 Microencapsulation methods and processes of applying microcapsules to textiles

2.1 Microencapsulation methods
The selection of microencapsulation process for added-value textile applications depends on the desired char-
acteristics and uses of the products. For example, microcapsule size, shape, wall material, active substance,
release mechanism, method of application, and compatibility with other components of the formulation must
be adapted to the requirements of textile processing methods, and uses of the final product.
Most often, microcapsules for textile applications have been prepared by one of the following technological
possibilities:
Coacervation processes (e.g. gelatin-gum arabic microcapsule walls) taking place in colloid systems, where
macromolecular colloid rich coacervate droplets surround dispersed microcapsule cores, and form a viscous
microcapsule wall, which is solidified with crosslinking agents (Figure 3).
Figure 3: Coating of microcapsules, produced by complex coacervation of gelatin and carboxymethyl cellulose (SEM, 630
×) with softer, elastic microcapsule walls.
Polymerization methods, where monomers polymerize around droplets of an emulsion and form a solid
polymeric wall. In in situ polymerization (e.g. aminoaldehyde resin walls), monomers or precondensates are
added only to the aqueous phase of emulsion (Figure 4), while in interfacial polymerization (e.g. polyamide,
polyester, polyurethane walls), one of the monomers is dissolved in the aqueous phase and the other in a
lipophylic solvent.
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DE GRUYTER Bojana and Marica
Figure 4: Coating of microcapsules, produced by in situ polymerization of aminoaldehyde precondensates (SEM, 1900 ×)
with impermeable, pressure-sensitive hard walls.
Physical/mechanical methods (e.g. spray-drying, fluidized bed coating, extrusion, deposition in vacuum,
solvent evaporation from emulsions, ultrasonic liposome formation), where the microcapsule wall is mechan-
ically applied, condensed or layered around the microcapsule core. Physical/mechanical microencapsulation
methods are used to design microcapsules that release their content during textile dyeing, washing or drying;
the walls are soluble or heat sensitive to dissolve or melt at a desired circumstance.
In situ polymerization is one of the chemical microencapsulation processes often used for techni-
cal applications, including textiles. The process takes place in oil-in-water emulsions; the result is nicely
smooth, spherical, reservoir-type microcapsules with transparent polymeric pressure-sensitive microcap-
sule walls (Figure 5 and Figure 6). Typical wall materials for in situ polymerization are aminoplast resins,
such as melamine–formaldehyde, urea-formaldehyde, urea–melamine-formaldehyde or resorcinol-modified
melamine–formaldehyde polymers. The in situ processes (Figure 7) can start either directly from amine and
aldehyde monomers, or from the precondensates. Typically, all materials for the formation of microcapsule
wall originate from the continuous aqueous phase of the oil-in-water emulsion system, and therefore have
to be water-soluble. To achieve better process control and improved mechanical properties of microcapsules,
modifying agents/protective colloids are added, such as styrene-maleic acid anhydride copolymers, polyacrylic
acid, or acrylamidopropylsulfonate and methacrylic acid/acrylic acid copolymers [3].
Figure 5: Spherical, reservoir-type microcapsules, produced by in situ polymerization in oil-in-water emulsion (SEM, left
500 ×, right 5000 ×).
Figure 6: Visualization of wall thickness in a container-type microcapsule, produced by in situ polymerization (SEM, 5000
×).
3
Figure 7: Example of microcapsules synthesis by in situ polymerization process.
For some technical applications the in situ aminoaldehyde microcapsules remain irreplaceable, due to some
superior characteristics, such as:
– the spherical reservoir-type shape with thin impermeable transparent walls (Figure 8);
– high chemical and thermal stability;
– high microcapsule resistance to harsh chemical environments (e.g. in detergents, softeners etc.);
– good storage stability;
– high microencapsulation yields (≥ 99%);
– effective microencapsulation process control;
– controllable microcapsule size and size distribution;
– good transferability of the in situ process to large-scale industrial production.
Figure 8: Spherical type pressure-sensitive microcapsules, produced by in situ polymerization, after the release of encap-
sulated core material (SEM, 7500 ×).
In addition, wall permeability and mechanical characteristics can be regulated and adapted, to obtain tailor-
made pressure-sensitive or more elastic microcapsules with controled diffusion, to support different release
mechanisms of the products [3, 4]. The main constraint of the in situ process is synthetic nature of aminoalde-
hyde microcapsule wall, and the residual formaldehyde in microcapsule suspension after the polycondensation
process, which limits the in situ microcapsules to technical products. However, with the optimised selection of
process parameters and application of formaldehyde scavengers, the concentration of free formaldehyde can
be minimized to meet the technical standards for textiles [5–9].
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2.2 Processes of applying microcapsules to textiles

Microcapsules have to be formulated for applications on woven or nonwoven textiles without substantially al-
tering the feel or color of textile products. Formulation additives usually consist of binders, crosslinking agents,
organic or inorganic pigments and fillers, antifoaming agents and/or other surfactants, and viscosity-controling
agents/thickeners.
Binders play a crucial role in microcapsule formulations for textiles. To a large extent, they determine the
quality, durability and washability of textile materials with microencapsulated ingredients. Typically, binders
are selected from the groups of:
– water-soluble polymers, such as polyvinyl alcohol, carboxymethyl cellulose, starch and modified starches,
xanthanes, alginates, and other natural gums;
– synthetic latexes, such as polyacrylate latexes, styrene-butadiene, polyvinyl-acetate, ethylene–vinyl acetate
copolymers;
– synthetic resins, such as such as urea–and melamine–formaldehyde resins, dimethylol ethylene urea,
dimethylol dihydroxy ethylene urea, dimethylol propylene urea, polyurethane and epoxy resins, vinyl ac-
etate resins;
– synthetic rubbers, such as polyurethanes, nitrile and chloroprene rubbers;
– silicones.
Different techniques can be used for applications of microcapsules to textiles. Patents describe incorporation of
microencapsulated compounds onto or into textiles by:
– coating with an air knife or rod coater;

– impregnation or immersion (Figure 9);
– printing techniques, such as screen-, photographic-, electrostatic-, pressure-transfer, thermal transfer and
inkjet printing;
– spraying on the surface of textiles;
– inclusion of microcapsules into the textile fibers during the spinning process, such as polyester, nylon or
modacryl fiber material;
– incorporation into polymer foams, coatings and multilayer composites that are placed or inserted into se-
lected parts of textile clothing or footwear.
Figure 9: An example of applying microcapsules to textile carriers by impregnation [10].
3 Purposes and release mechanisms of microcapsules in textile products

Mechanisms of releasing active ingredients from the microcapsule cores depend on the purpose of microen-
capsulation, on functions and desired effects of encapsulated components, and on the microcapsule wall char-
acteristics, particularly on permeability. An overview of microencapsulation purposes and release mechanism
in textile products is given below, with examples of patented inventions presented in Chapter 4.
In textile applications, microcapsules with permeable walls enable:
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– Prolonged/sustained release of active components from the core. This principle is used in long-lasting per-
fumes and deodorants on textile carriers, in insect repellent textiles, and in sustained release cosmetic and
medical textiles.
– Separation of low and high molecular weight molecules can be applied in microencapsulated enzymes in
detergent compositions for machine washing of textiles.
Microcapsules with impermeable walls are used in formulations and products where temporary isolation and
quick release of active components are necessary. Examples of useful functions and effects, achieved by applying
impermeable microcapsules to textiles, include the following:
– Protection of substances against environmental effects: microcapsule walls protect unstable components
against environmental influences, and release them only under the desired circumstances. For instance,
microencapsulated vitamins, lipids and essential oils in cosmetic textiles are protected against oxidation;
microencapsulated enzymes and oxidants are stabilized when added to laundry formulations for textiles.
– Separation of reactive components: this is used when leuco dyes are separated from color developers in
thermochromic textiles, or to separate reactants in formulations of multicomponent adhesives and binders
for textile bonding.
– Locally limited activity is applied to enable special color effects, such as reversible color changes, speckled
patterns and glossy effects, or to reduce the migration of dyes in multicolor textile printing.
– Reduction/prevention of volatility: this ensures that volatile compounds, such as perfumes, fragrances and
antimicrobial essential oils are retained in fragranced textiles until they are released in a target situation.
– Conversion from a liquid into a solid state: this is beneficial in formulations of powdered adhesives with
microencapsulated solvents for textile-containing laminate bonding; liquid crystals are encapsulated and
used in color changing textiles.
To release microencapsulated active components from microcapsule cores, numerous ways of release mecha-
nisms have been invented and applied in added-value textile products (Figure 10), such as:
6
Figure 10: Purposes of microencapsulation and release mechanisms of microencapsulated active ingredients in textile
applications.
– The mechanism of external pressure, which breaks the microcapsule wall and releases the core, was the first
developed and is still widely used, for instance in antimicrobial agents for socks and textile shoe inserts
(mechanical pressure caused by walking), fragranced textiles, such as t-shirts, ties, handkerchiefs, pillows
and linen (release by pressure and rubbing), and pressure-sensitive multicomponent adhesives for textile
bonding (activation in a mechanical press).
– In some applications, microcapsule wall breaks because of inner pressure. This happens if the core contains
substances which, under special conditions (e.g. UV light), decompose into gaseous components. The effect
is used in blowing agents in the production of light synthetic leather.
– The core substance can be released by abrasion of the microcapsule wall, e.g. in antistatics and fragrances in
textile washing and drying.
– In many applications, core materials are released by heat that causes melting of microcapsule wall at a specifi-
cally designed temperature. Examples include components in cosmetic and medical textiles (release at body
temperature), and textile softeners and fragrances in formulations for dryers (release by heat).
– Microencapsulated fire retardants or extinguishers, released by burning, are used in fire-proof textile mate-
rials for carpets, curtains, fire-protecting clothes, and car interiors.
– Microcapsules in photographic and light-sensitive textile printing processes are decomposed or hardened by
light.
– In textile washing/cleaning compositions, microcapsules with active ingredients dissolve in a specific solvent
(most often water), sometimes only at a selected pH value of the washing cycle.
– In textile processing formulations, selected reagents may be released by enzymatic degradation of target
microcapsules.
– In specific applications, permanent enclosure of the core material within the resistant microcapsules is essen-
tial. Examples include microencapsulated phase change materials (PCMs) for active thermal control, where
microcapsules hold the PCM solid-liquid transitions, and for liquid crystals in reversible color changing
textiles.
4 Applications of microcapsules in textile products

The possibilities for using microencapsulation technologies in textile products are numerous, and include col-
oring materials, enzymes, fire retardants, adhesives, fragrances, perfumes, insect repellents, disinfectants, cos-
metic additives, decontaminants, PCMs, UV absorbers and self-healing agents (see Figure 11).
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Figure 11: Applications of microcapsules in added-value functional textile products.
4.1 Microencapsulated dyes and pigments for textile dyeing and printing
Microencapsulation of dyes and pigments for dyeing and printing is one of the oldest microencapsulation
applications in textile processing. The idea of including microencapsulated dyes and pigments found their
place in different techniques, such as dyeing and printing by electrostatic fields, solvent dyeing, dot dyeing and
multicolored speckled printing, pressure or thermal transfer printing, screen printing, photographic screen
printing, and ink jet textile printing (Table 1).
Table 1 Examples of inventions applying microcapsules in textile dyeing and printing.

Invention Patent applicant (reference)
Electrostatic textile printing with powders and Sandoz [11]
microcapsules containing dyes in water or alcohol, to
obtain sharper, clearer printings at lower electrostatic
field strengths.
Solvent dyeing of polyester textiles with organic dyes, Sumitomo [12]
microencapsulated in polyethylene wax shells.
Microcapsules and dispersion pastes used for dot dyeing Totoki [13]
of textiles.
High contrast dot printing, achieved by gelatin-gum Toa Gosei [14]
arabic coacervation microencapsulation of powder or
liquid textile colorants.
Woven nylon or silk fabric ribbon for mechanical transfer National Cash Register [15]
printing, coated with pressure-sensitive ink
microcapsules, produced by coacervation.
8
Production of semi-permeable gelatin-gum arabic Sakai Textile [16, 17]

coacervate microcapsules with dyes for speckled screen
printing on acrylic, cotton, polyester, nylon, wool, and
rayon fabrics.
Transfer printing process with polyurethane Dickinson Robinson [18]
microencapsulated dyes for synthetic textiles.
Photographic screen printing on cotton, polyester, wool, Nippon Kayaku [19]
or acrylic fabrics, with pastes containing
microencapsulated yellow, red and blue dyes.
Printing inks for transfer printing on polyester fabrics, Seiren [20]
containing microencapsulated trichlorobenzene or
biphenyl solvents to swell the polyester fibers.
Printing inks for transfer printing on cotton fabrics with Fuji Photo Film [21]
improved washfastness, containing microencapsulated
reactive or acid dyes and microencapsulated dye fixing
agents.
Multicolored speckled printing on polyester, acrylic or Hayashi [22]
wool, achieved by microencapsulated yellow, red and
blue dyes.
Textile printing process with microencapsulated dyes, Milliken Research [23]
resulting in reduced dye migration and improved pattern
definition.
Transfer printing on textiles with microencapsulated Mihara [24]
indigo dyes.
Thermal imaging system for transferring photographic Foto-Wear [25, 26]
images to textiles, leather, ceramics, glass or plastics, with
heat responsive dye-precursor microcapsules.
Technology for rapidly dyeing of polyester fiber cloth by Jiangsu Shunyuan Textile [27]
dispersible dye microcapsules.
Modified one-bath dyeing technology of polyester/rayon Shaoxing Dongshi Textile [28]
fabric, with dispersed microencapsulated active dye.
Method for dyeing natural protein textile fibres’ with Ferrini [29]
microcapsules containing polymeric pendants on the
surface, to anchor to the fibres.
Ink compositions for ink jet textile printing. Seiko Epson [30]
4.2 Textiles with microencapsulated thermochromic materials

Thermochromism, the reversible dependence of color on temperature, utilizes temperature change to initiate
color development or color fading. Thermochromic systems can involve inorganic compounds, such as transi-
tion metal and organometallic systems, or organic compounds, including liquid crystals, stereoisomerism and
molecular rearrangement. Thermochromic systems based on liquid crystals and molecular rearrangement have
been applied successfully in textiles on a commercial scale [31]. Examples are presented in Table 2.
Table 2 Examples of microcapsule-based inventions for the production of thermochromic textiles.

Textile material for clothing, comprising a fabric or Ruggeri [32]
leather support, coated with a composition of
microencapsulated cholesteric liquid crystals.
Production of textile fibers exhibiting reversible color Pilot Ink [33]
changes, based on microencapsulated color reversible
thermochromic systems with leuco dyes (crystal violet
lactone), color developers (benzyl-4-hydroxybenzoate)
and stearyl phenoxyacetate.
Thermochromic textiles with a broader color range for a Pilot Ink [34]
given temperature, coated with binders and
microencapsulated thermochromic pigments.
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Thermo- or photochromic cellulose fiber textiles, based Matsui Shikiso [35, 36]
on reversibly changeable microencapsulated
thermochromic or photochromic materials. When worn,
the resulting T-shirts exhibit color changes according to
heat transmission from the body.
Color changing fabrics, based on synthetic fabrics, coated MATEO report [37]
with microencapsulated thermochromic dyes. With the
combination of four basic colors, each in two shades, a
total of 56 fabric colors are achieved.
Production of composite sensor fiber, comprising Commonwealth Scientific and Industrial Research
microencapsulated thermoresponsive materials, and their Organisation [38]
applications in fiber fabrics.
Thermochromic pigments in microcapsules of very small Chromatic Technologies [39]
sizes.
4.3 Textiles with microencapsulated photochromic materials
Photochromic dyes absorb quanta in the visible or near-infrared light region. The excited state of a dye must
last long enough to undergo a chemical reaction. Applications of photochromic dyes are known for invisible
writing, erasable recording media, darkening of sunglasses, or darkening of textile products, such as curtains,
t-shirts and sportswear [40]. Microencapsulation of photochromic dyes for textile applications is presented in
Table 3.
Table 3 Examples of inventions with microencapsulated photochromic materials.

Light- and washfast reversible photochromic fabrics Unitika [41]
coated with spironaphthoxazine derivatives,
microencapsulated in hollow porous inorganic
microspheres, for applications in curtains.
Photochromic inks for textiles, containing reversible Japan Capsular Products & Mitsubishi [42, 43]
photochromic dyes, microencapsulated by a gelatin
coacervation method, formulated with an acrylic binder,
used for screen printing on cotton fabrics.
Reversible photochromic textiles, resistant to fastness due Matsui Shikiso [44]
to abrasion or washing, containing microencapsulated

photochromic substances and binders, used for the
production of photochromic shirts.
Textile printing pastes, comprising microencapsulated Matsui Shikiso [45]
photochromic amine dyes, such as 6′-substituted
spironaphthoxazines or 3-substituted naphthopyrans,
and acrylic oligomers as binders.
Production of microencapsulated photochromic Nippon Paint [46]
substances for textile dyeing and printing.
Photochromic double-shell microcapsules, prepared by China Tex. Acad. [47]
interfacial and in situ polymerization, for textile printing
applications.
4.4 Microencapsulated catalysts and enzymes for special textile effects
Patents on microencapsulated catalysts and enzymes in textile treatment describe methods for achieving special
effects, such as wrinkle recovery, crease retention or biomechanical visual effects on fabric surfaces, resulting
in opalescence, reflection, or matting (Table 4).
Table 4 Examples of microencapsulated catalysts and enzymes for textile treatment.

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Microencapsulated catalysts and crosslinking agents for Cluett, Peabody & Co. [48]
improved wrinkle recovery and crease retention of
durable press cotton, linen and regenerated cellulose
fabrics.
Sandoz’s Sirrix Luna treatment, containing Sandoz [49]
microencapsulated enzymes (e.g. hydrolases) to produce
special effects on fabric surfaces – opalescence, moonlight
effects, cat’s eye reflection, and washed down
appearances.
4.5 Textiles with microencapsulated fire retardants
One of the shortcomings of untreated textile materials used for decoration and construction purposes is their
flammability. As a solution, flame retardant textiles have been developed with incorporated fire retardants. A
review of microencapsulation of flame retardant formulations suitable for application in textiles was published
by Salaün et al. [50]. Microencapsulation can be used to avoid reactions of fire retardants with textile polymers,
prevent sublimation or exudation of fire retardants from the polymer, or to eliminate substance hydrophilicity.
The idea of microencapsulated fire retardants for textiles was first launched by the industrial producers in the
beginning of the 1970s. Textiles treated with microencapsulated fire retardants have been used for military and
civilian clothing and tents, for carpets, furniture and car interiors (Table 5).
Table 5 Some inventions on fire-resistant textiles with microencapsulated fire retardants.

Impregnation of textiles with microencapsulated active Kanegafuchi Spinning [51]
substances, including fire retardants (Unflame BP) in
polyurethane, polyorganosiloxane, polyolefin, or epoxy
resin walls.
Microencapsulated fire retardants, incorporated into Kanegafuchi Spinning [52]
synthetic fibers or applied on fabrics, released from
microcapsules at the ignition temperature of textiles. Wall
materials include polystyrene, polyvinyl alcohol,
phenol–formaldehyde resins and urethane polymers.
Self-extinguishing and laundering resistant textiles, Asahi Chemical [53]
impregnated with a dispersion of microencapsulated fire
retardants in polymeric walls, and acrylate binders.

Fire-resistant fibers, containing microencapsulated fire Japan Exlan [54]
retardants and perfumes, formulated with
acrylamide–methyl acrylate polymer binders.
Flame resistant polyamide or polyester carpets, Champion International [55]
containing volatile fire retardants in heat sensitive
urea–formaldehyde or melamine-formaldehyde
polymeric wall microcapsules.
Washfast fire-resistant polyester fabrics, based on Matsumoto [56]
microencapsulated halogenated fireproofing agents and
acrylate copolymer binders.
A fire retardant material, comprising both ammonium Dartex Coatings [57]
polyphosphate particles microencapsulated within a
melamine or melamine-based resin, and melamine-based
particles retained in a base material. The material can be
applied to textiles.
Microcapsulation of flame retardants by in situ Aero [8]
polymerization of aminoaldehyde resins, for applications
in textiles and other technical products.
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4.6 Microencapsulated agents for textile sizing and adhesive bonding
Microencapsulated sizing agents, adhesives, adhesive activators and crosslinking agents have been used for
textile sizing and bonding. The microcapsule core release mechanisms include pressure, heat or a combination
of both (Table 6).
Table 6 Inventions on microencapsulated agents for textile sizing and bonding.

Treatment of knitted fabrics with microencapsulated Carlier [58]
sizing agents, composed of vinyl adhesives, solvents, or
other compounds susceptible to reactions with textiles.
Cold sealable textiles, based on microencapsulated Hermann Windel Co. [59]
adhesive components, applied in systems of cold
adhesive bonding, reinforcing and stiffening, used in
clothing, shoe, leather, and fur industries.
Textile adhesive composites with microencapsulated Lainiere de Picardie [60]
crosslinking agents, useful for reinforcement of textiles by
hot pressing.
4.7 Microencapsulated blowing agents and expandable microcapsules for leather substitutes
Applications of expandable microcapsules in textile products include flexible light weight leather substitutes,
waterproof coatings, anti-slip materials for carpets, and expandable sewing threads (Table 7).
Table 7 Examples of inventions on blowing agents and expandable microcapsules.

Foamable microcapsules for the production of leather Achilles Corporation [61]
substitutes.
Composition of thermally expandable microcapsules in a Bando Chemical [62]
polymeric resin, and production of light weight flexible
leather substitute by hot pressing.
Compositions of colored hollow silicate microspheres, Meisei Rejinokara [63]

coupling agents and organic polymer binders for light
weight leather substitutes on textile fabric supports.
Anti-slip adhesive nonwoven textiles, containing Nippon Kako Seishi [64]
polyester supports, laminated with a polyethylene film
and microcapsules that expand by heating to produce an
anti-slip foam.
4.8 Microencapsulation for textile water proofing
Increased impermeability and water proofing of textile surfaces can be achieved by expanding a layer of mi-
crocapsules on a porous support into an impermeable layer, or by applying microencapsulated water proofing
agents, and releasing them from microcapsule cores. In both cases, heat treatment plays a crucial role in micro-
capsule activation (Table 8).
Table 8 Examples of inventions using microcapsules for textile water proofing.

Waterproof sewing threads, impregnated with heat Nippon Rubber [65]
expandable thermoplastic compositions containing
microcapsules, used for sewing leather substitutes,
textiles for raincoats, tents and shoes.
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Textile coating compositions, containing waterproofing Toray Industries [66]

agents in inorganic porous microcapsules, give water
resistance by heat treatment.
Thermally treated coating of synthetic resin Takashimaya Nippatsu [67]
microcapsules expands into an impermeable surface layer
on porous polyurethane support.
Heat expandable microcapsules with a thermoplastic Owari Seisen [68]
resin wall and a gas generating core, formulated with a
binder, expand by heating and give flexible light weight
waterproof woven, knit or nonwoven textiles.
4.9 Microcapsules in textile softening and antistatic compositions
Fabric softeners and antistatics for textile washing and drying employ microcapsules to solve the incompatibil-
ity of antistatic compounds and anionic surfactants in detergents, to incorporate liquid ingredients into solid
formulations, to add hydrophobic components into water-based formulations, and to achieve a prolonged re-
lease of fragrances (Table 9).
Table 9 Examples of textile softening and antistatic compositions with microcapsules.

Polyurethane foam sponge to be added to wet laundry in Colgate Palmolive [69]
a rotating dryer, containing microencapsulated fabric
softeners and perfumes in coacervation microcapsules.
Pre-softener and washing composition with Procter and Gamble [70]
pressure-sensitive microcapsules, comprising a perfume
core and urea resin wall.
Softening antistatic agents, microencapsulated by Procter and Gamble [71]
interfacial polymerization, released by heat and abrasion.
Fabric softening formulations comprising both International Flavors and Fragrances [72]
microencapsulated and free fragrances; with
microcapsule walls made of gelatin, dextrin, gum arabic,
modified starch, urea-formaldehyde resin or other
polymers.
Aqueous textile softener compositions for the rinse stage Procter and Gamble [73]
of laundering, containing microencapsulated perfumes in

a complex coacervate shells of gelatin and a polyanion.
Cationic polymer stabilized microcapsule compositions Colgate Palmolive [74]
for fabric softeners.
Friable perfume microcapsules for dryer-added fabric Procter & Gamble [75]
conditioning.
Use of a cross-linked cationic polymer to provide stability Procter & Gamble [76]
to microcapsules in a fabric softener composition.
4.10 Microencapsulated ingredients in textile detergents
There are patents on microencapsulated components in detergent formulations for washing textile goods. The
main applications include microencapsulated enzymes (Table 10); bleaching and whitening agents (Table 11);
and perfumes and other additives, such as dry defoamers, dyes and cleaning chemicals (Table 12 and Table 13).
Table 10 Examples of patents on microencapsulated enzymes for textile detergent formulations.

Production of microencapsulated enzymes for detergents Toyo Jozo & Fuji [77]
by spray-drying of compositions consisting of inorganic
salts, water-soluble binders and enzymes.
13
Spray cooled microencapsulated proteases with fatty acid Henkel [78]

or fatty alcohol walls, incorporated into sodium perborate
bleach compositions.
Mixed granulate bleach and enzyme compositions, Procter and Gamble [79]
consisting of a dry peroxy acid bleach, and enzyme
microcapsules.
Liquid detergent formulations with microencapsulated Showa Denko [80]
enzymes.
Microencapsulation of enzymes for detergents with a Lever Brothers [81]
mixture of hard and soft waxes for wall materials.
Microencapsulation of proteases, lipases and amylases Olson [82]
into dual-walled microcapsules, to achieve time release
and prevent enzyme deactivation by halogen bleaches in
mixed bleach/enzyme detergent compositions.
Microencapsulation of enzymes with water-soluble alkali Clorox [83]
metal silicates and additives, to achieve prolonged
enzyme storage stability in the presence of oxidant
bleaches.
Liquid detergent concentrate with microencapsulated Novo Nordisk [84]
enzymes; microcapsule polymeric walls remain
permeable for water and small molecules.
Liquid detergent composition, comprising Novozymes [85]
microencapsulated enzymes; microcapsules are produced
by crosslinking of a polybranched polyamine.
Table 11 Examples of patents on microencapsulated bleaching agents and whiteners in textile laundry formulations.
Microencapsulated fluorescent whiteners, protected from Prurex [86]
the oxidative degradation by NaOCl bleach.
Spray-dried microcapsules of perborate activators for Henkel [87]
bleaching and washing liquors.
Microencapsulated fluorescent bis(triazinylamino) Henkel [88]
stilbenedisulfonate brighteners for white and colored
fabrics.
Fatty acid microencapsulated ethylenediamine Henkel [89]
tetraacetate for bleaches and detergents containing active
oxygen.
Fatty acid microencapsulated tetraacetylglycoluril Henkel [90]
activator for sodium perborate in detergents.
Free flowing granular laundry detergents, containing Ciba-Geigy [91]
chlorine donors and microencapsulated fluorescent
whiteners in carboxymethyl cellulose microcapsules,
produced by spray-drying.
Molten fatty acids microencapsulation of peroxide Nobel Hoechst Chimie [92]
bleaching agent activators, such as tetraacetylglycoluril
and tetraacetilethylenediamine.
Fluidized bed microencapsulation for the production of Lever Brothers [93]
free flowing potassium dichloroisocyanourate bleach
particles, encapsulated by an inner layer of fatty acid, and
an outer layer of a water-soluble fatty acid salt.
Fluidized bed technology, using poly(vinylpyrrolidone) Unilever [94]
wall material for microencapsulation of sodium perborate
bleaching agents for detergent compositions.
Spray coating process of active chlorine bleach Unilever [95]
microgranules with two layer walls, utilizing a mixture of
fatty acids and waxes.
Fluidized bed technology for the encapsulation of sodium Interox [96]
percarbonate with a molten polyethylene wax.
Microencapsulated bleaching agents consisting of an Lever Brothers [97]
active halogen oxidizing material, and a fatty acid soap
wall.
14
Clear detergent gel compositions, comprising Lever Brothers [98]

microencapsulated chlorine and oxygen bleaches, bleach
precursors, enzymes, fabric softeners, surfactants and
perfumes.
Compositions of molecularly encapsulated preformed Procter & Gamble [99]
peroxyacids and bleach catalysts.
Table 12 Examples of microencapsulated antifoaming agents in textile detergents.

Detergent composition for machine washing, containing Unilever [100]
antifoaming agents, microencapsulated by gelatin-gum
arabic walls.
Low foaming detergent compositions, containing silicon Henkel [101]
defoamers, microencapsulated with methyl- or
carboxymethyl cellulose.
Table 13 Examples of patented microencapsulated perfumes, dyes, softeners and other additives in laundry detergents.
Microcapsule formulations for textile dry cleaning, Werner und Mertz [102]
containing microcapsules of foam forming liquid
detergents or soaps, produced by coacervation.
Detergent compositions including a microencapsulated Dainichiseika Colour and Chemicals [103]
water-soluble dyes, bleaching agents, surfactants and a
perfumes.
Laundry detergents containing perfumes in Procter and Gamble [104]
water-insoluble friable microcapsules. The microcapsules
remain intact during laundering, and are fractured
during handling of the laundered textiles, thus releasing
the perfume.
Microencapsulation of cationic softeners with wall Procter and Gamble [105]
materials including waxes, fatty acids, fatty alcohols or
fatty esters with the melting points above 50 °C; and their
inclusion into powder detergents, to prevent undesired
precipitation with anionic surfactants during the fabric
laundering, but releasing the softener in a heated dryer.
Microencapsulated photoactivator dye compositions that Procter & Gamble [106]
are quickly soluble in water, for applications in
detergents.
Synthesis of microcapsules containing fragrances or BASF [107]
perfumes for laundry detergents or cleaning products.
Structured liquid detergents formulations with Unilever [108]
incorporated microcapsules.
Storage stable microcapsules of scents in detergent Henkel [109]
compositions that are low in formaldehyde, produced by
reacting aromatic alcohols or ethers and aldehydic
components, and optionally a (meth)acrylate-polymers.
Laundry detergent compositions comprising Procter & Gamble [110]
microcapsules, pH tuneable di-amido gellants and
surfactants.
4.10.1 Enzymes
In early patents, enzyme encapsulation improved detergent storage stability, reduced dusting and minimized
health hazards in detergent factories and households. Subsequently microencapsulation was used to protect
15
enzymes against the activity of aggressive additives, especially bleaches. Newer patents used the advantage of
encapsulation to incorporate enzymes into liquid and gelled detergent formulations (Table 10).
4.10.2 Bleaching agents and whiteners
Microencapsulated bleaching agents in laundry formulations have the advantages of being separated from the
oxidation sensitive components in the detergent compositions, to prevent reduction of their bleaching capacity,
and to reduce the damage to fabrics (Table 11).
4.11 Textiles with microencapsulated fragrances and perfumes
Fragranced textiles, containing microencapsulated essential oils, aromas and perfumes, have been developed
to either slowly release their contents through permeable walls, or to have completely impermeable walls, and
open only by application of mechanical pressure and rubbing whenever the wearer moves. A combination of
both release mechanisms is also possible. After the problems of controling the release have been solved, and bet-
ter washfast binders introduced, a new generation of aromatic textiles entered the market that remain fragrant
over a prolonged period of time, resist dry cleaning, or keep the microcapsules over several washing cycles.
Applications of microencapsulated fragrances, perfumes and antimicrobial essential oils in woven and nonwo-
ven textiles range from perfumed curtains, bed linen, shirts, socks and hosiery to antimicrobial towels, shoe
insoles, and textiles for seats in public transportation (Table 14). Figure 12–Figure 15 illustrate some examples
of our own research [111].
Table 14 Examples of patents on fragrant microcapsules in textile products.

Microcapsule-coating of fabrics for fragranced linings and Eurand [112]
ribbons, coated with gelatin-gum arabic coacervate
microcapsules of lavender or pine oil.
Fragranced towels containing microencapsulated Shibata Towel [113]
perfumes. Coating composition include acrylic polymer
binders and pressure-sensitive microencapsulated
perfumes.
Fragrant textiles that retain fragrances after repeated Kanebo [114–119]
washing. Coating compositions contain urea resin

microencapsulated fragrances and silicone binders, such
as epoxy modified dimethyl siloxane. Applications
include dyed and softener treated fragrant silk scarves
and handkerchiefs; washfast silk neckties with lasting
fragrances; fragrant hand knitting and handicraft yarns;
fragrant leather substitutes and cotton jersey shirts;
fragrant cotton bedding with improved washfastness;
waterproofed polyester textiles with jasmine
microcapsules; and waterproofed woven fabrics, knits
and yarns, treated with urea resin jasmine flower
perfume microcapsules.
Synthesis of essential oil microcapsules by in situ Aero [120]
polymerization, and a technological process for preparing
textile carriers saturated or coated with
microencapsulated scents.
Garments, interior materials, filters and automobile Osaka Juki [121]
interiors, composed of nonwoven textiles, coated with
essential oils in cyclodextrin and porous silica
microspheres.
Fragrant textiles with improved durability and slow Kanebo [122]
release of fragrances, comprising hollow fibers with
microencapsulated perfumes.
Microencapsulated grass aroma in rattan-imitating mat Shanghai Shuixing Home Textile [123]
surface materials in home textiles.
16
Incorporation of a polyester microencapsulated Iangsu Zja New Material Co. [124]

fragrances into spinning materials to produce fragrant
fibers.
Figure 12: Scanning electron microscope (SEM) photograph of microcapsules with a rose fragrance (left,), and eucalyptus
essential oil (right), prepared by in situ polymerization, to be applied in fragranced textiles (SEM 2000 ×).
Figure 13: Nylon pantyhose textile with microencapsulated rose oil in pressure-sensitive microcapsules, produced by in
situ polymerization (SEM, left 50 ×, right 1000 ×).
Figure 14: Scanning electron microscope (SEM) of pressure-sensitive microencapsulated fragrances on a decorative wrap-
ping ribbon; fragrances are released by mechanical pressure, applied by handling (SEM, left 500 ×, right 2000 ×).
Figure 15: Nonwoven textile handkerchief with microencapsulated decongestant eucalyptus oil (SEM, left 50 ×, right
1000).
4.12 Textiles with microencapsulated animal repellents

To obtain prolonged insecticidal and insect repellent effects of fibers and textiles, and to reduce the toxicity and
volatility of active compounds, insect repellents and/or insecticides can be microencapsulated and applied to
textiles (Table 15).
Table 15 Examples of patents on repellent and insecticide microcapsules in textile products.
17

Insect repelling carpets, curtains and sheets, Hosokawa Textile [125]
manufactured by the application of a sustained release
microencapsulated diethyltoluamide insect repellent in a
polyamine resin.
Fabrics and panty hoses with durable insect repellence, Toyobo [126]
finished with a composition containing aminoaldehyde
polymer microcapsules of N,N-diethyl-m-toluamide
repellent and acrylic polymer binder.
Long-lasting mosquito repelling panty hoses, treated Toyobo [127]
with microencapsulated repellents, such as Deet.
Durable microencapsulated insect repellents as Kanebo [128]
household sprays for textile products, e.g. for
mothproofing.
Improved fixing process of repellent microcapsules on Hasokawa Textile [129]
textile fibers, contributing to better washfastness.
Production of insecticidal microcapsules for fibers or Union Kagaku [130]
textiles, and applications in insecticide-processed fibers
or textiles.
Insect repellent textiles comprising a natural or synthetic Innovatec [131]
fabric, a microencapsulated insect repellent, and a binder.
Microencapsulated biocide and repellent compositions Mateo Herrero María Pilar [132]
with a double repellence action, used in textile garments.
In addition to insect repellents, other animal repellents have been microencapsulated. For instance, pro-
longed release microencapsulated deer and rabbit repellents on nonwoven textiles were developed for horti-
cultural and agricultural use [133].
4.13 Textiles with microencapsulated antimicrobial, disinfectant and deodorant components
Several essential oils and plant extracts have antimicrobial and deodorant properties. Because they are liquids,
microencapsulation is required for the conversion into the solid state. At the same time, a prolonged activity of
microencapsulated active substances can be achieved.
Inventions on microencapsulated antimicrobials for textile applications include various textile coating com-
positions with antimicrobial effects, as well as specific coating procedures and additives (Table 16).
Table 16 Examples of textile inventions with microencapsulated antimicrobial, disinfectant and deodorant components.
Deodorant textiles, coated with porous microcapsules Toray [134]
containing plant oils and extracts, such as wood oil and
camellia leaf extract.
Bactericidal printing compositions for garments, Tokyo Houlaisha [135]
containing porous microcapsules with bactericides.
Manufacturing of antibacterial garments by printing Tokyo Houlaisha [136]
fabrics with a mixture of binders and porous bactericide
microcapsules.
Production of washfast antibacterial fabrics by immersing Asahi [137]
polyester-cotton knits in a dispersion of melamine resin
wall microcapsules, containing N,N-diethyl-m-toluamide
core, and a polyurethane binder.
Microencapsulated disinfectants, such as Flamel Technologies [138]
dimethyldidecylammonium chloride and glycerol, in
ethylene-vinyl acetate copolymer walls, for applications
in wound dressings, medical and surgical gloves, textiles,
and paper products.
Textile fiber structures with adhered gelatin Toray [139]
microcapsules, containing biocides, such as
gamma-oryzanol in olive oil, and silicone binders.
18
Preparation of textile carriers, coated or saturated with Aero [120]

microencapsulated antimicrobial essential oils, produced
by in situ polymerization of aminoaldehyde resins.
Industrial textiles with fungicidal and bactericidal Elb Company [140]
activity, containing microencapsulated catechins and/or
saponins.
Anti-mite and antibacterial polyester staple fibers, Shanghai Different Chemical Fibre Co. [141]
prepared by spinning, containing micro anti-mite ceramic
powders and silver-loaded nano titanium dioxide
composites.
As an example of our work, we developed antimicrobial textile shoe insoles, based on nonwoven polyester
textiles, impregnated with a mixture of microencapsulated essential oils of sage, lavender and rosemary (Figure
16). Pressure-sensitive aminoaldehyde resin microcapsules with partially permeable walls were prepared using
a modified in situ polymerization method. For the impregnation of textiles, a technique for the transport of
the textile carrier through the impregnation basin was used. Product testing proved the sustained release of
essential oils from microcapsules in worn shoe insoles, and antimicrobial activity of the essential oil mixture
against the microorganisms Staphylococcus aureus, Candida albicans and Trichophyton mentagrophytes [142, 143].
Figure 16: Nonwoven textile for shoe insoles, impregnated with pressure-sensitive microcapsules, containing an antimi-
crobial composition. Essential oils are protected from oxidation until the microcapsules open by mechanical pressure
during walking (SEM, left 50 ×, right 1000 ×).
4.14 Bioactive medical and cosmetic textiles with microencapsulated ingredients

In the 1990, the first inventions of medical and cosmetic textiles introduced added-value textile products with
prolonged effects, such as antimicrobial effects, accelerating blood circulation, improving the physiological con-
dition of skin, skin hydration, ageing prevention, or skin whitening. Soon other inventions followed, aiming
at pain relief, itch suppression, accelerating the metabolism of water, reducing cellulite, and similar effects.
The microcapsules are typically not broken when produced, processed, or laundered, but gradually burst open
when the textiles are worn. The formulations are applied to the fabrics by soaking, coating or spraying; micro-
capsules can also be formulated as sprays, which tightly adhere the microcapsules to textile structures, such as
hosiery, underwear, bedlinen, and bandages (Table 17).
Table 17 Examples of inventions including microcapsules in cosmetic and medical textiles.

Pressure-sensitive microencapsulated physiologically Kanebo [144]
active compounds, adhered to textile fibers by polymeric
binders, with a prolonged antimicrobial and blood
circulation accelerating effects.
Textile structures with microencapsulated substances for Kanebo [145]
improving the physiological conditions of human skin,
such as functional vitamin C, vitamin E, seaweed extracts,
antipruritic and analgesic agents, and/or aromatic agents
– designed for medical auxiliary materials, bed clothes,
stockings and underwear.
Medical/cosmetic textiles with microencapsulated Toray [146]
subcutaneous fat controllers – extracts of medicinal plants
– to disperse fats, accelerate the metabolism of water,
reduce stasis and cellulite.
19
Bioactive moisturizing polyamide and silk protein elastic Dim S. A [147]

textiles with microencapsulated moisturizers, used in
direct contact with skin as bandages, elastic supports, and
hosiery.
Microencapsulation of bioactive body care substances by Ted Lapidus [148]
coacervation of gelatin-alginate complexes.
Microcapsules are fixed on textile supports by
crosslinking alginate or chitosan polysaccharides.
Pharmaceutical and medical functional textiles Blücher GmbH [149]
comprising a textile carrier and microencapsulated
physiologically active substances.
Clothing for daily pharmacological treatment of fungal InnovaTec [150]
infections, consisting of microcapsules grafted on the
textile material to manage moisture, and of
microencapsulated antifungal agents.
4.15 Textile decontaminants, filters and odor absorbers
Some patents describe the incorporation of microcapsule bearing absorbents and decontaminants into textiles
for special purposes, such as waste water purification, odor absorption, and military decontamination (Table
18).
Table 18 Examples of microencapsulated components in textile-based filters, odor absorbers and decontaminants.
Invention Patent applicant
Microencapsulated conventional decontamination agents, US Dept of the Army [151]
effective for the deactivation of toxic mustard blistering
agents or toxic nerve agents, applied to clothing fabrics in
acrylic resinous binder finishes.
Coagulation filter textiles, coated with organic polymeric Kanai Hiroyuki [152]
or inorganic coagulants, microencapsulated by
microporous inorganic walls, for applications in waste
water treatment.
Textile odor-absorbing car interior linings with GM Global Technology Operations [153]
odor-absorbing microcapsules.
Functional textiles comprising a backing with Blücher Gmbh [154]

microencapsulated active ingredients, used in protective
clothing for civil and military use, and in filters for
removing harmful materials, odors and poisons.
4.16 Textiles for active thermal control
Textiles for active thermal control have been one of the fast growing product areas of microencapsulation tech-
nology applications (Table 19). In addition to attempts to convert sunlight energy into chemical and later ther-
mal energy, a wave of inventions and practical applications utilized microencapsulated PCMs that absorb or
emit heat at their phase change transition temperature (Figure 17). Typical examples of PCMs are strait chain
paraffinic hydrocarbons with 13 to 28 carbon atoms, and the phase change temperatures ranging from −5.5
°C to +61 °C. As they are flammable and liquid above the phase transition temperature, microencapsulation is
essential for their practical use in various thermal management applications. In functional textiles, microencap-
sulated PCMs function as heat absorbers or as barriers against cold, and are incorporated into products with
enhanced thermal properties and active thermal control [155].
Table 19 Examples of microcapsule involving inventions in functional textile products with heat storing and releasing
properties.
Incorporation of PCM microcapsules into textile fibers by Triangle R&D [157]
adding microcapsules to the molten polymer or to the
polymer solution before spinning.
20
Textile materials with heat storing properties, capable of Kiyokawa [158]

converting sunlight energy into chemical energy, and
store it for later release, based on microencapsulated
norbornadiene derivatives and catalysts, formulated in
resin binders.
Coating compositions for textile fibers, containing PCM Triangle R&D [159]
microcapsules, and binders as liquid polymers or
polymer solutions (polyurethanes, nitrile and
chloroprene rubbers, polyvinyl alcohol, silicones,
ethylene/vinyl acetate copolymers, and acrylic polymers).
Synthetic foam inserts with anisotropically distributed Bryant & Colvin [160, 161]
leak resistant dual-walled PCM microcapsules, used in
textile products.
Applications of PCM microcapsule containing insulation Buckley [156]
materials in shoe insoles, ski boot liners, thermal socks,
gloves and face masks for cold weather activities, diver’s
wet suits, heating or cooling blankets for treating
hypothermia or fever patients, and therapeutic heating or
cooling orthopaedic joint supports.
Applications of microencapsulated PCMs in thermal USA Secretary of the Navy [162]
protection liners for diver’s wetsuits, dry suits and hot
water suits for extreme cold water diving, hot water
diving, or as emergency backup heat sources.
Inclusion of PCM microcapsules in composites with Buckley [163]
several layers, for improved thermal control and comfort
of the wearer.
Three-layered thermal insulating fabric structure, Outlast Technologies [164]
containing microencapsulated paraffinic PCMs,
providing a dynamic thermal response in clothing.
Metal oxide gel coated microcapsules, containing PCMs, Frisby Technologies [165]
with improved mechanical stress and flame resistance, to
be incorporated into foams, fibers, slurries, coatings.
Nonwoven textiles with reversible enhanced thermal Carl Freudenberg [166]
control, containing a web bonded by polymeric binder
and a microencapsulated PCM.
Nanostructured PCMs used for thermoregulatory Bioastra Tech. [167]
coatings for use in a wide range of applications, including
cooling textiles and wipes.
Two-piece wearable absorbent articles, such as diapers, Procter & Gamble [168]
comprising microencapsulated PCMs and absorbent

inserts.
Figure 17: Scanning electron microscope (SEM) photograph of microcapsules containing a paraffinic PCM, prepared by in
situ polymerization, to be applied in functional textiles (SEM 2000 ×).
The choice of suitable PCMs depends on the latent heat of the phase change and the transition temperature.
In general, the higher the PCM’s latent heat of phase change, the more thermal energy a material can store.
According to their phase change temperature ranges, the PCMs are categorized into three main groups – the
heating, the cooling and the buffering PCMs [156]:
– The phase transition temperature of the heating PCMs is above the body’s normal skin temperature. When
a heating PCM is warmed above its transition temperature and placed in thermal contact with the skin, the
temperature gradient flows from the PCM into the body.
21
– The cooling PCMs have a phase transition temperature below the body’s normal skin temperature. When
chilled below their transition temperature, the temperature gradient flows from the body into the PCM.
– The phase transition temperature of the buffering PCMs is slightly below the normal body temperature.
These materials absorb or release heat depending on environmental and metabolic conditions.
To include PCM microcapsules into textile products, different systems have been developed, such as:
– the incorporation of PCM microcapsules into the textile fibers before or during the spinning process;
– the coating of fibers and fabrics with compositions of PCM microcapsules and binders;
– the insertion of polymer foams with microcapsules PCM into textile products;
– the preparation of complex composites with three or more layers.
4.17 Microcapsules in self-cleaning textiles and self-healing fibers
A new generation of high-tech functional textiles is emerging, known also as smart textiles; some of them
contain various microencapsulated components to achieve self-refreshing, self-cleaning, abrasion-resistant, or
self-healing properties (Table 20).
Table 20 Examples of inventions of self-cleaning surfaces and self-healing fibers, containing microencapsulated compo-
nents.
Microcapsules for self-refreshing textiles, containing Despature et fils [169]
microencapsulated polyols.
Silicone textile surface treatment (conditioning, Dow Corning [170]
hydrophobing, softening) with silicate wall
microcapsules.
Particles with a structural surface, prepared by siloxane or Wacker Chemie [171]
silane emulsion polymerization, useful to produce
abrasion resistant self-cleaning surfaces.
Hybrid high-strength carbon fiber/epoxy composites, NDSU Res. Foundation [172]
reinforced with ultrathin toughening and self-healing
core-shell fibers.
Combination of a self-healing polymer matrix and carbon NASA [173]
fiber reinforcement, designed to be used in space
missions.
5 Concluding remarks
The idea of using microencapsulation technology in added-value textile products was born soon after the in-
troduction of the large-scale production of microcapsules for pressure-sensitive copying papers. Microencap-
sulation for textiles became a research and development area with a strong industrial intellectual property
protection, as patent documents outnumbered scientific articles. In the past some reviews were prepared to
summarize research and development achievements [111, 174–178]. The survey in this chapter, prepared by
analysis of inventions from the beginning of the microencapsulation technology to the present day, reveals
that the first burst of patents on microcapsules for textiles in the 1970s brought the following microencapsulated
products: (i) dyes and pigments for special textile dyeing and printing techniques; (ii) catalysts, crosslinking
agents and enzymes for textile treatment; (iii) reagents for textile sizing and bonding; (iv) fire retardants for
fire-resistant textiles; (v) expandable microcapsules for the production of light weight leather substitutes and
water proofing of porous textile surfaces; (vi) fragrant textiles with microencapsulated essential oils and aro-
mas; (vii) ingredients in textile detergents and softeners, including enzymes, bleaches, softeners and antistatics
for textile washing and drying compositions.
After a short stagnation of research in the beginning of the 1980s, there was a second wave of textile mi-
crocapsule patents, with new concepts of the following microecnapsulated products: (viii) thermochromic ma-
22
terials, which utilized temperature changes for color development and fading, and microencapsulated pho-
tochromic dyes – the results being thermochromic sports and leisure garments, and photochromic curtains,
sportswear and shirts; (ix) blowing agents and expandable microcapsules for leather substitutes and textile
water proofing; (x) components in textile filters, odor absorbers and decontaminants.
After 1990, the inventions were further extended and upgraded to: (xi) prolonged release bioactive medical
and cosmetic textiles with microencapsulated bioactive/healing components; (xii) antimicrobial, disinfectant
and deodorant textiles; (xiii) repellent and insecticidal textiles, (xiv) functional textiles with heat storing and
releasing properties, based on microencapsulated PCMs, applied in sportswear and special technical apparel
with active thermal control.
After the year 2000, new inventions appeared in almost all previously known application fields, particu-
larly in the domains of microencapsulated thermochromic and photoschromic dyes for color changing fabrics
and sensor fibers; new techniques and solutions in textile dyeing and printing, involving microcapsules; and
microencapsulation of additives in sophisticated compositions of textile detergents and softeners.
Since 2010 a new generation of microcapsule-based inventions have been emerging, applying microencap-
sulated components to achieve (xv) self-cleaning and/or self-healing properties of high-tech smart textiles.
Acknowledgments
The research on microencapsulation was financially co-supported by: the Faculty of Natural Sciences and En-
gineering, University of Ljubljana; the Slovenian Research Agency (projects L2-5571, L1-6230 and L4-1562); and
by the ERO, Chemical, Graphic and Paper Manufacturers, d.d. Celje, Slovenia. Samples of textiles with micro-
capsules for SEM imaging were kindly provided by Boštjan Šumiga, Ph.D., and Mr. Emil Knez from the AERO
company.
This article is also available in: Giamberini (et al.), Microencapsulation. De Gruyter (2015), isbn 978-3-11-
033187.
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DE GRUYTER Physical Sciences Reviews.

Boh Podgornik Bojana1 / Starešinič Marica1

Microencapsulation technology and applications

Boh Podgornik Bojana is the corresponding author.

2 Microencapsulation methods and processes of applying microcapsules to textiles

Figure 7: Example of microcapsules synthesis by in situ polymerization process.

– good transferability of the in situ process to large-scale industrial production.

2.2 Processes of applying microcapsules to textiles

– coating with an air knife or rod coater;

lected parts of textile clothing or footwear.

Figure 9: An example of applying microcapsules to textile carriers by impregnation [10].

3 Purposes and release mechanisms of microcapsules in textile products

4 Applications of microcapsules in textile products

Figure 11: Applications of microcapsules in added-value functional textile products.

Table 1 Examples of inventions applying microcapsules in textile dyeing and printing.

Production of semi-permeable gelatin-gum arabic Sakai Textile [16, 17]

4.2 Textiles with microencapsulated thermochromic materials

Table 2 Examples of microcapsule-based inventions for the production of thermochromic textiles.

4.3 Textiles with microencapsulated photochromic materials

Table 3 Examples of inventions with microencapsulated photochromic materials.

to abrasion or washing, containing microencapsulated

4.4 Microencapsulated catalysts and enzymes for special textile effects

Table 4 Examples of microencapsulated catalysts and enzymes for textile treatment.

4.5 Textiles with microencapsulated ﬁre retardants

Table 5 Some inventions on fire-resistant textiles with microencapsulated fire retardants.

retardants in polymeric walls, and acrylate binders.

4.6 Microencapsulated agents for textile sizing and adhesive bonding

Table 6 Inventions on microencapsulated agents for textile sizing and bonding.

Table 7 Examples of inventions on blowing agents and expandable microcapsules.

Compositions of colored hollow silicate microspheres, Meisei Rejinokara [63]

4.8 Microencapsulation for textile water prooﬁng

Table 8 Examples of inventions using microcapsules for textile water proofing.

Textile coating compositions, containing waterproofing Toray Industries [66]

4.9 Microcapsules in textile softening and antistatic compositions

Table 9 Examples of textile softening and antistatic compositions with microcapsules.

of laundering, containing microencapsulated perfumes in

4.10 Microencapsulated ingredients in textile detergents

Table 10 Examples of patents on microencapsulated enzymes for textile detergent formulations.

Spray cooled microencapsulated proteases with fatty acid Henkel [78]

Clear detergent gel compositions, comprising Lever Brothers [98]

Table 12 Examples of microencapsulated antifoaming agents in textile detergents.

4.10.2 Bleaching agents and whiteners

4.11 Textiles with microencapsulated fragrances and perfumes

Table 14 Examples of patents on fragrant microcapsules in textile products.

washing. Coating compositions contain urea resin

Incorporation of a polyester microencapsulated Iangsu Zja New Material Co. [124]

4.12 Textiles with microencapsulated animal repellents

Table 15 Examples of patents on repellent and insecticide microcapsules in textile products.

Invention Patent applicant (reference)

4.13 Textiles with microencapsulated antimicrobial, disinfectant and deodorant components

Preparation of textile carriers, coated or saturated with Aero [120]

4.14 Bioactive medical and cosmetic textiles with microencapsulated ingredients

Table 17 Examples of inventions including microcapsules in cosmetic and medical textiles.

Bioactive moisturizing polyamide and silk protein elastic Dim S. A [147]

4.15 Textile decontaminants, ﬁlters and odor absorbers

Functional textiles comprising a backing with Blücher Gmbh [154]

4.16 Textiles for active thermal control

Textile materials with heat storing properties, capable of Kiyokawa [158]

comprising microencapsulated PCMs and absorbent