TWI251009B - Polymer/clay nanocomposites containing far-infrared-radiating clay - Google Patents

Abstract

Disclosed herein is a polymer/clay nanocomposite containing far-infrared-radiating clay, which comprises a polymer matrix and a layered clay material having the function of far-infrared radiation. The layered clay material is present in the polymer matrix in a nanodispersed form. The nanocomposite of the present invention can be employed in synthetic fibers and textiles.

Description

1251009 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Technical Field The present invention relates to a far infrared/clay nano composite material. The utility model can be applied to a polymer material for a functional clay, a health care patch, and the like. "Man-made fiber, fabric, heat preservation [Prior technology] In the 21st century today, due to the increasing living standards of human-made clothing fabrics (such as hats, umbrellas, and clothes), the requirements for the aspect have been satisfied by the past. (Building materials, curtains) Kang's special functional needs, and nowadays, it is the most important ^=J旎 and health care H-infrared fiber. The far-infrared fiber is ☆= The product is referred to as the abbreviation. The fiber absorber can emit the line of the radiation function fiber after the heat is absorbed, and the far-infrared rays are easily absorbed by the body to absorb the far-infrared metabolism of the body and increase the immune function, and are promoted by the blood circulation. It is a kind of health-care fiber. The Japanese shine in the moon. Therefore, it is a special health care product for skin care, wrist care and neck protection. It is used in knee pads, socks and jackets. In recent years, far red ^, , blending underwear, pants, wicking, leisurely, has been widely used, such as Deng: ΐΪ ΐΪ 品, currently marketed far-infrared fabrics, mainly used and functional ceramics After the material is ground into a powder, it is added to the fiber. These powders with far-infrared function are added to the fiber.

Hill· Page 5 0424-10097TW(Nl);02920008; PATOICIA.ptd 1251009 V. INSTRUCTIONS (2) By: Kind of way · 1 · Immersion/adsorption or coating during fabric post-processing, the disadvantage is infrared machine: ^ 1 Exist, the fabric is washed a few times and then lost when it is far or when it is spun, and the disadvantage is a six ★ 曰齢 a ^ ' 2 · 5 into a reaction, Tian Shi Dan secret ^ eight shortcomings 疋 add 虿 虿, higher cost . With the fine particles of the hardness, the processing equipment will wear due to the high-speed operation during the subsequent extension and false twist processing. Moreover, the reduction in the production cost due to the reduction of the powder's and the corresponding reduction in the rotational speed has become the main reason for the unsatisfactory unit price of the infrared fiber. The development of Yuanhong 2 fabrics in recent years has focused on how to improve it and make it easier to use. It is more effective and more resistant to washing. Therefore, how to develop low-added bismuth, with recyclability, low hardness, and dispersion with fiber Darney The material of far-infrared radiation energy is the current trend and focus of international research and development. Moreover, the existing fibers with far-infrared radiation function mainly add ceramics with far-infrared radiation function through fiber,,, = surface treatment or synthesis reaction. Powder to achieve its effect. Only durable, it needs to be heated to 8 〇 to have far-infrared radiation function, which is inconvenient in application. In the manufacture of rayon or fabric with far-infrared radiation function, because man-made fiber itself does not have Radiation function, so it needs to contain, adsorb or coat during fabric processing, or add inorganic materials with far-infrared radiation function during polymer synthesis reaction or spinning. Therefore, the difference of inorganic raw materials and inorganic raw materials and fibers or The difference in the way of mixing polymers, the quality, performance, and cost of the products. China Patent No. 1 24 0 No. 70 reveals a kind of far infrared radiation

1251009 V. INSTRUCTIONS (3) The method for producing fibers is to grind 25% magnesium oxide, 40% oxidation, 6.5 zirconia, 15% cerium oxide, 2% cerium and 11 5% cerium into one. The micron powder is mixed and made into a far-infrared ceramic powder with high hardness. The Republic of China Patent Publication No. 4 0 9 1 54 discloses a material for the radiation of the far-infrared radiation and the synthetic fiber of the composite material, and the manufacturer of the material is a cerium oxide and an oxygen compound. At 30 °C, the temperature is above 65%, the radiation is more than ~35 wt% ~8 wt%, CaO w"/〇, Fe2 03 1 temperature, the wavelength 8 is high. CN 1 contains cerium dioxide, high hardness The method and the molded article, wherein the far-infrared material is added as powdered niobium carbide or zirconium dioxide, and the hardness is high. Japanese Patent No. 422898 discloses a heat storage and heat-insulating fiber and a cloth method in which a materialization having far-infrared radiation function is added. Aluminum, titanium dioxide, kaolin, magnesia, etc. and its mixture under the range of wavelength 4~25/zm, its average radiation · 'hardness. CN 1167097 discloses a material with far infrared ray, its composition is A 12 03 25~ 40 wt%, Si 0 , ZnO 3 〜10 wt%, Mg"~5 ..., β_23 3 10 wt%, Sb203 2 〜8 Wt%, T i〇2 2 〜it% ' and B2〇3 2 ~ 5 ” % of ceramic powder 2, often umiH · 祀 circumference, its average emissivity is not less than 90% , gas: a far-infrared ray-regulating fiber, ferric oxide, or copper oxide pottery powder. The above documents have far-infrared radiation function y knife polymerization and dispersion methods are micron dispersion ",, machine materials and # 曰Japanese Patent Laid-Open No. 9-77961 discloses a high hardness of a material. The line administers a polyester composition containing an average particle size of 12 5 cut-offs of far infrared and an average particle size of 8.0 to 13.0 followed by a mica former worker. =5·〇_The ratio of the weight of the mica set is

1251009 V. INSTRUCTIONS (4) Dispersion 4/6 to j/2), the technique of polymerization and dispersion is micron-division, and the nano-dispersion cannot be achieved. SUMMARY OF THE INVENTION In view of the above-described disadvantages of the prior art, the object of the present invention comprising a polymer of far-infrared radiant functional clay/clay is provided. The composite material can excite the far-infrared-meter composite material at 4 ° C. It has a wide application and is low in hardness, and has the advantages of low hardness, recyclable line t-shooting function, and durability. Difficult infra-red machine, this I use the natural far-infrared light-shooting 贞 can ^ ^ surgery to disperse a small amount of clay in the polymer substrate to Nai · contains far infrared ray light energy clay 'Formation of a kind of far-infrared light-transmitting machine V-clay scorpion/clay nano composite material of the present invention, which comprises (1) a south molecular matrix, and (1) a far infrared ray The layered layer of radiation is dispersed in the above polymer matrix. Inch in the form of non-wood form = Γ Γ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the polymer matrix, it exists in a nano-dispersed state, which has the advantages of low hardness, recyclability, high-infrared radiation at 401, and long-lasting infrared function. [Embodiment]

0424-10097TWF(N1);02920008;PATRICIA.ptd Page 81251009 V. INSTRUCTIONS (5) " A '---, the polymer/clay nano composite material of the present invention containing far-infrared radiation functional clay A layered clay material having far-infrared radiation is used, for example, a layered clay material having a far-infrared ray emission average emissivity of more than 5% at a far infrared wavelength of 4 to 20 #m at 40 C. The layered clay material is more preferably further having an ion exchange amount of from 7 to 20 meq/l 〇〇 g. Examples of layered clay materials are, for example, smectite clay, Vermicu Hte, sericite, mica, and combinations thereof. The vermiculite clay may be montmorillonite ((4)ntm〇rillonite), bentonite (sap〇nite), ampeleite (beidellite), 夕石石(n〇ntronite), hectorite sac (hectorite), Or a mixture thereof. Among them, it is preferably sericite, montmorillonite, and sapphire containing iron-magnesium-titanium silicate compound, and more preferably a natural source of vermiculite clay, medlar or mica having the following chemical composition formula Layered clay material: , (Je AlJgJvnI(Si4xyAlxFey)IV〇i〇(〇H)2Mn+^^ ^ , , where X and y are between 〇 and 4 (excluding 〇 and 4), z^ is The number between 〇 (excluding 〇 and 2), and m is the number from 0.5 to 3.0. The layered clay material used in the specific embodiment of the present invention is selected as a stick, which has a distance of 4 (TC) Infrared wavelength 4 to 2 〇 ^ circle, ', medium 遂 infrared radiation average emissivity greater than 5 〇% and ion exchange capacity to | 200 meq / 1 〇〇 g. The reason for choosing this layered clay is that the rate is very In addition to high (see Table 丨), it has a layered structure, the same ion exchange characteristics, and can be combined with rayon to form a polymer-inorganic hybrid nanocomposite. Table i shows the use of 叮_11^ spectrum g black body

1251009 V. Inventive Note (6) (black body) Comparing the test methods obtained, the test sample number ρΚ 802 (composition: montmorillonite), PK 805 (composition: stellite) and CL11 (composition·know mica) . It is at 40. Under C, it has an emissivity of more than 84% in the infrared wavelength range of 5 to 20 //m. Table 1 Far infrared radiation test sample of clay material (No. " Emissivity (wavelength 5~20 μηι) Radiation power (W/m2) Montmorillonite (ΡΚ802) 0.919 3.70 X 1〇2 Neodymium iron (ΡΚ805) 0.927 3.74 X 1〇2 sericite (CL11) 0.873 3.47 X 1〇2 The polymer matrix of the polymer/clay nanocomposite containing the infrared ray-inhibiting functional clay of the present invention, which can be various thermoplastic or thermosetting polymer materials or mixture. Examples thereof include nylon 6 (Ny ι〇η 6), PET, PP, PS, PMMA, ABS, epoxy resin (Ep〇xy), rubber, PI, PU, and the like. Suitable materials can be used depending on the intended use of the nanocomposite. The amount of the layered clay material used in the present invention is preferably from 0.05% by weight to 1% by weight based on the total weight of the nanomaterial, more preferably from 〇1 by weight to 7% by weight. If the content of the layered clay material is more than 1% by weight, the composite material is also collapsed, but the layered clay material cannot sufficiently form an effective nano dispersion in the composite material. If the content is less than 〇 〇 5% by weight, the 兮 material does not provide an effective far-infrared radiant function. ~ΰ

1251009 V. INSTRUCTIONS (7) What is clay? Infrared ray-carrying polymer clay polymer / soil material: material 'made of man-made fiber or fabric, wherein the layered viscosity weight % of the total weight of the two materials, 1% by weight to 3 wire force ... is fast, can not be commercial Use value. The radiance of Bei 1j is less than 0.6% 'The manufacture of nano composites without the invention, the soil material' is modified by the method of clay surface, the above-mentioned layered viscous method, the catalyst intercalation modification method, „戈起:: Shouting ammonium salt modifier to change the clay. Then use; molecular/clay/= such as dazzle blending, training, oligo intercalation, unconformity, ancient materials, making square enamel clay Divided into early agglutination + ^ secondary body polymerization method, so that the organic reform: · with the same knife and slabs, so that the clay to de-layered oUated) evenly dispersed, and in the polymer structure with sorrow, forming a nanocomposite Material: Non-water knife policy The Mohs hardness of the finished composite material used in the spinning clay is 2, hard production, gn... Due to the use of the material, and because of the Le +, the ancient ^ section process It does not wear out.., it sticks to the middle of the knife and exists in the dispersed state of nanometer. The dispersion is 1 large, and the clay with high far-infrared emissivity can fully enhance the function of far-infrared radiation. The effect 'low cost, resistant to washing, and not due to back to 2 _ bad, derogation function. j used to be broken The invention can also add an organic or inorganic filler, an antioxidant, a predetermined sputum, a first stabilizer, an antistatic agent, a plasticizer, and a hindrance additive, depending on the application required, the secondary π d temple

1251009

EXAMPLES Example 1 After purification, sodium ion i PK802) 15 g, its + θ parent 1 modified montmorillonite (sample number stomach wavelength 4 to 2. ί at 4 ° ° ° in far infrared ray 0.919,盥CPL· (the average emissivity of the infrared radiation from the inside) is 二, Η3Ρ〇4 to 15〇〇: 23. 5 : 5· ja for atmospheric polymerization. Blowing with nitrogen After stirring for about 5 minutes, 'Li, 〇 C for 1 to 3 hours, the temperature was raised to 260 ° C and dehydrated. Then, at 260 C, 15 C·C· amount of water was injected in 1 hour. 2 at 60 ° C. 'Reaction for 5 hours. Cutting, pelletizing, washing to a CPL residue of less than 5 drying' to obtain the molecular/clay nanocomposite of the present invention containing far-infrared radiation functional clay. Electron micrographs, as shown in Figure 1, can be seen in the figure. The layered clay material is dispersed in the matrix of the Minnan molecule (Nylon 6) in the nanometer size, and the far infrared ray is measured at 4 〇 °c. The average radiation emissivity is 0. 88 4. Example 2 The far infrared ray of the present invention is produced in the same manner as in Example 1.

0424-10097TW(Nl);02920008;PATRICIA.ptd Page 12 1251009

V. Description of invention (9) Polymers of clay capable of clay/clay nano: chemical, nano-ion exchange modified... (10 complexes =: 彳: with Vr in soil. Shishi iron and CPL, M, H3P〇4m.i27, instead of Montjo 5· ^ I. m mV;, 2 ffl"J I1:00 , 2:·!: Clay button n large, L t such as the Z picture, can be seen from the picture The layered system occupies the soil material and disperses Φ in the nanometer size. ^ η V ^ y, A knife (for nylon 6) matrix A and measured far infrared ray A + sub μ 1 at 40 c Example 3 κ 卜 ^ 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千 千m nano-ion exchange modified "mother (sample braided muscle (1), its thousand-average particle size is 5 # m, at 40 t, 扃, soil, from A ★ e, 夕 夕 梦 阁 a soil 卜 遮 in the infrared wavelength 4 to 20 β \ Ά soil infrared (four) shot average emissivity of 0.873, instead of montmorillonite fly mica and cpl, H2 〇, h3P () 4 ^ u_i5qq: 23.5: clay material 枓 in the size of the nanometer. And the molecular (for money 6) matrix was measured at 4GtT. The average radiation emissivity of 0 · 847.

1251009 V. INSTRUCTIONS (ίο) Table 2 Far-infrared radiation test of the polymer/clay nano composite of the present invention Example No. Polymer / Clay content emissivity (wavelength 5~20 μηι) Radiation power (W/m2) 1 resistance 6/ lwt% PK802 0.884 3.57 X 102 2 and 6/lwt% PK805 0.888 3.58 X 102 3 resistance, giving 6 / lwt% CL11 0.847 3.30 X 102 Although the invention has been disclosed above by way of a preferred embodiment, However, it is not intended to limit the invention, and those skilled in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The definition is subject to change.

0424-10097TWF(N1);02920008; PATRICIA.p t d Page 14 1251009 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a scanning electron micrograph of a nanocomposite obtained in Example 1 of the present invention. Fig. 2 is a scanning electron micrograph of a nanocomposite obtained in Example 2 of the present invention. Fig. 3 is a scanning electron micrograph of a nanocomposite obtained in Example 3 of the present invention. 0424 -10097TW (Ν1); 02920008; PATRICIA. p t d Page 15

Claims (1)

1251009 Case No. 92116618 VI. Patent Application Range 1. A high-decimeter composite material containing far-infrared radiation functional clay, including: ★ ^ (1) a polymer matrix, and (2) a layered clay with far-infrared radiation The material, too 2 in the above polymer matrix t, wherein the layered clay material: two in the range of the infrared wavelength of 4 to 20 # m, the far-infrared re-radiation rate is greater than 50%. The average shot of the outer line is 2. The polymer/clay nano composite containing the far-reaching clay as described in the first paragraph of the patent application, wherein the high-boiler is composed of a thermoplastic polymer, a thermosetting polymer, and a combination thereof. Choose a group. The polymer/clay nanocomposite containing far-infrared radiation-gathering clay as described in the third paragraph of the patent application, wherein the layered clay and the material are at a far infrared wavelength of 4 to 40 C The average emissivity of far red radiation in the range of 2 〇# m is greater than 84%. 4. The line/amp; 4. The polymer/clay nano composite material containing far-infrared radiation functional clay as described in claim 1, wherein the layered clay material has an ion parent for 1 to 200 meq /100 g. 5. The polymer/clay nano composite material containing far-infrared radiation functional clay as described in the scope of the patent application, wherein the layered clay material is selected from the group consisting of smecHte clay and vermiculite. A group of (vermiculite), sericite, mica, and mixtures thereof. 6 · The far-infrared radiation machine as described in item 5 of the patent application scope 1251009 Case No. 92116618 Amendment 6. The polymer/clay nano composite material of the patentable range of clay, wherein the vermiculite clay is montmorillonite, saponite, and aluminum-rich soil Beidellite), nontronite, hector i te, or a mixture thereof. 7. The polymer/clay nanocomposite containing far-infrared radiant functional clay as described in claim 1, wherein the layered clay material has a chemical composition of (?62_"人1^')川1 (8丨4_"八1彳~)1¥〇1() (0H)2Mn+(x+y+z)/n.mH20 natural layered clay, where X and y are between 〇 and 4 (Excluding 〇 and 4), z and * are the number between 〇 and 2 (excluding 〇 and 2) ' and m is 0.5 to 3.0. 8. The polymer/clay nano composite material containing far-infrared radiation functional viscosity as described in claim 1, wherein the layered clay material content is the polymer/clay naphthalene containing the far-infrared radiation functional clay总·重量5 wt% to 1 wt% of the total weight of the rice composite. 9. A polymer/clay nanocomposite containing far-infrared radiant functional clay as described in claim 1 of the patent scope, which has far-infrared radiation at 4 to 6 Torr. '10. The polymer/clay nanocomposite containing far-infrared radiation functional clay as described in claim 1 or 7 is made into artificial fabric or fabric. ' Π • The polymer/clay nanocomposite containing far-infrared radiant functional clay as described in Clause 1 of the patent application, wherein the layered clay material is a polymer containing the far-infrared radiant functional clay/ The total weight of the clay nanocomposite is 〇·丨% by weight to 3% by weight. 1251009 Case No. 92116618_年月日日__ VI. Patent application scope 1 2 · The polymer/clay nano composite material containing far-infrared radiation functional clay as described in claim 1 or 7 is made into heat preservation. Use objects. 1 3. A polymer/clay nanocomposite containing far-infrared radiation functional clay as described in claim 1 or 7 is a warm-applied patch for body care. 0424-10097TWF1(N1);02920008;kingandchen·ptc第18页