JP2008037985A - Polymer-modified silicon compound/polyurethane composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To remarkably improve mechanical characteristics of a conventional composite obtained by directly dispersing organized clay, etc., prepared by modifying silica or clay which is a silicon compound in a polyurethane. <P>SOLUTION: The compatibility of interfaces between particles and the polyurethane is improved by previously modifying silicon compound particles with a polymer of an ethylenically unsaturated monomer in a polyurethane composite obtained by dispersing and compositing the silicon compound particles such as aluminosilicate particles or polysilicic acid particles in the polyurethane. For example, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate or butyl methacrylate is preferably used as the ethylenically unsaturated monomer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymer-modified silicon compound / polyurethane composite. More specifically, the present invention relates to a polymer-modified silicon compound / polyurethane composite that has excellent mechanical properties and can be applied to various fields of building structural materials, industrial members, and vehicle materials.

  A silicon compound / polyurethane composite is an organic / inorganic composite (composite) containing polyurethane as a matrix as an organic component and silicon compound particles as an inorganic component. The polyurethane composite has mechanical properties such as elastic modulus. In particular, it can be suitably used as a structural member.

  Conventionally, with respect to such a composite, in particular, when the silicon compound which is an inorganic component is silica having silanol which is polysilicic acid, and a clay which is an aluminosilicate represented by montmorillonite, a polyutalene composite Many proposals have been made so far.

  Here, for an organic / inorganic composite in which silica particles (hereinafter, simply referred to as “silicon compound”, “silica”, etc.) as silicon compound particles are inorganic components and polyurethane is an organic component, for example, the following method is used. It is known that That is, (1) a method of blending (mixing) finely divided silica, (2) a method of mixing colloidal silica, and (3) a sol-gel method using alkoxysilane are known.

  Thus, the composite production method obtained by the mixing method of (1) and (2) can be most easily carried out, but the silica in the normal mixing method is a nanoporous structure such as calcined silica or colloidal silica. This is a composite obtained by blending silica particles that do not have, and is fundamentally different from the composite of the present invention obtained from particles having a nanoporous structure as described later.

  As the method of (3) by the sol-gel method, a method of obtaining a silica-polyurethane nanocomposite from a cationic polyurethane by a sol-gel method (Non-Patent Document 1), and a method of obtaining a polyurethane-silica composite from a polyurethane resin solution by a sol-gel method (Non-Patent Document 2) has been proposed.

  It is shown that the silica in these sol-gel composites is in the form of particles that do not have a clear hollow structure with an interface whose silica phase exceeds 50 nm and forms an independent phase. Yes. These composites are not composites in which a specific polymer is used as a compatibilizing agent in order to highly disperse silica and polyurethane in the nano order as in the present invention described later.

  Moreover, the silicon compound is a clay that is an aluminosilicate represented by montmorillonite, and the composite of this and polyurethane is typically (1) a clay obtained by organicizing a clay such as montmorillonite with an alkylamine (hereinafter referred to as a clay). , "Organized clay") is known to be blended with polyurethane. In this regard, for example, an example of a combination of an organized clay and a thermoplastic polyurethane (Patent Document 1), an example of a combination with a solvent type polyurethane for use in elastic fibers (Patent Document 2), and a combination with an aqueous polyurethane An example (Patent Document 3) has been proposed.

  On the other hand, (2) An example of obtaining a foam composite while blending the above organic raw clay with a urethane raw material in advance to produce polyurethane (Patent Document 4), or an example of obtaining an elastic composite (Patent Document) 5) etc. are also proposed.

  Also, clay obtained by reacting clay such as montmorillonite with an isocyanate and compounding with an amine-containing compound (hereinafter referred to as “isocyanate-reactive organized clay”) is used at the time of polyurethane production. A method is also known in which a composite of an isocyanate-reactive organic clay and polyurethane is used as a raw material for polyurethane (Non-patent Document 3).

  However, any of these methods is a method in which an organic clay is directly dispersed in polyurethane to obtain a composite. As in the present invention described later, in order to highly disperse particles such as clay in the nano-order in the polyurethane, It is not a composite that is modified with a specific polymer having a solubilizing function.

  The composite obtained by using organically modified clay modified with silica or clay, which is a silicon compound, as described above, has a limit in improving its mechanical properties, such as elastic modulus, In addition, it has drawbacks such as deterioration of hue.

JP-A-10-168305 (Claims (Claims 1 to 9)) JP 2000-513414 A (Claims (Claims 1 to 40)) JP 2006-143991 A (Claims (Claims 9 to 11)) JP 2003-335831 A (Claims (Claims 1 to 6)) JP-A-2005-139272 (Claims (Claims 1 to 6)) Yan Zhu et al, "Preparation of Silicon Dioxide / Polyurethane Nanocomposites by Sol-Gel Process", Journal of Applied Polymer Science, 2004, Vol.92, p2013-2016 Hideki Goda, “Material Properties of Polyurethane-Silica Hybrid”, Polymer Papers, Vol.59, No.10, p596-601 (2002) Asim Pattanayak et al, "Properties of bulk-polymerized thermoplastic polyurethane nanocomposites", Polymer, 2005, Vol.46, p3394-3406

The object of the present invention is to use a conventional polyurethane composite, that is, an elastic clay in a conventional composite obtained by dispersing silica directly into polyurethane using silica or clay that is a silicon compound. The object is to provide a silicon compound / polyurethane composite that exceeds the limit of mechanical properties and further improves the mechanical properties with a smaller amount of silicon compound compared to the conventional one.
Another object of the present invention is to solve the problems often pointed out in the past, such as deterioration of hue in composites.

  As a result of intensive studies in view of the importance of the above problems, the present inventors have previously modified the silicon compound particles with a specific polymer having a function as a compatibilizer so that the silicon compound particles can be further contained in polyurethane. It was found that a composite having excellent mechanical properties and the like that can be highly dispersed in the nano order can be formed, and the present invention has been completed.

According to the present invention, the following polymer-modified silicon compound / polyurethane composite is provided.
[1]
A polymer-modified silicon compound / polyurethane composite, characterized in that, in a silicon compound / polyurethane composite in which silicon compound particles are dispersed and composited in polyurethane, the silicon compound particles are polymer-modified particles that have been polymer-modified in advance.

[2]
The polymer-modified silicon compound / polyurethane composite according to [1], wherein the silicon compound particles are aluminosilicate particles and / or polysilicate particles.

[3]
The polymer-modified silicon compound / polyurethane composite according to [1] or [2], wherein the silicon compound particles are polymer-modified particles modified with a polymer of an ethylenically unsaturated monomer.

[4]
The polymer-modified silicon compound particle according to [3], wherein the polymer-modified silicon compound particle is obtained by polymerizing the ethylenically unsaturated monomer in the dispersion medium of the particle in the presence or absence of a dispersant. Compound / polyurethane composite.

[5]
Ethylenically unsaturated monomers are methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, lauryl methacrylate, glycidyl Acrylate, glycidyl methacrylate, 2-dimethylaminoethyl methacrylate, 2-dimethylaminoethyl acrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-alkyl substituted acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, acrylonitrile, styrene, α-methylstyrene, p-hydroxystyrene, α-butylstyrene, butadiene, isoprene, divinylbenzene, vinyl acetate, ethylene glycol dimethacrylate, diallyl phthalate, ethylene glycol diacrylate, The polymer-modified silicon compound / polyurethane composite according to [3] or [4], which is at least one ethylenically unsaturated monomer selected from the group consisting of allyl acrylate and allyl methacrylate.

  The polymer-modified silicon compound / polyurethane composite of the present invention is presumed to have an unprecedented novel organic / inorganic composite structure as described in detail below, and mechanical properties such as elastic modulus Is greatly improved.

  More specifically, in the case of a combination of a polymer-modified silicon compound and a thermoplastic polyurethane, the composite has excellent recyclability while maintaining thermoplasticity, and despite a slight inorganic component content. In addition, it exhibits a significant improvement in elastic modulus and has the effect of having a good hue.

  Also, in the case of a combination with a thermosetting polyurethane, the effect of exhibiting a large improvement in elastic modulus is exhibited in spite of a slight inorganic component content.

Hereinafter, the present invention will be described in detail.
(Polymer-modified silicon compound particles)
The silicon compound / polyurethane composite of the present invention is characterized in that the silicon compound particles are polymer-modified particles that have been polymer-modified in advance. Preferably, the silicon compound particles are aluminosilicate particles or polysilicate particles.

(Aluminosilicate particles)
As the aluminosilicate to be polymer-modified, ordinary ones can be used and are not particularly limited, but preferably include a clay mineral (hereinafter simply referred to as “clay”), a phyllosilicate, and the like. Smectite clays montmorillonite, bentonite, nontronite, beidellite, vorconite, hectorite, saponite, sauconite, stevensite, magadiite, kenyanite, herosite, vermiculite clay vermiculite, antigolite clay anti Golite, chrysotile and the like are exemplified as usable.

  Also, kaolinite kaolinite, halloysite, nacrite and virophilite clay, mica or mica or muscovite mica, phlogopite mica, margarite, swelling mica, tetrasilic mica, teniolite Can also be used as aluminosilicates.

  These clays and the like have a particle size of about 1 nm to 10 μm, preferably about 1 nm to 5 μm, and particularly preferably nanoscale. A layered structure or a multilayer structure is preferred.

  In addition, as these clays or the like, those having preferable characteristics can be obtained as commercial products depending on the purpose. For example, “Kunipia-F” marketed by Kunimine Industries Co., Ltd. has a cation exchange capacity of 115 mm. An equivalent (meq) / 100 g smectite clay montmorillonite, which can be suitably used in the present invention. The company's “Kunipia-G” and “Smecton-SA” are also preferably used.

(Polysilicate particles)
The polysilicic acid to be polymer-modified may be, for example, natural or synthetic layered polysilicic acid such as Kenyaite, macatite, islayite, kanemite, octosilicate, or a salt thereof, and is preferably porous silica (porous silica).

  Among them, the mesoporous silica disclosed in “Studies in Surface Science and Catalysis”, 84, p125-132 (1994) and “Studies in Surface Science and Catalysis”, 92, p143-148 (1995) is particularly preferable. . These are porous silicas generally called FMS (Folded Sheet Mesoporous material), the pores of which are about 1.5 to 4.0 nm, and the particle diameters are distributed from μm order to 10 μm order. It is. As such porous silica, for example, those commercially available from Taiyo Kagaku under the trade name: NPM (Nano Porous Material) -4 can be suitably used in the present invention. In the present invention, polysilicate includes polysilicate.

  When the silicon compound particles preferably have a multilayer structure or a porous structure, the monomer of the modifying polymer such as polymethyl methacrylate (PMMA) does not enter the interlayers or pores (or nanopores) of the particles when the polymer is modified. Polymerize in the state. That is, since a large amount of the polymer can be taken into the particle, the particle can be coated with a large amount of the modifying polymer. In this case, as shown in the examples described later, it is also preferable that PMMA or the like that penetrates and polymerizes between layers of a multilayer structure spreads the layer of the layer structure of the particles and peels (peel separation). At that time, the silicon compound particles or the surface-exfoliated particles may be dispersed in PMMA or the like.

  Since the modifying polymer PMMA or the like has high compatibility with polyurethane, in the step of blending and kneading the polymer-modified silicon compound particles with polyurethane, the PMMA or the like is mutually compatible with the matrix polyurethane. In order to function as a compatibilizer between the particles and the polyurethane, the silicon compound particles are considered to form a composite that is stably dispersed in the polyurethane via PMMA or the like.

(Modifying polymer)
In the present invention, the silicon compound particles are polymer-modified in advance. The modifying polymer is not particularly limited as long as it can act as a kind of compatibilizer between the silicon compound particles and polyurethane. Is done.

  Such a polymer used for polymer modification is preferably a compound (polymer) obtained by polymerizing an ethylenically unsaturated monomer.

  Examples of the ethylenically unsaturated monomer include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and lauryl. Methacrylate, lauryl methacrylate, glycidyl acrylate, glycidyl methacrylate, methacrylate having tertiary amino group such as 2-dimethylaminoethyl methacrylate; acrylate having tertiary amino group such as 2-dimethylaminoethyl acrylate; acrylic Acid, methacrylic acid, acrylamide, methacrylamide, N-alkyl substituted acrylamide, N, N-di Tilaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylonitrile, styrene, α-methylstyrene, p-hydroxystyrene, α-butylstyrene, butadiene, isoprene, It is preferably at least one ethylenically unsaturated monomer selected from the group consisting of divinylbenzene, vinyl acetate, ethylene glycol dimethacrylate, diallyl phthalate, ethylene glycol diacrylate, allyl acrylate and allyl methacrylate.

  Further, by using a methacrylate having a tertiary amino group such as 2-dimethylaminoethyl methacrylate or an acrylate having a tertiary amino group such as 2-dimethylaminoethyl acrylate, for example, in a water system, the dispersant is not used. A polymer can be obtained in the presence.

(Dispersion medium, dispersant, etc.)
The polymerization reaction of the ethylenically unsaturated monomer is not particularly limited to a polymerization terminal species such as ionic polymerization or radical polymerization, but radical polymerization is preferred.

  The dispersion medium for carrying out the polymerization reaction is not particularly limited, and water, organic solvent system, liquefied carbon dioxide, supercritical carbon dioxide and the like are preferably used. Among these, water is preferable as the dispersion medium in consideration of economy.

  The polymerization is carried out in the presence or absence of a dispersant (surfactant). When a dispersant (surfactant) is used, any nonionic, cationic, or anionic surfactant can be used. In particular, sodium lauryl sulfate is preferable as a dispersant when water is selectively used as a dispersion medium and a polymer is obtained by radical polymerization.

  The amount of the dispersing agent used is at most 0.1 to 20 parts by mass, preferably about 0.5 to 10 parts by mass with respect to 100 parts by mass of the produced polymer.

(Polymer modification reaction)
The reaction apparatus (mixing dispersion polymerization apparatus) for carrying out the polymerization reaction (modification reaction) is not particularly limited, but has a stirring means for sufficiently dispersing the silicon compound particles, and preferably a heating means, a temperature. A stirring tank type equipped with control means, raw material supply means (dropping means, etc.) and the like is preferably used. The stirring means may be a normal three-blade swept blade type, a saddle type, a paddle type, a propeller type, a turbine type, or the like, or by a gas blow such as air, and in order to promote dispersion, Along with mixing, air blowing or ultrasonic application can be used in combination.

  In the present invention, the polymer-modified silicon compound particles are obtained by polymerizing the ethylenically unsaturated monomer in the dispersion medium of the silicon compound particles, preferably in the presence or absence of a dispersant, using such a reactor. Obtained.

  Here, a case where water is used as a dispersion medium will be described as a representative example, but the same can be applied to a dispersion medium other than water.

  First, it is preferable that silicon compound particles such as clay and / or porous silica and water as a dispersion medium are charged into the reactor, and the particles are sufficiently dispersed in water as a medium in advance. The temperature during dispersion is 10 to 90 ° C., preferably about 20 to 80 ° C., and the dispersion time is 0.1 to 20 hours, preferably 0.2 to 15 hours, more preferably about 0.5 to 10 hours. It is.

  In addition, when using a dispersing agent, it mixes at this stage, Furthermore, a part or whole quantity of an ethylenically unsaturated monomer can also be mixed at this stage if desired. The amount of the ethylenically unsaturated monomer used is 0.1 to 100 parts by mass, preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 1 part by mass of the particles.

  The concentration of the silicon compound such as clay and / or porous silica is 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably about 5 to 100 parts by weight with respect to 100 parts by weight of water as the dispersion medium. It is.

  In the preliminary dispersion stage, when a part of the ethylenically unsaturated monomer is mixed, the concentration of the monomer is 0.1 to 200 parts by mass, preferably 1 to 150 parts by mass with respect to 100 parts by mass of water. Part, more preferably about 5 to 100 parts by mass.

  Hereinafter, an example of the operation of the polymerization reaction will be described in the case of radical polymerization, but the same procedure is performed when the polymerization terminal species is an ion. When using a dispersant, the total amount of the ethylenically unsaturated monomer (or the remaining amount when a part of the ethylenically unsaturated monomer is mixed in the premixing stage) is added in advance to the above temperature at a temperature of room temperature to 70 ° C. The prepared dispersion of silicon compound particles such as clay and / or porous silica is uniformly mixed and dispersed. In this case, it is also possible to use ultrasonic waves together with mechanical stirring in order to promote dispersion as described above.

  As described above, the dispersion time is about 0.1 to 20 hours, preferably about 0.2 to 15 hours, and more preferably about 0.5 to 10 hours.

  Subsequently, an aqueous solution of potassium peroxodisulfate or the like, which is a radical polymerization initiator, is dropped to initiate polymerization. The usage-amount of the said initiator is 0.01-20 mass parts with respect to 100 mass parts of ethylenically unsaturated monomers, Preferably it is about 0.01-10 mass parts. As the initiator, those generally marketed as radical polymerization initiators other than potassium peroxodisulfate can be used.

  The polymerization temperature is 20 to 90 ° C., preferably about 30 to 80 ° C., and the polymerization time is 3 to 60 hours, preferably 6 to 48 hours, more preferably about 8 to 24 hours.

On the other hand, when the dispersant is not used, the same operation is basically performed.
That is, using the same reaction apparatus, first, silicon compound particles such as clay and / or porous silica are dispersed in water and a part of the ethylenically unsaturated monomer.

  The temperature at the time of dispersion is room temperature to 90 ° C., preferably 20 to 80 ° C., and the dispersion time is 1 to 20 hours, preferably 2 to 12 hours.

  Subsequently, the residual amount of the ethylenically unsaturated monomer for radical polymerization, an aqueous solution of an initiator such as potassium peroxodisulfate, a methacrylate having a tertiary amino group such as 2-dimethylaminoethyl methacrylate such as 2-dimethylaminoethyl methacrylate, An acrylate having a tertiary amino group such as 2-dimethylaminoethyl acrylate is added dropwise to proceed the polymerization.

  The usage-amount of an initiator is 0.01 mass part-10 mass parts with respect to 100 mass parts of ethylenically unsaturated monomers. As the initiator, in addition to potassium peroxodisulfate, those generally marketed as radical polymerization initiators can be used.

The usage-amount of 2-dimethylaminoethyl methacrylate etc. is 1-20 mass parts with respect to 100 mass parts of ethylenically unsaturated monomers.
The polymerization temperature is preferably about 40 ° C to 80 ° C, and the polymerization time is preferably about 6 to 48 hours.

  As described above, in both cases where the dispersant is used and not used, after the polymerization reaction is completed, the reaction solution is added to an appropriate precipitation medium, for example, methanol, 2 to 5 times the amount of the reaction solution used. In addition, after polymer-modified clay and / or polymer-modified porous silica is deposited, it is solid-liquid separated by means of filtration and the like, and further washed with methanol or the like, and then dried under reduced pressure, for example, at a temperature of about 50 ° C. for preferably 12 hours or more To obtain a target denatured product.

  In addition, in order to precipitate and separate polymer-modified clay and / or polymer-modified porous silica, it is possible to pre-process using a centrifuge.

(Preparation of polyurethane)
The method for producing polyurethane as a substrate (matrix) in the composite of the present invention is not particularly limited, and known methods can be employed. Usually, a polyurethane is obtained by reacting a polyisocyanate, a polyol and a chain extender in the presence or absence of a catalyst, and further in the presence of water, an organic solvent or no solvent.

  Specifically, for example, basic production methods such as G. Oertel's “POLYURETHANE HANDBOOK” 2nd edition (HANSER, 1994) disclose general methods for producing various polyurethanes. Various forms of polyurethane, such as foams, fibers, films, coatings, and beads, can be produced.

  Examples of the polyisocyanate that is one of the components constituting the polyurethane are as exemplified in pages 73 to 83 of the above-mentioned document. For example, in the present invention, preferable polyisocyanates include tolylene diisocyanate. Nert, diphenylmethane diisocyanate (MDI), polymeric MDI, orthotoluyl diisocyanate, naphthylene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate (IPDI), norbornane diisocyanate (NBDI) 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), etc., and these may be used alone or in combination. Mixed It can also be used. Furthermore, polyfunctional polyisocyanates obtained by introducing urethane bonds, burette bonds, or isocyanurate bonds into these isocyanates can also be suitably used.

  The blending amount of the polymer-modified silicon silica compound particles with respect to the polyurethane is 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polyurethane. Part.

  On the other hand, the polyol can be selected from those described in, for example, pages 55 to 71 of the above-mentioned document. As a preferable polyol for the present invention, an acid such as adipic acid and an alcohol such as neopentyl glycol are used. Polyester polyol obtained from cyclic ester, e-polycaprolactone polyester polyol obtained from cyclic ester, polycarbonate diol obtained from polyhydric alcohol and alkyl carbonate, polyoxytetramethylene glycol which is an oligomer of tetrahydrofuran, propylene oxide And polyoxyalkylene polyols obtained from ethylene oxide and the like. Moreover, the olefin type polyol which has an active hydrogen group at the terminal, or the polyol derived from natural products, such as a castor oil, can also be used.

  Furthermore, the chain extender and the catalyst are also described in, for example, pages 98 to 106 of the above-mentioned literature. As the chain extender preferable for the present invention, 2 such as neopentyl glycol and 1,4-butanediol are used. Divalent alcohols, water, diamines such as hydrazine and isophoronediamine, and alkanolamines such as ethanolamine are preferred. A chain extender having 3 or more functional groups such as trimethylolpropane and diethanolamine can also be used.

Further, as the catalyst, commonly used dibutyltin dilaurate can be used.
Polyurethanes having various properties for various applications are sold by many manufacturers, and it is also possible to select and use polyurethanes according to purposes.

(Preparation of polymer-modified silicon compound / polyurethane composite)
The polymer-modified silicon compound / polyurethane composite of the present invention can be prepared by a kneading method in which polymer-modified silicon compound particles prepared in advance and polyurethane prepared in advance are blended (kneaded) as described above in detail. When reacting polyisocyanate, polyol, and chain extender in the presence or absence of a catalyst, a polymer-modified silicon compound particle prepared in advance is added to and mixed with the raw material, and then a polyurethane is produced (reaction method) ). By applying the kneading method, it is possible to prepare a polymer-modified silicon compound / polyurethane composite that is sufficiently excellent in quality.

  When blending solvent-free polyurethane and polymer-modified silicon compound particles in the kneading method, two-roll (roll mill), extruders such as screw extruders, Banbury mixer, kneader mixer, internal mixer, Brabender mixer, etc. The polymer-modified silicon compound and polyurethane are mixed using a mixer, preferably a kneader or a kneader, and sufficiently kneaded to form a composite.

  The kneading temperature may be appropriately selected between room temperature and 260 ° C. exceeding the melting point of polyurethane. The kneading time may vary depending on the temperature, the type of polyurethane, the amount of silicon compound particles to be blended with the polyurethane, and is usually about 1 to 10 hours.

  On the other hand, in the case of polyurethane using water and / or a solvent, after the polymer-modified silicon compound particles are mixed and dispersed in a polyurethane solution containing water and / or a solvent, the water and / or the solvent is heated, etc. A composite can be formed by removing with. The dispersion in this case does not require a special dispersing device, but it is preferable to use a dispersing device having a high shear rate in order to improve the dispersion efficiency and promote the dispersion of the aggregates.

  In addition, when blending polymer-modified silicon compound particles with polyurethane raw materials in the reaction method, extruders such as two-roll (roll mill), screw extruder, Banbury mixer, kneader mixer, internal mixer, Brabender mixer A mixer such as can be used.

  The polymer-modified silicon compound / polyurethane composite of the present invention can be used as a structural material in various forms according to its purpose, such as films, sheets, plates, rods, disks, and other complex shapes. can do.

Hereinafter, the present invention will be described by way of examples. However, these are merely examples of embodiments, and the technical scope of the present invention is not construed as being limited thereto. Unless otherwise specified, “%” means “% by mass”.
Test items and test methods in this example are as follows.

(A) (Thermogravimetric analysis (TGA))
Using a differential type differential thermal balance (Thermo plus TG8120, manufactured by Rigaku Denki Co., Ltd.), measurement is performed under conditions of a temperature range of 30 to 900 ° C and a heating rate of 10 ° C / min under an air stream (flow rate 200ml / min). It was.

(B) (Differential scanning calorimetry (DSC measurement))
Using a differential scanning calorimeter (Thermo plusDSC8230, simple cooling unit 8384J1, manufactured by Rigaku Corporation), in the case of Mt / PMMA hybrid (modified particles) described later, temperature range 30 to 200 ° C, heating rate 10 ° C / min, air In the case of an Mt / PMMA / TPU composite under an atmosphere, the glass transition temperature (Tg) was confirmed by measuring in a temperature range of 100 to 200 ° C., a heating rate of 10 ° C./min, and an air atmosphere. In addition, Al ₂ O ₃ was used as a standard sample.

(C) (X-ray diffraction measurement (XRD measurement))
X-ray diffraction was performed using a X-ray diffractometer (RINT2200V type, manufactured by Rigaku Corporation) at a voltage of 40 kV and a current of 30 mA. The test sample was a powder. The interlayer distance of the modified clay was determined from the XRD peak position using the Bragg equation. The Bragg equation is nλ = 2d sin θ (n = order, λ = X-ray wavelength, d = interlayer distance, θ = diffraction angle).

(D) (Measurement of tensile properties)
The sheet-molded sample was punched into a No. 3 dumbbell mold to obtain a test piece. The measuring machines used were RTA-100 and AR-6600-7 flat pet recorders manufactured by Orientec. The measurement temperature was room temperature, and the measurement was performed until breakage under the conditions of a tensile speed of 100 mm / min. Each temperature was measured after holding at the set temperature for 5 minutes. The measured values are the elastic modulus at 100% elongation at M100 (MPa), the elastic modulus at 200% elongation at M200 (MPa), the elastic modulus at 300% elongation at M300 (MPa), and the elastic modulus at 400% elongation. Indicated by M400 (MPa). The elastic modulus at break was indicated by TS (MPa), and the elongation at break was indicated by EL (%).

(E) (Soxhlet extraction test)
About 10 g of the synthesized sample is taken, and after the sample is precisely weighed, it is put into a cylindrical filter paper and put into a Soxhlet tube. A flask containing toluene is provided under a Soxhlet tube, and toluene is refluxed for 48 hours while heating to extract a toluene-soluble component. Then, an extraction residue sample is dried under reduced pressure at 70 ° C., and the remaining amount is precisely weighed. The residual extraction rate (%) is calculated from the sample amount before and after extraction.

[Example 1]
(Synthesis of polymer-modified clay)
(1) In a 4-neck 1000 ml glass separable reactor equipped with a stirrer, a heating device, a reflux device, and a dropping device, 400 ml of a 0.5% by mass aqueous sodium lauryl sulfate solution was weighed, and montmorillonite ( 4.44 g of Kunipia F, cation exchange capacity 115 meq / 100 g, manufactured by Kunimine Kogyo Co., Ltd. (hereinafter sometimes abbreviated as “Mt”) was added and mixed uniformly while applying ultrasonic waves.

  To this, 40.02 g of methyl methacrylate for polymer modification was added, and the mixture was uniformly dispersed by applying ultrasonic waves at 60 ° C. for 30 minutes. Next, under stirring at 60 ° C., an initiator aqueous solution in which 0.48 g of potassium peroxodisulfate as a polymerization initiator is dissolved in 100 ml of distilled water is dropped from the dropping device in 2 hours, and the reaction (polymer modification reaction) is performed. went. The reaction time was 12 hours.

  The reaction product was placed in a 2000 ml beaker, 1000 ml of methanol was added, and polymer-modified clay was precipitated. The precipitated polymer-modified clay was suction filtered, washed with 500 ml of methanol, and dried under reduced pressure at 50 ° C. for 48 hours to obtain 30.68 g of polymer-modified clay.

  As a result of thermogravimetric analysis, the mass% of inorganic components in the polymer-modified clay (hereinafter sometimes referred to as “MtEM”) was 16.2. Further, in order to examine how the interlayer distance of the montmorillonite, that is, the spacing between the surfaces of the montmorillonite was changed by this polymer modification, an X-ray diffraction measurement was performed. The results are shown in FIG. The diffraction angle (θ) of unmodified montmorillonite (hereinafter sometimes referred to as “Mt”) was 3.5 °, and the interlayer distance (plane spacing) was 12.6 mm. On the other hand, since no diffraction line is observed in MtEM, it is considered that montmorillonite surface peeling (layer peeling) occurs. In FIG. 1, the sample indicated as PMMA indicates a polymethyl methacrylate homopolymer.

  As a result of Soxhlet extraction test with toluene, the residual extraction rate of MtEM was 94.7%. From this result, it can be seen that the polymer component and the inorganic component in the polymer-modified clay do not exist separately and have some strong interaction.

(Preparation of polymer-modified clay / polyurethane composite (kneading method))
The synthesized polymer-modified clay (MtEM) was kneaded with polyurethane to prepare a polymer-modified clay / polyurethane composite.

A commercially available product (manufactured by BASF Japan, trade name: 1180A50) was used as the polyurethane. First, the polyurethane is kneaded in a roll machine (using a 6-inch two-roll machine) to form a sheet, and then 0.6 g of MtEM is added to 20 g of the polyurethane, and 1 at a roll interval of 1 mm at room temperature. Kneaded for hours. Furthermore, after confirming that it was sufficiently dispersed visually, the polymer-modified clay / polyurethane composite (hereinafter referred to as “MtEM-3p”) was prepared by passing through 10 times with a roll interval of 3 mm. Next, the composite MtEM-3p was molded in a hot plate press machine under the conditions of a temperature of 150 ° C., a pressure of 150 kg / cm ² , and a pressurization time of 30 minutes, and a colorless 2 mm thick sheet (hereinafter, this sheet is referred to as “MtEM”). -3p-S ").

(Characteristics of polymer-modified clay / polyurethane composite)
FIG. 2 shows the results of differential scanning calorimetry (DSC) of MtEM-3p-S obtained as described above. In addition, as a control in FIG. 2 (hereinafter, also referred to as “Comparative Example 1”), the characteristics of only polyurethane (manufactured by BASF Japan: trade name: 1180A50) were shown. FIG. 2 shows that the polyurethane has a soft segment glass transition temperature of −41 ° C. and a hard segment melting temperature of 165.4 ° C. It was also confirmed that there was no change in the transition temperature of both polyurethane segments even after the composite sheet (MtEM-3p-S) was produced. This suggests that even when kneaded with the polymer-modified clay, the polymer-modified clay does not greatly affect both segments of the polyurethane to be kneaded. Furthermore, it indicates that the low temperature characteristics and melting behavior of the composite are not worse than the control.

  Table 1 shows the measurement results of tensile properties of MtEM-3p-S. That is, in Table 1, the elastic modulus at 100% elongation (M100 (MPa), the elastic modulus at 200% elongation (M200 (MPa)), the elastic modulus at 300% elongation (M300 (MPa)), and 400% elongation. The elastic modulus (M400 (MPa)) at break, the elastic modulus at break (TS (MPa)), and the elongation at break (EL (%)) are shown.

  The inorganic component content mass% in the MtEM-3p-S is 3 × 0.162 / 103 × 100 = 0.47. From Table 1, the M100 improvement rate of MtEM-3p-S is (9.41−5.7) /5.7×100=65.1%.

  The above results are compared with the prior art (non-patent document 3) in which the organized clay is directly dispersed in polyurethane. When the improvement rate of the elastic modulus is calculated from the elastic modulus data disclosed in Table 3 on page 3400 of the non-patent document, the inorganic component content mass% is 0. 76, the improvement rate is 21.4%, 2.3 is 64.3%, and 3.8 is 114%.

  On the other hand, in the examples of the present invention, the inorganic component content by mass is 0.47, and the improvement rate of the elastic modulus is 65.1%. Although it is low, it shows a much higher improvement rate, and it can be seen how large the improvement rate is.

  In Example 2 of the prior art (Patent Document 2), data on the tensile modulus of the composite using 1-dodecylammonium modified montmorillonite is disclosed. When 3% by mass of 1-dodecylammonium modified montmorillonite is used, the improvement rate of the tensile modulus is 54.7%, which is worse than the improvement rate in the examples of the present invention.

  As described above, although the composite obtained by the present invention has almost the same thermal properties as the original polyurethane as a dispersion medium, it contains a small amount of an inorganic component, so that its elastic modulus is greatly increased. It became clear that it improved.

  In addition, when montmorillonite modified with a long chain amine as in the prior art is used as clay, the hue of the composite deteriorates and slightly yellows, whereas the composite of the present invention has no hue change and the hue is extremely good Met.

[Example 2]
(Preparation of polymer-modified clay / polyurethane composite)
In Example 1, the synthesized polymer-modified clay (MtEM) was used and kneaded with polyurethane in the same manner to prepare a polymer-modified clay / polyurethane composite.
The same polyurethane as in Example 1 (BASF Japan, trade name: 1180A50) was kneaded with the same roll machine (using a 6-inch two-roll machine) to form a sheet, and then 1. 0 g of MtEM was added, and the mixture was kneaded at room temperature for 1 hour at a roll interval of 1 mm. Furthermore, after confirming that it was sufficiently dispersed by visual observation, the polymer-modified clay / polyurethane composite (hereinafter referred to as “MtEM-5p”) was prepared by passing through 10 times with a roll interval of 3 mm. Next, the composite MtEM-5p was molded with a hot plate press machine under conditions of a temperature of 150 ° C., a pressure of 150 kg / cm ² , and a pressurization time of 30 minutes, and a colorless 2 mm-thick sheet (hereinafter referred to as “MtEM”). -5p-S ").

(Characteristics of polymer-modified clay / polyurethane composite)
FIG. 2 shows the results of differential scanning calorimetry of MtEM-5p-S obtained as described above. It was found that there was no change in the transition temperature of both soft and hard segments even after kneading with polymer-modified clay to form a composite.

Table 1 shows the measurement results of tensile properties of MtEM-5p-S.
That is, in Table 1, the elastic modulus at 100% elongation (M100 (MPa), the elastic modulus at 200% elongation (M200 (MPa)), the elastic modulus at 300% elongation (M300 (MPa)), and 400% elongation. The elastic modulus (M400 (MPa)), elastic modulus at break (TS (MPa)), and elongation at break (EL (%)) are shown.

  The inorganic component content mass% in the MtEM-5p-S is calculated to be 0.77 in the same manner as described above. The M100 improvement rate of MtEM-5p-S is 88.9% similarly from Table 1.

  As mentioned above, the elastic modulus of the composite of the present invention is greatly improved by containing a small amount of an inorganic component even though the thermal property is almost the same as that of the original polyurethane as a dispersion medium. It became clear. In addition, when montmorillonite modified with a long-chain amine as in the prior art is used as clay, the hue of the composite deteriorates slightly, while the composite of the invention has no change in hue and the hue is extremely good. .

Example 3
(Preparation of polymer-modified clay / polyurethane composite)
In Example 1, the synthesized polymer-modified clay (MtEM) was used and kneaded with polyurethane in the same manner to prepare a polymer-modified clay / polyurethane composite.
The same polyurethane as in Example 1 (BASF Japan, trade name: 1180A50) was kneaded in the same roll machine (using a 6-inch two-roll machine), made into a sheet, and then 0. 2 g of MtEM was added and kneaded at room temperature for 1 hour at a roll interval of 1 mm. Furthermore, after confirming that it was sufficiently dispersed by visual observation, the polymer-modified clay / polyurethane composite (hereinafter referred to as “MtEM-1p”) was prepared by passing through 10 times with a roll interval of 3 mm. Next, the composite MtEM-1p was molded on a hot plate press machine under conditions of a temperature of 150 ° C., a pressure of 150 kg / cm ² , and a pressing time of 30 minutes, and a colorless sheet having a thickness of 0.2 mm (hereinafter, this sheet was referred to as “sheet”). "MtEM-1p-S") was obtained.

(Characteristics of polymer-modified clay / polyurethane composite)
FIG. 2 shows the results of differential scanning calorimetry analysis of MtEM-1p-S obtained as described above. It was found that there was no change in the transition temperature of both soft and hard segments even after kneading with polymer-modified clay to form a composite.

  Table 1 shows the measurement results of tensile properties of MtEM-1p-S. That is, in Table 1, the elastic modulus at 100% elongation (M100 (MPa), the elastic modulus at 200% elongation (M200 (MPa)), the elastic modulus at 300% elongation (M300 (MPa)), and 400% elongation. The elastic modulus (M400 (MPa)) at break, the elastic modulus at break (TS (MPa)), and the elongation at break (EL (%)) are shown.

  The inorganic component content mass% in the MtEM-1p-S is calculated to be 0.16 in the same manner as described above. The M100 improvement rate of MtEM-1p-S is 38.1% in the same manner as in Table 1.

  As mentioned above, the elastic modulus of the composite of the present invention is greatly improved by containing a small amount of an inorganic component even though the thermal property is almost the same as that of the original polyurethane as a dispersion medium. It became clear. In addition, when the conventional montmorillonite modified with a long-chain amine is used as the clay, the hue of the composite deteriorates and slightly yellows, whereas the inventive composite has no hue change and the hue is extremely good. It was.

Example 4
(Synthesis of polymer-modified clay)
To a four-necked 1000 ml glass separable reactor equipped with a stirrer, a heating device, a reflux device and a dropping device, montmorillonite (Kunipia F, cation exchange capacity 115 meq / 100 g, manufactured by Kunimine Kogyo Co., Ltd., hereinafter “Mt” 3.60 g of distilled water and 350 ml of distilled water were added, and the mixture was ultrasonically dispersed for 12 hours at 80 ° C. and then cooled to room temperature. The initiator was potassium peroxodioate. 0.35 g was obtained and stirred and mixed at room temperature for 1 hour to uniformly disperse.

To this, 33.20 g of methyl methacrylate and 1.05 g of dimethylaminomethacrylate for forming a modifying polymer were added and reacted at 60 ° C. for 12 hours.
The reaction product was placed in a 2000 ml beaker and 1000 ml of methanol was added to precipitate polymer-modified clay. The precipitated polymer-modified clay was filtered by suction, washed with 500 ml of methanol, and dried under reduced pressure at 70 ° C. for 48 hours to obtain 34.66 g of polymer-modified clay.

  As a result of thermogravimetric analysis, the mass% of inorganic components in the polymer-modified clay (hereinafter sometimes referred to as “MtSF”) was 11.5. Further, in order to examine how the interlayer distance of the montmorillonite, that is, the spacing between the surfaces of the montmorillonite was changed by this polymer modification, an X-ray diffraction measurement was performed. The results are shown in FIG. When montmorillonite is compared with polymer-modified clay MtSF, no diffraction lines are observed in polymer-modified clay MtSF, and it is considered that surface separation of montmorillonite occurs.

  On the other hand, as a result of Soxhlet extraction test with toluene for MtSF, the extraction residual ratio was 95.6%. This result shows that the polymer component and the inorganic component in the polymer-modified clay do not exist separately and have some strong interaction.

(Preparation of polymer-modified clay / polyurethane composite)
The synthesized polymer-modified clay (MtSF) was kneaded with polyurethane to prepare a polymer-modified clay / polyurethane composite.
Similarly, a commercially available product (manufactured by BASF Japan, trade name: 1180A50) was used as the polyurethane. First, the polyurethane was kneaded into a sheet by using a roll machine (using 6 inches of 2 rolls), 0.2 g of MtSF was added to 20 g of the polyurethane, and kneaded at room temperature for 1 hour at a roll interval of 1 mm. . Furthermore, after confirming that it was visually dispersed, the polymer-modified clay / polyurethane composite (hereinafter referred to as “MtSF-1p”) was prepared by passing through 10 times with a roll interval of 3 mm. Next, the composite MtSF-1p was molded with a hot plate press machine under conditions of a temperature of 150 ° C., a pressure of 150 kg / cm ² , and a pressurization time of 30 minutes, and a colorless 2 mm-thick sheet (hereinafter referred to as “MtSF”). -1p-S ").

(Characteristics of polymer-modified clay / polyurethane composite)
FIG. 3 shows the results of differential scanning calorimetry analysis of MtSF-1p-S obtained as described above. Further, as a control (Comparative Example 1) in FIG. 3, only the characteristic of polyurethane (manufactured by BASF Japan, trade name: 1180A50) was shown. FIG. 3 shows that the polyurethane has a glass transition temperature of −41 ° C. in the soft segment and a melting temperature of 165.4 ° C. in the hard segment. It was also confirmed that there was no change in the transition temperature of both segments even after the composite sheet (MtSF-1p-S) was produced. This suggests that the polymer-modified clay does not significantly affect both segments. Furthermore, it shows that the low temperature properties and melting behavior of the composite are not worse than the control.

  Table 1 shows the measurement results of tensile properties of MtSF-1p-S. That is, in Table 1, the elastic modulus at 100% elongation (M100 (MPa), the elastic modulus at 200% elongation (M200 (MPa)), the elastic modulus at 300% elongation (M300 (MPa)), and 400% elongation. The elastic modulus (M400 (MPa)) at break, the elastic modulus at break (TS (MPa)), and the elongation at break (EL (%)) are shown.

  The inorganic component content mass% in the MtSF-1p-S is 1 × 0.115 / 101 × 100 = 0.11. The M100 improvement rate of MtSF-1p-S is (6.82-5.7) /5.7×100=19.6% from Table-1.

  As described above, in the examples of the present invention, the content% of the inorganic component is 0.11 and the improvement rate of the elastic modulus is 19.6%, so the content of the inorganic component is low compared to the prior art. Regardless, it can be seen that it shows a much higher modulus of elasticity improvement. In addition, when montmorillonite modified with a long-chain amine, which is a conventional technique, is used, the hue of the composite is deteriorated and slightly yellowed. However, the composite obtained by the present invention has no change in hue and the hue is extremely good.

Example 5
(Preparation of polymer-modified clay / polyurethane composite)
(1) In Example 4, a polymer-modified clay / polyurethane composite was prepared by kneading with polyurethane in the same manner using the synthesized polymer-modified clay (MtSF).
The same polyurethane as in Example 4 (BASF Japan, trade name: 1180A50) was kneaded with the same roll machine (using a 6-inch two-roll machine) to form a sheet, and then 0. 6 g of MtSF was added and kneaded at room temperature for 1 hour at a roll interval of 1 mm. Furthermore, after confirming that it was sufficiently dispersed by visual observation, the polymer-modified clay / polyurethane composite (hereinafter referred to as “MtSF-3p”) was prepared by passing through 10 times with a roll interval of 3 mm. Next, the composite MtSF-3p was molded by a hot plate press machine under conditions of a temperature of 150 ° C., a pressure of 150 kg / cm ² , and a pressurization time of 30 minutes, and a colorless 2 mm-thick sheet (hereinafter referred to as “MtSF”). -3p-S ").

(Characteristics of polymer-modified clay / polyurethane composite)
FIG. 3 shows the results of differential scanning calorimetry analysis of MtSF-3p-S obtained as described above. Moreover, as a control (Comparative Example 1) in FIG. 3, only the characteristic of polyurethane (manufactured by BASF Japan: trade name: 1180A50) was shown. FIG. 3 shows that the polyurethane has a glass transition temperature of −41 ° C. in the soft segment and a melting temperature of 165.4 ° C. in the hard segment. It was also found that there was no change in the transition temperature of both soft and hard segments even after kneading with polymer-modified clay to produce a composite. This suggests that the polymer-modified clay does not significantly affect both segments. That is, it shows that the low temperature characteristics and melting behavior of the composite are not worse than the control.

Table 1 shows the measurement results of tensile properties of MtSF-3p-S. That is, in Table 1, the elastic modulus at 100% elongation (M100 (MPa), the elastic modulus at 200% elongation (M200 (MPa)), the elastic modulus at 300% elongation (M300 (MPa)), and 400% elongation. The elastic modulus (M400 (MPa)) at break, the elastic modulus at break (TS (MPa)), and the elongation at break (EL (%)) are shown.
The inorganic component content mass% in the MtSF-3p-S is 0.33 in the same manner as described above. The M100 (elastic modulus at 100% elongation) improvement rate of MtSF-3p-S is 29.3% in the same manner as shown in Table 1.

  As described above, the composite of the present invention has an inorganic component content by mass of 0.33 and an elastic modulus improvement rate of 29.3%. Regardless, the rate of improvement is much greater. Further, when montmorillonite modified with a long chain amine is used as in the prior art, the hue of the composite is deteriorated and slightly yellowed. However, the composite of the present invention has no change in hue and the hue is extremely good.

Example 6
(Preparation of polymer-modified clay / polyurethane composite)
(1) In Example 4, a polymer-modified clay / polyurethane composite was prepared by kneading with polyurethane in the same manner using the synthesized polymer-modified clay (MtSF).
The same polyurethane as in Example 4 (BASF Japan, trade name: 1180A50) was kneaded with the same roll machine (using a 6-inch two-roll machine) to form a sheet, and then 1. 0 g of MtSF was added, and the mixture was kneaded at room temperature for 1 hour at a roll interval of 1 mm. Furthermore, after confirming that it was sufficiently dispersed by visual observation, the polymer-modified clay / polyurethane composite (hereinafter referred to as “MtSF-5p”) was prepared by passing through 10 times with a roll interval of 3 mm. Next, the composite MtSF-5p was molded by a hot plate press machine under conditions of a temperature of 150 ° C., a pressure of 150 kg / cm ² , and a pressurization time of 30 minutes, and a colorless 2 mm thick sheet (hereinafter referred to as “MtSF”). -5p-S ").

(Characteristics of polymer-modified clay / polyurethane composite)
FIG. 3 shows the results of differential scanning calorimetry of MtSF-5p-S obtained as described above. Moreover, as a control (Comparative Example 1) in FIG. 3, only the characteristic of polyurethane (manufactured by BASF Japan: trade name: 1180A50) was shown. FIG. 3 shows that the polyurethane has a glass transition temperature of −41 ° C. in the soft segment and a melting temperature of 165.4 ° C. in the hard segment. It was also found that there was no change in the transition temperature of both soft and hard segments even after kneading with polymer-modified clay to produce a composite. This suggests that the polymer-modified clay does not significantly affect both segments. That is, it shows that the low temperature characteristics and melting behavior of the composite are not worse than the control.

Table 1 shows the measurement results of tensile properties of MtSF-5p-S. That is, in Table 1, the elastic modulus at 100% elongation (M100 (MPa), the elastic modulus at 200% elongation (M200 (MPa)), the elastic modulus at 300% elongation (M300 (MPa)), and 400% elongation. The elastic modulus (M400 (MPa)) at break, the elastic modulus at break (TS (MPa)), and the elongation at break (EL (%)) are shown.
The inorganic component content mass% in the MtSF-5p-S is 0.55 in the same manner as described above. The improvement rate of M100 (elastic modulus at 100% elongation) of MtSF-5p-S is 50.44% in the same manner as shown in Table 1.

  As described above, the composite according to the present invention has an inorganic component content by mass of 0.55 and an elastic modulus improvement rate of 50.4%. Regardless, the rate of improvement is much greater. Further, when montmorillonite modified with a long chain amine is used as in the prior art, the hue of the composite is deteriorated and slightly yellowed. However, the composite of the present invention has no change in hue and the hue is extremely good.

Example 7
(Synthesis of polymer-modified porous silica)
4. 43.0 g of methyl methacrylate is taken in a 100 ml beaker, and porous silica (porous silica having a pore diameter of about 1 to 10 nm) (trade name: NPM (Nano Porous Material) -14, manufactured by Taiyo Kagaku Co., Ltd.) is used as the silicon compound. 77 g was added, and ultrasonic waves were applied to uniformly mix and disperse.

  400 ml of 0.5% by mass aqueous sodium lauryl sulfate solution was weighed into a four-necked 1000 ml glass separable reactor equipped with a stirrer, a heating device, a reflux device, and a dropping device, and the porous silica previously prepared The whole amount of methyl methacrylate dispersion was added, and the mixture was uniformly dispersed by applying ultrasonic waves at 60 ° C. for 30 minutes.

  While stirring at 60 ° C., an initiator aqueous solution in which 0.48 g of initiator potassium peroxodisulfate was dissolved in 100 ml of distilled water was dropped from the dropping device over 2 hours to carry out a reaction (polymer modification reaction). The reaction time was 12 hours.

  The reaction product was placed in a 2000 ml beaker and 1000 ml of methanol was added to precipitate polymer-modified porous silica. The precipitated polymer-modified porous silica was suction filtered, washed with 500 ml of methanol, and dried under reduced pressure at 50 ° C. for 48 hours to obtain 30.68 g of polymer-modified porous silica.

  As a result of thermogravimetric analysis, the mass% of silica which is an inorganic component in the polymer-modified porous silica (hereinafter sometimes abbreviated as “NsEM”) was 0.12. Further, as a result of Soxhlet extraction with toluene, the extraction residual ratio was 98.7%.

(Preparation of polymer-modified porous silica / polyurethane composite)
The synthesized polymer-modified porous silica (NsEM) was kneaded with polyurethane to prepare a polymer-modified porous silica / polyurethane composite.
A commercially available product (manufactured by BASF Japan, trade name: 1180A50) was used as the polyurethane. First, the polyurethane was kneaded in a roll machine (using 6 inch two rolls) to form a sheet, then 2 g of NsEM was added to 20 g of the polyurethane, and kneaded at room temperature for 1 hour at a roll interval of 1 mm. Furthermore, after confirming that it was visually dispersed, the polymer-modified porous silica / polyurethane composite (hereinafter sometimes referred to as “NsEM-1p”) was prepared by passing through 10 times with a roll interval of 3 mm. Next, the composite NsEM-1p was molded in a hot plate press machine under the conditions of a temperature of 150 ° C., a pressure of 150 kg / cm ² , and a pressurization time of 30 minutes, and a colorless 2 mm thick sheet (hereinafter referred to as “NsEM”). -1p-S ").

(Characteristics of polymer-modified porous silica / polyurethane composite)
FIG. 4 shows the results of differential scanning calorimetry analysis of NsEM-1p-S. As a control of FIG. 4, the characteristic of only polyurethane (BASF Japan company make: brand name: 1180A50) was shown. FIG. 4 shows that the polyurethane has a glass transition temperature of −41 ° C. in the soft segment and a melting temperature of 165.4 ° C. in the hard segment. Moreover, after producing the composite, the transition temperature of the soft segment changed slightly to the high temperature side, and the melting temperature of the hard segment changed slightly to the low temperature side.

  Table 1 shows the measurement results of tensile properties of NsEM-1p-S. That is, in Table 1, the elastic modulus at 100% elongation (M100 (MPa), the elastic modulus at 200% elongation (M200 (MPa)), the elastic modulus at 300% elongation (M300 (MPa)), and 400% elongation. The elastic modulus (M400 (MPa)), elongation at break (EL (%)), and elastic modulus at break (TS (MPa)) were shown.

  The inorganic component content mass% in the NsEM-1p-S is 0.11. From Table 1, the improvement rate of Ms (elastic modulus at 100% elongation) of NsEM-1p-S is 7.9%. In the composite of the present invention, the inorganic component content mass% is 0.11, and the elastic modulus improvement rate is 7.9%. Therefore, although the inorganic component content is low compared to the prior art, how It can be seen whether the improvement rate of the elastic modulus is large.

Example 8
(Preparation of polymer-modified porous silica / polyurethane composite)
In Example 7, the synthesized polymer-modified porous silica (NsEM) was used and kneaded with polyurethane in the same manner to prepare a polymer-modified porous silica / polyurethane composite.
The same polyurethane as in Example 7 (BASF Japan, trade name: 1180A50) was kneaded in the same roll machine (using a 6-inch two-roll machine), made into a sheet, and then 0.6 g of 20 g of polyurethane. NsEM was added and kneaded at room temperature for 1 hour at a roll interval of 1 mm. Furthermore, after confirming that it was visually dispersed, the polymer-modified porous silica / polyurethane composite (hereinafter referred to as “NsEM-3p”) was prepared by passing through 10 times with a roll interval of 3 mm. Next, the composite NsEM-1p was molded in a hot plate press machine under the conditions of a temperature of 150 ° C., a pressure of 150 kg / cm ² , and a pressurization time of 30 minutes, and a colorless 2 mm thick sheet (hereinafter referred to as “NsEM”). -3p-S ").

(Characteristics of polymer-modified porous silica / polyurethane composite)
FIG. 4 shows the results of differential scanning calorimetry analysis of NsEM-3p-S obtained as described above. As the control of FIG. 4 (Comparative Example 1), only the characteristics of polyurethane (manufactured by BASF Japan, trade name: 1180A50) were shown. FIG. 4 shows that the polyurethane has a glass transition temperature of −41 ° C. in the soft segment and a melting temperature of 165.4 ° C. in the hard segment. In addition, after the composite was formed, the transition temperature of the soft segment changed to the high temperature side, and the melting temperature of the hard segment changed to the low temperature side.

  Table 1 shows the measurement results of tensile properties of NsEM-3p-S. That is, in Table 1, the elastic modulus at 100% elongation (M100 (MPa), the elastic modulus at 200% elongation (M200 (MPa)), the elastic modulus at 300% elongation (M300 (MPa)), and 400% elongation. The elastic modulus (M400 (MPa)), elongation at break (EL (%)), and elastic modulus at break (TS (MPa)) were shown.

  The inorganic component content mass% in the NsEM-3p-S is calculated to be 0.35 in the same manner as described above. From Table 1, the elastic modulus improvement rate of M100 of NsEM-3p-S is 27.9%. In the composite of the present invention, the inorganic component content mass% is 0.35 and the elastic modulus improvement rate is as large as 27.9%. It can be seen whether the elastic modulus improvement rate is large.

Example 9
(Preparation of polymer-modified porous silica / polyurethane composite)
In Example 7, the synthesized polymer-modified porous silica (NsEM) was used and kneaded with polyurethane in the same manner to prepare a polymer-modified porous silica / polyurethane composite.

The same polyurethane as that used in Example 7 (BASF Japan, trade name: 1180A50) was kneaded with the same roll machine (using a 6-inch two-roll machine), made into a sheet, and then 1.0 g of 20 g of polyurethane. NsEM was added and kneaded at room temperature for 1 hour at a roll interval of 1 mm. Furthermore, after confirming that it was visually dispersed, a polymer-modified porous silica / polyurethane composite (hereinafter referred to as “NsEM-5p”) was prepared by passing through 10 times with a roll interval of 3 mm. Next, the composite NsEM-5p was molded on a hot plate press machine under conditions of a temperature of 150 ° C., a pressure of 150 kg / cm ² , and a pressurization time of 30 minutes. "NsEM-5p-S") was obtained.

(Characteristics of polymer-modified porous silica / polyurethane composite)
FIG. 4 shows the results of differential scanning calorimetry analysis of NsEM-5p-S obtained as described above. As the control of FIG. 4 (Comparative Example 1), only the characteristics of polyurethane (manufactured by BASF Japan: trade name: 1180A50) were shown. It can be seen from FIG. 4 that the polyurethane has a glass transition temperature of the soft segment of −41 ° C. and a melting temperature of the hard segment of 165.4 ° C. In addition, after the composite was formed, the transition temperature of the soft segment changed to the high temperature side, and the melting temperature of the hard segment changed to the low temperature side. That is, it can be seen that the movement of the soft segment is somewhat limited, but retains the property of thermoplasticity.

  Table 1 shows the measurement results of tensile properties of NsEM-5p-S. That is, in Table 1, the elastic modulus at 100% elongation (M100 (MPa), the elastic modulus at 200% elongation (M200 (MPa)), the elastic modulus at 300% elongation (M300 (MPa)), and 400% elongation. The elastic modulus (M400 (MPa)), elongation at break (EL (%)), and elastic modulus at break (TS (MPa)) were shown.

  From Table 1, the elastic modulus improvement rate of the NsEM-5p-S at M100 was 44.0%.

  The above result is compared with the result of the prior art (nonpatent literature 2) about the polyurethane containing a silica. The prior art page 599 discloses data on improvement in elastic modulus of polyurethane containing 7% by mass of silica, and the elastic modulus improvement rate at a silica content of 7% by mass is 82.6%. On the other hand, in the composite of the present invention, even when the inorganic component content mass% is only 0.57, the elastic modulus improvement rate is 44.0%. It is understood how the elastic modulus improvement rate is large despite being much lower.

  Note that the polyurethane / silica composite in Non-Patent Document 2 does not have the melting behavior as the composite of the present invention, and is a cross-linked composite, so that the cross-linking effect is considered to contribute to the improvement of the modulus. That is, this type of composite does not have thermoplasticity and lacks recyclability.

  Thus, it can be seen that the effect of improving the elastic modulus of the composite having thermoplasticity of the present invention is much greater than that of the crosslinked type.

  The polymer-modified silicon compound / polyurethane composite of the present invention has a large elastic modulus improving effect despite a slight inorganic component content. Further, when a thermoplastic polyurethane is used as a matrix, the polymer-modified silicon compound / polyurethane composite has excellent thermoplasticity. It has recyclability and has excellent performance from the viewpoint of environmental protection.

  In addition, since the composite is excellent in mechanical properties such as high elastic modulus and high strength and in hue, it can be applied to various fields of structural materials for construction, industrial members, and materials for vehicles. The above applicability is enormous.

1 is an X-ray diffraction diagram of a polymer-modified clay in the present invention. It is a DSC curve of the polymer modified clay compound / polyurethane composite obtained in Examples 1 to 3 of the present invention. It is a DSC curve of the polymer modified clay compound / polyurethane composite obtained in Examples 4 to 6 of the present invention. It is a DSC curve of the polymer modified porous silica compound / polyurethane composite obtained in Examples 7 to 9 of the present invention.

Claims (5)

  A polymer-modified silicon compound / polyurethane composite, characterized in that, in a silicon compound / polyurethane composite in which silicon compound particles are dispersed and composited in polyurethane, the silicon compound particles are polymer-modified particles that have been polymer-modified in advance.   The polymer-modified silicon compound / polyurethane composite according to claim 1, wherein the silicon compound particles are aluminosilicate particles and / or polysilicate particles.   The polymer-modified silicon compound / polyurethane composite according to claim 1 or 2, wherein the silicon compound particles are polymer-modified particles modified with a polymer of an ethylenically unsaturated monomer.   The polymer-modified silicon compound particle according to claim 3, wherein the polymer-modified silicon compound particle is obtained by polymerizing the ethylenically unsaturated monomer in the dispersion medium of the particle in the presence or absence of a dispersant. Compound / polyurethane composite. Ethylenically unsaturated monomers are methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, lauryl methacrylate, glycidyl Acrylate, glycidyl methacrylate, 2-dimethylaminoethyl methacrylate, 2-dimethylaminoethyl acrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-alkyl substituted acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, acrylonitrile, styrene, α-methylstyrene, p-hydroxystyrene, α-butylstyrene, butadiene, isoprene, divinylbenzene, vinyl acetate, ethylene glycol dimethacrylate, diallyl phthalate, ethylene glycol diacrylate, The polymer-modified silicon compound / polyurethane composite according to claim 3 or 4, which is at least one ethylenically unsaturated monomer selected from the group consisting of allyl acrylate and allyl methacrylate.

Images