JP5084211B2 - Materials for housing equipment - Google Patents

Description

  The present invention relates to a material for housing equipment that has both high crack resistance and high compressive strength.

  From the viewpoint of cost reduction, weight reduction is required for members used in housing equipment, and various foamed plastics are used for many parts.

  As foamed plastics, urethane foam, bead foam molded body in which foamed particles are molded, and extruded foam are often used. Polypropylene foam, styrene modified polyethylene foam, polystyrene foam, acrylonitrile / styrene Copolymer foams are used in various parts as materials for housing equipment.

  Housing equipment includes bathtubs, vanities, unit bath ceiling panels, unit bath wall panels, doors, waterproof pans, bathtubs, etc., bathrooms, toilets, septic tanks, water tanks for thermal insulation, housing treatment tanks Such as sanitary facilities such as kitchen supplies, kitchen sinks, capsule beds, storage boxes, furniture, etc.

  The materials used for these housing equipment are often made of foamed plastic materials from the viewpoint of crack resistance, compressive strength, compression set, energy absorption performance, weight reduction, recyclability, and cost, but all can be satisfied. There is currently no foamed plastic on the market.

  Polystyrene foam is a foam that can be provided at the lowest cost among the foamed plastics used for materials for housing equipment. Unlike urethane foam, since it is a thermoplastic resin, it is easy to recycle.

  As a general tendency, when comparing the compressive strength of foams of the same density, the compressive strength of polystyrene foam tends to be higher than the compressive strength of polypropylene foam or styrene-modified polyethylene foam. In general, in a foam, the smaller the density, the lower the compressive strength. Therefore, when obtaining an equivalent compressive strength, the polystyrene foam is a lower density foam than the polypropylene foam. This is advantageous in terms of weight reduction. Acrylonitrile / styrene copolymer foams are slightly inferior in cost to polystyrene foams, but tend to have the same tendency as polystyrene foams in terms of compressive strength.

  However, when comparing crack resistance with foams of the same density, polystyrene foams and acrylonitrile / styrene copolymer foams tend to crack more easily than polypropylene foams and styrene modified polyethylene foams. . Usually, in foams, crack resistance tends to deteriorate as the density decreases. Therefore, polystyrene foam and acrylonitrile / styrene copolymer foams are polypropylene-based in order to have equivalent crack resistance. Higher density foams are required than foams and styrene modified polyethylene foams.

  As described above, in the materials for housing equipment, from the viewpoint of cost, it is required to achieve both high compressive strength and high crack resistance in order to reduce the weight, but it is difficult to achieve both high compressive strength and high crack resistance. It was.

  An object of the present invention is to provide a material for housing equipment that has both high crack resistance and high compressive strength.

  As a result of intensive studies, the present inventors have found that a foam having a predetermined density can achieve both crack resistance and compressive strength, thereby completing the present invention.

That is, the present invention is,
A material for housing equipment comprising a foam having a density of 16.6 to 100 kg / m ³ ,
Thermoplastic resin particles obtained by polymerizing a foam by starting a polymerization reaction after dispersing a monomer composition comprising a macromonomer in an aqueous medium in the presence of a polymerization initiator and other additives The foamed thermoplastic resin particles obtained by impregnating the thermoplastic resin particles with a foaming agent to form foamed particles, and the foamed particles obtained by in-mold molding of the foamed particles,
The gel fraction of the foam is 1 wt% or more and 40 wt% or less, and
Compression strength A (MPa) at 25% strain in the static compression test of the foam, half-break height B (cm) in the falling ball impact test of the foam, and density C (kg / m ³ ) of the foam It is related with the material for housing equipment characterized by consisting of the foam which satisfy | fills following formula (1) (2) together.
A ≧ 0.0113 × C−0.09 (1)
B ≧ 0.9 × C-3.5 (2)

As a preferred embodiment,
( 1 ) A monomer in which the foam is composed of a styrene monomer, a vinyl cyanide monomer, and an acrylate ester macromonomer having at least two polymerizable reactive groups at each molecular end. It was obtained by forming thermoplastic resin particles obtained by polymerizing the composition, foaming thermoplastic resin particles obtained by impregnating the thermoplastic resin particles with a foaming agent to form foamed particles, and molding the foamed particles in a mold. A foam,
( 2 ) The material for the housing equipment is a bathtub, a vanity, a ceiling panel of a unit bath, a wall panel of a unit bath, a door, a waterproof pan, a bathtub, a toilet tub, a septic tank, a water tank for thermal insulation, and a processing tank for a house. A material constituting one or more housing equipment selected from kitchen sinks, capsule beds, storage boxes, and furniture.
The present invention relates to the material for housing equipment described above.

  The material for housing equipment of the present invention has high compressive strength and high crack resistance. Because of having such properties, the material for housing equipment of the present invention is related to the bathroom such as bathtub, vanity, ceiling panel of unit bath, wall panel of unit bath, door, waterproof pan, bathtub, etc. Hygiene facilities such as stool tanks, septic tanks, water tanks for heat insulation and cold storage, treatment tanks for houses, water circulation relations such as kitchen sinks, relief / absorption of shocks such as capsule beds, storage boxes, furniture, etc. It is suitable for members for required housing equipment.

The material for housing equipment according to the present invention is a material for housing equipment made of a foam having a density of 16.6 to 100 kg / m ³ , and compression at 25% strain in a static compression test conducted based on JIS K 7220. Strength A (MPa), half-destructive height B (cm) in the falling ball impact test of the foam based on JIS K 7211, and density C (kg / kg) of the foam based on JIS K 6767 The relationship m ³ ) is made of a foam satisfying both the following formulas (1) and (2).
A ≧ 0.0113 × C−0.09 (1)
B ≧ 0.9 × C-3.5 (2)

In order to further reduce the weight, the following formulas (3) and (4) are preferable.
A ≧ 0.0113 × C−0.083 (3)
B ≧ 0.9 × C-2.8 (4)
And more preferably, the following formulas (5) and (6):
A ≧ 0.0113 × C−0.075 (5)
B ≧ 0.9 × C-2.10 (6)
It is a foam that satisfies both.

  The foam used for the housing equipment material of the present invention is not particularly limited as long as the above formulas (1) and (2) are satisfied, but a monomer composition containing a macromonomer is polymerized. It is preferable to use a thermoplastic resin obtained by polymerizing a monomer composition containing a macromonomer into thermoplastic resin particles, and the thermoplastic resin particles are impregnated with a foaming agent. A foam obtained by foaming thermoplastic resin particles to form foamed particles, and molding the foamed particles in a mold, wherein the foam has a gel fraction of 1% by weight to 40% by weight Is preferably used.

  Furthermore, a monomer composition comprising a styrene monomer, a vinyl cyanide monomer, and an acrylate macromonomer having at least one polymerizable reactive group at each of two molecular ends is polymerized. It is preferable to use a thermoplastic resin obtained from the above, specifically, a styrene monomer, a vinyl cyanide monomer, an acrylic having at least two polymerizable reactive groups at each molecular end. Thermoplastic resin particles obtained by polymerizing a monomer composition comprising an acid ester-based macromonomer, foamable thermoplastic resin particles impregnated with a foaming agent in the thermoplastic resin particles are expanded to form expanded particles, and the expanded foam It is preferable to use a foam obtained by molding particles in a mold.

  In the present invention, the macromonomer is a high molecular weight monomer having a polymerizable reactive group at the end of the polymer, and the number average molecular weight is not particularly limited, but is preferably in the range of 1,000 to 200,000. More preferably, it is 100,000 or less, and most preferably 40,000 or less. When the molecular weight is larger than 200,000, the viscosity of the macromonomer becomes high and handling tends to be difficult.

  The macromonomer used in the present invention is preferably such that the resulting foam has a gel fraction of 1% by weight or more and 40% by weight or less, and the gel fraction is more preferably 20% by weight or less, particularly preferably. Is 15% by weight or less. When the gel fraction exceeds 40% by weight, it tends to take time to foam.

  In the measurement of the gel fraction of the foam in the present invention, 20 test pieces of a predetermined size are cut out from the foam, 80 g of xylene is used per 1 g of foam, and extraction with boiling xylene is performed. After 2 hours from the start of boiling, filter through a 200 mesh wire mesh, remove the filtrate, extract the filtrate again with boiling xylene for 2 hours from the start of boiling, filter again through a 200 mesh wire mesh, and remove the filtrate. The remaining filtrate is again extracted with boiling xylene for 1 hour from the start of boiling, filtered through a 200 mesh wire net, the filtrate is made into a gel that cannot be extracted into boiling xylene, and the resulting gel is dried at 150 ° C. And dried for 1 hour, and the ratio relative to the original foam weight is defined as the gel fraction.

  In order to obtain a foam having such a gel fraction, for example, it can be adjusted by the number of terminal reactive groups, number average molecular weight, number of added parts, etc. of the macromonomer used. It is preferable to use those having at least one polymerizable reactive group at each of at least two molecular ends.

  The thermoplastic resin obtained by polymerizing a monomer composition containing a macromonomer used in the present invention has a soluble content when dissolved in tetrahydrofuran (hereinafter sometimes referred to as a tetrahydro-soluble component). The weight average molecular weight is preferably 100,000 or more and 400,000 or less. When the weight average molecular weight is less than 100,000, the strength of the foamed molded product tends to be small, and when the weight average molecular weight is more than 400,000, it tends to take too much time to achieve a high expansion ratio during preliminary foaming. .

  In the present invention, the weight-average molecular weight of the tetrahydrofuran-soluble component is calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). After adding 0.2 g of the foamable thermoplastic resin to 20 ml of tetrahydrofuran and stirring for 8 hours, the supernatant tetrahydrofuran solution is collected and the weight average molecular weight of the solution filtered through a 0.2 μm filter is measured.

The polymerizable reactive group present at the molecular end of the macromonomer is not particularly limited, and examples thereof include an allyl group, a vinylsilyl group, a vinyl ether group, a dicyclopentadienyl group, and the like. In view of copolymerization reactivity, at least one of them is preferably a carbon-carbon double bond, and further, the following general formula: —OC (O) C (R) ═CH ₂
The group represented by these is preferable.

In the formula, R is not particularly limited as long as it is hydrogen or an organic group having 1 to 20 carbon atoms. Among them, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n is It represents an integer of 2 or more 19 or _{less), - C 6 H 5,} -CH 2 OH, a group selected from among -CN preferably, more preferably -H, a -CH _3.

  Although the manufacturing method of the polymer which is the main chain of the macromonomer used in the present invention is not particularly limited, it is preferably manufactured by radical polymerization.

  Among them, for example, the “living radical polymerization method” described in the pamphlet of WO99 / 65963 is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. In addition, a polymer having a narrow molecular weight distribution (for example, Mw / Mn of about 1.1 to 1.5) can be obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator. it can.

  Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. In the present invention, the method for producing a macromonomer having a specific functional group as described above is a more preferable polymerization method.

  Other examples of the “living radical polymerization method” include cobalt porphyrin complexes as shown in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943. , Those using radical scavengers such as nitroxide compounds as shown in Macromolecules, 1994, 27, 7228, transitions starting from organic halides or sulfonyl halides, etc. Examples thereof include “Atom Transfer Radical Polymerization (ATRP)” using a metal complex as a catalyst.

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the “living radical polymerization method”. In addition to its original features, it has halogens that are relatively advantageous for functional group conversion reactions at the end, and has a large degree of freedom in designing initiators and catalysts, so as a method for producing macromonomers having specific functional groups Is more preferable. Examples of the atom transfer radical polymerization method include, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules 1995. 28, 7901, Science 1996, 272, 866, WO 96/30421 pamphlet, WO 97/18247 pamphlet, WO 98/01480 pamphlet, WO 98/40415 pamphlet, or Sawamoto et al., Macro. Macromolecules, 1995, 28, 1721, JP-A-9-208616, JP-A-8-41117, and the like. It is.

  There are no particular restrictions on the macromonomer production method in the present invention, including which of these methods is used, but the living radical polymerization method is preferably used because of ease of control, and the atom transfer radical polymerization method is most preferred. .

  There is no restriction | limiting in particular as a monomer which comprises the polymer principal chain of a macromonomer, Various things can be used. For example, acrylic acid, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-tert-butyl, acrylic acid-n-pentyl, acrylic Acid-n-hexyl, cyclohexyl acrylate, acrylate-n-heptyl, acrylate-n-octyl, acrylate-2-ethylhexyl, nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate , Benzyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-amino acrylate ethyl, Ethylene oxide adduct of crylic acid, trifluoromethyl methyl acrylate, 2-trifluoromethyl ethyl acrylate, 2-perfluoroethyl ethyl acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl acrylate, acrylic acid 2-perfluoroethyl, perfluoromethyl acrylate, diperfluoromethyl methyl acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl acrylate, 2-perfluorohexyl ethyl acrylate, 2-perfluoro acrylate Acrylic acid monomers such as decylethyl and 2-perfluorohexadecylethyl acrylate;

Methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, tert-butyl methacrylate, methacrylic acid-n-pentyl, methacrylic acid n-hexyl, cyclohexyl methacrylate, methacrylate-n-heptyl, methacrylate-n-octyl, methacrylate-2-ethylhexyl, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, methacryl Benzyl acid, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, stearyl methacrylate, methacrylate Glycidyl acid, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of methacrylic acid, trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-par methacrylate Fluoroethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-perfluoromethyl-2 methacrylate -Methacrylic acid monomers such as perfluoroethylmethyl, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate;

Styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; vinyltrimethoxysilane, vinyltri Silicon-containing vinyl monomers such as ethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide , Maleimide series such as butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate Examples include esters; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; allyl chloride and allyl alcohol.

  These may be used singly or may be copolymerized using a plurality. Of these, styrenic monomers, acrylic acid monomers, and methacrylic acid monomers are preferred in view of the physical properties of the product. Acrylic acid ester monomers and methacrylic acid ester monomers are more preferred, acrylic acid ester monomers are more preferred, ethyl acrylate and butyl acrylate are particularly preferred, and butyl acrylate is most preferred. In the present invention, the above monomers may be copolymerized with monomers other than those described above, and in that case, the above monomers are preferably contained in an amount of 40% by weight or more.

  The glass transition temperature of the macromonomer is preferably −20 ° C. or lower. When the glass transition temperature is higher than −20 ° C., the flexibility of the obtained thermoplastic resin is lowered, so that it takes time for foaming or the vapor pressure during molding tends to increase in order to fuse the foamed particles. is there.

  The macromonomer used in the present invention has a molecular weight distribution, that is, a ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (hereinafter sometimes referred to as GPC). ) Is preferably less than 1.8, more preferably 1.6 or less, and particularly preferably 1.4 or less. In the GPC measurement in the present invention, usually, a polystyrene gel column or the like is used with chloroform or tetrahydrofuran as a mobile phase, and the molecular weight value is obtained in terms of polystyrene. A macromonomer having a broad molecular weight distribution may cause the copolymerization reaction to become non-uniform, and unreacted macromonomer may remain.

  The amount of the macromonomer in the monomer composition constituting the thermoplastic resin in the present invention is preferably 1% by weight or more and 20% by weight or less. More preferably, they are 2 weight% or more and 15 weight% or less, Especially preferably, they are 4 weight% or more and 10 weight% or less. If it is less than 1% by weight, the effect of improving crack resistance tends to be small, and if it exceeds 20% by weight, foaming tends to take time.

  In the monomer composition constituting the thermoplastic resin of the present invention, the monomer component other than the macromonomer is not particularly limited, but a vinyl monomer is preferably used.

  When a vinyl monomer is used in addition to the macromonomer in the monomer composition, the amount is preferably 80% by weight or more and 99% by weight or less in the monomer composition, more preferably 85%. % By weight or more and 98% by weight or less. Within the range, foaming can be performed in an appropriate time.

  Examples of vinyl monomers include styrene monomers, vinyl cyanide monomers, acrylic acid monomers, and methacrylic acid monomers. Among these vinyl monomers, it is preferable to use a styrene monomer or a mixture of a styrene monomer and a vinyl cyanide monomer.

  When a styrene monomer is used as the vinyl monomer, the vinyl monomer amount can be used as the styrene monomer amount.

  Examples of the styrene monomer used in the present invention include various monomers such as styrene derivatives such as styrene, α-methyl styrene, paramethyl styrene, t-butyl styrene and chlorostyrene. These monomers can be used alone or in admixture of two or more. Of these, styrene is particularly preferred.

  Examples of the vinyl cyanide monomer used in the present invention include acrylonitrile and methacrylonitrile. These monomers can be used alone or in combination. Of these, acrylonitrile is particularly preferred. In addition, maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid, fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid, maleimide monomers, amide group-containing vinyl monomers such as acrylamide, methacrylamide, etc. Various monomers may be copolymerized without departing from the spirit of the present invention.

  When a mixture of a styrene monomer and a vinyl cyanide monomer is used as the vinyl monomer, the amount of the styrene monomer in the monomer composition is 50% by weight or more and 89% by weight or less. It is preferable. The amount of vinyl cyanide monomer is preferably 10% by weight to 30% by weight, more preferably 12% by weight to 25% by weight in the monomer composition. If the amount of vinyl cyanide monomer is less than 10% by weight, the effect of using the vinyl cyanide monomer tends to be difficult, and if it exceeds 30% by weight, foaming tends to take too much time.

  In the present invention, the monomer composition is polymerized to obtain a thermoplastic resin. The polymerization method is not particularly limited, but the monomer composition is preferably subjected to aqueous polymerization. Further, the polymerization may be performed by at least one polymerization method selected from emulsion polymerization, suspension polymerization, and fine suspension polymerization. preferable.

  As the suspension stabilizer used in the present invention, for example, water-soluble polymers such as polyvinyl alcohol, methyl cellulose, polyvinyl pyrrolidone, and polyacrylamide, sparingly soluble inorganic salts such as magnesium pyrophosphate, calcium phosphate, and hydroxyapatite are used. In addition, a surfactant may be used in combination. When a hardly soluble inorganic salt is used, it is preferable to use an anionic surfactant such as sodium alkyl sulfonate or sodium dodecylbenzene sulfonate together.

  In the present invention, as a polymerization initiator used when the monomer composition is polymerized into a thermoplastic resin, a radical generating polymerization initiator generally used for the production of a thermoplastic polymer can be used. For example, benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, t-butyl perpivalate, t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, 2,2-di-t- Butyl peroxybutane, di-t-butylperoxyhexahydroterephthalate, 1,1-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane 1,1-di (t-amylperoxy) 3,3,5-trimethylcyclohexane And 1,1-di (t-amyl peroxy) cyclohexane organic peroxides such as azobisisobutyronitrile, an azo compound such as azo-bis-dimethyl valeronitrile. These polymerization initiators can be used alone or in admixture of two or more.

  In the polymerization of the monomer composition in the present invention, it is generally used for polymerization of mercaptan chain transfer agents such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and acrylonitrile-styrene resins. Α-methylstyrene dimer or the like may be used as a polymerization regulator. Use of α-methylstyrene dimer is preferred because the odor of the foam is reduced.

  Further, a plasticizer may be added to the foamable thermoplastic resin of the present invention in order to adjust foamability and the like. Conventional plasticizers can be used, but when it is necessary to reduce the emission of volatile organic components from the foam, it is better to use a plasticizer having a high boiling point or a plasticizer having no boiling point at room temperature. Specifically, phthalic acid esters such as dioctyl phthalate, di-2-ethylhexyl phthalate, dibutyl phthalate, butyl benzyl phthalate, fatty acid esters such as dibutyl sebacate, dioctyl adipate, diisobutyl adipate, palm oil, palm kernel oil, palm oil Glycerin fatty acid esters such as rapeseed oil, rapeseed hardened fractionated oil, and hardened soybean oil. These may be used alone or in combination of two or more.

  Furthermore, additives generally used in the production of expandable polystyrene resin particles such as a flame retardant, an ultraviolet absorber, an antistatic agent, a conductive agent, and a particle size distribution modifier can be appropriately added.

  As a specific method for obtaining expandable thermoplastic resin particles that can be used in the present invention, a macromonomer, a styrene monomer, and a vinyl cyanide monomer are used in the presence of a polymerization initiator and other additives. And a method of starting the polymerization reaction after dispersing in an aqueous medium and adding a foaming agent during the polymerization, or impregnating the foaming agent after the polymerization.

  Examples of the blowing agent that can be used in the present invention include generally well-known aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, and hexane, and alicyclic hydrocarbons such as cyclohexane, cyclopentane, and cyclobutane. A volatile blowing agent having a boiling point of 80 ° C. or lower, such as halogenated hydrocarbons such as trifluoromonochloroethane and difluorodichloromethane, can be used. Moreover, these can be used individually or in combination of 2 or more types. In order to reduce shrinkage and deformation during molding, it is preferable to use butane or / and pentane, and butane is particularly preferable.

  In the present invention, it is preferable to make foamed thermoplastic resin particles by impregnating particulate thermoplastic resin particles with a foaming agent. As the method, it may be added during the polymerization step or after the completion of the polymerization step.

  The foaming agent is usually supplied in such an amount that the foaming agent content in the foamable thermoplastic resin particles is preferably 3% by weight or more and 15% by weight or less. More preferably, it is 4 to 10% by weight. If it is less than 3% by weight, sufficient foamability may not be obtained, and if it exceeds 15% by weight, shrinkage and deformation during foam molding tend to increase.

  The amount of residual styrenic monomer contained in the material for housing equipment of the present invention is preferably 1000 ppm or less, and more preferably 500 ppm or less because it is necessary to reduce the emission of volatile organic components from the foam. It is particularly preferred that it is not detected.

  The amount of residual styrenic monomer contained in the housing equipment material is of course measured for the housing equipment material itself, but the foaming heat for producing the foam constituting the housing equipment material It is also possible to measure the amount of residual styrene monomer in the plastic resin particles. This is because the amount of residual styrene monomer in the expandable thermoplastic resin particles tends to be smaller than the amount of residual styrene monomer in the foam.

  The amount of residual styrene monomer contained in the expandable thermoplastic resin particles of the present invention was measured by adding 0.2 g of expandable thermoplastic resin particles to 20 ml of methylene chloride, stirring for 8 hours, and then supernatant methylene chloride. A solution is collected and measured by gas chromatography. The amount of residual styrene monomer contained in the foam can be measured in the same manner.

  Since the material for housing equipment according to the present invention has the properties as described above, it can be suitably used as a material for housing equipment that is required to relieve / absorb impacts or to withstand load. . As the housing equipment, specifically, for bathrooms such as bathtubs, vanities, unit bath ceiling panels, unit bath wall panels, doors, waterproof pans, bathtubs, etc. Sanitary facilities such as water tanks and housing treatment tanks, water circulation relations such as kitchen sinks, capsule beds, storage boxes, furniture, and the like can be mentioned, which are suitable for these members.

  Examples and Comparative Examples are given below, but the present invention is not limited thereby. Unless otherwise specified, “parts” and “%” are based on weight.

(Production Example 1) Synthesis of acryloyl group-terminated poly (n-butyl acrylate) This was carried out based on the method described in Production Example 2 and Example 2 of JP-A No. 2004-203932. The number average molecular weight of the purified macromonomer was 25600, the molecular weight distribution was 1.25, and the glass transition temperature was −54 ° C.

In addition, the number average molecular weight and the molecular weight distribution (ratio of the weight average molecular weight to the number average molecular weight) were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). A GPC column filled with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.
The glass transition temperature of the macromonomer was measured by DSC.

(Examples 1-4)
<Manufacture of expandable thermoplastic resin particles>
In a 6 L autoclave equipped with a rotary stirrer, 2250 g of distilled water, 3.5 g of tricalcium phosphate, and 0.14 g of α-olefin sulfonic acid soda were charged. Next, 6 g of benzoyl peroxide and 1,1-di (t-butylperoxy) cyclohexane were added to a mixed solution of 1777.5 g of styrene, 337.5 g of acrylonitrile, and 135 g of a macromonomer having acryloyl groups at both ends prepared in Production Example 1. 3.5 g, 4.5 g of 2,4-diphenyl-4-methyl-1-pentene and 22.5 g of coconut oil were dissolved and charged into an autoclave. Next, the autoclave was heated to a temperature of 85 ° C. and polymerized at the same temperature for 4 hours, and then 180 g of mixed butane (weight ratio: normal / iso = 75/25) was injected, and then the autoclave was 115 ° C. The resulting polymer particles were impregnated with mixed butane over 8 hours. Thereafter, the reaction system was gradually cooled to a temperature of 30 ° C. to complete the polymerization.

  The obtained foamable thermoplastic resin particles were dehydrated with a centrifuge, dried, and classified with a particle size of 0.84 to 1.19 mm.

<Analysis of foamable thermoplastic resin particles>
(Measurement of molecular weight)
The weight average molecular weight measurement of the foamable thermoplastic resin particles of the present invention was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). (GPC Tosoh Corporation HLC-8020, column: TSKgel GMHXL 30 cm × 2, column temperature: 35 ° C., flow rate: 1 ml / min) Tetrahydrofuran was used as a GPC solvent.

  20 ml of tetrahydrofuran was put into a sample bottle containing 0.2 g of expandable thermoplastic resin particles and stirred for 8 hours, and then the supernatant tetrahydrofuran solution was collected and filtered with a 0.2 μm filter (Mishori Disc H-13 manufactured by Tosoh Corporation). The weight average molecular weight was measured with the solution filtered in 2).

(Measurement of amount of residual styrene monomer)
20 ml of methylene chloride was put into a sample bottle containing 0.2 g of expandable thermoplastic resin particles and stirred for 8 hours, and then the supernatant methylene chloride solution was collected and gas chromatographed (GC-14B, manufactured by Shimadzu Corporation, column: 3 m, filler PEG-20M 25%, column temperature: 110 ° C.).

(Analysis of gel fraction)
Twenty test pieces having a size of 10 mm in length, 10 mm in width, and 2 mm in thickness are cut out from the foam constituting the material for housing equipment. Let Ag be the weight of the test piece before extraction. Extraction with boiling xylene is carried out in a round bottom flask equipped with a reflux condenser using 80 g of xylene per gram of foam. After 2 hours from the start of boiling, the mixture is filtered through a 200-mesh wire mesh, the filtrate is removed, and extraction with boiling xylene is performed again with the filtrate for 2 hours from the start of boiling. The mixture was filtered again with a 200 mesh wire mesh, the filtrate was removed, and the remaining filtrate was again extracted with boiling xylene for 1 hour from the start of boiling, and filtered with a 200 mesh wire mesh to obtain a gel that was not extracted into boiling xylene. .

  The obtained gel content is dried for 1 hour with a dryer at 150 ° C. to evaporate xylene. After allowing to cool at room temperature, the gel weight Bg is measured. The gel fraction is calculated by gel fraction (%) = B / A × 100 (%).

(Measurement of foaming agent content)
The foaming agent content was measured by heating loss at 150 ° C. for 30 minutes. It was 8.2% by weight.

<Manufacture of foam>
Expandable thermoplastic resin particles to a density of 50 kg / m ³ (Example 1), 33.3 kg / m ³ (Example 2), 25 kg / m ³ (Example 3), and 20 kg / m ³ (Example 4). Pre-foamed particles were obtained by pre-foaming. After the pre-expanded particles were cured at room temperature for 1 day, they were filled in a 300 × 600 × 25 mm mold cavity and heated with 0.1 MPa water vapor for 20 seconds to obtain a foam.

<Measurement of physical properties>
(Static compressive strength)
The static compression test for examining the compressive strength of the foam is performed based on JIS K 7220. A 50 mm × 50 mm × 25 mm test piece is cut out from the foam. The thickness of 25 mm remains the thickness of the foam. That is, two surfaces of 50 mm × 50 mm remain as surface skins, and four surfaces of 50 mm × 25 mm are surfaces cut out by a vertical slicer.

  The compression test is performed at a test speed of 10 mm / min so that the surface with the surface skin is up and down.

  The value A (MPa) of the compressive strength is expressed by the stress when the test piece is compressed by 25%.

As the “density” of the foam for measuring compressive strength, the density C (kg / m ³ ) of the foam was determined according to the following formula in accordance with JIS K 6767.
C = G / V
(However, G: Weight of foam (kg), V: Volume of foam (m ³ ))
G and V were calculated by measuring the weight, vertical, horizontal and height dimensions of the compressive strength test sample. Measuring tools and accuracy are in accordance with JIS K 6767.

(Falling ball impact test)
A falling ball impact test indicating the strength of crack resistance of the foam is performed based on JIS K 7211. A 200 mm × 40 mm × 20 mm test piece is cut out from the foam with a vertical slicer. This test piece has two surfaces of 200 mm × 40 mm, one of which is the surface skin of the foam (the surface skin of the foam is the part exposed on the surface of the foam when the foam is molded) (It is different from the inside of the foam cut out by the vertical slicer.) The other side is the surface cut out by the vertical slicer. In addition, two surfaces of 200 mm × 20 mm and two surfaces of 40 mm × 20 mm are surfaces cut out by a vertical slicer. Prepare 20 test pieces.

  A hard ball of 321 g is dropped with the surface having the surface skin of the test piece as the surface on which the falling ball collides. The half fracture height B (cm) is obtained by a predetermined calculation formula. It shows that crack resistance is so large that a numerical value is large.

Ｈ５０ ：半数破壊高さ（ｃｍ）
Ｈｉ ：高さ水準（ｉ）が０のときの試験高さ（ｃｍ）であり、試験片が破壊することが予測される高さ。
ｄ ：試験高さを上下させるときの高さ間隔（ｃｍ）
ｉ ：Ｈ１のときを０とし、１つずつ増減する高さ水準（ｉ＝…−３、−２、−１、０、１、２、３、…）
ｎｉ ：各水準において破壊した（または破壊しなかった）試験片の数
Ｎ ：破壊した（または破壊しなかった）試験片の総数（Ｎ＝Σｎｉ）。いずれか多いほうのデータを使用する。なお、同数の場合はどちらを使用してもよい。
±０．５：破壊したデータを使用するときは負を、破壊しなかったデータを使用するときは正とする。

H50: Half fracture height (cm)
Hi: Test height (cm) when the height level (i) is 0, and the height at which the test piece is expected to break.
d: Height interval when moving the test height up and down (cm)
i: Height level when H1 is 0, and a level that increases or decreases by 1 (i =... -3, -2, -1, 0, 1, 2, 3,...)
ni: number of test pieces destroyed (or not destroyed) at each level N: total number of test pieces destroyed (or not destroyed) (N = Σni). Use the larger of the data. In the case of the same number, either may be used.
± 0.5: Negative when using destroyed data, positive when using non-destructed data.

As the “density” of the foam for falling ball impact test, the density C (kg / m ³ ) of the foam was determined according to the following formula based on JIS K6767.
C = G / V
(However, G: Weight of foam (kg), V: Volume of foam (m ³ ))
G and V measured the weight of the test piece of the falling ball impact test and the vertical, horizontal, and height dimensions, and adopted the average value of 20 test pieces. Measuring tools and accuracy are in accordance with JIS K 6767.

(Examples 5 to 8)
The same procedure as in Examples 1 to 4 was carried out except that the amount of styrene charged was 1609.5 g and the amount of acrylonitrile charged was 505.5 g.

(Examples 9 to 12)
The same procedure as in Examples 1 to 4 was carried out except that the amount of styrene charged was 1732.5 g and the amount of the macromonomer having acryloyl groups at both ends was 180 g.

(Examples 13 to 16)
The same procedure as in Examples 1 to 4 was conducted except that the amount of styrene charged was 1678 g, the amount of acrylonitrile charged was 527 g, and the amount of macromonomer having acryloyl groups at both ends was 45 g.

（比較例１〜４）
発泡性ポリスチレン樹脂粒子（（株）カネカ製、製品名：カネパールＮＳＧ）を使用する以外は実施例１〜４と同様に行い、成形体を作製した。

(Comparative Examples 1-4)
Except for using expandable polystyrene resin particles (manufactured by Kaneka Co., Ltd., product name: Kanepal NSG), the same procedure as in Examples 1 to 4 was performed to prepare a molded body.

(Comparative Examples 5 to 8)
Expandable modified styrene resin particles were obtained according to the description in Example 2 of the pamphlet of WO2001 / 048068. Others were carried out in the same manner as in Examples 1 to 4, and molded articles were produced.

(Comparative Examples 9-12)
The same procedure as in Examples 1 to 4 was conducted except that the amount of styrene charged was 2250 g, the amount of acrylonitrile charged was 0 g, the amount of macromonomer having acryloyl groups at both ends was 0 g, and 0.45 g of divinylbenzene was added. A molded body was produced.

(Comparative Examples 13 to 16)
The same procedure as in Examples 1 to 4 was performed except that the amount of styrene charged was 2250 g, the amount of acrylonitrile charged was 0 g, the amount of macromonomer having acryloyl groups at both ends was 0 g, and 1.35 g of divinylbenzene was added. A molded body was produced.

（比較例１７〜２０）
スチレンの仕込量を１７０７．１ｇ、アクリロニトリルの仕込量を５３６．１ｇ、両末端にアクリロイル基を有するマクロモノマーの仕込量を６．７５ｇとした以外は実施例１〜４と同様に行い、成形体を作製した。

(Comparative Examples 17-20)
Except that the charged amount of styrene was 1707.1 g, the charged amount of acrylonitrile was 536.1 g, and the charged amount of the macromonomer having acryloyl groups at both ends was changed to 6.75 g. Was made.

(Comparative Examples 21-24)
A molded body was produced in the same manner as in Examples 1 to 4, except that the amount of styrene charged was 1712.3 g, the amount of acrylonitrile charged was 537.8 g, and the amount of macromonomer having acryloyl groups at both ends was 0 g. did.

(Comparative Examples 25-28)
A styrene-modified polyethylene foam was produced according to the description in Example 1 of JP-A-8-59754.

表１に示すように本発明で得られた発泡体は圧縮強度が高くかつ耐割れ性が高く、住宅機材用材料として最適な発泡体である。

As shown in Table 1, the foam obtained by the present invention has high compressive strength and high crack resistance, and is an optimum foam as a material for housing equipment.

Claims (3)

A material for housing equipment comprising a foam having a density of 16.6 to 100 kg / m ³ ,
The foam is polymerized by initiating the polymerization reaction after dispersing the entire monomer composition comprising the macromonomer in the presence of the polymerization initiator and other additives in the aqueous medium, and the thermoplastic resin. A foam obtained by foaming foamable thermoplastic resin particles obtained by impregnating the thermoplastic resin particles with a foaming agent to form foamed particles, and molding the foamed particles in a mold;
The gel fraction of the foam is 1 wt% or more and 40 wt% or less, and
Compression strength A (MPa) at 25% strain in the static compression test of the foam, half-break height B (cm) in the falling ball impact test of the foam, and density C (kg / m ³ ) of the foam The material for housing equipment is characterized by comprising a foam satisfying the following formulas (1) and (2).
A ≧ 0.0113 × C−0.09 (1)
B ≧ 0.9 × C-3.5 (2)   A monomer composition in which the foam is composed of a styrene monomer, a vinyl cyanide monomer, and an acrylate macromonomer having at least two polymerizable reactive groups at each molecular end. A foam obtained by polymerizing thermoplastic resin particles, foaming foamable thermoplastic resin particles obtained by impregnating the thermoplastic resin particles with a foaming agent to form foamed particles, and molding the foamed particles in a mold. The material for housing equipment according to claim 1, wherein the material is for housing equipment. The material for the housing equipment is a bathtub, a vanity, a ceiling panel of a unit bath, a wall panel of a unit bath, a door, a waterproof pan, a bathtub, a toilet tub, a septic tank, a water tank for thermal insulation, a processing tank for a house, and a kitchen sink. The material for housing equipment according to claim 1 or 2 , wherein the material is one or more housing materials selected from capsule beds, storage boxes, and furniture.