JP5724388B2 - Thermoplastic resin composition and molded product obtained by molding the same - Google Patents

Description

  The present invention relates to a thermoplastic resin composition that provides a molded article having excellent heat resistance and flexibility, and a molded article obtained by molding the thermoplastic resin composition.

Among thermoplastic resins, in particular, soft materials are introduced and flexible materials called elastomers, etc., are often processed into film shapes and then bonded to dissimilar materials as parts of various electrical and electronic equipment products. Used.
For example, an acrylic soft resin film is used in a field where design and processability are particularly required, taking advantage of the material having excellent transparency and weather resistance.
However, regarding the physical properties required for such a resin for a film, there is a problem that it is difficult to achieve both flexibility and heat resistance.

  For example, in the manufacturing process of various products, processing accuracy is required as a film part, and when integrated with other parts, the film is required to have flexibility to follow deformation, and exposed to high temperatures together with other parts. In some cases, the film is required to have heat resistance in order to suppress deformation. However, in an acrylic soft resin, when the composition is improved in order to further increase the softness, the heat resistance generally decreases (Patent Document 1), and the flexibility and heat resistance of the film are compatible with the resin composition. It was difficult to do.

On the other hand, addition of inorganic fillers and the like has been studied as a method for improving the physical properties of general thermoplastic resins, and in recent years, a small amount of nano-sized and high aspect ratio fillers have been proposed (Patent Documents). 2).
In the method proposed in Patent Document 2, the surface hardness and the antistatic property are improved by taking advantage of the characteristics of the high aspect ratio filler, but no improvement in heat resistance is suggested.

JP-A-57-140161 JP 2010-132897 A

  In order to cope with product design and part processing accuracy that have become more complex in recent years, a resin composition capable of improving the flexibility and heat resistance of a flexible film is required.

As a result of intensive studies, the present inventors have found that it is possible to achieve both flexibility and heat resistance by blending a specific inorganic compound-containing polymer with a soft thermoplastic resin, and have reached the present invention. .
That is, the present invention
1. Measured with a durometer D containing an inorganic compound-containing polymer (A) obtained by polymerizing a vinyl monomer (a2) in the presence of an aluminum-based inorganic compound (a1) and a soft thermoplastic resin (B) A thermoplastic resin composition having a measured hardness of less than 90;
2. 2. The thermoplastic resin according to 1 above, wherein the inorganic compound-containing polymer (A) is obtained by polymerizing the vinyl monomer (a2) in an aqueous dispersion containing the aluminum-based inorganic compound (a1). 2. a composition; and A molded product obtained by molding the thermoplastic resin composition according to the above 1 or 2 is provided.

  According to the present invention, it is possible to improve heat resistance without impairing the excellent properties of the flexible thermoplastic resin. The present invention can be applied as, for example, an acrylic resin film having excellent transparency, and achieves a higher level of part processing accuracy so that it can cope with a complicated product design. Is extremely expensive.

  The inorganic compound-containing polymer (A) used in the present invention is obtained by polymerizing the vinyl monomer (a2) in the presence of the aluminum-based inorganic compound (a1). As one mode of the polymerization, a method of starting the polymerization in a state where the aluminum-based inorganic compound (a1) is dispersed in the vinyl monomer (a2) can be mentioned. As another embodiment, there is a method in which the polymerization is started in a state where the vinyl monomer (a2) is dissolved in an organic solvent and the aluminum-based inorganic compound (a1) is dispersed in the solution. Yet another embodiment includes a method in which polymerization is initiated in a state where both the vinyl monomer (a2) and the aluminum-based inorganic compound (a1) are dispersed in a medium such as water. As a method for obtaining the inorganic compound-containing polymer (A), it is preferable to polymerize the vinyl monomer (a2) in an aqueous dispersion containing the aluminum-based inorganic compound (a1).

  Examples of the aluminum-based inorganic compound (a1) include at least one selected from allophane, imogolite, and halloysite. As allophane, imogolite and halloysite, natural products obtained as weathered products or synthesized products in volcanic ash soil can be used. Artificially synthesized allophane and imogolite are preferred because the resulting molded article has excellent molding appearance, surface hardness, antistatic properties, crystallinity, and the like.

As the aluminum-based inorganic compound (a1), it is possible to use a spherical shape (granular shape), a needle shape (fiber shape), a plate shape, or the like. In particular, allophane tends to be spherical (granular) and imogolite and halloysite tend to be acicular (fibrous).
When the shape is spherical (granular), the average particle diameter is preferably 1 nm to 1 μm, more preferably 1 to 100 nm, and still more preferably 1 to 50 nm. In the present invention, the average particle diameter means a 50% volume average particle diameter obtained by dispersing the aluminum-based inorganic compound (a1) in deionized water and using a laser diffraction / scattering particle size distribution analyzer.
When the shape is acicular (fibrous), it is preferable to have an aspect ratio of 5 to 10,000. Specifically, the average diameter of the fiber shape is preferably 0.5 to 100 nm, more preferably 0.5 to 20 nm, and still more preferably 0.5 to 5 nm. The average length of the fiber shape (average length in the longitudinal direction) is preferably 5 nm to 200 μm, more preferably 10 nm to 100 μm, and still more preferably 10 nm to 50 μm.

Examples of the method for synthesizing allophane, imogolite, and halloysite include a reaction of sodium orthosilicate and aluminum chloride.
Such a reaction is weakly acidic in an aqueous solution and can be performed with heating as necessary. In addition, the reaction product can be used after being concentrated, washed and dried, if necessary.
For example, the aqueous solution after the reaction can be made weakly alkaline to precipitate the product and separate the supernatant. Moreover, it can also freeze-dry and take out as a solid substance.

  In addition, since the stability in the production process of the inorganic compound-containing polymer (A) obtained in the present invention and the molding appearance and physical properties of the obtained thermoplastic resin composition are improved, the reaction product is concentrated and washed. It is preferable to use it in the next step without performing a drying operation, with the weakly acidic aqueous solution after the reaction.

Examples of the method for confirming that the product is allophane, imogolite, or halloysite include measurement of X-ray diffraction, transmission electron microscope (TEM), and infrared absorption spectrum (IR).
In the measurement of X-ray diffraction, peaks peculiar to imogorat can be confirmed around diffraction angles (2θ) of 6 °, 11 °, and 16 °. In the observation by TEM, it is possible to confirm a form in which particles having a diameter of about 5 nm are aggregated in the case of allophane, and a form in which fibers are aggregated in the case of imogolite. In the IR measurement, absorption near 900 to 1000 cm ⁻¹ derived from the Si—O—Al bond can be confirmed.

  Allophane, imogolite and halloysite are preferably pretreated with a phosphate compound. The treatment with a phosphoric acid compound can be carried out, for example, by adding a phosphoric acid compound to an aqueous dispersion containing allophane, imogolite or halloysite. As the phosphoric acid compound, those exemplified as the phosphoric acid compound (a3) described later can be used. By performing pretreatment with a phosphoric acid compound, the dispersibility of the aluminum inorganic compound (a1) in the resulting thermoplastic resin composition is improved, and as a result, the surface scratch resistance and antistatic properties of the molded product are improved. , Heat distortion resistance can be improved.

  Examples of the vinyl monomer (a2) used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth). Acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and its hydrochloride, cyanoethyl (meth) acrylate, cyanobutyl (meth) acrylate, allyl (meth) acrylate , Ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, (meth) acrylate such as trimethylolpropane tri (meth) acrylate; (meth) acrylic acid; 2,2,2-trifluoro Fluorinated (meth) acrylates such as ethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate; aromatic vinyl monomers such as styrene and α-methylstyrene; vinyl cyanide monomers such as acrylonitrile; acrylamide, Examples include acrylamide monomers such as N, N-dimethylacrylamide and N-isopropylacrylamide. These may be used alone or in combination of two or more.

  Among these, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate , Ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, (meth) acrylic acid, 2,2,2-trifluoroethyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, Styrene and acrylonitrile are preferred because of the excellent molded appearance, surface hardness, crystallinity, and the like of the resulting molded product. Methyl (meth) acrylate, n-butyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate , Su Ren, acrylonitrile is more preferable. Here, (meth) acrylate represents acrylate or methacrylate, and (meth) acrylic acid represents acrylic acid or methacrylic acid.

When the vinyl monomer (a2) is polymerized in the aqueous dispersion containing the aluminum-based inorganic compound (a1), it is preferable that the phosphoric acid-based compound (a3) is allowed to coexist in the aqueous dispersion. Dispersibility of the aluminum inorganic compound (a1) in the thermoplastic resin composition obtained by pretreatment of the aluminum inorganic compound (a1) with the phosphoric acid compound by coexisting the phosphoric acid compound. As a result, the surface damage resistance, antistatic property and heat distortion resistance of the molded product can be improved.
The phosphoric acid compound (a3) may be any inorganic compound or organic compound as long as it has a phosphoric acid group, such as an alkali metal salt, alkaline earth metal salt, ammonium salt, or alkylammonium salt of phosphoric acid. Phosphate, phosphoric acid monoester or phosphoric diester of an organic hydroxy compound is preferred.

  Examples of the organic hydroxy compound used for producing the phosphate ester as the phosphoric acid compound (a3) include vinyl group-containing alcohol, propanol, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, heptanol, and cycloheptanol. , Octanol, cyclooctanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol, heptadecanol, methoxyethanol, trifluoroethanol, hexafluoropropanol, phenol, benzyl alcohol, ethylene glycol, triethylene glycol. Among these, vinyl group-containing alcohols are preferable because of the excellent molding appearance, surface hardness, crystallinity, and the like of the obtained molded body. Examples of the vinyl group-containing alcohol include 2-hydroxyethyl (meth) acrylate and polyalkylene glycol mono (meth) acrylate.

  Examples of phosphoric esters obtained using these organic hydroxy compounds include monoesters and diesters composed of 2-hydroxyethyl (meth) acrylate and phosphoric acid, and monoesters composed of polyalkylene glycol mono (meth) acrylate and phosphoric acid. And diesters are preferred.

  Examples of commercially available products that can be used as the phosphoric acid compound (a3) include Phosmer M, Phosmer PE, Phosmer P (manufactured by Unichemical Corporation); JPA-514, JPA-514M (all ), Light ester P-1M, light acrylate P-1A (above, manufactured by Kyoeisha Chemical Co., Ltd.), MR200 (manufactured by Daihachi Chemical Industry Co., Ltd.), Kayamar (manufactured by Nippon Kayaku Co., Ltd.), ethylene Examples include glycol methacrylate phosphate (manufactured by Aldrich). These commercially available products may be a mixture of a monoester and a diester, and may contain a component that does not contain a vinyl group as an impurity, but may be used as it is as the phosphoric acid compound (a3). it can. A phosphoric acid type compound (a3) may be used individually by 1 type, and may use 2 or more types together.

  The aluminum-based inorganic compound (a1) is preferably used in an amount of 0.00001 to 100 parts by mass with respect to 100 parts by mass of the vinyl monomer (a2), and the molding appearance, surface hardness, antistatic properties, and crystals of the resulting molded product From the viewpoint of excellent properties and the like, it is more preferable to use 0.001 to 50 parts by mass, still more preferably 0.01 to 30 parts by mass, and particularly preferably 0.05 to 20 parts by mass.

  The phosphoric acid compound (a3) is preferably used in an amount of 1 to 10000 parts by mass with respect to 100 parts by mass of the aluminum inorganic compound (a1). The molding appearance, surface hardness, antistatic properties, crystallinity, etc. of the resulting molded product Therefore, it is more preferable to use 1 to 1000 parts by mass, still more preferable to use 2 to 500 parts by mass, and particularly preferable to use 5 to 200 parts by mass.

  The amount of water used as a dispersion medium in the aqueous dispersion is not particularly limited, but is preferably 10 to 10,000 parts by weight with respect to 100 parts by weight of the vinyl monomer (a2) because of excellent polymerization stability and productivity. 100-2000 mass parts is more preferable.

  As a method for polymerizing the vinyl monomer (a2) in an aqueous dispersion containing the aluminum-based inorganic compound (a1), a radical polymerization method in a suspension system or an emulsion system can be used. Specifically, the phosphoric acid compound (a3) is added to the aluminum inorganic compound (a1) dispersed in water as necessary, and then the vinyl monomer (a2) and the polymerization initiator are added. The radical polymerization can be carried out by heating.

  Examples of the polymerization initiator used for the polymerization of the vinyl monomer (a2) include t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, benzoyl peroxide, di-t-butyl peroxide, and di-t-amyl. Organics such as peroxide, di-t-hexyl peroxide, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, diisopropylperoxycarbonate, etc. And peroxides; persulfates such as potassium persulfate and ammonium persulfate; and azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together. Among these, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile and azobis-2 1,4-dimethylvaleronitrile is preferred. Moreover, the said organic peroxide and persulfate can also be used as a redox system in combination with a reducing agent.

The polymerization of the vinyl monomer (a2) can be performed at a temperature of 65 to 100 ° C., and can be performed in a polymerization time of 1 to 10 hours.
If necessary, the polymerization can be carried out in two stages. For example, after carrying out the polymerization for a predetermined time at a predetermined temperature, it can be held at a higher temperature to complete the polymerization.

Furthermore, in the polymerization of the vinyl monomer (a2), polymerization additives such as a chain transfer agent, a dispersant, a dispersion aid, and an emulsifier can be used as necessary.
Examples of the chain transfer agent include octyl mercaptan, dodecyl mercaptan, and α-methylstyrene dimer.
Examples of the dispersant include poly (meth) acrylic acid alkali metal salts, (meth) acrylic acid alkali metal salts and (meth) acrylic acid ester copolymers, and (meth) acrylic acid sulfoalkyl alkali metal salts. And (meth) acrylic acid ester copolymer, polystyrenesulfonic acid alkali metal salt, styrenesulfonic acid alkali metal salt and (meth) acrylic acid ester copolymer, polyvinyl alcohol having a saponification degree of 70 to 100% And methyl cellulose. These may be used alone or in combination of two or more. Among these, a copolymer of an alkali metal salt of (alkyl) sulfoalkyl (meth) acrylate and (meth) acrylic acid ester having good dispersion stability during suspension polymerization is preferable. Examples of the dispersion aid include sodium sulfate and manganese sulfate.
As the emulsifier, known anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers can be used.
In the present invention, the mass average molecular weight of the polymer obtained by carrying out the production method of the above-described inorganic compound-containing polymer by the same operation except that the inorganic compound is not included is used as the inorganic compound-containing polymer ( The estimated molecular weight of A). The estimated molecular weight of the inorganic compound-containing polymer (A) is preferably 10,000 to 1,000,000, more preferably 30,000 to 500,000, and particularly preferably 50,000 to 200,000 as the mass average molecular weight by gel permeation chromatography (GPC). preferable.

Examples of the flexible thermoplastic resin (B) used in the present invention include acrylic resins, fluorine resins, styrene resins, olefin resins, polyester resins, and urethane resins. These may be used alone or in combination of two or more.
Among these, acrylic resins and fluorine resins are preferred because the resulting molded article has good transparency and weather resistance.

As an example of the soft thermoplastic resin (B), there is a soft acrylic resin (B1).
As a vinyl monomer which is a constituent component of the soft acrylic resin (B1), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, alkyl (meth) acrylates such as i-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate; benzyl (meth ) Aromatic (meth) acrylates such as acrylate and phenyl (meth) acrylate; ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylo Polyfunctional (meth) acrylates such as lepropane tri (meth) acrylate; reactive group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, and allyl (meth) acrylate Can be mentioned. These may be used alone or in combination of two or more.
The flexible acrylic resin (B1) may use butadiene, styrene, acrylonitrile, or the like as a constituent component at a ratio of less than 50% by mass as necessary.

  The soft acrylic resin (B1) can be produced by a known method. For example, after the monomer mixture which has alkyl acrylate as a main component is superposed | polymerized, the monomer method which has alkyl methacrylate as a main component may be graft-polymerized, and the manufacturing method which obtains a multistage polymer may be sufficient. A plurality of soft acrylic resins may be mixed and used.

The soft acrylic resin (B1) preferably has a hardness measured with a durometer D of less than 90.
In order to make the hardness measured with the durometer D less than 90, the ratio of the polymer component having a glass transition temperature of 25 ° C. or lower is preferably 10% by mass or more of the resin (B1), and 20% by mass or more. Is more preferable, and it is still more preferable that it is 35 mass% or more.

Another example of the soft thermoplastic resin (B) is a fluororesin (B2).
Examples of the fluororesin (B2) include perfluorinated polymers such as polytetrafluoroethylene (PTFE); poly (ethylene trifluoride) chloride (PTCFE, CTFE), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). ) And the like; tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), tetrafluoroethylene-6 fluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer ( ETFE) and fluorinated copolymers such as ethylene-trifluoroethylene chloride copolymer (ECTFE). Among these, considering the transparency and weather resistance of the resulting resin composition, PVDF, PVF, and PFA are preferable, and PVDF is more preferable.
The fluororesin (B2) preferably has a hardness measured with a durometer D of less than 90.

  The thermoplastic resin composition of the present invention can be obtained by blending a soft thermoplastic resin (B) with an inorganic compound-containing polymer (A). In the resin composition of the present invention, the proportion of the inorganic compound-containing polymer (A) and the flexible thermoplastic resin (B) is, when the total amount is 100 parts by mass, the inorganic compound-containing polymer (A). 0.001 to 99 parts by mass, the flexible thermoplastic resin (B) is preferably 1 to 99.999 parts by mass, and the inorganic compound-containing polymer (A) is 0.1 parts by mass. It is more preferable that the thermoplastic thermoplastic resin (B) is 30 parts by mass or more and 99.9 parts by mass or less, and the inorganic compound-containing polymer (A) is 0.5 parts by mass or more and 40 parts by mass or less. More preferably, the soft thermoplastic resin (B) is 60 parts by mass or more and 99.5 parts by mass or less.

The hardness of the thermoplastic resin composition according to the present invention is a hardness measured according to JIS K-7215, and a value measured with a durometer D is used. A thermoplastic resin composition having a hardness measured with a durometer D of 90 or more is difficult to produce and use as a film, and is particularly difficult to handle in terms of strength and workability.
The thermoplastic resin composition of the present invention uses a soft thermoplastic resin having a hardness measured with a durometer D of less than 90 as the flexible thermoplastic resin (B), and contains an inorganic compound so that the hardness is maintained. It can be prepared by blending the polymer (A).

  In the thermoplastic resin composition of the present invention, if necessary, a thermoplastic resin different from the flexible thermoplastic resin (B) can be contained so as to be less than 50% by mass of the total components. Other thermoplastic resins include, for example, acrylic resins such as polymethyl methacrylate (PMMA) and methyl methacrylate-acrylate copolymer; polystyrene, high impact polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene. Styrene resins such as copolymers, styrene-butadiene copolymers, hydrogenated styrene-butadiene copolymers; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polypropylene, low density polyethylene, linear low density Olefin resins such as polyethylene, high density polyethylene, ethylene-propylene copolymer, and cyclic olefin-containing polymers; aliphatic polyester resins such as polylactic acid, polycaprolactone, and polybutylene succinate; polyethylene terephthalate Aromatic polyester resins such as polyethylene naphthalate, polytrimethylene glycol terephthalate and polybutylene terephthalate; dihydroxy diaryl compounds such as 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and phosgene or carbonic acid diester compounds Polycarbonate resins such as polymers obtained by reaction; polyoxymethylene, polyphenylene ether, polyether ketone, and polyether ether ketone.

  In the thermoplastic resin composition of the present invention, if necessary, additives for resins such as antioxidants, light stabilizers, flame retardants, plasticizers, pigments, glass fibers, carbon fibers, talc, calcium carbonate, A filler such as kenaf or bacterial cellulose can be contained.

  In the thermoplastic resin composition of the present invention, the inorganic compound-containing polymer (A) and the flexible thermoplastic resin (B) are blended together with the above-described thermoplastic resin, resin additive, filler and the like as necessary. Can be prepared. Examples of the blending method include a melt blending method using a batch kneader and a single-screw or multi-screw extruder.

  The thermoplastic resin composition of the present invention can be used as various resin molding materials, binder resins for paints, and toners.

  The molded article of the present invention can be obtained by molding a thermoplastic resin composition containing the inorganic compound-containing polymer (A). When molding a molded body using the thermoplastic resin composition containing the above-mentioned inorganic compound-containing polymer (A), molding methods such as extrusion molding, injection molding, press molding, inflation molding and calendar molding can be applied. . For example, a film-like or sheet-like molded body can be obtained.

  The said molded object can be used for the components of a motor vehicle, a household appliance, and OA apparatus, for example.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited by this. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively.

[X-ray diffraction]
Using an X-ray diffractometer (RINT2500 (trade name) manufactured by Rigaku Corporation), the acceleration voltage is 40 kV, the acceleration current is 300 mA, Cu-Kα rays are applied, and the diffraction angle (2θ) ranges from 5 to 85 °. The diffraction pattern was measured.

[TEM]
Using a transmission electron microscope (JEM-1200EXII (trade name) manufactured by JEOL Ltd.), observation was performed at an acceleration voltage of 100 KV and a magnification of 100,000 times.

[IR]
Using a Fourier transform infrared spectrophotometer (FTIR-8700 (trade name) manufactured by Shimadzu Corporation), an absorption spectrum in the range of 400 to 4000 cm ⁻¹ was measured by a transmission method for a sample prepared by the KBr method. .

[BET specific surface area]
Using a specific surface area measuring device (Monosorb (trade name) manufactured by Yuasa Ionics Co., Ltd.), the sample was degassed at 120 ° C. for 2 hours and then measured.

[Mass average molecular weight]
The mass average molecular weight of the polymer was measured using gel permeation chromatography (GPC150C (trade name) manufactured by Waters). Polymethyl methacrylate was used as the standard and chloroform was used as the mobile phase.

[Gel content]
The soft acrylic resin (B1) was weighed (mass before extraction) and refluxed in acetone. After centrifugation, the supernatant was removed, and the acetone-insoluble matter was dried and weighed (mass after extraction). The gel content was determined by the following formula (1).
Gel content (mass%) = mass after extraction (g) / mass before extraction (g) × 100 (1)

[Rubber content]
Components of the soft acrylic resin (B1) having a glass transition temperature of 25 ° C. or lower of the polymer obtained in each step were summed, and the ratio relative to the entire resin (B1) was defined as the rubber content.
The glass transition temperature (Tg) of the polymer at each stage is calculated from the Fox equation (the following formula (2) from the glass transition temperature (Tgi) of the homopolymer corresponding to each monomer and its ratio (φi). )) (See "Polymer Handbook" Wiley InterScience edition, edited by J. Brandrup, IV version).
1 / Tg = Σ (φi / Tgi) (2)

[Dispersed state of inorganic compound]
The appearance of the obtained film (thickness: 200 μm) was visually observed. Evaluation was performed according to the following criteria.
○: The presence of the inorganic compound could not be confirmed visually.
(Triangle | delta): Presence of an inorganic compound has been confirmed visually. No reduction in film strength was observed.
X: The presence of the inorganic compound could be confirmed visually. A decrease in strength of the film was observed, and the physical property evaluation was stopped.

[Durometer D hardness]
The resin composition was melt-kneaded at a barrel temperature of 200 ° C. for 5 minutes using a desktop compact kneader (CS-183 (trade name) manufactured by Custom Scientific Instruments) and then injected into a mold. (Length 20 mm, width 10 mm, thickness 2 mm).
The durometer D hardness of the obtained molded product was measured according to JIS K-7215.

[Heat-resistant]
Using the obtained film (thickness 200 μm, width 4 mm) as a test piece, using a thermomechanical analyzer (model name “TMA / SS6100”, manufactured by Seiko Instruments Inc.), conditions of tensile mode and tensile stress 29 mN A test piece was attached at a distance of 10 mm between chucks, and the deformation rate determined by the following equation was recorded while the temperature was raised from 20 ° C. to 150 ° C. at 5 ° C./min.
As the deformation start temperature, in the case of the soft acrylic resin (B1), the deformation rate reached 2%, and in the case of the fluororesin / acrylic resin blend, the time reached 5%.
Deformation rate [%] = Increase in chuck distance / Initial value of chuck distance x 100

[transparency]
The obtained film (thickness: 200 μm) was used as a test piece, and the total light transmittance and haze were measured according to JIS K-7105. Evaluation was performed according to the following criteria.
A: Total light transmittance is 95% or more and haze is less than 5%.
A: Total light transmittance is less than 95%, and haze is 5% or more and less than 60%.
X: Total light transmittance is less than 95%, and haze is 60% or more.

[Scratch resistance]
The obtained film (thickness: 200 μm) was used as a test piece, and a pencil scratch test was performed in accordance with JIS K-5400. However, the test was performed by placing a test piece on a PMMA sheet (thickness 3 mm) as a base material.

[Antistatic property]
After rubbing the surface of the obtained film (thickness: 200 μm) for a predetermined number of times with a dry cotton cloth, the adhesion of the ash when the film surface was brought close to a cigarette ash on a flat surface by 10 mm was evaluated. The evaluation was performed in an environment of 23 ° C. and 50% RH. In addition, the film was used in advance in this environment for one day.
○: Ash did not adhere even after rubbing 10 times with a cotton cloth.
(Triangle | delta): Ash adhered when it rubbed 10 times with the cotton cloth. When rubbed three times, no ash adhered.
X: Ash was adhered after rubbing three times with a cotton cloth.

[Storage modulus]
Using the obtained film (thickness: 200 μm) as a test piece, using a thermomechanical analyzer (model name “TMA / SS6100”, manufactured by Seiko Instruments Inc.), conditions of tension mode, temperature 25 ° C., frequency 1 Hz Below, a test piece was attached at a distance between chucks of 10 mm, and the storage elastic modulus was measured.
When the storage elastic modulus is high, creep resistance and stress relaxation resistance are improved, and durability is improved.

[Production Example 1] Production of aqueous dispersion of aluminum-based inorganic compound (a1) In a reaction vessel with a stirrer (internal volume 60 L) made of titanium metal, 8.6 L of sodium orthosilicate solution having a Si concentration of 0.01 M was placed. Stir. Next, 21 L of an aluminum chloride solution having an Al concentration of 0.01 M was added and stirred for 30 minutes.
Then, 18.5 L of 0.01 M NaOH solution was added over 1 hour. The pH of the suspension at this time was 4.5 (25 ° C.). The suspension was heated to 95 ° C., held for 24 hours, and then cooled to room temperature over 24 hours.
At this time, the pH of the reaction suspension was 4.2, which was extremely high in transparency. The solid content of the obtained aqueous dispersion of (a1) was 0.04%.

[Production Example 2] Production of powder of aluminum-based inorganic compound (a1) The aqueous dispersion of aluminum-based inorganic compound (a1) obtained in Production Example 1 was gradually heated from minus 40 ° C with a freeze dryer. Then, drying was performed for 28 hours to obtain a powder.
The following analysis was performed on the obtained powder. From this analysis result, it was confirmed that the aluminum-based inorganic compound (a1) was imogolite.

X-ray diffraction: Broad peaks were observed near diffraction angles (2θ) of 6 °, 11 ° and 16 °.
TEM: A fibrous image was seen.
IR: Doublet absorption around 950 to 1000 cm ⁻¹ derived from Si—O—Al bond was observed.
These features are unique to imogolite.
Moreover, the BET specific surface area of the obtained aluminum type inorganic compound (a1) was 325 m < ² > / g.

[Production Example 3] Production of inorganic compound-containing polymer (A1) Aluminum-based inorganic compound (a1) obtained in Production Example 1 in a reaction vessel equipped with a stirrer, a heating device, a thermometer, a cooling tube, and a nitrogen introduction tube ) In 1000 parts (0.4 part as the solid content of (a1)) was stirred and stirred at room temperature.
After adding 10 parts of 10% aqueous ammonia solution and stirring for 30 minutes, 0.04 part of acid phosphooxyethyl methacrylate (trade name “Phosmer M”, manufactured by Unichemical Co., Ltd.) was added and stirred for 30 minutes.

Subsequently, 100 parts of methyl methacrylate (MMA), 0.1 part of n-octyl mercaptan (OM) as a chain transfer agent, and 0.05 part of azobisisobutyronitrile (AIBN) as a polymerization initiator were added.
The temperature was raised to 80 ° C. under a nitrogen stream and stirred for 2 hours, and then the temperature was raised to 90 ° C. and stirred for 30 minutes. After cooling the reaction vessel, the product was separated and dried to obtain an inorganic compound-containing polymer (A1).
In order to estimate the molecular weight of the obtained inorganic compound-containing polymer (A1), Production Example 3 was carried out in the same manner except that the aluminum-based inorganic compound (a1) was not included. When the mass average molecular weight of the obtained polymer was measured by GPC, it was 100,000. This was the estimated molecular weight of the inorganic compound-containing polymer (A1).

[Production Example 4] Production of inorganic compound-containing polymer (A2) 300 parts of an aqueous dispersion of an aluminum-based inorganic compound (a1) (0.12 parts as the solid content of (a1)) and acid phosphooxyethyl methacrylic acid An inorganic compound-containing polymer (A2) was obtained in the same manner as in Production Example 3, except that 0.012 part of ester (trade name “Fosmer M”, manufactured by Unichemical Co., Ltd.) was used.
In order to estimate the molecular weight of the obtained inorganic compound-containing polymer (A2), Production Example 4 was carried out in the same manner except that the aluminum-based inorganic compound (a1) was not included. When the mass average molecular weight of the obtained polymer was measured by GPC, it was 100,000. This was the estimated molecular weight of the inorganic compound-containing polymer (A2).

[Production Example 5] Production of flexible acrylic resin (B1-1) After charging 10.8 parts of deionized water in a container equipped with a stirrer, 0.3 part of MMA, n-butyl acrylate (n-BA) 4 A monomer comprising 0.5 part, 0.2 part of 1,3-butylene glycol dimethacrylate (1,3-BD), 0.05 part of allyl methacrylate (AMA) and 0.025 part of cumene hydroperoxide (CHP) The components were added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Industry Co., Ltd., trade name “Phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.
Next, 139.2 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 75 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of deionized water was charged into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was added dropwise to the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization of the monomer mixture (IA-1).

Subsequently, a monomer component consisting of 9.6 parts of MMA, 14.4 parts of n-BA, 1.0 part of 1,3-BD and 0.25 part of AMA was added dropwise to the polymerization vessel over 90 minutes together with 0.016 part of CHP. Thereafter, the reaction was continued for 60 minutes to complete the polymerization of the monomer mixture (IA-2) to obtain a polymer. The Tg determined from the FOX formula of the polymer obtained from the monomer mixture (IA-1) is −48 ° C., and the polymer FOX obtained from the monomer mixture (IA-2) Tg calculated | required from the type | formula was -10 degreeC.
Subsequently, a monomer component consisting of 6 parts of MMA, 4 parts of methyl acrylate (MA) and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes to polymerize. Was done. Tg calculated | required from the formula of FOX of the polymer obtained from a monomer mixture (IB) was 60 degreeC.

Subsequently, the monomer component (IC) consisting of 57 parts of MMA, 3 parts of MA, 0.264 part of OM and 0.075 part of t-butyl hydroperoxide (t-BH) was dropped into the polymerization vessel over 140 minutes. The reaction was continued for 60 minutes to obtain a polymer latex of the rubber-containing polymer (I). The Tg determined from the FOX formula of the polymer obtained from the (IC) monomer mixture was 99 ° C. The mass average particle diameter of the rubber-containing polymer (I) measured after polymerization was 0.11 μm.
The polymer latex of the rubber-containing polymer (I) thus obtained was filtered using a vibration type filtration device equipped with a SUS mesh (average opening: 62 μm) as a filter medium, and then 3.5 parts of calcium acetate was added. Salting out was carried out in an aqueous solution containing, recovered by washing with water, and then dried to obtain a powdery rubber-containing polymer (I). The gel content of the rubber-containing polymer (I) was 70%. The rubber content of the rubber-containing polymer (I) was 30%.

Also, 214.3 g of the obtained rubber-containing polymer (I) was added to 1500 mL of acetone filtered through a nylon mesh having an opening of 25 μm and stirred for 3 hours to prepare an acetone dispersion of the rubber-containing polymer (I). did. Next, this dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and then the nylon mesh was washed in chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. Next, the captured substance after ultrasonic cleaning is put into 150 mL of acetone filtered through a nylon mesh having an opening of 25 μm together with the nylon mesh, and this liquid is subjected to ultrasonic treatment for 15 minutes, after which the nylon mesh is removed, A 150 mL acetone dispersion of the trapped material was prepared. Subsequently, 70 mL of this dispersion was measured at 25 ° C. with an automatic liquid particle counter (model: KL-01) manufactured by Rion Co., Ltd., and the number of particles having a diameter of 55 μm or more was determined. It was a piece.
75 parts of the resulting rubber-containing polymer (I) and thermoplastic polymer (III) [MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g)] 25 parts were mixed using a Henschel mixer. This mixture was supplied to a degassing extruder heated to 230 ° C. (PCM-30 (trade name) manufactured by Ikekai Tekko Co., Ltd.), kneaded, extruded while removing foreign matter with a 300 mesh screen mesh, and pellets Got.

[Production Example 6] Production of soft acrylic resin (B1-2) After charging 8.5 parts of deionized water into a container equipped with a stirrer, 0.3 part of MMA, 4.5 parts of n-BA, 1, 3 -A monomer mixture (II-A-1) consisting of 0.2 part of BD, 0.05 part of AMA and 0.025 part of CHP was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Industry Co., Ltd., trade name “Phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.
Next, 186.5 parts of deionized water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 70 ° C. Further, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of deionized water was charged into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was dropped into the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization.

Subsequently, a monomer mixture (II-A-2) consisting of 1.5 parts of MMA, 22.5 parts of n-BA, 1.0 part of 1,3-BD and 0.25 part of AMA was added together with 0.016 part of CHP to 90 parts. After dripping into the polymerization vessel over a period of 60 minutes, the reaction was continued for 60 minutes to complete the polymerization.
The Tg determined from the formula of FOX of the polymer obtained from the monomer mixture (II-A-1) is −48 ° C., and the FOX of the polymer obtained from the monomer mixture (II-A-2) The Tg determined from the formula was -48 ° C.
Subsequently, a monomer mixture (II-B) consisting of 6 parts of MMA, 4 parts of n-BA and 0.075 part of AMA was dropped into the polymerization vessel over 45 minutes together with 0.0125 parts of CHP, and then the reaction was continued for 60 minutes. It was. Tg calculated | required from the formula of FOX of the polymer obtained from a monomer mixture (II-B) was 20 degreeC.

Subsequently, a monomer mixture (II-C) consisting of 55.2 parts of MMA, 4.8 parts of MA, 0.19 part of OM and 0.08 part of t-BH was added dropwise to the polymerization vessel over 140 minutes, and then reacted for 60 minutes. This was continued to obtain a polymer latex of the rubber-containing polymer (II). Tg calculated | required from the formula of FOX of the polymer obtained from a monomer mixture (II-C) was 84 degreeC. The mass average particle diameter of the rubber-containing polymer (II) measured after polymerization was 0.12 μm.
The polymer latex of the rubber-containing polymer (II) thus obtained was filtered using a vibration type filtration device equipped with a SUS mesh (average opening: 62 μm) as a filter medium, and then 3.0 parts of calcium acetate was added. Salting out was carried out in an aqueous solution containing, recovered by washing with water, and then dried to obtain a powdery rubber-containing polymer (II). The gel content of the rubber-containing polymer (II) was 60%. The rubber content of the rubber-containing polymer (II) was 40%.
Also, 214.3 g of the obtained rubber-containing polymer (II) was added to 1500 mL of acetone filtered through a 25 μm nylon mesh and stirred for 3 hours to prepare an acetone dispersion of the rubber-containing polymer (II). did. Next, this dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and then the nylon mesh was washed in chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. Next, the captured substance after ultrasonic cleaning is put into 150 mL of acetone filtered through a nylon mesh having an opening of 25 μm together with the nylon mesh, and this liquid is subjected to ultrasonic treatment for 15 minutes, after which the nylon mesh is removed, A 150 mL acetone dispersion of the trapped material was prepared. Subsequently, 70 mL of this dispersion was measured at 25 ° C. with an automatic liquid particle counter (model: KL-01) manufactured by Rion Co., Ltd., and the number of particles having a diameter of 55 μm or more was determined. It was a piece.

[Examples 1 to 4]
The inorganic compound-containing polymer (A1) obtained in Production Example 3 or the inorganic compound-containing polymer (A2) obtained in Production Example 4, and the soft acrylic resin (B1-1) or soft acrylic resin (B1- 2) are mixed at a ratio shown in Table 1 and melt kneaded at a barrel temperature of 200 ° C. using a kneader (trade name “Plasticcoder”, manufactured by Brabender Co., Ltd., with an internal volume of 50 cm ³ ). Obtained.
The obtained resin composition was sandwiched between molds (two steel plates with a thickness of 2 mm, spacers) and heated to 200 ° C. (hydraulic press manufactured by Oji Machinery Co., Ltd., maximum load 37 tons, maximum working pressure 210 kg / cm ² ), the gauge pressure was increased to 30 kg / cm ² over 5 minutes. After moving to a press machine (Shioji Tekko Co., Ltd. hydraulic press machine, maximum load 100 tons, normal pressure 200 kg / cm ² , water-cooled), hold the mold for 5 minutes together with the mold. The film-like molded product was removed. The molding conditions were adjusted so that the thickness was 0.2 mm. Table 1 shows the results of evaluating the physical properties using the obtained film.

[Comparative Example 1]
The soft acrylic resin (B1-1) obtained in Production Example 5 and PMMA were mixed at the ratio shown in Table 1, and a kneader (trade name “Plasticcoder”, manufactured by Brabender, internal volume 50 cm ³ ) was used. The resin composition was obtained by melt-kneading at a barrel temperature of 200 ° C. The resulting resin composition was sandwiched between molds (2 mm thick iron plates, spacers) and heated to 200 ° C. (press hydraulic machine manufactured by Oji Machinery Co., Ltd., maximum load: 37 tons, maximum working pressure: 210 kg / Cm ² ), the gauge pressure was increased to 30 kg / cm ² over 5 minutes. After moving to a press machine (Shioji Tekko Co., Ltd. hydraulic press machine, maximum load 100 tons, normal pressure 200 kg / cm ² , water-cooled), hold the mold for 5 minutes together with the mold. The film-like molded product was removed. The molding conditions were adjusted so that the thickness was 0.2 mm. Table 1 shows the results of evaluating the physical properties using the obtained film.

[Comparative Example 2]
A film was formed by the same operation as in Comparative Example 1 except that the soft acrylic resin (B1-1) was replaced with (B1-2) obtained in Production Example 6, and the physical properties were evaluated. The results are shown in Table 1.

[Comparative Examples 3 and 4]
The powder of the inorganic compound simple substance (a1) obtained in Production Example 2 and the soft acrylic resin (B1-2) were mixed in the proportions shown in Table 1, respectively, and melt-kneading was performed in the same manner as in Comparative Example 1. The obtained resin composition was molded into a film shape and evaluated for physical properties. The physical property evaluation results are shown in Table 1.

ＰＭＭＡ：三菱レイヨン（株）製アクリペットＶＨ（商品名）

PMMA: Mitsubishi Rayon Co., Ltd. Acripet VH (trade name)

As shown in Examples 1 to 4, it is clear that a flexible film excellent in flexibility and heat resistance can be obtained by combining the inorganic compound-containing polymer of the present invention with, for example, an acrylic soft resin. It was.
As shown in Comparative Examples 1 and 2, in the case of the conventional soft acrylic resin, although it is excellent in either flexibility or heat resistance, it is inferior to the other, and it is difficult to achieve both.
More specifically, when Example 1 using the resin (B1-1) as the flexible thermoplastic resin (B) is compared with Comparative Example 1, in Example 1, the heat resistance is maintained while maintaining flexibility. Was found to improve by 5 ° C. When Example 2 using the resin (B1-2) was compared with Comparative Example 2, it was found that in Example 2, the heat resistance was improved by 15 ° C. while maintaining flexibility.
As shown in Comparative Examples 3 and 4, when an inorganic compound powder is used in place of the inorganic compound-containing polymer of the present invention, only a resin composition in which inorganic components are non-uniformly aggregated can be obtained. The effect of manifesting physical properties as in the present invention could not be found.

[Example 5]
The inorganic compound-containing polymer (A1) obtained in Production Example 3 and PVDF are mixed in the proportions shown in Table 2, and melt kneaded by the same operation as in Example 1, and the resulting resin composition is formed into a film. And physical properties were evaluated. The physical property evaluation results are shown in Table 2.

[Example 6]
A film was formed by the same operation as in Example 5 except that the inorganic compound-containing polymer (A1) was replaced with the inorganic compound-containing polymer (A2) obtained in Production Example 4, and the physical properties were evaluated. The results are shown in Table 2.

[Comparative Example 5]
PVDF and PMMA were mixed in the proportions shown in Table 2, melt kneaded by the same operation as in Comparative Example 1, and the resulting resin composition was formed into a film and evaluated for physical properties. The physical property evaluation results are shown in Table 2.

[Comparative Example 6]
The powder of inorganic compound (a1) obtained in Production Example 2, PMMA and PVDF were mixed in the proportions shown in Table 2, and melt kneaded by the same operation as in Comparative Example 1, and the resulting resin composition Was formed into a film and evaluated for physical properties. The physical property evaluation results are shown in Table 2.

ＰＭＭＡ：三菱レイヨン（株）製アクリペットＶＨ（商品名）
ＰＶＤＦ：アルケマ社製カイナー７２０（商品名）

PMMA: Mitsubishi Rayon Co., Ltd. Acripet VH (trade name)
PVDF: Kyner 720 (trade name) manufactured by Arkema

As shown in Examples 5 and 6, it was revealed that the soft resin film containing the inorganic compound-containing polymer of the present invention was excellent in heat resistance, storage elastic modulus, scratch resistance, and antistatic properties.
As shown in Comparative Example 5, the soft resin film made of PVDF and PMMA is inferior in heat resistance, storage elastic modulus, scratch resistance, and antistatic property.
Specifically, when Examples 5 and 6 using the resin (B-2) as the flexible thermoplastic resin (B) were compared with Comparative Example 5, the flexibility was maintained in Examples 5 and 6. It was revealed that the heat resistance was improved by 10 ° C.
As shown in Comparative Example 6, when an inorganic compound powder is used instead of the inorganic compound-containing polymer of the present invention, only the resin composition in which the inorganic components are non-uniformly aggregated can be obtained. It was not possible to find a physical property expression effect.

Claims (3)

Inorganic compound-containing polymer (A) obtained by polymerizing vinyl monomer (a2) in the presence of aluminum-based inorganic compound (a1) and soft thermoplastic resin having a hardness measured by durometer D of less than 90 A thermoplastic resin composition containing (B) and having a hardness measured with a durometer D of less than 90.   The thermoplastic resin according to claim 1, wherein the inorganic compound-containing polymer (A) is obtained by polymerizing the vinyl monomer (a2) in an aqueous dispersion containing the aluminum-based inorganic compound (a1). Resin composition.   The molded object obtained by shape | molding the thermoplastic resin composition of Claim 1 or 2.