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WO2003066734A1 - Composition de resine de polyester et son procede de production - Google Patents

Composition de resine de polyester et son procede de production Download PDF

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Publication number
WO2003066734A1
WO2003066734A1 PCT/JP2003/001379 JP0301379W WO03066734A1 WO 2003066734 A1 WO2003066734 A1 WO 2003066734A1 JP 0301379 W JP0301379 W JP 0301379W WO 03066734 A1 WO03066734 A1 WO 03066734A1
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WO
WIPO (PCT)
Prior art keywords
polyester resin
weight
parts
double hydroxide
layered double
Prior art date
Application number
PCT/JP2003/001379
Other languages
English (en)
Japanese (ja)
Inventor
Takeshi Yatsuka
Hirotoshi Kizumoto
Katsumasa Yamamoto
Katsuya Shimeno
Original Assignee
Toyo Boseki Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2002032739A external-priority patent/JP2003231743A/ja
Priority claimed from JP2002167465A external-priority patent/JP4139991B2/ja
Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Priority to AU2003207208A priority Critical patent/AU2003207208A1/en
Publication of WO2003066734A1 publication Critical patent/WO2003066734A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals

Definitions

  • the present invention relates to a polyester resin composition having improved mechanical strength, hardness, rigidity, gas barrier properties, and the like, and a method for producing the same.
  • the present invention relates to a polyester resin composition which is a composite of a polyester resin and layered inorganic particles and has excellent performance, and a method for producing the same.
  • Polyester resins such as polyethylene terephthalate and polybutylene terephthalate have excellent mechanical strength, heat resistance, and sanitation, and are widely used in the fields of fibers, films, potts, molding materials, etc. .
  • Various functions are provided by blending these polyester resins with an inorganic reinforcing material and various additives.
  • various additives For example, weather resistance, flame retardancy, antistatic properties, coloring properties, sliding properties, surface properties, antibacterial properties, crystallinity, transparency, impact resistance, blocking resistance, conductivity, gas barrier properties, etc.
  • various additives have been added to the inorganic reinforcing material.
  • nylon clay (montmorillonite, etc.) hybrids using a monomer compound in an inorganic layered compound have been actively studied, and have been put into practical use as a nanocomposite for automobile parts and the like.
  • the filler inorganic reinforcing material, etc.
  • the filler used in the nanocomposite clay minerals such as smectites such as montmorillonite and savonite, and power olins such as force olinate, and silicate compounds are used.
  • a layered double hydroxide represented by hydrotalcite As one of the particles of such an inorganic layered compound, a layered double hydroxide represented by hydrotalcite is known.
  • Compounds of layered double hydroxides (such as hydrated talcites) are substances having a layered structure with anions between the layers, and are used as heat stabilizers, etc., when they are mixed with polyvinyl chloride in the form of fine particles. ing. It is also used as an agricultural film when added to an olefin film to have a heat storage effect, and is also used as an antacid for pharmaceuticals because it dissolves in acid and has a pH control function.
  • WO 01/43253 discloses the use of hydrotalcites as a polyester polymerization catalyst.
  • Japanese Patent Publications Nos. 2002-500253 and 2002-500254 disclose nanocomposite materials in which at least 20% of anions are compatible and / or reactive with a polymer matrix. It has been disclosed that a polyester resin is mixed with a hydro
  • An object of the present invention is to provide a composition comprising a polyester resin and layered inorganic particles, in which the layered inorganic particles are extremely finely dispersed in the polyester resin, and the mechanical strength, hardness, rigidity, gas barrier properties, and the like have been improved.
  • the purpose is to provide a polyester resin composition.
  • the present invention provides the following method for producing a polyester resin composition and a polyester resin composition produced by the method.
  • a method for producing a polyester resin composition comprising 100 parts by weight of a polyester resin and 0.1 to 10 parts by weight of a layered double hydroxide, the layered double hydroxide is added until the polycondensation of the polyester resin is completed.
  • a method for producing a polyester resin composition comprising: completing the polycondensation after blending at an optional stage of the above.
  • the layered double hydroxide is a hydrotalcite (1) A method for producing the polyester resin composition as described above.
  • a method for producing a polyester resin composition comprising 100 parts by weight of a polyester resin and 0.1 to 10 parts by weight of a layered double hydroxide, comprising the steps of: after polycondensation in the polymerization process is blended at any stage until completion, process for producing a polyester resin composition characterized in that allowed to complete the polycondensation of the polyester resin (
  • the layered double hydroxide used in the present invention has a general formula [MS + + x (OH) 2 ]
  • divalent metal (M 2+ ) is replaced by trivalent metal (M 3+ )
  • M 2+ divalent metal
  • M 3+ trivalent metal
  • the layer is positively charged, forming a structure in which anions (A 11 —) exist between the layers.
  • Divalent metals include magnesium, nickel, and zinc
  • trivalent metals include aluminum, iron, and the like.
  • Chromium (n is an integer of 1 to 3, X is a value of 0.15 to 0.5, z is a value of 5 or less)
  • monovalent metals such as lithium It may contain a tetravalent metal such as titanium.
  • the method for producing the layered double hydroxide used in the present invention is not particularly limited.
  • the method described in S. Miya, Clays Clay Miner., Vol. 28, page 50 (issued in 1980) is simple and preferred.
  • a layer fired at a temperature of 300 to 800 ° C. may be used.
  • the layered double hydroxide used in the present invention is particularly preferably a hydrotalcite.
  • the polyester resin composition of the present invention can be obtained by blending the layered double hydroxide swollen with ethylene glycol at an arbitrary stage until the polycondensation is completed in the polyester polymerization step, and then completing the polycondensation. .
  • the layered double hydroxide When the layered double hydroxide is added at any stage in the polymerization step of the polyester until the polycondensation is completed, it is important that the layered double hydroxide be swelled with glycol to widen the layer interval. Necessary to achieve the purpose. Swelling of the layered double hydroxide with glycol is performed by heating in glycol. The heating temperature is preferably from 50 to 20 Ot: or less, more preferably from 100 to 180 and below.
  • the step of swelling the layered double hydroxide with glycol can be performed in a polyester polymerization step, or may be performed in advance in a step different from the polymerization step.
  • a dibasic acid which is a component of the polyester raw material may be present.
  • the layered double hydroxide can be efficiently dispersed in the polyester resin, and the separation of the layer of the layered double hydroxide can be promoted.
  • the layered double hydroxide can be dispersed in the polyester resin in a nanometer size, so that molecular reinforcement can be achieved, and properties such as mechanical strength, hardness, rigidity, and gas barrier properties can be improved. .
  • glycol used for swelling the layered double hydroxide with glycol ethylene glycol, diethylene glycol and triethylene glycol are preferred. Particularly, ethylene glycol is preferred. These glycols are considered to be replaced by water existing between the layers of the hydrotalcite by heating.
  • the layered double hydroxide used in the present invention preferably has a surface area of 5 to 200 m 2 / g.
  • the surface area is less than 5 m 2 Zg, the layered double hydroxide cannot be dispersed efficiently, and the transparency of the obtained polyester resin composition may be reduced. If it exceeds 20 O ms / g, the melt viscosity during polymerization sharply increases. As a result, the resin having the desired molecular weight may not be obtained.
  • the layered double hydroxide is blended in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyester resin. If it exceeds 10 parts by weight, the melt viscosity becomes too high, making it difficult to increase the molecular weight of the polyester resin, and the resulting polyester composition may be very brittle. When the amount is less than 0.1 part by weight, the effect of adding the layered double hydroxide is reduced.
  • dibasic acid component of the polyester resin used in the present invention terephthalic acid, isophthalic acid, orthophthalic acid> naphthalenedicarboxylic acid, aromatic dibasic acids such as diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, succinic acid, Examples thereof include aliphatic dibasic acids such as adipic acid, azelaic acid, sebacic acid, dimer acid, and cyclohexanedicarboxylic acid.
  • glycol components of the polyester resin used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, and 1,5-pentanediol.
  • 1,6-hexanediol diethylene glycol, triethylene glycol, 3_methyl-1,5, -pentynediol, neopentylglycol, 2-ethyl-2-butyl-1,3-propanediol, diethyleneglycol, 1 , 4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, or polyether glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Can be .
  • a lactone component such as ⁇ -force prolactone and ⁇ -valerolactone and an oxycarboxylic acid component such as ⁇ -hydroxyethoxybenzoic acid can be used as raw materials for the polyester resin used in the present invention.
  • a trifunctional or higher functional component such as trimethylolpropane, pentaerythritol, and trimellitic anhydride may be used in combination.
  • a polar group such as a sulfonic acid metal base
  • a polar group such as a sulfonic acid metal base
  • a raw material for introducing a metal sulfonic acid salt into a polyester resin there are 5-sodium sulfoisophthalic acid, 5-calidosulfonic acid, sodium sulfoterephthalic acid, 2-sodium sulfo-1,4-butane
  • Examples include diols, dicarboxylic acids such as 2,5-dimethyl-3-sodium sulfo_2,5-hexanediol, and glycols.
  • the amount of the metal sulfonate group introduced into the polyester resin is preferably from 0.5 mol% to 20 mol% of the total dicarboxylic acid component. If it is less than 0.5 mol%, the effect of improving the dispersibility and delamination property of the layered double hydroxide is not remarkably obtained, and if it is more than 20 mol%, the thermal stability of the polyester resin tends to deteriorate, so that it is preferable. Absent.
  • the polyester resin composition of the present invention can be produced by a usual polyester polymerization method.
  • a dibasic acid is subjected to an esterification reaction with glycol under the condition of excess glycol
  • melt weight is subjected to deglycolization and polycondensation under high temperature and high vacuum in the presence of a metal catalyst such as antimony, titanium, and germanium.
  • a metal catalyst such as antimony, titanium, and germanium.
  • a synthetic method or a method in which a methyl ester compound of a dibasic acid and an glycol are subjected to an ester exchange reaction and then similarly polycondensed can be used.
  • the polyester resin obtained by these methods is subjected to solid phase polymerization at a temperature not higher than the melting point of the resin to increase the molecular weight.
  • the polycondensation is completed after blending the hydrated talcite at an arbitrary stage until the polycondensation is completed.
  • hydrotalcite be dispersed in glycol beforehand.
  • Ethylene glycol and diethylene glycol are preferred as the glycol used for dispersion.
  • Ethylene glycol, diethylene glyco It is considered that the polyester is replaced with water existing between the layers of the hydrotalcite during heating during polyester polymerization.
  • hydrotalcites obtained by dibasic acid oxidation There are two methods for obtaining hydrotalcites obtained by dibasic acid oxidation: (1) using dibasic acid as a source of anion when synthesizing the hydrotalcite, (2) previously obtained hydrotalcites. (3) A method of exchanging water with a dibasic acid anion; (3) A hydrotalcite of the original structure obtained by adding water to a talcite having a porosity that excludes interlayer anions by firing in the range of 300 to 800. For example, there is a method using a dibasic acid as a source of anion when converting the acid to an acid.
  • polyester resin composition of the present invention can be added to the polyester resin composition of the present invention in order to impart desired properties according to the purpose.
  • inorganic reinforcing materials, fiber reinforcing materials, heat stabilizers, antioxidants, antistatic agents, weathering agents, mold release agents, lubricants, coloring agents such as dyes and pigments, etc. can be added. .
  • the reduced viscosity was measured at 30 at a composition concentration of 0.4 g Zd1 using phenol tetrachloride (6/4 weight ratio) as a solvent.
  • the sample was measured by DSC under the following conditions, and the glass transition temperature Tg was measured according to JISK 71. Determined in accordance with 21.
  • Heating start temperature -100
  • Heating rate 20 ° C / niin.
  • the interlayer distance was measured by a powder X-ray diffraction method using an X-ray diffractometer, Rigaku Corporation, Geigerflex RAD-II.
  • composition of the polyester was measured by 1 H-NMR under the following conditions.
  • the tensile modulus at 50% elongation was measured under the following conditions.
  • the dynamic storage modulus at 1 Ot was measured under the following conditions.
  • the polyester resin composition obtained to examine the degree of dispersion of the layered double hydroxide was dissolved in methyl ethyl ketone / toluene (1/1 weight ratio) at a solid content of 10%, and the solution was stable after storage at room temperature for 1 week. By observing the properties, those with no sedimentation of the layered double hydroxide were evaluated as ⁇ , those with slight sedimentation ⁇ , and those with significant sedimentation as X.
  • the ratio of the oxygen permeation amount of a polyester resin having the same composition not containing the layered double hydroxide was calculated and evaluated. The smaller the number, the higher the barrier property.
  • the oxygen permeation amount was measured according to JIS K7126.
  • the composition of the polyester was analyzed by 1 H-NMR.
  • the obtained composition was dissolved in phenol / tetrachloroethane (6Z4 weight ratio), and the reduced viscosity was measured.
  • a membrane was obtained. The strength and elongation of the coating film, the storage modulus in the glass state, and the water vapor barrier property were measured. Table 1 shows the evaluation results.
  • Example 1A In the same manner as in Example 1A, except that the concentration of the 3-methyl-1,5-pentyldiol Z hydrotalcite dispersion was changed to obtain polyester compositions having different hydrotalcite contents. Evaluation was performed in the same manner as in Example 1. Table 1 shows the evaluation results.
  • Example 1A As in Example 1A, but without the use of 5.9 parts by weight of dimethyl 5-sodium sulfoisophthalate, the dispersion of isophthalic acid and 3-methyl-1,5-pentanediol / "hydrotalcite A polyester resin composition was obtained from the product, which was evaluated in the same manner as in Example 1 A. The evaluation results are shown in Table 1.
  • Example 5A as in Example 1A, except that the talcite used in Example 1A dispersed in ethylene glycol at 6.3% by weight was 40 parts by weight, and 3-methyl-1,5 was used. — 16.5 parts by weight of pen diol and isophthalate The reaction was carried out with 1666 parts by weight ofucic acid.
  • Example 6A as in Example 1A, except that the talcite used in Example 1A was dispersed at 4% by weight in diethylene glycol, 62 parts by weight, 3-methyl-1,5-pentene were used. 16.5 parts by weight of evening diol and 1666 parts by weight of isofluoric acid were reacted.
  • a polyester resin having the same composition as in Examples 1A and 4A was obtained without using a hydrotalcite. Evaluation was performed in the same manner as in Example 1A. Table 1 shows the evaluation results.
  • Comparative Example 1 Hydrotalcite was mixed with the polyester resin solution of 1A (solvent: methyl ethyl ketone toluene: 1 Z 1 weight ratio) at a solids weight ratio of 100: 2, and glass beads were added. The mixture was shaken and dispersed in a paint shaker for 6 hours. From this dispersion, a dried coating film was obtained in the same manner as in Example 1A. Evaluation was performed in the same manner as in Example 1A. Table 1 shows the evaluation results.
  • Example 1A As in Example 1A, except that the concentration of the 3-methyl-1,5-pentanediol Z hydrotalcite dispersion was changed to obtain polyester compositions having different hydrotalcite contents.
  • Comparative Examples 4A and 5A the content of the hide mouth talcite is out of the range of the present invention. Evaluation was performed in the same manner as in Example 1A. Table 1 shows the evaluation results. In Comparative Example 5A, the obtained coating film was very brittle, and the 50% tensile modulus and the water vapor barrier property could not be measured. Table 1 Properties of polyester resin composition
  • IPA isophthalic acid MPD: 3-methyl-1,5-pentanol
  • DSN 5-sodium sulfoisophthalic acid
  • EG ethylene glycol
  • a hydrotalcite (Mg 4 Al 2 (OH) 12 (TA), which was prepared from terephthalic acid anion synthesized by the method described in Inorganic Chemistry, vol. 27, 462, p. ⁇ 4 ⁇ 2 0), (the T Alpha was dispersed) 1 0 parts by weight represents terephthalic acid ion to 90 by weight of ethylene glycol.
  • Example 1A In a reaction vessel equipped with a thermometer, a stirrer, and a distilling cooling tube used in Example 1A, 166 parts by weight of terephthalic acid and 18.9 parts by weight of ethylene glycol in which the above-mentioned hydrosite was dispersed (18.9 parts by weight) 1.9 parts by weight of hydrotalcite, 17 parts by weight of ethylene glycol) and 107 parts by weight of ethylene glycol were charged, and the esterification reaction was carried out under pressure. During that time, the temperature reached 230. 0.07 parts by weight of tetrabutyl titanate was charged as a polycondensation reaction catalyst, and then the pressure inside the system was gradually reduced to finally reach 0.1 mm Hg. The temperature at that time was maintained at 27 Ot :. Thus, a high-viscosity polyethylene terephthalate (also referred to as PET) composition containing 1% by weight of hydrotalcite was obtained.
  • PET high-viscosity polyethylene terephthalate
  • the obtained composition was dissolved in phenolnotetrachloroethane, and the reduced viscosity was measured.
  • the oxygen barrier properties of the film obtained by the hot pressing method (a method in which the resin is melted by heating to above the melting point and softening point of the resin, stretched by applying pressure, and then rapidly cooled by water cooling) are measured in accordance with JISK 7126. It was measured.
  • Table 2 shows the oxygen barrier properties of the films obtained by the same method using PET containing no talcite.
  • Example 8A the hydrotalcite used in Example 7 was dispersed in 1,3-propanediol to obtain polytrimethylene terephthalate (PTT) in which the hydrotalcite was dispersed by the same polymerization method.
  • PTT polytrimethylene terephthalate
  • Example 9A polytetramethylene terephthalate (PBT) in which hydrotalcite was dispersed was obtained in the same manner as in Example 8.
  • Table 2 shows the respective reduced viscosities and oxygen barrier properties. Table 2 Properties of polyester resin composition
  • T P A Terephthalic acid
  • Examples 1A to 9A in which the hydrated talcite was added during the polyester polycondensation, were Comparative Examples 1A and 2A without the hydrotalcite and polycondensation.
  • the strength, elastic modulus, and gas barrier properties are significantly higher than those of Comparative Example 3A, which is simply blended after completion, and Comparative Examples 4A, 5A, which have a hydrotalcite content outside the scope of the claims. It can be seen that it has improved.
  • Hydrotalcite as layered double hydroxide in a glass reactor equipped with a stirrer (Hydrotal talcite manufactured by Toda Kogyo Co., Ltd., average particle size 0.15 / zm, Mg / Al molar ratio 2.7, B (ET surface area 18 m 2 / g) 20 parts by weight and 80 parts by weight of ethylene glycol were added, and the content was heated at 130 for 10 minutes.
  • the ethylene glycol solution containing hydrotalcite turned into a paste with high viscosity. According to the measurement by X-ray diffraction, the interlayer distance of the talcite at the mouth was widened from 7.5 A to 8.4 A by heating in ethylene glycol.
  • the composition of the polyester was analyzed by 1 H-NMR.
  • the reduced viscosity, glass transition temperature, 50% tensile modulus, storage modulus, solution stability, and water vapor barrier properties of the coating film were evaluated. Table 3 shows the results.
  • Example 3B As in Example 1B, except that the hydrotalcite / ethylene glycol (2Z8) solution used in Example 1B 6.2 parts by weight and the ethylene glycol 15 parts by weight, the hydrotalcite 0.5 parts by weight % Of a polyester resin composition. Evaluation was performed in the same manner as in Example 1B. Table 3 shows the results. (Example 3B)
  • a reaction vessel equipped with a thermometer, a stirrer, and a distilling cooling tube was charged with 19.8 parts by weight of the hydrotalcite used in Example 1B and 40 parts by weight of ethylene glycol, and stirred at 150 for 10 minutes. Further, 194 parts by weight of dimethyl isophthalate, 236 parts by weight of 3-methyl-1,5-pentanediol, and 0.08 parts by weight of tetrabutyl titanate as a reaction catalyst were charged, and the transesterification reaction was carried out in the same manner as in Example 1. A polycondensation reaction was carried out to obtain a polyester composition containing 8% by weight of hydrotalcite. Evaluation was performed in the same manner as in Example 1B. Table 3 shows the results. (Comparative Example 1B)
  • Example 1B A polyester resin having the same composition as in Example 1B was obtained without using a hydrotalcite. Evaluation was performed in the same manner as in Example 1B. Table 3 shows the evaluation results.
  • Example 4B In the same manner as in Example IB, except that the concentration of the hydrated talcite-to-ethylene glycol dispersion was changed to obtain a polyester composition having a different hydrotalcite content.
  • Comparative Examples 3B and 4B the content of the talcite at the mouth was out of the scope of the present invention. Evaluation was performed in the same manner as in Example 1B. Table 3 shows the evaluation results.
  • Comparative Example 4B the obtained coating film was very brittle, and the 50% tensile modulus and the water vapor barrier property could not be measured.
  • the obtained composition was dissolved in phenol / tetrachloroethane, and the reduced viscosity was measured.
  • the polyester resin composition is heated and melted at 280 by a heat press method, and is then thinned by applying pressure between fluorine-based resin films having a thickness of 0.2 mm.
  • a method for obtaining a film-like resin composition having a thickness of about 25 m) was measured for oxygen barrier properties.
  • Table 4 shows the oxygen barrier effect of the layered double hydroxide as a reduction ratio of the amount of oxygen permeated by the layered double hydroxide.
  • Example 4B shows the results.
  • the same layered double hydroxide was used for Example 5B and Comparative Example 6B, Example 6B and Comparative Example 7B, and Example 7B and Comparative Example 8B.
  • TPA Terephthalic acid
  • the layered double hydroxide is extremely finely dispersed in the polyester resin, and the mechanical strength, hardness, rigidity, gas barrier property, and the like are improved. Since an improved polyester resin composition can be obtained, the polyester resin composition of the present invention can be used as an engineering plastic as various molded articles such as electric and electronic parts by utilizing its properties. It is also applicable to films, paints, and fibers, and is particularly useful as a raw material for paints and films because the layered double hydroxide is extremely finely dispersed in the polyester resin.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé de production d'une composition de résine de polyester comprenant 100 parties en poids d'une résine de polyester et entre 0,1 et 10 parties en poids d'un hydroxyde composite lamellaire. Ce procédé se caractérise en ce qu'il consiste à incorporer l'hydroxyde composite lamellaire gonflé avec un glycol à n'importe quel stade de la polycondensation en vue d'une production de résine de polyester, puis à terminer la polycondensation. L'invention concerne également une composition de résine de polyester produite au moyen de ce procédé.
PCT/JP2003/001379 2002-02-08 2003-02-10 Composition de resine de polyester et son procede de production WO2003066734A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003207208A AU2003207208A1 (en) 2002-02-08 2003-02-10 Polyester resin composition and process for producing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2002032739A JP2003231743A (ja) 2002-02-08 2002-02-08 ポリエステル樹脂組成物及びその製造方法
JP2002-32739 2002-02-08
JP2002-167465 2002-06-07
JP2002167465A JP4139991B2 (ja) 2002-06-07 2002-06-07 ポリエステル樹脂組成物及びその製造方法

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WO2003066734A1 true WO2003066734A1 (fr) 2003-08-14

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999035186A1 (fr) * 1998-01-09 1999-07-15 Nederlandse Organisatie Voor Toegepast Natuurweten Schappelijk Onderzoek Tno Materiau nano-composite

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999035186A1 (fr) * 1998-01-09 1999-07-15 Nederlandse Organisatie Voor Toegepast Natuurweten Schappelijk Onderzoek Tno Materiau nano-composite

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