SK288000B6 - Polypropylene fiber with improved barrier properties against UV radiation - Google Patents

Abstract

Described fiber comprises from isotactic polypropylene in an amount from 96.0% to 99.9% by weight and inorganic additives of nanoparticles of titanium dioxide in aa amount from 0.1% to 4.0% by weight. Additive is a rutile or anatase crystal modification of TiO2 in an amount of 48.8% to 96.9% by weight with a particle size in the range from 14 to 30 nm and a specific surface area ranging from 30.0 m2 / g to 70.0 m 2 / g .

Description

Technical field

The present invention is in the field of polymer chemistry of chemical fibers and relates to polypropylene fiber with improved UV barrier properties which provide a defined addition of an inorganic nanoTi ₂ additive to the polypropylene fiber mass.

BACKGROUND OF THE INVENTION

Climate change and increased amounts of UV radiation due to ozone holes have recently led to a significantly increased risk of skin cancer in the human population. A similar danger exists with industrial technologies with the occurrence of UV radiation, eg. when welding metals. Therefore, now and especially for the future, UV protection is an essential condition for the healthy existence of humanity. One of the most important forms of protection against UV radiation are garments consisting of natural and / or chemical fibers, as well as shading fabrics (parasols, awnings, etc.) that also fulfill the protective (barrier) function in terms of blocking the penetration of UV radiation to human skin .

To improve (increase) the barrier protective properties against UV radiation of shading and clothing fabrics, various modifications of the fabrics, respectively, are applied. the fibers of which the fabrics are made. Fiber producers have placed fibers on the market with special treatment in this way.

Sorona PET fibers from DuPont are known, made from a special modified PET polymer with high UV resistance, as well as UV-resistant Eclipse ™ PA fibers from AlliedSignal, also intended for textiles with UV-intensive applications. Lenzing Modal Sun cellulose fibers are known in which permanent UV protection is incorporated in pigment form in the fiber mass. Modified core-sheath PES fibers of Sunpaque ™ from Asahi-kasei with UV protection, which is provided by the presence of special ceramic particles in the core of the fiber. Kurraray Lecture hollow bilayer PES UV protective fibers with TiO ₂ content in the lower and ceramic particles in the upper fiber layer are also known, as well as Oboe PAN staple fibers for UV yarn and knitted fabrics offered by Mitsubisi Rayon.

Furthermore, polyester copolymers containing UV absorbing and inorganic particles intended for the preparation of PES fibers having UV-barrier properties according to patent TW448254B are also known.

Furthermore, surface treatments of textiles by binding UV absorbers or ceramic particles to enhance the barrier properties of the fabric against UV penetration are known. E.g. CIBA's Solartex CEL and Solartex UPV are applied to the fabric's dyeing or color printing process to provide increased UV protection for the fabric.

Material systems containing UV absorbers and inorganic resp. metal particles of different material nature and composition according to WO 03008699, WO 09118944, DE 20221400U, CN 1807750, WO 2006100278, as well as multifunctional systems according to CN 1763302. Further, in-situ preparation of UV-protective (barrier) PES polymer containing TiO ₂ nanoparticles according to CN 1552764.

Said known systems providing an enhanced protective function against UV penetration relate to PET, PA, cellulose and PAN fibers, respectively. surface treatment of textiles which improve (increase) the barrier properties of textiles against UV penetration.

The present invention provides polypropylene (PP) fibers with improved UV barrier properties by modifying additive inorganic nanoTiO ₂ particles into the mass of the polypropylene fiber matrix.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides a polypropylene fiber with improved ultraviolet barrier properties, comprising isotactic polypropylene in a proportion of from 96.0 to 99.9% by weight and nanoparticulate titanium dioxide in a proportion of from 0.1 to 4.0% by weight. The nanoparticulate form of titanium dioxide consists of a crystalline or anatase crystalline modification in a proportion of 48.8 to 96.9% by weight, with a primary particle size in the range of 14 to 30 nm and a specific surface in the range of 30.0 to 70.0 m ² / g.

An advantage of the polypropylene fiber having improved barrier properties against penetration of the ultraviolet radiation of the present invention is the use of a nanoparticulate form of titanium dioxide as a modifier into the fiber mass that is thermally stable, does not migrate in the mass and surface of the fiber, providing long term, permanent ultraviolet barrier it does not cause odor in the preparation of the modified fiber, nor in the final UV protective and protective UV barrier textiles, and its application to textile products is fully acceptable from a hygienic, environmental and toxicological point of view.

The nanoparticulate form of titanium dioxide as an inorganic additive is incorporated into the mass of polypropylene fiber, in particular by a process defined to melt its concentrate with a polypropylene carrier into the melt of the main stream of isotactic polypropylene in the process of producing polypropylene fibers with improved ultraviolet barrier properties.

The polypropylene fiber with improved UV-barrier barrier properties of the present invention may be in the form of an infinite smooth, respectively. molded textile silk, filament yarn, filament yarn (BCF), as well as staple fibers of different lengths of cut. It can be manufactured on existing standard discontinuous and continuous machinery and under the same technological conditions of production as the equivalent types of standard unmodified fibers in the ranges of textile silk, technical silk, textile cable (BCF) and staple fibers.

Polypropylene fiber with improved barrier properties against the penetration of ultraviolet radiation allows direct preparation of textile and technical textiles with increased barrier protection function against ultraviolet radiation.

DETAILED DESCRIPTION OF THE INVENTION

In the following examples, inorganic additives from nanoparticles of titanium dioxide (nanoTiO ₂ ) were used in the production of polypropylene fibers with improved barrier properties against the penetration of ultraviolet radiation, the characteristics of which are shown in the following Table. First

Tab. 1: Characteristics of inorganic additives from titanium dioxide nanoparticles

Characteristics of nanoTi0 ₂ additives Identification of nanoTi0 ₂ additives A B C D E TiO ₂ content [%] 96.9 86.4 82.2 48.8 80.5 Inorganic coating [%] 3.0 6.3 15.5 50 19 Organic coating [%] 0.1 7.3 2.3 1.2 0.5 Surface type <- hydrophobic -► Particle size [nm] 15 17 14 15 30 Specific surface [m ² / g] 50 40 70 30 65 Type TiO ₂ modification anatase tore through tore through tore through tore through

In the following examples, the evaluation and comparison of ultraviolet (UV) barrier properties - Ultraviolet Protection Factor (UPF) of the polypropylene fiber fabrics of the present invention and of the same type of UPF of the same type of fabric prepared from standard unmodified polypropylene fibers prepared by the same process as the preparation of the UPF modified polypropylene fibers of the present invention.

In the evaluation of UV protection factor of UPF fabrics from standard and UPF modified polypropylene fibers according to the present invention, the test method according to STN EN 13758-1: 2003 "Textiles. Protective properties against solar UV radiation. Part 1: Method for testing textile fabrics'.

Example 1

Smooth polypropylene silk of 3.1 dtex of isotactic polypropylene in a proportion of 99.8 wt. and nanoTiO ₂ type A (according to Table 1) in a proportion of 0.2 wt. A standard plain unmodified polypropylene silk of 3.1 dtex per unit length was prepared by the same process. UV protection factor for standard smooth unmodified UPF = 1.9, for similar modified UPF = 2.2, ie 15.8% higher.

Example 2

Smooth polypropylene silk of unitary density of 2.9 dtex consisting of isotactic polypropylene in a proportion of 99.7 wt. and nanoTiO ₂ type D (according to Table 1) in a proportion of 0.3 wt. A standard smooth unmodified polypropylene silk of unitary density of 2.9 dtex was prepared by the same technological procedure, UV protection factor at standard smooth unmodified UPF = 1.85, modified according to the invention UV protection factor UPF = 2.3, ie by 24.3 % higher.

Example 3

Smooth polypropylene silk per unit length of 2.7 dtex made of isotactic polypropylene in a proportion of 99.6% by weight was prepared by a standard technological process using batch LOY production technology. and nanoTiO ₂ type C (according to Table 1) in a proportion of 0.4 wt. A standard plain unmodified polypropylene silk of 2.7 dtex per unit length was prepared by the same process. The UV protection factor UPF = 1.85, when modified according to the invention, the UV protection factor UPF = 2.4, i.e., 29.7% higher than that of standard unmodified silk.

Example 4

Smooth polypropylene silk of a unit length of 2.7 dtex, consisting of isotactic polypropylene in a proportion of 99.5 wt. and nanoTiO ₂ type B (according to Table 1) in a proportion of 0.5 wt. A standard plain unmodified polypropylene silk of 2.7 dtex per unit length was prepared by the same process. The UV protection factor UPF = 1.85, with the modified plain polypropylene silk of the present invention, the UV protection factor UPF = 2.6, ie 40.5% higher.

Example 5

Smooth polypropylene silk per unit length of 2.7 dtex was produced using standard LOY production technology consisting of isotactic polypropylene in a proportion of 99.4% by weight. a nanoTiO? % of type E (according to Table 1) in a proportion of 0.6 wt. A standard plain unmodified polypropylene silk of 2.7 dtex per unit length was prepared by the same process. The UV protection factor UPF = 1.85, with the modified plain polypropylene silk of the present invention, the UV protection factor was UPF = 4.0, i.e., the UV protection factor. j. 116.2% higher.

Example 6

Smooth polypropylene silk of 3.1 dtex of isotactic polypropylene in a proportion of 99.2 wt. and nanoTiO ₂ type A (according to Table 1) in a 0.8 wt. A standard plain unmodified polypropylene silk of 3.1 dtex per unit length was prepared by the same process. UV protection factor UPF = 1.9, when modified according to the invention, UV protection factor UPF = 4.1, i.e. 115.8% higher.

Example 7

Smooth polypropylene silk per unit length of 2.9 dtex isotactic polypropylene in a proportion of 99.0 wt. and nanoTiO ₂ type E (according to Table 1) in a 1.0 wt. A standard plain unmodified polypropylene silk of 2.9 dtex per unit length was prepared by the same process. The UV protection factor UPF = 2.1, when modified according to the invention, the UV protection factor UPF = 6.3, ie 200.0% higher.

Example 8

Smooth polypropylene silk of unitary density of 2.9 dtex consisting of isotactic polypropylene in a proportion of 98.5 wt. and nanoTiO ₂ type E (according to Table 1) in a 1.5 wt. A standard plain unmodified polypropylene silk of 2.9 dtex per unit length was prepared by the same process. UV protection factor UPF = 2.1, when modified according to the invention, UV protection factor UPF = 8.6, ie 309.5% higher.

Example 9

Smooth polypropylene silk of 3.1 dtex of isotactic polypropylene in a proportion of 98.0 wt. a nanoTiO? % of type A (according to Table 1) in a 2.0 wt. A standard plain unmodified polypropylene silk of 3.1 dtex per unit length was prepared by the same process. The UV protection factor UPF = 1.9, when modified according to the invention, the UV protection factor UPF = 4.3, i. j. 126,3% higher.

Example 10

Smooth polypropylene silk of unitary density of 2.9 dtex was produced by standard technology of continuous production technology, consisting of isotactic polypropylene in a proportion of 97.5% by weight. % of ananoTiO ₂ type E (according to Table 1) in a proportion of 2.5 wt. A standard plain unmodified polypropylene silk of 2.9 dtex per unit length was prepared by the same process. The UV protection factor UPF = 2.1, when modified according to the invention, the UV protection factor UPF = 9.3, ie 342.9% higher.

Example 11

Smooth polypropylene silk of 3.1 dtex of isotactic polypropylene in a proportion of 97.0 wt. a nanoTiO? % of type A (according to Table 1) in a proportion of 3.0 wt. A standard plain unmodified polypropylene silk of 3.1 dtex per unit length was prepared by the same process. UV protection factor UPF = 1.9, when modified according to the invention, UV protection factor UPF = 5.2, i. j. 173,7% higher.

Example 12

Smooth polypropylene silk of unitary density of 2.9 dtex was produced by a standard process of continuous production technology, consisting of isotactic polypropylene in a proportion of 96.5% by weight. and nanoTiO ₂ type E (according to Table 1) in a proportion of 3.5 wt. A standard plain unmodified polypropylene silk of 2.9 dtex per unit length was prepared by the same process. UV protection factor UPF = 2.1, when modified according to the invention, UV protection factor UPF = 9.7, ie 361.9% higher.

Example 13

Smooth polypropylene silk per unit length of 1.9 dtex was produced by a standard process of continuous production technology, consisting of isotactic polypropylene in a proportion of 98.5% by weight. and nanoTiO ₂ type E (according to Table 1) in a 1.5 wt. A standard plain unmodified polypropylene silk of 1.9 dtex per unit length was prepared by the same process. UV protection UPF = 1.6, when modified according to the invention, UV protection UPF = 3.2, ie 100.0% higher.

Example 14

Smooth polypropylene silk of 3.7 dtex of isotactic polypropylene in a proportion of 98.5 wt. and nanoTiO ₂ type E (according to Table 1) in a 1.5 wt. A standard plain unmodified polypropylene silk of 3.7 dtex per unit length was prepared by the same process. UV protection factor UPF = 1.8, when modified according to the invention, UV protection factor UPF = 5.5, ie 205.6% higher.

Example 15

Smooth polypropylene silk per unit length of 4.9 dtex made of isotactic polypropylene in a proportion of 98.5 wt. and nanoTiO ₂ type E (according to Table 1) in a 1.5 wt. A standard plain unmodified polypropylene silk of 4.9 dtex per unit length was prepared by the same process. The UV protection factor UPF = 1.85, when modified according to the invention, the UV protection factor UPF = 6.7, ie 262.2% higher.

Example 16

By means of a standard technological process using discontinuous POY production technology, a molded polypropylene silk of 3.2 dtex per unit area, consisting of isotactic polypropylene in a proportion of 99.4% by weight, was prepared. and nanoTiO ₂ type E (according to Table 1) in a proportion of 0.6 wt. A standard shaped unmodified polypropylene silk of 3.2 dtex per unit length was prepared by the same process. The UV protection factor UPF = 2.5, when modified according to the present invention, the UV protection factor UPF = 27.2, ie 988.0% higher.

Example 17

By means of a standard technological process using discontinuous POY production technology, a molded polypropylene silk of 3.2 dtex per unit area was produced, consisting of isotactic polypropylene in a proportion of 98.5% by weight. % ananoTiO ₂ type E (according to Table 1) in a 1.5 wt. A standard shaped unmodified polypropylene silk of 3.2 dtex per unit length was prepared by the same process. UV protection factor UPF = 2.5, when modified according to the invention, UV protection factor UPF = 48.5, ie 1840.0% higher.

Example 18

By means of a standard technological process using discontinuous POY production technology, a molded polypropylene silk of 3.2 dtex per unit area, consisting of isotactic polypropylene in a proportion of 97.5% by weight, was prepared. and nanoTiO ₂ type E (according to Table 1) in a proportion of 2.5 wt. A standard shaped unmodified polypropylene silk of 3.2 dtex per unit length was prepared by the same process. UV protection UPF = 2.5, when modified according to the invention, UV protection UPF = 62.7, ie 2408.0% higher.

Example 19

By means of a standard technological process of continuous low-speed production technology, a shaped polypropylene staple of 4.0 dtex was prepared consisting of isotactic polypropylene in a proportion of 99.4% by weight. and nanoTiO ₂ type A (according to Table 1) in a proportion of 0.6 wt. A standard shaped unmodified polypropylene staple of 4.0 dtex per unit length was prepared by the same technological procedure. AATCC TM 183: 1998 was used for evaluation. For standard molded unmodified polypropylene staple, the UV protection factor UPF = 5.0 was determined, while the modified according to the invention, the UV protection factor UPF = 50.0 was 900.0% higher.

Industrial usability

Polypropylene fiber with improved barrier properties against UV penetration is suitable for the following areas of clothing, home and technical textiles with enhanced UV penetration protection:

(a) clothing fabrics:

- knitwear - knitwear for women, men and children,

- casual wear for casual wear and casual wear: summer dresses, costumes, skirts, vests, trousers, turtlenecks, t-shirts, vests, polo shirts, summer scarves, gloves, headgear, uniforms, etc.,

- sportswear: sportswear (cycling, water sports, jogging, etc.), jerseys, shorts, socks, swimwear, beach tunics, etc.,

- women's, men's and children's underwear,

- women's, men's and children's fabrics,

- casual wear for casual wear and leisure: dresses, costumes, blouses, shirts, men's suits, children's overalls, headgear - hats, hats, caps, etc.,

- work clothing: protective clothing for health care workers and workers exposed to direct sunlight during the performance of their work,

(b) soft furnishings: soft furnishings - curtains, curtains, tablecloths and others.

(c) Technical textiles:

- fabrics: awnings, sunshades, blankets, blinds, sun visors and upholstery fabrics for the automotive industry, strollers and others,

- nonwovens - fine layers of clothing for sports and leisure, UV barrier layers for upholstery and technical applications, packaging materials, shading materials and others.

Polypropylene fiber with improved barrier properties against UV penetration can be applied to textile and technical textiles in 100% design, as well as in blends with natural fibers and other types of chemical fibers.

Claims (2)

Polypropylene fiber with improved UV barrier properties, characterized in that it consists of isotactic polypropylene in a proportion of from 96.0 to 99.9% by weight and inorganic nanoparticulate titanium dioxide additive in a proportion of 0.1 to 4.0% by weight. Polypropylene fiber with improved ultraviolet barrier barrier properties according to claim 1, characterized in that the nanoparticulate titanium dioxide consists of rutile or anatase crystalline modification in a proportion of from 48.8 to 96.9% by weight, with a primary particle size. particles with a specific surface in the range of from 30.0 to 70.0 m ² / g.