JP2009084544A - Resin composition and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin containing surface coated oxide particles, allowing improvement in impact resistance, elastic modulus and heat dimensional stability. <P>SOLUTION: It is achieved by a resin composition consisting of: oxide particles; a long chain compound having a plurality of chemical binding capacities for the surfaces of the oxide particles; and the thermoplastic resin. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to resin compositions and methods for producing them.

  Since polymer nanocomposites in which a nano-sized inorganic filler is included in a resin can impart new physical properties to the resin, many techniques have been disclosed from various industrial fields. For example, Toyoda Chuken's “Composite material and its manufacturing method” (Patent Document 1), Ube Industries and other “Polyamide composite material and its manufacturing method” (Patent Document 2), Showa Denko's “Polyolefin composite” Materials and manufacturing methods thereof (Patent Document 3).

  In Patent Document 2 mentioned above, a nylon raw material caprolactam is impregnated between the layers of clay mineral filler montmorillonite and polymerized to obtain a composite of nylon and a filler (montmorillonite). Although this composite is a resin material that is industrially effective due to a sufficient improvement in mechanical properties, there are limitations on the choice of resin and inorganic filler in the disclosed method. The physical properties could not be imparted.

  In recent years, instead of clay mineral fillers, nano-sized inorganic fillers such as oxide particles such as silica, titania and alumina, fine metal particles such as gold and silver, functional nano-materials such as carbon nanotubes, fullerenes and silsesquioxanes Organic materials have become widely used. Since these materials exhibit unique physical and chemical properties that are different from those of the bulk when they are in the nano region, researches are being conducted in various fields to apply these unique properties to materials.

  For example, Ishihara Sangyo Co., Ltd. “Acicular Conductive Titanium Oxide and Method for Producing the Same” (Patent Document 4) coated nano-sized acicular titania with oxides and antimony oxide to increase the conductivity of nanoparticles. An antistatic resin material is provided by preparing a composite material by adding it to vinyl chloride. In addition, although not described in the text, it can be inferred that the use of needle-like particles having a high aspect ratio significantly improves the mechanical properties such as elastic modulus and tensile strength.

  However, these nano-sized inorganic fillers not only give unique properties to the resin, but also cause physical properties to decline unexpectedly. For example, the resin is decomposed by the active chemical species on the particle surface, the molecular weight is lowered, and discoloration occurs, and the value as a resin material is lost, for example, the appearance and impact resistance to be maintained are lost. This problem becomes more apparent as the inorganic filler becomes finer, that is, has a single nano size. That is, as the particle surface area increases and the interface between the resin and the particles increases, the physical properties are also improved, but the decomposition reaction is also activated at the same time, which cancels the expected effect. For this reason, taking into account the trade-off between the balance of physical properties and resin deterioration, the amount of filler added is reduced, a resin that does not cause decomposition is used, or the particle surface is chemically modified. There was a method to prevent the resin and the particle surface from touching directly.

  For example, as an example of modifying the surface of a nano-sized inorganic filler, there is Teijin Ltd. “Coated fibrous aluminum oxide filler and thermoplastic resin composition containing the same” (Patent Document 5). Here, a silane coupling agent is allowed to act on the γ-alumina filler to form a surface-coated filler and a film to which this is added to improve the elastic modulus and softening point temperature without impairing the surface properties. This is because the interaction between the particles and the resin is improved by surface modification. However, this method still leaves a bare surface of the inorganic filler and cannot completely prevent the surrounding resin from being decomposed.

Polyplastics Co., Ltd. “Flame Retardant Resin Composition” (Patent Document 6) mixes a glass fiber coated with a novolac type epoxy resin with a flame retardant and a polyester resin to provide flame retardancy and dripping at high temperatures. Is imparted to the resin composition. The novolac epoxy resin has a hydroxyl group and is difficult to burn, and it exhibits flame retardancy by carbonizing itself, but there is no functional group that interacts with the filler and epoxy resin, and it has further mechanical properties. We cannot expect improvement. Moreover, even if various nanofillers are modified with novolac type epoxy resin by applying the disclosed technology, the modification is removed during kneading because the interaction between the filler and the epoxy resin is poor, and the particle interface is exposed. The resin was decomposed.
Japanese Patent No. 2519045 Japanese Patent Publication No. 7-47644 Japanese Patent Laid-Open No. 10-30039 Japanese Patent Publication No. 6-17231 JP 2004-149687 A International Publication No. 03/046083 Pamphlet

  An object of the present invention is to provide a thermoplastic resin containing surface-coated oxide particles, which can improve impact resistance, elastic modulus, and thermal dimensional stability, and a method for producing the same.

The present inventors have intensively studied to solve the above problems. As a result, the following facts were found. Hereinafter, it demonstrates using drawing. FIG. 3 is an explanatory diagram showing a multipoint adsorption reforming model in a resin composition formed by mixing oxide particles, a long-chain compound, and a thermoplastic resin. Among these, FIG. 3A is a drawing schematically showing a state before a reaction or interaction between a long-chain compound having one adsorption point (functional group: COOH) and oxide particles. FIG. 3B is an explanatory diagram schematically showing a state in which a thermal history is added to a product obtained by reacting or interacting with the long-chain compound and oxide particles in FIG. 3A. FIG. 3C is a drawing schematically showing a state before a reaction or interaction between a long-chain compound having a large number of adsorption points (functional groups) and oxide particles. FIG. 3D is an explanatory view schematically showing a state in which a thermal history is added to a substance in which the long-chain compound and the oxide particles in FIG. 3C are reacted or interacted to be immobilized (multi-point adsorption). . In the following description using the drawings, examples of —COOH are shown as the adsorption points (functional groups) of the compounds 13 and 14 in FIGS. 3A and 3C. Even if the adsorption point (functional group) is —SO ₃ H (sulfo group) or —PO ₃ H ₂ (phosphonic acid group), the basic principle does not change. For reference, FIG. 4 shows an example in which the adsorption point (functional group) is —SO ₃ H (sulfo group). The description of FIGS. 4A to 4D is the same as the description of FIGS. 3A to 3D described above, except that the type of functional group is different, and will not be described. 3B and 3D show an example of Al as the metal element in the oxide particles 11, and the AlOH on the surface of the oxide particles 11 and the COOH (carboxyl group) at the adsorption points of the compounds 13 and 14 react or interact with each other. In this example, an Al—O bond is formed and fixed between Al and COO ⁻ by acting. In this case as well, the basic principle does not change even if the adsorption point (functional group) is —SO ₃ H (sulfo group) or —PO ₃ H ₂ (phosphonic acid group) (for —SO ₃ H, FIG. 4B, See D.). Based on the following multi-point adsorption reforming model, the present inventors have found that there is an optimum amount and a more preferable range for the number of adsorbents and the structure desired for the adsorbent.

  Chemically active hydroxyl groups (—OH) represented by Al—OH and Si—OH are present on the surfaces of oxide particles, for example, alumina particles and silica particles. Therefore, when mixed with a thermoplastic resin, this active group becomes the starting point, attacking the electrically, binding and sterically fragile parts contained in the thermoplastic resin, causing hydrolysis and oxidative degradation, It was found that the resulting thermoplastic resin composition causes problems such as molecular weight reduction and discoloration. To solve these problems, as shown in FIGS. 3A and 3B and FIGS. 4A and 4B, a compound 14 having one adsorption point (functional group) that reacts or interacts with the hydroxyl group (—OH) on the surface of the oxide particle 11 is prepared. It may be fixed by a chemical reaction. Thereby, by making the oxide particle 11 surface into an oxide particle modified with the compound 14, the interface between the particle 11 and the thermoplastic resin 15 can be reduced, and the active group becomes a base point and the thermoplastic resin 15 is used as a base point. It was expected to be able to prevent attack. However, it was found that the compound 14 is easily detached from the surface of the particles 11 with respect to the thermal history received during molding when the resin composition is kneaded. In other words, the bond breaking image between the surface of the particle 11 and the compound 14 due to thermal motion is represented by reference numeral 17, but if the compound 14 having one adsorption point is fixed by reaction or interaction in this way, it is detached due to thermal motion. It was easy to construct and was found to be extremely unstable. Therefore, if a fragile portion of the thermoplastic resin 15 comes to the AlOH (active group) on the surface of the oxide particles 11 from which the compound 14 is removed, this active group becomes a base point, and decomposition is promoted as in the conventional case. It will cause molecular weight. As a result, it was found that problems such as molecular weight reduction and discoloration of the obtained thermoplastic resin composition could not be sufficiently solved.

  From this point of view, the present inventors have made many adsorption points (functional groups) that react or interact with the hydroxyl groups on the surface of the oxide particles 11 in order to deactivate (seal) the hydroxyl groups that cause the above problems. The compound 13 having a group) is fixed by a chemical reaction (see FIGS. 3C and D and FIGS. 4C and D). That is, the hydroxyl groups (active sites) that cause the above problems are efficiently sealed with a large number (the number of adsorption points of the compound 13). As a result, the (inorganic) oxide is formed by thickly covering the surface of the particle 11 with the compound 13 by multipoint adsorption (fixation) to the many active sites on the surface of the particle 11 by the adsorption point of the compound 13. The surface of the particle 11 can be an (inorganic) oxide particle modified with the compound 13. As a result, the interface between the particles 11 and the thermoplastic resin 15 can be remarkably reduced, and the active group can be prevented from attacking the thermoplastic resin 15 as a base point. In addition, even when the resin composition is kneaded, the heat history received during molding exhibits a stable adsorbing force without detaching from the surface of the particles 11 and solves various problems such as molecular weight reduction and discoloration of the molded product. It is what. That is, as shown in FIG. 3B and FIG. 4B by the reference numeral 17, the image of the bond between the surface of the particle 11 and the compound 13 due to thermal motion is represented by reference numeral 17, so that the compound 13 having a large number of adsorption points is adsorbed by reaction or interaction. By doing so, even if a part is removed due to thermal motion, the rest is adsorbed. Therefore, it is a structure that is extremely difficult to come off when viewed as a whole of the compound 13, and as a whole, can be stably adsorbed, which is extremely advantageous for stable dispersion of the particles 11. Further, even if a part of the adsorption point is removed due to thermal motion (see bond cutting image 17), the remaining many adsorption points can secure a structure in which the compound 13 is thickly coated. Since 15 does not approach the active point, it is extremely effective for maintaining the molecular weight of the resin 15. Further, by maintaining the molecular weight in this way, the original properties of the thermoplastic resin 15 remain, and as a result, the elongation of the resin composition can be improved and excellent toughness can be ensured, and the impact resistance can be improved. Is. Furthermore, it can also contribute to ensuring the transparency of the resin composition obtained (see FIGS. 2a to 2f for comparison). Moreover, the refractive index matching effect of the resin composition obtained can also be show | played.

  Furthermore, by making the compound 13 having a large number of adsorption points into a copolymer-type long-chain compound, it is possible to adjust the molecular weight of the compound and the ratio of the adsorption points contained in the molecule. The surface of the oxide particles 11 can be covered with the compound (long-chain compound) 13. In addition, the long-chain compound binds adjacent particles and blends them into the thermoplastic resin, so that a three-dimensional network can be built up among the particles in the thermoplastic resin.

In FIG. 3, the adsorption point (functional group) is represented by a —COOH group, but even if it is —SO ₃ H (sulfo group) or —PO ₃ H ₂ (phosphonic acid group), the basic principle described here is used. does not change (with respect to the -SO ₃ H, see Figure 4.).

  The resin composition thus obtained has excellent impact resistance, elastic modulus, and thermal dimensional stability.

  Therefore, the object of the present invention is achieved by a resin composition comprising oxide particles, a long-chain compound having a plurality of chemical bonding ability with respect to the surface of the oxide particles, and a thermoplastic resin. can do.

  According to the present invention, hydrolysis or oxidation is performed by sealing the hydroxyl groups on the surface of the oxide particles at a number of adsorption points and blending the oxide particles modified with a compound having the effect of binding the particles into the thermoplastic resin. A thermoplastic resin composition having further high mechanical properties can be obtained without causing deterioration.

  Hereinafter, other features and advantages of the present invention will be described in detail based on the best mode for carrying out the invention.

<Oxide particles>
The oxide particles of the present invention are not limited as long as chemically active groups (such as hydroxyl groups) are present on the surface of the oxide particles, but are preferably alumina (aluminum oxide). ) Or silica (silicon oxide). Among them, alumina particles that are easy to obtain fine and high aspect ratio particles are preferable from the viewpoint of mechanical properties, and among them, the production method is easy, and the trihydrate type (Al ₂ O) from the viewpoint of market availability and low cost. ₍₃ · 3H ₂ O) boehmite, γ alumina, and α alumina are preferred. Alumina includes not only alumina having different crystal compositions (α, γ, χ, η, δ, θ, κ) but also hydrate type (Al ₂ O ₃ .nH ₂ O).

  The shape of the oxide particles may be any of a fiber shape, a spindle shape, a rod shape, a needle shape, a column shape, a plate shape, a spherical shape, and the like. However, amorphous particles, for example, particles containing a large amount of hydroxide as a particle precursor contain a large amount of water and cause deterioration of the long-chain compound, which is not suitable.

  Moreover, since it is more advantageous for the particle diameter and length of the oxide particles to use the nano-sized high aspect ratio particles for the mechanical properties of the resin composition, the particle diameter is 1 nm to 20 nm, and the length is 50 nm to 1000 nm. When the fiber shape is good and used as a reinforcing agent for a transparent resin material, the particle diameter is preferably 10 nm or less and the length is 100 nm to 400 nm in consideration of light scattering of particles in the resin. The aspect ratio of the oxide particles is preferably in the range of 10 to 100, more preferably 30 to 70, since the use of high aspect ratio particles is advantageous for the mechanical properties of the resin composition. For example, the flexural modulus, which is one of the mechanical properties, remarkably improves with the aspect ratio, but the improvement margin becomes small when the aspect ratio exceeds 50.

  Here, the particle diameter, length, and aspect ratio (length / particle diameter) of the oxide particles were all observed, measured, and calculated with a transmission electron microscope (TEM).

(Particle shape)
A sample of water-dispersed oxide particles (for example, water-dispersed boehmite) was diluted with pure water of two-stage distilled water and then washed with an ultrasonic cleaner for 15 minutes. Next, after applying the sample to a hydrophilically treated carbon-coated collodion film copper mesh for transmission electron microscope measurement, it was naturally dried to prepare an observation sample. An electron microscope image of the sample was taken and observed with a transmission electron microscope at 120 kV, 70 mA, 100,000 times.

-Copper mesh for transmission electron microscope (TEM): Micro Grit 150-B mesh, carbon reinforced (manufactured by Oken Shoji Co., Ltd.)
Transmission electron microscope: JEOLJEM-1200EXII (manufactured by JEOL Ltd.)
(Particle diameter, length)
A photograph taken with a transmission electron microscope was captured as electronic data with a commercially available scanner, and the particle length was measured with commercially available software. Specifically, randomly selected 100 individuals, the long axis in the minor axis diameter thickest visible portion (see L ₂ in FIG. 1) of the particles in the image, the longest visible portion (see L ₁ in FIG. 1) The aspect ratio was calculated by measuring the diameter.

Measurement software: Scion Image for Windows (Scion corp.)
Incidentally, as shown in FIG. 1, the length of the oxide particles 11 is determined as oxides long axis length of the particles (major axis diameter) L _1. Particle diameter of the oxide particles 11 (= minor axis length) is obtained as _{L 2.} The aspect ratio is determined as the ratio of the length to the particle diameter of the oxide particles _(L 1 _/ L _2). Even when the oxide particles have a hollow shape or a sea-island shape, the particle diameter, length, and aspect ratio of the oxide particles can be obtained in the same manner as the solid particles in FIG.

<Long-chain compound>
The long-chain compound that can be used in the present invention is a functional group that reacts or interacts with a chemically active group (hydroxyl group) on the surface of the oxide particle (partial structure having a chemical bonding ability to the surface of the oxide particle). ) In a large amount. The long chain compound is a copolymer having a number average molecular weight of 30,000 or less, and a copolymer having a repeating unit of a monomer having a functional group that reacts or interacts with a hydroxyl group on the surface of the oxide particle. According to these long chain compounds, the active hydroxyl groups on the surface of the oxide particles described above can be efficiently deactivated.

  The content of the long-chain compound with respect to the oxide particles is 3 to 50 parts by weight with respect to 100 parts by weight of the oxide particles depending on the number of hydroxyl groups on the surface of the oxide particles and the number of functional groups of the long-chain compound. However, when the content of the oxide particles relative to the thermoplastic resin is low, for example, when the oxide particles are contained in a proportion of 20 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin, the content of the long-chain compound is reduced to the oxide. It is preferable to set it as 3-15 weight part with respect to 100 weight part of particle | grains. If the content of the oxide particles is small and the amount of the long-chain compound is large, the oxide particles are not uniformly dispersed in the thermoplastic resin, and are unevenly distributed or aggregates are formed. The physical properties are reduced. On the other hand, when it contains oxide particles exceeding 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin, it may contain a long chain compound of more than 15 parts by weight to 50 parts by weight. When the oxide particles exceeding 20 parts by weight are present in the thermoplastic resin, the distance between the particles becomes narrower as the particle diameter approaches the particle size or less, so that a long-chain compound is sandwiched between binders, and adhesion between the particles is reduced. At the same time, the network of particles can be made dense by actively increasing the long-chain compounds. Linking particles with a long-chain compound is the same as that of the Thai molecule.

  The functional group in the long-chain compound preferably has any one of an oxygen atom, a nitrogen atom, a phosphorus atom and a sulfur atom in its molecular structure. Specific chemical structure examples include chemical structures having only a single bond with a carbon atom such as an ether bond or a tertiary amino group, a ketone group, an aldehyde group, a carboxyl group or an ester group thereof, a carbonate bond, a urethane bond, and an amide bond. Chemical structure having a carbonyl group such as, aromatic ring (pyridine, pyrrole) group containing hetero atom, sulfo group (sulfonic acid group) or its ester group, phosphonic acid group or its ester group, phosphinic acid group or its ester group Etc. Among the above, carboxyl group-containing compounds and derivatives thereof, such as acrylic acid and methacrylic acid, which are reactive with a hydroxyl group on the surface of the oxide particles and have radical polymerization properties, and vinyl sulfone. It is preferably derived from a readily available sulfo group (sulfonic acid group) -containing compound such as an acid and derivatives thereof, or an easily available phosphonic acid group-containing compound such as vinylphosphonic acid and derivatives thereof. The derivatives here are basically those in which the acidic H atoms of these organic acids are retained.

  The long-chain compound has a monomer having an unsaturated bond having a functional group that reacts or interacts with a hydroxyl group on the oxide particle surface, and a functional group that reacts or interacts with a hydroxyl group on the oxide particle surface. Copolymer (copolymer) composed of monomers having no unsaturated bond, random, alternating, periodic, block (including graft) with repeating units (monomer units; structural units) derived from each monomer A copolymer having such a structure is desirable. In such a long-chain compound, the modification rate of the oxide particle surface may be controlled by an arbitrary blending amount of each monomer (= changing the proportion of structural units derived from each monomer). For example, an unsaturated bond having a monomer unit (structural unit) represented by the following formulas (1) and (2) and having a functional group that reacts or interacts with a hydroxyl group on the surface of the oxide particle. 40 to 98 mol%, preferably 50 to 95 mol%, more preferably 60 to 85 mol%, and more preferably 60 to 85 mol% of the monomer unit (structural unit) of the formula (1), which is a structural unit derived from a monomer having The monomer unit (structural unit) of the formula (2), which is a structural unit derived from a monomer having an unsaturated bond having a functional group that reacts or interacts with a hydroxyl group, is 2 to 60 mol%, preferably 5 to 50 mol%. A radical polymerization type copolymer which is preferably 15 to 40 mol% can be mentioned. The composition ratio (mol%) of the monomer unit of the formula (2) containing a functional group selected from a carboxyl group, a sulfo group, or a phosphonic acid group (also simply referred to as “organic acid group”) is the total monomer unit in the copolymer. If the amount is less than 2 mol%, the adsorptive power on the particle surface becomes insufficient, and if it exceeds 60 mol%, the particles are aggregated. In addition, the said copolymer may be comprised from 3 or more types of monomer units. In that case, when a plurality of components represented by the formula (1) are used, the total mol% may be 40 to 98 mol%, and a plurality of components represented by the formula (2) are used. In this case, the total mol% may be 2 to 60 mol%.

The above formula (1) may be a unit that is generated as a result of polymerization of the radical polymerizable monomer, and R _{1 to} R ₄ in the above formula (1) are not particularly limited. Preferably, in the formula (1), R _{1 to} R ₄ may be the same or different from each other, and may be a hydrogen atom or a straight chain having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. A branched alkyl group, an aromatic ring group, a carboxylate group (—COOR ₉ ; where R ₉ is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, an aromatic ring. Group), a halogen atom (for example, a chlorine atom, a fluorine atom, a bromo atom, an iodine atom, etc.), an amide group (—CON (R ₁₀ ) R ₁₁ group; where R ₁₀ and R ₁₁ are the same. Or a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, an aromatic ring group), a nitrile group (-CN group), 1 Valent unsaturated (chain) hydrocarbon groups (eg vinyl (-CH = _CH 2), an allyl group _{(-CH 2} CH = CH 2), etc.).

R _{5 to} R ₈ in the above formula (2) may be the same or different from each other, and are a hydrogen atom or a linear or branched group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. An alkyl group or an aromatic ring group, but one or more of R _{5 to} R ₈ are a carboxyl group (—COOH group) or a C 1-8 aliphatic or aromatic hydrocarbon containing a carboxyl group Group, a sulfo group (—SO ₃ H group) or a C 1-8 aliphatic or aromatic hydrocarbon group containing a sulfo group, or a phosphonic acid group (—PO ₃ H ₂ group) or a phosphonic acid group It is a C1-C8 aliphatic or aromatic hydrocarbon group. Here, examples of the aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms including a carboxyl group include a carboxyalkyl group (e.g., a carboxymethyl group, a carboxyethyl group, a carboxypropyl group) and a carboxyphenyl group. -R ₁₂ COOH (wherein R ₁₂ is an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms). Examples of the aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms including a sulfo group include —R ₁₃ such as a sulfoalkyl group (for example, a sulfomethyl group, a sulfoethyl group, a sulfopropyl group, etc.) and a benzenesulfonic acid group. And a group represented by SO ₃ H (where R ₁₃ is an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms). Examples of the aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms including a phosphonic acid group include, for example, alkylphosphonic acid groups (for example, methylphosphonic acid group, ethylphosphonic acid group, propylphosphonic acid group, etc.) and phenylphosphonic acid groups And groups represented by —R ₁₄ PO ₃ H ₂ (wherein R ₁₄ is an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms) such as a group or a benzylphosphonic acid group.

As an example, when R ₅ = R ₆ = R ₇ = H and R ₈ = COOH, the above formula (2) is consistent with a polymerized unit of acrylic acid. In the case of R ₅ = R ₆ = R ₇ = H and R ₈ = SO ₃ H, the above formula (2) is consistent with the polymerized unit of vinyl sulfonic acid. In the case of R ₅ = R ₆ = R ₇ = H and R ₈ = PO ₃ H ₂ , the above formula (2) is consistent with the polymerized unit of vinylphosphonic acid.

Furthermore, the long-chain compound preferably has a functional group (organic acid group) selected from a carboxyl group, a sulfo group, or a phosphonic acid group, and an organic acid ester group. In particular, the long-chain compound preferably has an organic acid monomer unit having a functional group selected from a carboxyl group, a sulfo group, or a phosphonic acid group, and a monomer unit having an organic acid ester group. The long-chain compound is a copolymer that can be obtained by radical polymerization, and the organic acid group or organic acid monomer unit is derived from a radical polymerizable organic acid, and has the organic acid ester group or organic acid ester group. The monomer unit is preferably derived from a radical polymerizable organic acid ester. Specifically, the long-chain compound is a copolymer obtainable by radical polymerization, and the organic acid group or the organic acid monomer unit is derived from a radical polymerizable carboxylic acid or a radical polymerizable sulfonic acid or a radical polymerizable. A monomer unit derived from phosphonic acid and having the organic acid ester group or organic acid ester group is derived from a radical polymerizable carboxylic acid ester, a radical polymerizable sulfonic acid ester or a radical polymerizable phosphonic acid ester. desirable. From this viewpoint, at least one of R _{1 to} R _{4 in} the above formula (1) has a carboxylic acid ester group, and at least one of R _{5 to} R _{8 in} the above formula (2) is a carboxylic group or a carboxyl group. It is more desirable to have a C1-C8 aliphatic or aromatic hydrocarbon group containing. Similarly, at least one of R _{1 to} R _{4 in} the formula (1) has a sulfonate group, and one or more of R _{5 to} R _{8 in} the formula (2) contains a sulfo group. It is more desirable to have 1-8 aliphatic or aromatic hydrocarbon groups. Further, at least one of R _{1 to} R _{4 in} the formula (1) has a phosphonic acid ester group, and one or more of R _{5 to} R _{8 in} the formula (2) has a phosphonic acid group. It is more desirable to have 1-8 aliphatic or aromatic hydrocarbon groups.

Examples of the raw material monomer that gives the unit represented by the above formula (1) include ethylene, propylene, styrene, methyl methacrylate, methyl acrylate, ethyl methacrylate, phenyl methacrylate, dimethyl maleate, dimethyl vinyl phosphonate, and vinyl phosphonic acid. Radical polymerizable compounds having a C = C bond such as diethyl, methyl vinylphosphinate, ethyl vinylphosphinate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, acrylamide, acrylonitrile, butadiene, isoprene, and derivatives thereof Is mentioned. Among these, carboxylic acid ester groups such as methyl methacrylate, methyl acrylate, ethyl methacrylate, and phenyl methacrylate (—COOR ₉ ; where R ₉ has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. A linear or branched alkyl group or an aromatic ring group) is preferable, and the effect is extremely high. The reason is not completely elucidated, but the M—OH group on the surface of the metal oxide particle due to the C═O bond in the carboxylic acid ester (where M is the metal element Al, Si, etc. in the metal oxide particle) (See the explanatory diagram of multi-point attachment reformation in FIGS. 3C and 3D.) In addition, even if it contains a sulfonate ester group or a phosphonate ester group, the interaction with the M-OH group on the surface of the metal oxide particle is caused by the S═O bond or the P═O bond in these organic acid esters. (See FIGS. 4C and 4D.) Therefore, it is considered that even those containing these organic acid ester groups can achieve a high effect.

  As a raw material monomer that gives a unit represented by the above formula (2), a carboxylic acid containing a carboxyl group (including a carboxyl group-containing compound and its derivative, a radical polymerizable carboxylic acid), acrylic acid, methacrylic acid, vinyl acetic acid, Monovalent unsaturated carboxylic acids such as crotonic acid, 4-pentenoic acid, 2-hexenoic acid, 3-hexenoic acid, 5-hexenoic acid, 2-octenoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, maleic acid And diunsaturated carboxylic acids such as fumaric acid, and unsaturated acid anhydrides capable of generating COOH by hydrolysis of maleic anhydride and 4-pentenoic anhydride can also be used. Among these, acrylic acid and methacrylic acid are particularly preferable from the viewpoint of polymerization reactivity.

  Among the raw material monomers that give the unit represented by the above formula (2), sulfonic acids containing sulfo groups (including sulfo group-containing compounds and derivatives thereof and radical polymerizable sulfonic acids) include vinyl sulfonic acid, allyl sulfone. Examples include sodium acid, sodium styrenesulfonate, and sulfoethyl methacrylate. Among these, vinylsulfonic acid is particularly preferable from the viewpoints of polymerization reactivity and ease of neutralization reaction operation.

  Among the raw material monomers giving the unit represented by the above formula (2), phosphonic acids containing phosphonic acid groups (including phosphonic acid group-containing compounds and derivatives thereof, radically polymerizable phosphonic acids) include vinylphosphonic acid and Examples thereof include monoesters, diesters, sodium salts, allylphosphonic acid, methallylphosphonic acid, esters thereof, and sodium salts. Among these, vinylphosphonic acid is particularly preferable from the viewpoint of polymerization reactivity, ease of hydrolysis and neutralization reaction operation.

  The molecular weight of the copolymer is not particularly limited, but is preferably a number average molecular weight of 30,000 or less, more preferably 500 to 20,000. The lower limit of the number average molecular weight is not particularly limited, but if it is less than 500, the adsorption point on the particle surface per molecule is insufficient, and there is a possibility that the merit as a long chain compound cannot be obtained. Conversely, if the number average molecular weight exceeds 30,000, the movement of the molecules is restricted, and the particles do not spread sufficiently on the surface of the particles, resulting in uneven modification, or because the molecules are long, other particles are involved and agglomerate. This causes disadvantages due to the poor solubility in the solvent used during the production, as well as the phenomenon that occurs. In addition, the compatibility in the thermoplastic resin is also lowered, which hinders uniform dispersibility, mechanical properties as a resin composition, and transparency.

  In the synthesis of the copolymer, a random copolymer can be easily synthesized by performing general radical polymerization. In this case, a plurality of types of monomers including both of the formulas (1) and (2) listed above are introduced into an organic solvent at a desired ratio, together with a radical initiator such as azobisisobutyronitrile. By heating and stirring, the copolymerization proceeds to obtain the desired copolymer. The obtained copolymer may be used as a solution as it is, and when used as a solid, it may be reprecipitated in a poor solvent such as hexane, filtered and dried.

  Furthermore, when synthesizing a block copolymer, RAFT (Reversible Addition Fragmentation chain Transfer; reversible addition fragmentation chain transfer, also known as MADIIX (Macromolecular), which has an active C = S bond, such as S-methoxycarbonylphenylmethyldithiobenzoate. If a living radical polymerization using a Design via the Interchange of Xanthates) catalyst is applied, block copolymers such as AB type, ABC type, and ABA type can be obtained relatively easily. For the RAFT catalyst, see J.A. Polymer Sci. Part A: Polymer Chemistry Vol. 43, 5347-5393 (2005).

<Method for introducing long-chain compound into oxide particles>
As a method for introducing a long-chain compound into oxide particles (a method for producing modified inorganic particles), there are the following methods.

(A) Method of mixing dry blend or solid powder state oxide particles and long chain compound (B) Method of mixing long chain compound into oxide particles dispersed in solvent (water or organic solvent) A method (first production method of modified inorganic particles) will be described. The method (A) is a method in which a long-chain compound diluted with powdered oxide particles and powder, or a solvent (water or organic solvent) is mixed, and a hydroxyl group on the surface of the oxide particles is modified with a long-chain compound. . As a mixing method, a method of stirring at high speed while heating using a Henschel mixer is preferable. This is because surface modification and removal of moisture contained in the oxide particles can be performed simultaneously.

  In the case of powder (oxide particles) and powder (long-chain compounds), for example, the oxide particles and long-chain compounds are placed in a Henschel mixer, and the temperature is 100 to 200 ° C. (up to the apparatus limit). In the case of an aqueous dispersion (oxide particles) and a long-chain compound, stirring is performed at 90 ° C., for example. Thereafter, a temperature equal to or higher than the boiling point of water is applied, water is distilled off to form powder, and the powder is heated in a temperature range of 100 ° C. to 200 ° C. to obtain surface-modified oxide particle powder. In the case of organic solvent dispersion (oxide particles) and a long-chain compound, for example, stirring is performed at a temperature 10 ° C. lower than the boiling point of the solvent. Thereafter, a temperature equal to or higher than the boiling point of the organic solvent is applied, the solvent is distilled off to form powder, and the powder is heated in a temperature range of 100 ° C. to 200 ° C. to obtain a surface-modified oxide particle powder.

  Next, the method (B) (second production method of modified inorganic particles) will be described. The method (B) is a method in which the long-chain compound is introduced after the oxide particles are dispersed in a solvent (in water or a predetermined organic solvent) or during the dispersion.

  When the long-chain compound is introduced, it is added directly to the oxide particles dispersed in water or an organic solvent, or added during the exchange of the solvent from the aqueous dispersion to the organic solvent. At this time, an appropriate amount of a dispersant may be used in addition to the long-chain compound in order to assist dispersion in the organic solvent.

  The dispersant other than the long chain compound is not particularly limited as long as it does not impair the effects of the present invention, and any dispersant can be used. For example, organic compounds represented by organic acids and organic acid esters, for example, organic group-substituted derivatives of sulfonic acid, carboxylic acid, and phosphoric acid. More specifically, sulfonic acid series: alkyl sulfonic acids such as methane sulfonic acid and ethane sulfonic acid, aromatic sulfonic acids such as benzene sulfonic acid, p-toluene sulfonic acid, styrene sulfonic acid and alkyl benzene sulfonic acid, and lower alcohols thereof. Esters, alkali metal salts, ammonium salts, carboxylic acids: acetic acid, propionic acid, butyric acid, valeric acid, stearic acid, linoleic acid, lactic acid, malonic acid, adipic acid, maleic acid, fumaric acid, acrylic acid and other alkyls Carboxylic acid, benzoic acid, phthalic acid isomers, aromatic carboxylic acids such as salicylic acid, and esters with these lower alcohols, alkali metal salts, ammonium salts, phosphoric acid derivative systems: tributyl phosphate, diethyl phosphate, methyl phosphate, etc. Monophosphate / / Phosphoric acid esters such as trialkyl esters and triphenyl phosphate, Phosphonic acid esters such as dimethylphenyl phosphonite, Phosphites such as tributyl phosphite and triphenyl phosphonite, Phosphine oxides such as triphenyl phosphine oxide Cyclic phosphites such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphonic acids such as methyl phosphonic acid, ethyl phosphonic acid and phenyl phosphonic acid, methyl phosphinic acid Phosphinic acids such as ethylphosphinic acid, phenylphosphinic acid and diphenylphosphinic acid, and esters with these lower alcohols, alkali metal salts, ammonium salts, and the like.

  The content of the dispersant other than the long-chain compound is not particularly limited as long as it does not impair the effects of the present invention, and is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the oxide particles. Preferably it is the range of 1-20 mass parts.

  Here, by introducing the long chain compound on the surface of the oxide particle by the above methods (A) to (B) (= reacted with the hydroxyl group on the surface of the oxide particle and the functional group of the long chain compound) ) Is also simply referred to as modified inorganic particles. The resin composition of the present invention is characterized by comprising oxide particles, a long-chain compound having a plurality of chemical bonding capacities with respect to the surface of the oxide particles, and a thermoplastic resin. Such oxide particles and long-chain compounds may be present in the form of the modified inorganic particles described above. Further, the modified inorganic particles may exist in a form in which a three-dimensional network is constructed through a long-chain compound in which oxide particles are introduced (chemically bonded) as described above.

  In addition, as an organic solvent used in the method of said (A) thru | or (B), arbitrary things can be used. Preferably, in the subsequent production process of the resin composition, the component (such as the thermoplastic resin) in the dissolved resin composition and the modified inorganic particles that can be at least partially mixed with the thermoplastic resin to be produced. What can be mixed uniformly can be used. Specifically, cyclic ethers such as tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, alkyl halides such as dichloromethane, 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane, etc. And aromatic hydrocarbons such as toluene, xylene, chlorobenzene and dichlorobenzene, and ketones such as methyl ethyl ketone, cyclohexanone, acetone, cyclopentanone and cyclohexanone. These organic solvents may be used alone or in a mixture. Particularly preferred are tetrahydrofuran, chloroform and cyclohexanone.

<Thermoplastic resin>
The thermoplastic resin is selected from any thermoplastic polymer, but the repeating unit of the chemical structure of the thermoplastic resin is an ester bond, an ether bond, an amide bond, an imide bond, a urethane bond, a sulfide bond, or a sulfone bond. Those containing at least one selected from the group consisting of:

  Examples of the thermoplastic resin include polycarbonate resins (PC), acrylic resins such as polymethyl methacrylate (PMMA) and polymethyl acrylate (PMA), polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), Polyarylate (PAR), polyphenylene ether (PPE), polysulfone (PSU), polyethersulfone (PES), polyetheretherketone (PEEK), phenoxy resin, polyamide resin (nylon resin), polyimide resin, urethane resin, polyacetal However, it is not limited to these. These thermoplastic resins may be used alone or in a mixture.

  In addition, the density | concentration of the modified | denatured inorganic particle in the resin composition in this invention is 1-70 mass% as solid content, Preferably it is 1-50 mass%, More preferably, it is the range of 1-30 mass%. When the concentration of the modified inorganic particles is less than 1% by mass, it is difficult to recognize improvement in various properties such as mechanical strength. If it exceeds 70% by mass, an increase in specific gravity cannot be ignored, and at the same time, brittleness cannot be ignored.

<Method for producing thermoplastic resin composition>
The (thermoplastic) resin composition of the present invention is produced from the above-mentioned thermoplastic resin and modified inorganic particles, and the specific production method can be carried out according to the following steps.

  The first production method is a direct kneading method. This method is the simplest method, and the modified inorganic particles obtained in the method (1) for introducing the long-chain compound into the oxide particles and the thermoplastic resin described above are directly kneaded, preferably melt-kneaded, The objective thermoplastic resin composition is obtained. In the above kneading, a general resin kneader may be used. For example, from a small machine such as a twin screw extruder, a vacuum microkneading extruder, a lab plast mill, to a large machine is selected according to the production scale. .

  In addition, the water obtained in the method (2) for introducing the long-chain compound into the oxide particles or the modified inorganic particles dispersed in the organic solvent is directly kneaded, preferably melt-kneaded with the thermoplastic resin described above. A thermoplastic resin composition may be obtained. In this method, it is necessary to provide a vent or the like with a decompression device for removing water and organic solvents.

  The temperature at the time of melt kneading may be equal to or higher than the melting temperature of the thermoplastic resin to be used, but from the viewpoint of the viscosity of the resin at the time of kneading (fluidity) and the thermal degradation (thermal stress) of the thermoplastic resin, The temperature is preferably 10 to 100 ° C., more preferably 10 to 50 ° C. higher than the melting temperature.

  After kneading to obtain a resin composition, the resin composition may be extruded as it is and shaped into a desired shape, or may be once stored as pellets of the resin composition.

  As a second production method, production can be performed using a so-called solvent dispersion method. In this method, the thermoplastic resin described above is dissolved and dispersed in the solution in which the modified inorganic particles are dispersed obtained in the method (2) for introducing the long-chain compound into the oxide particles, and after sufficiently stirring and mixing, In this method, the solvent is distilled off to obtain a desired thermoplastic composition.

  As the organic solvent used in the present method, the organic solvent exemplified above, which is used when the long-chain compound described above is introduced into the oxide particles, is used. In particular, when polycarbonate is used as the thermoplastic resin, tetrahydrofuran, chloroform, 1,2-dichloromethane, 1,4-dioxane, cyclohexanone, cyclopentanone, tetrachloroethane, chlorobenzene, o-dichlorobenzene, and the like are preferably used. it can.

  The method for distilling off the solvent is not particularly limited, but from the viewpoint of solvent reuse, it is desirable to distill off only the solvent under high temperature and reduced pressure using a distillation apparatus with a cooling trap or the like. .

  Here, as a temperature condition at the time of solvent distillation, it is preferable to make it 100-200 degreeC under pressure reduction after solvent removal. This is because removal of water adsorbed on the particles requires 100 ° C. or higher regardless of the degree of vacuum. The pressure is about 100 hPa or less.

  As a third production method, it can be produced using a so-called melt polymerization method. In this case, the modified inorganic particles obtained in the method (1) or (2) for introducing the long-chain compound into the oxide particles as described above (= first or second production method of modified inorganic particles) were dispersed. In the solution, a condensable monomer constituting the thermoplastic resin is mixed and mixed to prepare a reaction solution. This reaction solution is heated with stirring under reduced pressure, for example, and the condensation polymerization of the monomer is performed while distilling off the solvent. The desired thermoplastic resin composition is obtained by proceeding and removing the resulting condensation by-product.

  For example, when polycarbonate is used as a thermoplastic resin, a monomer diaryl carbonate compound and a bisphenol compound are mixed and mixed in a solution in which modified inorganic particles are dispersed in an organic solvent, and preheating is performed at about 160 ° C. for about 20 minutes. The condensation reaction of the carbonate compound and bisphenols is started. During this preheating, most of the monomer is consumed and quantified oligomers are formed. Next, the reaction system is heated to 230 ° C. over 30 minutes. By stirring at this temperature for about 150 minutes at a reduced pressure of 20 hPa or less to allow condensation to proceed, the polymerization degree of the polycarbonate is greatly improved. Further, the reaction system is heated to 250 ° C. over 30 minutes. By stirring at this temperature for about 30 minutes at a reduced pressure of 13 hPa or less, unreacted oligomer components are sufficiently reduced. Finally, it is allowed to stand in the range of 260 ° C. to 290 ° C. for about 15 minutes while maintaining the degree of vacuum. When the above heating temperature and heating time are exceeded, undesirable side reactions such as oxidative degradation due to heat occur, so it is necessary to avoid a reaction at a high temperature for a long time. By doing so, a polycarbonate composition can be obtained.

  Further, when a vinyl polymer such as an acrylic resin is used for the thermoplastic resin, a solution polymerization method can be used. In the solution polymerization method, the desired thermoplastic resin composition is prepared by dissolving the monomer in the modified inorganic particle solution dispersed in the organic solvent, allowing the polymerization to proceed with a radical initiator, and pouring the poor solvent after completion of the reaction. The product can be precipitated.

  For example, in the case of methyl methacrylate, α, α-azobisisobutyronitrile is used as a radical initiator, radical polymerization is carried out in toluene, and the desired thermoplastic resin composition is precipitated if injected into hexane. Can do.

  The radical initiator is not particularly limited, and may be appropriately determined according to the type of monomer used. Examples thereof include dilauroyl peroxide, benzoyl peroxide, di-t-butyl peroxide, and t-butyl hydroperoxide. And organic peroxides such as cumene hydroperoxide; azo compounds such as α, α-azobisisobutyronitrile and azobiscyclohexanecarbonitrile.

  The poor solvent (including insoluble poor solvent) is not particularly limited, and may be appropriately determined according to the completed thermoplastic resin. For example, methanol, ethanol, n-butanol, t-butanol, Examples include n-pentane, n-hexane, cyclohexane, n-heptane, and water.

  Examples are given below, but the present invention is not limited thereto. In addition, the analysis method and the analytical equipment employed in the present invention are as follows.

  The ash content in the resin was measured using a differential thermal and thermogravimetric simultaneous measurement device (TG-DTA) (TG-DTA320 manufactured by Seiko Instruments Inc.). The measurement conditions were a measurement temperature: room temperature to 700 ° C., and a temperature increase rate of 20 ° C./min.

  The number average molecular weight (Mn) and the weight average molecular weight (Mw) were both measured using gel permeation chromatography (GPC) (System 8000 manufactured by Tosoh Corporation). The measuring method measured the solution which melt | dissolved the resin piece in chloroform and filtered with the filter of 0.5 micrometer. The column is PL GEL mixed-D and the detector is UV (254 nm).

  The flexural modulus was measured using a universal testing machine (5867 tabletop Instron). The test speed is 1.0 mm / min, and the test temperature is 23 ° C.

  The Izod impact test (Izod impact strength test) was measured using an Izod impact tester (195LFR manufactured by Yasuda Seiki Seisakusho). The measurement was carried out after the V-notch processing, leaving it for 24 hours at a temperature of 23 ° C. and a humidity of 50%.

  The linear expansion coefficient was measured using a thermomechanical measuring device (TMA120C manufactured by Seiko Electronics Co., Ltd.).

  The haze value was measured using a haze meter (HM-65 manufactured by Murakami Color Research Laboratory) according to JIS K7136 (ISO14782) “How to determine haze of plastic-transparent material”. Separately from the measurement of physical properties, the test piece was a 2 mm thick test piece using a hot press.

(Long-chain compound)
In the following synthesis, the reagent used was Aldrich. However, the vinyl sulfonic acid used was Asahi Kasei Finechem Corporation. The solvent used was Kanto Chemical Co., Ltd.

1. Copolymer _{1: P (MMA 75 -co-} AA 25)
In a 1 L round bottom flask, 30 g (0.30 mol) of commercially available methyl methacrylate (MMA) and 7.21 g (0.10 mol) of acrylic acid (AA) were added to 400 mL of tetrahydrofuran (hereinafter referred to as THF). After adding 0.66 g (4 mmol) of azobisisobutyronitrile (hereinafter referred to as AIBN), nitrogen gas was purged for 5 minutes. Thereafter, while stirring at a stirring speed of 250 rpm using a magnetic stirrer, refluxing (refluxing) was performed for 7 hours in an oil bath set at 85 ° C. to proceed the polymerization. After the obtained copolymer solution was cooled to room temperature, a small amount of THF was added so that the total weight of the solution would be 379 g to obtain a solution of copolymer 1 prepared to have a copolymer content of 10.0 wt%. The copolymer 1 had a number average molecular weight of 8,200. This copolymer is a random copolymer type long chain compound having a carboxyl group, wherein R ₁ , R ₃ , R ₅ , R ₆ , R _{7 in the} formulas (1) and (2) are hydrogen atoms, and R ₂ is methyl. The group R ₄ is a COOCH ₃ group and R ₈ is COOH. Further, in this copolymer, the monomer unit (structural unit) of the formula (1) is 75 mol%, and the monomer unit (structural unit) of the formula (2) is 25 mol%.

Such copolymer 1 is referred to as P (MMA ₇₅ -co-AA ₂₅ ) as described above. Here, P in front of the parenthesis is an abbreviation of “poly”, and MMA on the left side in the parenthesis indicates the monomer unit of the formula (1) generated as a result of polymerization of methyl methacrylate, and the subscript number 75 Represents the mol% of the monomer unit of the formula (1). Similarly, AA on the right side in parentheses indicates the monomer unit of the formula (2) generated as a result of polymerization of acrylic acid, and the subscript number 25 represents the mol% of the monomer unit of the formula (2). Further, co in parentheses represents a (random) copolymer of left and right MMA and AA.

  The same applies to the following copolymers 2 to 14. The PhMA of copolymer 2 refers to the monomer unit of the formula (1) generated as a result of polymerization of phenyl methacrylate. S in the copolymer 5 indicates the monomer unit of the formula (1) generated as a result of polymerization of styrene. The 4-Vi benzoic acid of the copolymer 6 refers to the monomer unit of the formula (2) generated as a result of polymerization of 4-vinyl benzoic acid. The 4-pentenoic acid of the copolymer 7 refers to the monomer unit of the formula (2) generated as a result of polymerization of 4-pentenoic acid. “B” in parentheses of the block copolymer 8 represents a block copolymer of left and right MMA and AA. As will be described later, the copolymer 10 indicates one monomer unit of the formula (1) generated as a result of polymerization of styrene on the left side in parentheses, and acrylamide is polymerized on AAm on the right side in parentheses. The other 1 type monomer unit of the said Formula (1) produced | generated as a result is pointed out. The VSA of the copolymer 12 refers to the monomer unit of the formula (2) generated as a result of polymerization of vinyl sulfonic acid. The VPA of the copolymer 14 refers to the monomer unit of the formula (2) generated as a result of polymerization of vinylphosphonic acid.

2. Copolymer 2: P (PhMA ₇₅ -co-AA ₂₅ )
In a 1 L round bottom flask, 24.3 g (150 mmol) of commercially available phenyl methacrylate and 3.6 g (50 mmol) of acrylic acid were added to 250 mL of THF, and 0.33 g (2.0 mmol) of AIBN was added. Argon gas was purged for 5 minutes. Thereafter, while stirring at a stirring speed of 200 rpm using a magnetic stirrer, refluxing was performed in an oil bath set at 85 ° C. for 5 hours to proceed the polymerization. After cooling the obtained copolymer solution to room temperature, a small amount of THF was added to obtain a solution of copolymer 2 prepared to have a copolymer content of 10.0 wt%. The copolymer 2 had a number average molecular weight of 5100. This copolymer is a random copolymer type long chain compound having a carboxyl group, wherein R ₁ , R ₃ , R ₅ , R ₆ , R _{7 in the} formulas (1) and (2) are hydrogen atoms, and R ₂ is methyl. The group R ₄ is a COOPh group and R ₈ is COOH. Further, in this copolymer, the monomer unit (structural unit) of the formula (1) is 75 mol%, and the monomer unit (structural unit) of the formula (2) is 25 mol%.

3. Copolymer _{3: P (MMA 60 -co-} AA 40)
In a 1 L round bottom flask, 15.0 g (150 mmol) of commercially available methyl methacrylate and 7.2 g (100 mmol) of acrylic acid were added to a mixed solvent of 300 mL of THF and 100 mL of isopropanol, and 0.4 g of AIBN (2.4 mmol) was added. ) And then purged with argon gas for 5 minutes. Thereafter, while stirring at a stirring speed of 200 rpm using a magnetic stirrer, polymerization was carried out by heating and stirring in an oil bath set at 75 ° C. for 5 hours. After cooling the obtained copolymer solution to room temperature, a small amount of THF was added to obtain a solution of copolymer 3 prepared to have a copolymer content of 10.0 wt%. The number average molecular weight of this copolymer 3 was 12700. This copolymer is a molar ratio isomer having the same combination of monomer units as copolymer 1. In this copolymer, the monomer unit (structural unit) of the formula (1) is 60 mol%, and the monomer unit (structural unit) of the formula (2) is 40 mol%.

4). Copolymer 4: P (MMA ₉₀ -co-AA ₁₀ )
A copolymer 4 solution was obtained in the same manner as in the above copolymer 3, except that 22.5 g (225 mmol) of methyl methacrylate and 1.8 g (25 mmol) of acrylic acid were used. This copolymer 4 had a number average molecular weight of 18,800. This copolymer is a molar ratio isomer having the same combination of monomer units as copolymer 1. In this copolymer, the monomer unit (structural unit) of the formula (1) is 90 mol%, and the monomer unit (structural unit) of the formula (2) is 10 mol%.

5). Copolymer 5: P (S ₇₅ -co-AA ₂₅ )
A copolymer 5 solution was obtained in the same manner as in the above copolymer 3, except that 23.4 g (225 mmol) of styrene and 5.4 g (75 mmol) of acrylic acid were used instead of methyl methacrylate. The number average molecular weight of this copolymer 5 was 13400. This copolymer is a random copolymer type long-chain compound having a carboxyl group, wherein R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R _{7 in the} formulas (1) and (2) are hydrogen atoms, R ₄ is a Ph group, and R ₈ is COOH. In this copolymer, the monomer unit (structural unit) of the formula (1) is 75 mol%, and the monomer unit (structural unit) of the formula (2) is 25 mol%.

6). Copolymer _{6: P (S 75 -co-} 4-Vi acid ₂₅₎
A copolymer 6 solution was prepared in the same manner as in the above copolymer 3 except that 15.6 g (150 mmol) of styrene was used instead of methyl methacrylate and 7.4 g (50 mmol) of 4-vinylbenzoic acid was used instead of acrylic acid. Got. The number average molecular weight of this copolymer 6 was 4900. This copolymer is a random copolymer type long-chain compound having a carboxyl group, wherein R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R _{7 in the} formulas (1) and (2) are hydrogen atoms, R ₄ is a Ph group, and R ₈ is a C ₆ H ₄ COOH group (the COOH group is in the para position). In this copolymer, the monomer unit (structural unit) of the formula (1) is 75 mol%, and the monomer unit (structural unit) of the formula (2) is 25 mol%.

7). Copolymer 7: P (S ₇₅ -co-4-pentenoic acid ₂₅ )
The same operation as in the above copolymer 3, except that 23.4 g (225 mmol) of styrene was used instead of methyl methacrylate and 7.5 g (75 mmol) of 4-pentenoic acid was used instead of acrylic acid, followed by heating and stirring for 50 hours. To obtain a solution of copolymer 7. The number average molecular weight of this copolymer 7 was 3800. This copolymer is a random copolymer type long-chain compound having a carboxyl group, wherein R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R _{7 in the} formulas (1) and (2) are hydrogen atoms, R ₄ is a Ph group, and R ₈ is CH ₂ CH ₂ COOH. In this copolymer, the monomer unit (structural unit) of the formula (1) is 75 mol%, and the monomer unit (structural unit) of the formula (2) is 25 mol%.

8). Block copolymers _{8: P (MMA 75 -b-} AA 25)
In a 1 L round bottom flask, 36.1 g (0.50 mol) of commercially available acrylic acid was added into 400 mL of THF, and 6.6 g (40 mmol) of AIBN and 6.0 g of S-methoxycarbonylphenylmethyldithiobenzoate (MCPDB) were added. After adding (20 mmol), nitrogen gas was purged for 5 minutes. Then, while stirring at a stirring speed of 250 rpm using a magnetic stirrer, refluxing was performed in an oil bath set at 80 ° C. for 20 hours to proceed polymerization of the acrylic acid block. Subsequently, 150 g (1.50 mol) of methyl methacrylate and 200 mL of THF were added, and refluxing was further performed at 80 ° C. for 20 hours with stirring to proceed the polymerization of the methyl methacrylate block. The obtained copolymer solution was cooled to room temperature, and then gently poured into 2000 mL of n-hexane cooled to 10 ° C. or lower to reprecipitate the crude copolymer. After filtering with filter paper, it was re-dissolved in 800 mL of THF, 32.8 g (0.20 mol) of AIBN was added, and nitrogen gas was purged for 5 minutes. Thereafter, reflux was performed at 70 ° C. for 15 hours to remove and replace the terminal MCPDB residue. After cooling to room temperature, it was gently poured into 3000 mL of n-hexane cooled to 10 ° C. or lower to reprecipitate the copolymer. After filtering with filter paper, drying was performed in a vacuum oven heated to 80 ° C. for 6 hours to obtain 123 g of dry copolymer 8. The number average molecular weight of this copolymer 8 was 18,800. This copolymer is a block copolymer type long-chain compound having a carboxyl group, wherein R ₁ , R ₃ , R ₅ , R ₆ , R _{7 in the} formulas (1) and (2) are hydrogen atoms, and R ₂ is methyl The group R ₄ is a COOCH ₃ group and R ₈ is COOH. Further, in this copolymer, the monomer unit (structural unit) of the formula (1) is 75 mol%, and the monomer unit (structural unit) of the formula (2) is 25 mol%.

9. Copolymer 9: P (MMA ₃₅ -co-AA ₆₅ )
A copolymer 9 solution was obtained in the same manner as in the above copolymer 3, except that 70 g (0.70 mol) of methyl methacrylate and 93.7 g (1.3 mol) of acrylic acid were used. The number average molecular weight of this copolymer 9 was 11,000. This copolymer is a molar ratio isomer having the same combination of monomer units as copolymer 1. Further, in this copolymer, the monomer unit (structural unit) of the formula (1) is 35 mol%, and the monomer unit (structural unit) of the formula (2) is 65 mol%.

10. Copolymer _{10: P (S 60 -co-} AAm 40)
A copolymer 10 solution was obtained in the same manner as in copolymer 3 except that 15.6 g (150 mmol) of styrene was used instead of methyl methacrylate and 7.1 g (100 mmol) of acrylamide was used instead of acrylic acid. The copolymer 10 had a number average molecular weight of 7,700. This copolymer is a random copolymer-type long-chain compound containing no carboxyl group, and is composed of two different types of the above formula (1), and one of the above formulas (1) R ₁ , R ₂ , R ₃ Is a hydrogen atom, R ₄ is a Ph group, the other R ₁ , R ₂ and R _{3 in the} formula (1) are hydrogen atoms, and R ₄ is CONH ₂ . Further, in this copolymer, the monomer unit (structural unit) of the formula (1) having the former Ph group is 60 mol%, and the monomer unit (structural unit) of the formula (1) having the latter CONH ₂ group is 40 mol%. It is.

11. Copolymer _{11: P (MMA 60 -co-} AA 40) - high molecular weight products of the copolymer 3, except that a reduced AIBN in 0.1 g (0.6 mmol) performs the same operation was allowed to proceed polymerization. After the obtained copolymer solution was cooled to room temperature, a small amount of THF was added to obtain a copolymer solution prepared to have a copolymer content of 10.0 wt%. However, even after stirring for 1 hour, an insoluble content remained at the bottom, resulting in a homogeneous solution. It did not become. The copolymer 11 had a number average molecular weight of 32200.

12 Copolymer _{12: P (S 80 -co-} VSA 20)
In a 1 L round bottom flask, 6.25 g (60 mmol) of commercially available styrene and 1.62 g (15 mmol) of vinyl sulfonic acid were added to 100 mL of THF, 0.82 g (5.0 mmol) of AIBN was added, and argon was added. The gas was purged for 5 minutes. Thereafter, while stirring at a stirring speed of 300 rpm using a magnetic stirrer, refluxing was performed in an oil bath set at 80 ° C. for 6 hours to proceed the polymerization. After cooling the obtained copolymer solution to room temperature, a small amount of THF was added to obtain a solution of copolymer 12 prepared to have a copolymer content of 10.0 wt%. The copolymer 12 had a number average molecular weight of 1400. This copolymer is a random copolymer type long-chain compound having a sulfo group, wherein R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , and R _{7 in the} formulas (1) and (2) are hydrogen atoms, R ₄ is a Ph group, and R ₈ is a SO ₃ H group. Further, in this copolymer, the monomer unit (structural unit) of the formula (1) is 80 mol%, and the monomer unit (structural unit) of the formula (2) is 20 mol%.

13. Copolymer _{13: P (MMA 80 -co-} VSA 20)
A copolymer 13 solution was obtained in the same manner as in the above copolymer 12, except that 6.01 g (60 mmol) of methyl methacrylate was used instead of styrene. The copolymer 13 solution was poured into a large excess of heptane to precipitate, filtered at normal pressure with a filter paper, and then dried overnight in an oven at 60 ° C. to obtain a white granular copolymer 13. The number average molecular weight of this copolymer 13 was 3200. This copolymer is a random copolymer type long-chain compound having a sulfo group, wherein R ₁ , R ₃ , R ₅ , R ₆ , R _{7 in the} formulas (1) and (2) are hydrogen atoms, and R ₂ is methyl Group, R ₄ is a COOCH ₃ group, and R ₈ is a SO ₃ H group. In this copolymer, the monomer unit (structural unit) of the formula (1) is 80 mol%, and the monomer unit (structural unit) of the formula (2) is 20 mol%.

14 Copolymer _{14: P (MMA 80 -co-} VPA 20)
A copolymer 14 solution was obtained in the same manner as in the copolymer 13 except that 1.62 g (15 mmol) of vinylphosphonic acid was used instead of vinylsulfonic acid. The number average molecular weight of this copolymer 14 was 2400. This copolymer is a random copolymer type long-chain compound having a phosphonic acid group, wherein R ₁ , R ₃ , R ₅ , R ₆ , R _{7 in the} formulas (1) and (2) are hydrogen atoms, and R ₂ is A methyl group, R ₄ is a COOCH ₃ group, and R ₈ is a PO ₃ H ₂ group. In this copolymer, the monomer unit (structural unit) of the formula (1) is 80 mol%, and the monomer unit (structural unit) of the formula (2) is 20 mol%.

(Modified inorganic particles)
1. Modified inorganic particle powder A (copolymer 1 modified boehmite particle powder)
“Cataloid-AS-3” (catalyst-AS-3) manufactured by Catalyst Kasei Kogyo Co., Ltd. (water-dispersed boehmite: boehmite major axis length 100 nm, minor axis length 10 nm, solid content 7 wt% in water-dispersed boehmite, specific gravity 1.05) 200 g (solid 14 g), a 28 g solution of copolymer 1 = P (MMA ₇₅ -co-AA ₂₅ ) (a copolymer solid content of 2.8 g) was added as a long-chain compound having a carboxyl group. Refluxing was performed for a period of time. After the heating, the operation of precipitating the particles using a centrifuge, adding distilled water thereto, redispersing the particles in water, and performing centrifugation again was repeated three times. Liquid nitrogen was introduced into a solution in which the solid content of the particles was adjusted to 5 wt% using distilled water, and the powder was dried using a freeze dryer. This powder was further dried in a vacuum oven at 100 ° C. for 4 hours to obtain a modified boehmite particle powder (modified inorganic particle powder A) modified with a long chain compound almost quantitatively.

2. Modified inorganic particle powder B (copolymer 1 modified silica particle powder)
“Quatron PL-1” manufactured by Fuso Chemical Industry Co., Ltd. (water-dispersed silica; silica particle diameter 15 nm (major axis length≈short axis length spherical particle), solid content 12 wt% in water-dispersed silica, specific gravity 1 0.07) was used, and the same treatment operation was performed by adding a long-chain compound so that the weight ratio was the same as that of the modified inorganic particle powder A (copolymer 1 modified boehmite particle powder). Modified silica particle powder (modified inorganic particle powder B) was obtained almost quantitatively.

3. Organic solvent dispersion modified inorganic particles C (Organic solvent dispersion copolymer 1 modified boehmite particles)
“Cataloid-AS-3” manufactured by Catalytic Chemical Industries, Ltd. (water-dispersed boehmite: boehmite major axis length 100 nm, minor axis length 10 nm, solid content in water-dispersed boehmite 7 wt%, specific gravity 1.05) 500 g (solid content 35 g) and cyclopentanone 1000 g were added, and 70 g of a copolymer 1 = P (MMA ₇₅ -co-AA ₂₅ ) solution as a long-chain compound having a carboxyl group while stirring well in the flask using a magnetic stirrer. (Copolymer solids 7.0 g) was added and stirring was continued for 30 minutes at room temperature. Next, water was removed using a rotary evaporator under reduced pressure. At this time, cyclopentanone azeotropes with water, so cyclopentanone was appropriately added. Distillation was performed until the sol in the flask became more transparent. Thereafter, the temperature in the flask is set to a temperature at which cyclopentanone can be distilled, the amount of cyclopentanone is adjusted so that the solid content of the sol in the flask is 5 wt%, and the long-chain compound is dispersed in cyclopentanone. Modified boehmite particles modified with (organic solvent dispersion-modified inorganic particles C) were obtained almost quantitatively. The yield at this time was 700 g, and the solid content was 5 wt%.

4). Organic solvent dispersion modified inorganic particles D (Organic solvent dispersion copolymer 1 modified silica particles)
“Quatron PL-1” manufactured by Fuso Chemical Industry Co., Ltd. (water-dispersed silica; silica particle diameter of 15 nm (major axis length≈short axis length spherical particles), solid content in water-dispersed silica of 12 wt% in the flask. , Specific gravity 1.07), distilled water was added to a solid content of 5 wt%, 1000 g of chlorobenzene was added to 1000 g of the aqueous solution (solid content 50 g), and the long chain having a carboxyl group was stirred well using a magnetic stirrer. As a compound, 100 g of a 10 wt% solution of copolymer 1 = P (MMA ₇₅ -co-AA ₂₅ ) (copolymer solid content: 10 g) was added, and stirring was continued for 30 minutes at room temperature. Next, water was removed using a rotary evaporator under reduced pressure. Since chlorobenzene azeotropes with water at this time, chlorobenzene was added appropriately. Distillation was performed until the sol in the flask became more transparent. After that, the temperature in the flask is set to a temperature at which chlorobenzene can be distilled, the amount of chlorobenzene is adjusted so that the solid content of the sol in the flask is 5 wt%, and the modification is dispersed in chlorobenzene and modified with a long-chain compound. Silica particles (organic solvent-dispersed modified inorganic particles D) were obtained almost quantitatively. The yield at this time was 1000 g, and the solid content was 5 wt%.

5). Organic solvent-dispersed modified inorganic particles E (organic solvent-dispersed copolymer 2 modified boehmite particles)
“Cataloid-AS-3” (aqueous dispersion boehmite, solid content 7 wt%) 500 g (solid content 35 g) manufactured by Catalyst Kasei Kogyo Co., Ltd. in the flask, copolymer 2 = P (PhMA) as a long chain compound having a carboxyl group _{75 -co-AA 25)} solution using 70 g (copolymer solids 7.0 g) were performed in the same way as when creating an organic solvent dispersed modified inorganic particles C of. The amount of cyclopentanone was adjusted so that the solid content of the sol was 5 wt%, and organic solvent dispersion-modified inorganic particles E were obtained almost quantitatively.

6). Organic solvent-dispersed modified inorganic particles F (organic solvent-dispersed copolymer 3 modified boehmite particles)
Using copolymer 3 = P (MMA ₆₀ -co-AA ₄₀ ) as a long-chain compound having a carboxyl group, the same operation as in the preparation of organic solvent-dispersed modified inorganic particles C was performed. The amount of cyclopentanone was adjusted so that the solid content of the sol was 5 wt%, and the organic solvent-dispersed modified inorganic particles F were obtained almost quantitatively.

7). Organic solvent-dispersed modified inorganic particles G (organic solvent-dispersed copolymer 4 modified boehmite particles)
The copolymer 4 = P (MMA ₉₀ -co-AA ₁₀ ) was used as the long-chain compound having a carboxyl group, and the same operation as in the preparation of the organic solvent dispersion-modified inorganic particles C was performed. The amount of cyclopentanone was adjusted so that the solid content of the sol was 5 wt%, and the organic solvent dispersion-modified inorganic particles G were obtained almost quantitatively.

8). Organic solvent-dispersed modified inorganic particles H (organic solvent-dispersed copolymer 5 modified boehmite particles)
Using copolymer 5 = P (S ₇₅ -co-AA ₂₅ ) as a long-chain compound having a carboxyl group, the same operation as in the preparation of organic solvent-dispersed modified inorganic particles C was performed. The amount of cyclopentanone was adjusted so that the solid content of the sol was 5 wt%, and the organic solvent dispersion-modified inorganic particles H were obtained almost quantitatively.

9. Organic solvent dispersed modified inorganic particles I (Organic solvent dispersed copolymer 6 modified boehmite particles)
Copolymers 6 = P The same procedure as when creating an organic solvent dispersed modified inorganic particles C with (S 75 _-co-4- vinylbenzoic acid ₂₅₎ was carried out as long chain compound having a carboxyl group. The amount of cyclopentanone was adjusted so that the solid content of the sol was 5 wt%, and organic solvent-dispersed modified inorganic particles I were obtained almost quantitatively.

10. Organic solvent dispersion modified inorganic particles J (organic solvent dispersion copolymer 7 modified boehmite particles)
The copolymer 7 = P (S ₇₅ -co-pentenoic acid ₂₅ ) was used as the long-chain compound having a carboxyl group, and the same operation as in the preparation of the organic solvent dispersion-modified inorganic particles C was performed. The amount of cyclopentanone was adjusted so that the solid content of the sol was 5 wt%, and organic solvent dispersion-modified inorganic particles J were obtained almost quantitatively.

11. Organic solvent-dispersed modified inorganic particles K (organic solvent-dispersed copolymer 8 modified boehmite particles)
The copolymer 8 = P (MMA ₇₅ -b-AA ₂₅ ) was used as a long-chain compound having a carboxyl group, and the same operation as in the preparation of the organic solvent-dispersed modified inorganic particles C was performed. At this time, since the copolymer 8 is solid, it was used after being dissolved in THF so as to be 10 wt%. The amount of cyclopentanone was adjusted so that the solid content of the sol was 5 wt%, and organic solvent dispersion-modified inorganic particles K were obtained almost quantitatively.

12 Organic solvent dispersion modified inorganic particles L (organic solvent dispersion copolymer 9 modified boehmite particles)
Using copolymer 9 = P (MMA ₃₅ -co-AA ₆₅ ) as a long-chain compound having a carboxyl group, the same operation as in the preparation of organic solvent-dispersed modified inorganic particles C was performed. The amount of cyclopentanone was adjusted so that the solid content of the sol was 5 wt%, and the organic solvent dispersion-modified inorganic particles L were obtained almost quantitatively. Since the copolymer 9 contained many COOH groups, the obtained organic solvent dispersion-modified inorganic particles L were slightly aggregated.

13. Organic solvent-dispersed modified inorganic particles M (organic solvent-dispersed copolymer 10 modified boehmite particles)
Using copolymer 10 = P (S ₆₀ -co-AAm ₄₀ ) as a long-chain compound having no carboxyl group, the same operation as in the preparation of organic solvent-dispersed modified inorganic particles C was performed. The amount of cyclopentanone was adjusted so that the solid content of the sol was 5 wt%, and the organic solvent-dispersed modified inorganic particles M were obtained almost quantitatively. Since the copolymer 10 did not contain any COOH group, the organic solvent-dispersed modified inorganic particles M were insufficiently modified and slightly aggregated.

14 Organic solvent-dispersed modified inorganic particles N (organic solvent-dispersed copolymer 11 modified boehmite particles)
Copolymers ₁₁ = P a long chain compound having a carboxyl group _{(MMA 60 -co-AA 40)} - with a high molecular weight product, performs an operation similar to when creating an organic solvent dispersed modified inorganic particles C. The amount of cyclopentanone was adjusted so that the solid content of the sol was 5 wt%, and an attempt was made to obtain organic solvent dispersion-modified inorganic particles N. However, since copolymer 11 has a large molecular weight, organic solvent dispersion-modified inorganic particles N Produced agglomeration.

15. Modified inorganic particle powder O (copolymer 12 modified boehmite particle powder)
A modified boehmite particle powder modified with a long chain compound is prepared by using the copolymer 12 = P (S ₈₀ -co-VSA ₂₀ ) as a long chain compound having a sulfo group and performing the same operation as in the preparation of the modified inorganic particle powder A. (Modified inorganic particle powder O) was obtained almost quantitatively.

16. Organic solvent-dispersed modified inorganic particles P (organic solvent-dispersed copolymer 13 modified boehmite particles)
Using copolymer 13 = P (MMA ₈₀ -co-VSA ₂₀ ) as a long-chain compound having a sulfo group, the same operation as in the preparation of organic solvent-dispersed modified inorganic particles C was performed. Since the copolymer 13 was granular, it was once made into a 10 wt% THF solution and then added to the water sol. The amount of cyclopentanone was adjusted so that the solid content of the obtained organic solvent-dispersed sol was 5 wt%, and organic solvent-dispersed modified inorganic particles P were obtained almost quantitatively.

17. Modified inorganic particle powder Q (copolymer 14 modified boehmite particle powder)
A modified boehmite particle modified with a long-chain compound by using the copolymer 14 = P (MMA ₈₀ -co-VPA ₂₀ ) as a long-chain compound having a phosphonic acid group and performing the same operation as in the preparation of the modified inorganic particle powder A A powder (modified inorganic particle powder Q) was obtained almost quantitatively.

Example 1
20 g of polycarbonate “Novalex 7030A” (weight average molecular weight 65000) manufactured by Mitsubishi Engineering Plastics Co., Ltd. and 7 g of modified inorganic particle powder A prepared above are mixed in “Vacuum microkneading extruder IMC-1170B type” manufactured by Imoto Seisakusho Co., Ltd. The mixture was kneaded at 230 ° C. for 10 minutes under reduced pressure to obtain a resin composition. The obtained resin composition had an ash content of 19 wt% and a weight average molecular weight of 58,000.

  Furthermore, this resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. The physical properties of the obtained resin composition sample pieces were a flexural modulus of 6.5 GPa, impact strength (Izod) of 60 J / m (23 ° C.), and thermal dimensional stability (linear expansion coefficient) of 38 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 10%.

Example 2
In a separable flask, 500 g (5 wt%) of the organic solvent-dispersed modified inorganic particle C solution and 60 g of polycarbonate “Novalex 7030A” (weight average molecular weight 65000) manufactured by Mitsubishi Engineering Plastics Co., Ltd. dissolved in 1800 g of methylene chloride. In addition, after the solvent was distilled off using an evaporator, the temperature was raised to 180 ° C. and kept under vacuum with a vacuum pump for 4 hours. The atmospheric pressure is returned to normal pressure with an inert gas, and the mixture is kneaded at 260 ° C. for 2 minutes under reduced pressure using a “vacuum microkneading extruder IMC-1170B type” manufactured by Imoto Seisakusho Co., Ltd. to obtain a resin composition. It was. The obtained resin composition had an ash content of 22 wt% and a weight average molecular weight of 55,000.

  Furthermore, this resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. As for the physical properties of the sample pieces of the obtained resin composition, the flexural modulus was 8 GPa, the impact strength (Izod) was 80 J / m (23 ° C.), and the thermal dimensional stability (linear expansion coefficient) was 30 ppm / K. Moreover, the transparency (Haze value) using another sample piece of this resin composition was 5% (see a in FIG. 2A).

Example 3
A resin composition was prepared in the same manner as in Example 1 except that the modified inorganic particle powder B was used. The obtained resin composition had an ash content of 20 wt% and a weight average molecular weight of 59000.

  Furthermore, this resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. As for the physical properties of the sample pieces of the resin composition obtained, the flexural modulus was 4 GPa, the impact strength (Izod) was 45 J / m (23 ° C.), and the thermal dimensional stability (linear expansion coefficient) was 55 ppm / K. Moreover, the transparency (Haze value) using another sample piece of this resin composition was 25%.

Example 4
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent dispersion-modified inorganic particles D were used. The obtained resin composition had an ash content of 23 wt% and a weight average molecular weight of 60,000.

  Furthermore, this resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. The physical properties of the obtained resin composition sample pieces were a flexural modulus of 4.2 GPa, an impact strength (Izod) of 50 J / m (23 ° C.), and a thermal dimensional stability (linear expansion coefficient) of 55 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 10%.

Example 5
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent-dispersed modified inorganic particles E were used. The resulting resin composition had an ash content of 20 wt% and a weight average molecular weight of 54,000.

  Furthermore, this resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. As for the physical properties of the sample pieces of the resin composition obtained, the flexural modulus was 6.9 GPa, the impact strength (Izod) was 65 J / m (23 ° C.), and the thermal dimensional stability (linear expansion coefficient) was 39 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 35% (see b in FIG. 2A).

Example 6
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent-dispersed modified inorganic particles F were used. The obtained resin composition had an ash content of 22 wt% and a weight average molecular weight of 58,000.

  The resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. The physical properties of the obtained resin composition sample pieces were a flexural modulus of 7.2 GPa, an impact strength (Izod) of 65 J / m (23 ° C.), and a thermal dimensional stability (linear expansion coefficient) of 38 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 10%.

Example 7
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent dispersion-modified inorganic particles G were used. The obtained resin composition had an ash content of 21 wt% and a weight average molecular weight of 56,000.

  The resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. The physical properties of the obtained resin composition sample pieces were a flexural modulus of 7.0 GPa, impact strength (Izod) of 75 J / m (23 ° C.), and thermal dimensional stability (linear expansion coefficient) of 39 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 10%.

Example 8
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent dispersion-modified inorganic particles H were used. The obtained resin composition had an ash content of 23 wt% and a weight average molecular weight of 52,000.

  The resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. The physical properties of the obtained resin composition sample pieces were a flexural modulus of 6.0 GPa, impact strength (Izod) of 60 J / m (23 ° C.), and thermal dimensional stability (linear expansion coefficient) of 45 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 25%.

Example 9
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent dispersion-modified inorganic particles I were used. The obtained resin composition had an ash content of 21 wt% and a weight average molecular weight of 51,000.

  The resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. As for the physical properties of the sample pieces of the resin composition obtained, the flexural modulus was 6.5 GPa, the impact strength (Izod) was 55 J / m (23 ° C.), and the thermal dimensional stability (linear expansion coefficient) was 39 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 20%.

Example 10
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent dispersion-modified inorganic particles J were used. The obtained resin composition had an ash content of 22 wt% and a weight average molecular weight of 55,000.

  The resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. The physical properties of the obtained resin composition sample pieces were a flexural modulus of 6.0 GPa, impact strength (Izod) of 60 J / m (23 ° C.), and thermal dimensional stability (linear expansion coefficient) of 40 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 25%.

Example 11
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent-dispersed modified inorganic particles K were used. The obtained resin composition had an ash content of 23 wt% and a weight average molecular weight of 59000.

  The resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. The physical properties of the sample pieces of the obtained resin composition were a flexural modulus of 8.0 GPa, an impact strength (Izod) of 90 J / m (23 ° C.), and a thermal dimensional stability (linear expansion coefficient) of 31 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 10%.

Example 12
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent dispersion-modified inorganic particles L were used. The obtained resin composition had an ash content of 22 wt% and a weight average molecular weight of 43,000.

  The resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. As for the physical properties of the sample pieces of the resin composition obtained, the flexural modulus was 6.3 GPa, the impact strength (Izod) was 35 J / m (23 ° C.), and the thermal dimensional stability (linear expansion coefficient) was 57 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 35%.

Example 13
A resin composition was prepared in the same manner as in Example 1 except that the modified inorganic particle powder O was used. The obtained resin composition had an ash content of 22 wt% and a weight average molecular weight of 54,000.

  The resin composition was hot-pressed at 185 ° C. to obtain a sample piece of a resin composition for physical property testing. The physical properties of the obtained resin composition sample pieces were a flexural modulus of 6.4 GPa, impact strength (Izod) of 55 J / m (23 ° C.), and thermal dimensional stability (linear expansion coefficient) of 43 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was as good as 5% (see e in FIG. 2B).

Example 14
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent dispersion-modified inorganic particles P were used. The obtained resin composition had an ash content of 23 wt% and a weight average molecular weight of 59000.

  The resin composition was hot-pressed at 185 ° C. to obtain a sample piece of a resin composition for physical property testing. The physical properties of the sample pieces of the obtained resin composition were a flexural modulus of 6.8 GPa, an impact strength (Izod) of 80 J / m (23 ° C.), and a thermal dimensional stability (linear expansion coefficient) of 38 ppm / K. . Further, the transparency (Haze value) using another sample piece of this resin composition was 2%, which was very good and the same level as polycarbonate (see f in FIG. 2B).

Example 15
A resin composition was prepared in the same manner as in Example 1 except that the modified inorganic particle powder Q was used. The obtained resin composition had an ash content of 22 wt% and a weight average molecular weight of 46,000.

  The resin composition was hot-pressed at 185 ° C. to obtain a sample piece of a resin composition for physical property testing. The physical properties of the obtained resin composition sample pieces were a flexural modulus of 6.1 GPa, an impact strength (Izod) of 45 J / m (23 ° C.), and a thermal dimensional stability (linear expansion coefficient) of 47 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 20%.

Example 16
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent dispersion-modified inorganic particles N were used. The resulting resin composition had an ash content of 20 wt% and a weight average molecular weight of 39000.

  The resin composition was hot-pressed at 185 ° C. to obtain a sample piece of a resin composition for physical property testing. As for the physical properties of the sample pieces of the resin composition obtained, the flexural modulus was 4.8 GPa, the impact strength (Izod) was 30 J / m (23 ° C.), and the thermal dimensional stability (linear expansion coefficient) was 59 ppm / K. . Further, the transparency (Haze value) using another sample piece of this resin composition was 30%, which was somewhat transparent, but there were some undesirable granular aggregates visible.

  The measurement results of the physical properties of the resin compositions obtained in the above examples are summarized in Table 1A and Table 1B. 2A and 2B are drawings showing photographs taken from above of Examples 2 and 5 and Examples 13 and 14, and test pieces at the time of measuring the haze values of the resin compositions of Comparative Examples 4 and 5 shown below. Shown in FIG. 2B.

Comparative Example 1
Liquid with respect to “Cataloid-AS-3” (water-dispersed boehmite; boehmite major axis length 100 nm, minor axis length 10 nm, solid content in water-dispersed boehmite 7 wt%, specific gravity 1.05) Nitrogen was introduced and the boehmite particles were powder-dried using a freeze dryer. 100 g of this powder was placed in an eggplant-shaped flask equipped with a reflux apparatus together with 1000 g of tetrahydrofuran (THF) and 300 g of methyltriethoxysilane as a surface modifier, and refluxed for 2 hours. Thereafter, hexane, which is a poor solvent, was added, and the surface-modified particles were taken out and washed well with hexane.

  Next, 10 g of the obtained particles and 30 g of polycarbonate “Novalex 7030A” (weight average molecular weight 65000) manufactured by Mitsubishi Engineering Plastics Co., Ltd. were reduced in pressure using “Vacuum microkneading extruder IMC-1170B type” manufactured by Imoto Seisakusho Co., Ltd. Then, the mixture was kneaded at 220 ° C. for 10 minutes to obtain a resin composition. The obtained resin composition had an ash content of 24 wt% and a weight average molecular weight of 42,000.

  Further, this resin composition was hot pressed at 175 ° C. to obtain a sample piece of a resin composition for physical property testing. As for the physical properties of the sample pieces of the resin composition obtained, the flexural modulus was 4.4 GPa, the impact strength (Izod) was 10 J / m (23 ° C.), and the thermal dimensional stability (linear expansion coefficient) was 50 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 65%.

Comparative Example 2
“Quatron PL-1” manufactured by Fuso Chemical Industry Co., Ltd. (water-dispersed silica; silica particle diameter 15 nm (major axis length≈short axis length spherical particle), solid content 12 wt% in water-dispersed silica, specific gravity 1 0.07), liquid nitrogen was introduced, and the silica particles were powder-dried using a freeze dryer. 100 g of this powder was placed in an eggplant-shaped flask equipped with a reflux device together with 1000 g of THF and 300 g of methyltriethoxysilane and allowed to dry for 2 hours. Thereafter, hexane, which is a poor solvent, was added, and the particles were taken out and washed well with hexane.

  Next, 30 g of the obtained particles and 90 g of polycarbonate “Novalex 7030A” (weight average molecular weight 65000) manufactured by Mitsubishi Engineering Plastics Co., Ltd. were dissolved in 2000 g of methylene chloride, and after stirring well, the solvent was distilled off using an evaporator. The temperature was raised to 180 ° C. and kept under vacuum with a vacuum pump for 4 hours. The atmospheric pressure is returned to normal pressure with an inert gas, and the mixture is kneaded at 180 ° C. for 2 minutes under reduced pressure using a “vacuum microkneading extruder IMC-1170B type” manufactured by Imoto Seisakusho Co., Ltd. to obtain a resin composition. It was. The obtained resin composition had an ash content of 22 wt% and a weight average molecular weight of 46,000.

  Further, this resin composition was hot pressed at 175 ° C. to obtain a sample piece of a resin composition for physical property testing. The sample properties of the obtained resin composition were as follows: flexural modulus 4 / GPa, impact strength (Izod) 35 J / m (23 ° C.), thermal dimensional stability (linear expansion coefficient) 58 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 60%.

Comparative Example 3
Liquid with respect to “Cataloid-AS-3” (water-dispersed boehmite; boehmite major axis length 100 nm, minor axis length 10 nm, solid content in water-dispersed boehmite 7 wt%, specific gravity 1.05) Nitrogen was introduced and the boehmite particles were powder-dried using a freeze dryer. 10 g of this powder particle and 30 g of polycarbonate “Novalex 7030A” (weight average molecular weight 65000) manufactured by Mitsubishi Engineering Plastics Co., Ltd. are used at 230 ° C. under reduced pressure using a “vacuum microkneading extruder IMC-1170B type” manufactured by Imoto Seisakusho Co., Ltd. For 10 minutes. During this kneading, 0.5 g of YDCN-701 manufactured by Sumitomo Bakelite Co., Ltd. was slowly added as an epoxy-based surface modifier over 10 minutes to obtain a resin composition. The obtained resin composition had an ash content of 25 wt% and a weight average molecular weight of 43,000.

  Further, this resin composition was hot pressed at 175 ° C. to obtain a sample piece of a resin composition for physical property testing. As for the physical properties of the sample pieces of the obtained resin composition, the flexural modulus was 5 GPa, the impact strength (Izod) was the lower limit of measurement, and the thermal dimensional stability (linear expansion coefficient) was 55 ppm / K. Moreover, the transparency (Haze value) using another sample piece of this resin composition was 45%.

Comparative Example 4: No modification 10 g of powder particles obtained by introducing liquid nitrogen into the above-mentioned “Cataloid-AS-3” and drying the boehmite particles using a freeze dryer, and the above-mentioned polycarbonate “Novalex 7030A” 30 g was kneaded at 230 ° C. for 10 minutes under reduced pressure. No surface modifier was used. The obtained resin composition had an ash content of 23 wt% and a weight average molecular weight of 29000.

  The resin composition was hot-pressed at 175 ° C. to obtain a sample piece of a resin composition for physical property testing. As for the physical properties of the sample pieces of the obtained resin composition, the flexural modulus was 5.1 GPa, the impact strength (Izod) was the lower limit of measurement, and the thermal dimensional stability (linear expansion coefficient) was 59 ppm / K. Moreover, the transparency (Haze value) using another sample piece of this resin composition was 75% (see c in FIG. 2A).

Comparative Example 5
A resin composition was prepared in the same manner as in Example 2 except that the organic solvent-dispersed modified inorganic particles M were used. The obtained resin composition had an ash content of 21 wt% and a weight average molecular weight of 35,000.

  The resin composition was hot-pressed at 190 ° C. to obtain a sample piece of a resin composition for physical property testing. As for the physical properties of the sample pieces of the resin composition obtained, the flexural modulus was 5.4 GPa, the impact strength (Izod) was 25 J / m (23 ° C.), and the thermal dimensional stability (linear expansion coefficient) was 55 ppm / K. . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 40% (see d in FIG. 2A). As can be seen from d in FIG. 2A, in the resin composition using the organic solvent-dispersed modified inorganic particles M, undesirable yellowing was observed.

Reference example: Commercially available PC (7030A)
Polycarbonate “Novalex 7030A” (weight average molecular weight 65000) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used as the resin composition. The ash content of this resin composition was 0 wt%.

  Further, this resin composition was hot pressed at 175 ° C. to obtain a sample piece of a resin composition for physical property testing. The sample properties of the obtained resin composition were as follows: flexural modulus 2.3 GPa, impact strength (Izod) 1020 J / m (23 ° C.), thermal dimensional stability (linear expansion coefficient) 70 ppm / K . Moreover, the transparency (Haze value) using another sample piece of this resin composition was 2%.

  Table 2 summarizes the measurement results of the physical properties of the resin compositions obtained in the above Comparative Examples and Reference Examples.

  * 1) “Measurement lower limit limit value” of impact strength in Table 1A, Table 1B, and Table 2 is 10. Therefore, the impact strength of Comparative Examples 3 and 4 is less than 10.

It is the schematic which represented typically how to take the particle diameter of the fibrous solid high aspect oxide particle of this invention, and length. It is drawing which represented the photograph which set the sample (test piece) for the measurement of the Haze value of the resin composition of an Example and a comparative example to the height of 10 mm, and was image | photographed from the upper direction. 2a is a test piece of the resin composition of Example 2, FIG. 2b is a test piece of the resin composition of Example 5, FIG. 2c is a test piece of the resin composition of Comparative Example 4, and FIG. 2d is a resin of Comparative Example 5. It is a test piece of the composition. Also, the chemical formula in the figure is that of long chain compound copolymers 1 and 2 which are oxide particle surface treatment agents used in the resin compositions of Examples 2 and 5 which are the samples (test pieces) of FIGS. Is. It is drawing which represented the photograph which set the sample (test piece) for the measurement of the Haze value of the resin composition of an Example to the height of 10 mm, and was image | photographed from the upper direction. 2e is a test piece of the resin composition of Example 13, and FIG. 2f is a test piece of the resin composition of Example 14. Also, the chemical formula in the figure is that of the long-chain compound copolymers 12 and 13 which are oxide particle surface treatment agents used in the resin compositions of Examples 13 and 14 which are the samples (test pieces) of FIGS. 2e and 2f, respectively. Is. It is explanatory drawing which shows the multipoint adsorption modification model in the resin composition formed by mixing an oxide particle, a (long chain) compound, and a thermoplastic resin. Among these, FIG. 3A is a drawing schematically showing a state before a reaction or interaction between a long-chain compound having one adsorption point (functional group: —COOH) and oxide particles. FIG. 3B is an explanatory diagram schematically showing a state in which a thermal history is added to a product obtained by reacting or interacting with the long-chain compound and oxide particles in FIG. 3A. FIG. 3C is a drawing schematically showing a state before a reaction or interaction between a long-chain compound having a large number of adsorption points (functional groups) and oxide particles. FIG. 3D is an explanatory view schematically showing a state in which a thermal history is added to a substance in which the long-chain compound and the oxide particles in FIG. 3C are reacted or interacted to be immobilized (multi-point adsorption). . It is explanatory drawing which shows the multipoint adsorption modification model in the resin composition formed by mixing an oxide particle, a (long chain) compound, and a thermoplastic resin. Among these, FIG. 4A is a drawing schematically showing a state before a reaction or interaction between a long-chain compound having one adsorption point (functional group: —SO ₃ H) and oxide particles. FIG. 4B is an explanatory diagram schematically showing a state in which a thermal history is added to a product obtained by reacting or interacting with the long-chain compound and oxide particles in FIG. 4A. FIG. 4C is a drawing schematically showing a state before a reaction or interaction between a long-chain compound having a large number of adsorption points (functional groups) and oxide particles. FIG. 4D is an explanatory view schematically showing a state in which a thermal history is added to a substance in which the long-chain compound and the oxide particles in FIG. 4C are reacted or interacted to be immobilized (multi-point adsorption). .

Explanation of symbols

11 oxide particles,
13 A long-chain compound having a large number of adsorption points (functional groups),
14 a long-chain compound having one adsorption point (functional group),
15 thermoplastic resin,
Long axis length of L ₁ oxide particles (major axis diameter),
Minor axis length of L ₂ oxide particles (minor axis diameter).

Claims (11)

  A resin composition comprising an oxide particle, a long-chain compound having a plurality of chemical bonding capabilities with respect to the surface of the oxide particle, and a thermoplastic resin.   The resin composition according to claim 1, wherein the long-chain compound has an organic acid monomer unit having a functional group selected from a carboxyl group, a sulfo group, and a phosphonic acid group.   3. The resin composition according to claim 1, wherein the long chain compound is a copolymer having a number average molecular weight of 30,000 or less.   The organic acid monomer unit having a functional group selected from a carboxyl group, a sulfo group, or a phosphonic acid group that the long chain compound has is included in one or more types of monomer units forming a copolymer, and the organic acid 4. The resin composition according to claim 1, wherein the composition ratio of the monomer units is in the range of 2 to 60 mol% of the total monomer units in the copolymer.   5. The long-chain compound has an organic acid monomer unit having a functional group selected from a carboxyl group, a sulfo group, and a phosphonic acid group, and a monomer unit having an organic acid ester group. The resin composition in any one.   The long-chain compound is a copolymer obtainable by radical polymerization, the organic acid monomer unit is derived from a radical polymerizable organic acid, and the monomer unit having the organic acid ester group is derived from a radical polymerizable organic acid ester The resin composition according to claim 1, wherein the resin composition is a resin composition.   The resin composition according to claim 1, wherein the oxide particles are at least one selected from alumina and silica.   The repeating unit of the chemical structure of the thermoplastic resin includes at least one selected from the group consisting of an ester bond, an ether bond, an amide bond, an imide bond, a urethane bond, a sulfide bond, and a sulfone bond. The resin composition according to any one of 1 to 7.   The thermoplastic resin composition is produced by mixing the thermoplastic resin after the oxide particles and the long-chain compound are allowed to act in a solvent or dry blend, and then melt-kneading the mixture. The manufacturing method of the resin composition in any one of thru | or 8.   After the oxide particles and the long-chain compound are allowed to act in a solvent, the thermoplastic resin is dispersed and mixed, and only the solvent is distilled off under high temperature and reduced pressure to produce a thermoplastic resin composition. The method for producing a resin composition according to any one of claims 1 to 8, wherein the method is characterized in that:   After the oxide particles and the long chain compound are allowed to act in a solvent, the thermoplastic resin monomer is blended and polymerized to produce a thermoplastic resin composition, The manufacturing method of the resin composition in any one of Claim 1 thru | or 8.