JP2012131954A - Foaming polystyrene-based colored resin particle for production of building heat insulating material, production method thereof, colored resin preliminarily foamed particle for production of building heat insulating material, and building heat insulating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foaming polystyrene-based colored resin particle for production of building heat insulating material, allowing a building heat insulating material uniformly colored without coloring unevenness to be easily produced, and to provide a production method thereof.SOLUTION: In the foaming polystyrene-based colored resin particle for production of building heat insulating material which is colored with a dye, Solvent Blue 78 is contained as the dye, and a flame retardant is also contained. The production method of the foaming polystyrene-based colored resin particle for production of building heat insulating material includes: placing a polystyrene-based resin particle in a pressure tight container; and inputting a dye, a foaming agent and a flame retardant thereto to impregnate the polystyrene-based resin particle with the foaming agent, the dye and the flame retardant. The dye contains Solvent Blue 78, and the dye is dispersed in an aqueous medium prior to the input thereof.

Description

  The present invention relates to an expandable polystyrene-based colored resin particle for manufacturing a heat insulating material for building, which includes a foaming agent and is made of colored polystyrene-based resin particles, and a method for manufacturing the same. The present invention relates to an expandable polystyrene-based colored resin particle for manufacturing a heat insulating material for building, which can easily manufacture a heat insulating material for building, a manufacturing method thereof, a colored resin pre-expanded particle for manufacturing a heat insulating material for building, and a heat insulating material for building.

Polystyrene resin foam moldings are widely used as transport containers and packaging containers. Among them, for the purpose of distinguishing from other containers, etc., it is used in color for the purpose of distinguishing it from other containers and the like in the application of architectural heat insulating materials.
For example, in a building heat insulating material, a foam molded body colored in blue, purple, orange, green or the like is used. Moreover, since it has the advantage that stain | pollution | contamination is not conspicuous if colored in gray color, it is often colored in gray color for the use used as a structural member. In order to produce a foam-molded article colored in gray, carbon black has generally been used as a colorant.
However, in order to produce expandable polystyrene colored resin particles containing carbon black, it is necessary to add at the polymerization stage of the polystyrene resin, and when impregnating the foaming agent, the resin particles can absorb carbon black. The manufacturing process becomes complicated.

In general, several methods are known for producing colored expandable resin particles.
For example, as disclosed in Patent Document 1 (Japanese Patent Publication No. 6-10270) and Patent Document 2 (Japanese Patent Publication No. 6-23266), a method of adding a dye in the process of adding a foaming agent is known.

Japanese Patent Publication No. 6-10270 Japanese Patent Publication No. 6-23266

In the conventional method, the coloring of the expandable polystyrene resin particles tends to be uneven. In particular, when two or more kinds of dyes are mixed and used, uneven coloring easily occurs, and a foamed molded product produced using expandable polystyrene-based colored resin particles tends to be inferior in appearance.
Further, in order to prevent the dye or pigment from detaching in the conventional method described above, there is a method of coating the surface of the resin particle with the dye or pigment using a coating agent. In this method, the inside can be uniformly colored. In addition to being unable to do so, there is a drawback that the manufacturing process becomes complicated due to the extra coating process.

  The present invention has been made in view of the above circumstances, and is a foamable polystyrene-based colored resin for manufacturing a heat insulating material for building, which can easily produce a heat insulating material having a uniform appearance and a uniform appearance without uneven coloring. It is an object of the present invention to provide particles, a method for producing the same, colored resin pre-foamed particles for manufacturing a building heat insulating material, and a building heat insulating material.

  In order to solve the above-mentioned problems, the present invention is characterized in that the foamable polystyrene-based colored resin particles for manufacturing a building heat insulating material colored with a dye contain Solvent Blue 78 as a dye and a flame retardant. An expandable polystyrene-based colored resin particle for manufacturing a heat insulating material for building is provided.

  In the expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material of the present invention, Solvent Blue 78 is preferably contained in a range of 0.003 to 0.4 mass%.

  In the expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material of the present invention, it is preferable to contain a brominated flame retardant as a flame retardant.

  In the expandable polystyrene colored resin particle for manufacturing a heat insulating material for building of the present invention, one or two selected from the group consisting of anthraquinone dyes other than blue, azo dyes and quinoline dyes in combination with SolventBlue 78 It is good also as a structure containing the above dyes.

  In the expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material of the present invention, the expandable polystyrene-based colored resin particles may include a polyolefin-based resin.

In the present invention, polystyrene resin particles are placed in a pressure-resistant container, and further, a dye, a foaming agent, and a flame retardant are added, and the polystyrene resin particles are impregnated with a foaming agent, a dye, and a flame retardant. In the method for producing expandable polystyrene-based colored resin particles,
Provided is a method for producing expandable polystyrene-based colored resin particles for producing a building heat insulating material, wherein the dye contains Solvent Blue 78 and the dye is dispersed in an aqueous medium in advance.

  In the method for producing expandable polystyrene colored resin particles for manufacturing a building heat insulating material of the present invention, the polystyrene resin particles are placed in a pressure-resistant container together with an aqueous medium, and the dye is added to cause the polystyrene resin particles to absorb the dye. After that, it is preferable that a foaming agent and a flame retardant are introduced into the container, the temperature inside the container is raised to 60 ° C. or higher, and the polystyrene-based resin particles absorb the foaming agent and the flame retardant.

  In the method for producing expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material of the present invention, the content of Solvent Blue 78 in the expandable polystyrene-based colored resin particles may be in the range of 0.003 to 0.4 mass%. preferable.

  In the method for producing expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material of the present invention, it is preferable to contain a brominated flame retardant as the flame retardant.

  1 type selected from the group consisting of non-blue anthraquinone dyes, azo dyes, and quinoline dyes in combination with Solvent Blue 78 in the method for producing expandable polystyrene colored resin particles for manufacturing heat insulating materials for buildings of the present invention. Or it is good also as a structure containing 2 or more types of dyes.

  In the method for producing expandable polystyrene colored resin particles for manufacturing a building heat insulating material of the present invention, the expandable polystyrene colored resin particles may contain a polyolefin resin.

  Moreover, this invention provides the colored resin pre-expanded particle for building heat insulating materials obtained by heating the said expandable polystyrene-type colored resin particle for manufacturing heat insulating materials for buildings, and pre-foaming.

  Further, the present invention provides the thermal conductivity measured based on JIS A 9511 obtained by filling the above-mentioned colored resin pre-expanded particles for manufacturing a building heat insulating material into a cavity of a mold, heating and molding in-mold. Is provided with a thermal insulation material satisfying the flammability standards described in JIS A 9511.

The expandable polystyrene-based colored resin particles for manufacturing a heat insulating material for building of the present invention contain SolventBlue 78 as a dye in the expandable polystyrene-based colored resin particles colored with a dye. It is possible to easily manufacture the heat insulating material for building.
In addition, Solvent Blue 78 can be colored beautifully and uniformly by combining a plurality of types of dyes of different colors and impregnating the surface of the polystyrene resin particles, so that variations in coloring can be increased.

  The method for producing expandable polystyrene colored resin particles for manufacturing a building heat insulating material according to the present invention includes the above-described foamable polystyrene colored resin particles for manufacturing a building heat insulating material from which a beautifully colored building heat insulating material can be obtained. It can be manufactured easily and at low cost.

  Since the architectural heat insulating material of the present invention contains Solvent Blue 78 as a dye, there is no uneven coloring, it has a uniformly colored and beautiful appearance, and the thermal conductivity measured based on JIS A 9511 is 0. 0.045 W / (m · K) or less, and has flame retardancy satisfying the flammability standards described in JIS A 9511, it is extremely useful as a heat insulating material for buildings.

  The expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material according to the present invention include a foamable polystyrene-based colored resin particle for manufacturing a building heat insulating material colored with a dye, and include Solvent Blue 78 as a dye and a flame retardant. It is characterized by that.

For example, polystyrene resin particles obtained by the following production methods (1) to (3) are used as the polystyrene resin particles used for the expandable polystyrene colored resin particles for manufacturing a building heat insulating material of the present invention. it can.
(1) A so-called suspension polymerization method in which a polymerizable monomer having a styrene monomer as a main component is dispersed in an aqueous suspension to perform polymerization to obtain polystyrene resin particles.
(2) After the polystyrene resin seed particles are dispersed in the aqueous suspension, the polymerizable monomer mainly containing a styrene monomer is absorbed into the seed particles to perform polymerization, and the polystyrene resin So-called seed polymerization method to obtain particles,
(3) A polystyrene resin is put into an extruder and melted by heating. The foaming agent mixed resin is extruded from the small holes of a die having a large number of small holes attached to the discharge side of the extruder, and immediately after that, cut in water. A so-called melt-extrusion method (also referred to as an underwater cutting method) that obtains polystyrene-based resin particles by rapid cooling.

Examples of the styrene monomer used in the above (1) suspension polymerization method and (2) seed polymerization method include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, i-propylstyrene, dimethylstyrene, bromo. The main component is a styrene monomer such as styrene, and the styrene monomer is usually contained in an amount of 50% by mass or more, preferably 80% by mass or more. Of these styrene monomers, styrene is particularly preferable.
Further, the polymerizable monomer that can be used in combination with the styrene monomer is not particularly limited as long as it is copolymerizable with the styrene monomer, and divinylbenzene, alkylene glycol dimethacrylate, acrylonitrile, methyl methacrylate, and the like. Is mentioned.

(2) When producing expandable polystyrene resin particles for manufacturing heat insulating materials for buildings by seed polymerization, polystyrene resin particles obtained by the suspension polymerization method are used as seed particles, or polystyrene resin is extruded. After adjusting to a desired particle diameter by a machine in advance, it may be used as seed particles.
(2) When seed particles are produced using an extruder in the seed polymerization method, or (3) polystyrene resins used in the melt extrusion method are commercially available ordinary polystyrene resins, suspension polymerization methods, etc. In addition to using polystyrene resins that are not recycled materials (virgin polystyrene), such as newly produced polystyrene resins by the method, use recycled materials obtained by reprocessing used polystyrene resin foam moldings. Can do. Examples of this recycled material include recycled polystyrene resin foam molded products such as fish boxes, household appliance cushioning materials, food packaging trays, etc., and recycled by the limonene dissolution method or heating volume reduction method. It is done.

  The particle diameter of the polystyrene-based resin particles is not particularly limited, but is usually about 0.3 to 2.0 mm from the filling property of the pre-expanded particles into the mold cavity at the time of molding, 1.4 mm is preferred.

  In the present invention, the molecular weight of the polystyrene-based resin used is preferably 170,000 to 700,000 in terms of mass average molecular weight (Mw) by GPC method. If the molecular weight of the polystyrene-based resin is less than 170,000, the strength of the foamed molded product finally obtained is lowered, and if it exceeds 700,000, it is difficult to obtain sufficient foamability, which is not preferable.

  The polymerization initiator used in the above (1) suspension polymerization method and (2) seed polymerization method is not particularly limited as long as it is usually used in suspension polymerization of styrene. For example, a radical generating polymerization initiator is used. Can be used. Specifically, benzoyl peroxide, lauryl peroxide, t-butyl peroxide, t-butyl peroxypivalate, t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, 2,2-t-butylperoxide Organic peroxides such as oxybutane, t-butylperoxy-3,3,5-trimethylhexanoate, di-t-butylperoxyhexahydroterephthalate, azobisisobutyronitrile, azobisdimethylvaleronitrile, etc. Of the azo compound. These polymerization initiators can be used alone or in combination of two or more.

In the polymerization described above, in order to reduce the styrene monomer remaining in the polystyrene resin particles, it is preferable to use a high temperature decomposition type polymerization initiator and set the final polymerization temperature to 115 ° C. or higher. Examples of the high-temperature decomposition type polymerization initiator include t-butyl peroxybenzoate, t-butyl peroxypivalate, t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, 2,2-t-butyl peroxy. Examples include butane having a temperature of 100 to 115 ° C. for obtaining a half-life of 10 hours. An excessive addition of a high temperature decomposition type polymerization initiator is not preferable because alcohols as decomposition byproducts are generated.
In the polymerization, the decomposition temperature for obtaining a half-life of 10 hours is in the range of 80 to 120 ° C. in terms of adjusting the molecular weight of the polystyrene resin particles and reducing the residual amount of monomer. It is preferable to use a combination of two or more polymerization initiators.

In carrying out the (1) suspension polymerization or (2) seed polymerization, a suspending agent may be used to disperse styrene monomer droplets or seed particles in an aqueous medium. Examples of the suspending agent include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, polyacrylamide, and polyvinyl pyrrolidone, and poorly water-soluble inorganic compounds such as tricalcium phosphate and magnesium pyrophosphate. In addition, when using a slightly water-soluble inorganic compound, it is preferable to use an anionic surfactant together.
Examples of the anionic surfactant include fatty acid soaps, N-acyl amino acids or salts thereof, carboxylates such as alkyl ether carboxylates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, dialkylsulfosuccinates, alkylsulfates. Sulfates such as acetates and α-olefin sulfonates; sulfates such as higher alcohol sulfates, secondary higher alcohol sulfates, alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates; alkyls And phosphoric acid ester salts such as ether phosphoric acid ester salts and alkyl phosphoric acid ester salts. The polystyrene resin particles obtained as described above are impregnated with a foaming agent, a dye and a flame retardant by a suspension polymerization impregnation method or a post-impregnation method, thereby producing expandable polystyrene resin particles for manufacturing a heat insulating material for buildings. can do.

  In the expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material of the present invention, the content of the Solvent Blue 78 is preferably in the range of 0.003 to 0.4 mass%, 0.005 to 0.30. More preferably, it is in the range of mass%. If the content of SolventBlue 78 is less than the above range, the coloration degree of the finally obtained heat insulating material for building will be weak. On the other hand, if the content of Solvent Blue 78 exceeds the above range, it is not preferable because not only the cost is increased but also the moldability is lowered.

  The foamable polystyrene-based colored resin particles for manufacturing a heat insulating material for building of the present invention can be colored in a desired color mixture by containing Solvent Blue 78 and another type of dye having a different color. The kind and combination of the dyes for obtaining the color mixture are not particularly limited.

  SolventBlue78 when combining other dyes, other dyes, for example, SolventYellow167 (COLOR INDEX GENERIC NAME, hereinafter the same), SolventYellow114, SolventYellow163, SolventYellow93, SolventYellow33, SolventYellow16, SolventGreen5, SolventYellow104, SolventOrange60, SolventYellow14, SolventOrange63, VatRed41 , SolventRed149, SolventRed111, SolventRed135, SolventRed179, SolventRed146, Solv ntRed22, SolventRed52, SolventViolet31, SolventViolet13, DisperseBlue165, DisperseBlue15, SolventGreen3, PigmentRed170 and the like.

  The flame retardant added to the expandable polystyrene-based colored resin particles for manufacturing the building heat insulating material of the present invention is not particularly limited as long as it can provide sufficient flame retardancy in the building heat insulating material obtained from the resin particles. These can be selected from commercially available flame retardants such as brominated flame retardants and inorganic flame retardants. Of these flame retardants, brominated flame retardants are preferred. Examples of brominated flame retardants include brominated aliphatic hydrocarbon compounds such as hexabromocyclododecane, tetrabromocyclooctane, tetrabromobutane, hexabromocyclohexane, tetrabromobisphenol A, tetrabromobisphenol F, 2, 4 Brominated phenols such as 1,6-tribromophenol, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetra Brominated phenol derivatives such as bromobisphenol A-diglycidyl ether, etc.

  The content of the flame retardant is preferably 0.3 to 2.0 parts by mass, more preferably 0.5 to 1.5 parts with respect to 100 parts by mass of polystyrene resin particles impregnated with the flame retardant. It is particularly preferable to adjust so as to be 0.7 to 1.0 part by mass so as to be part by mass. When the content of the flame retardant is less than the above range, the flame resistance of the resulting building heat insulating material may be reduced. On the other hand, when the content is large, the heat insulating property and the foam moldability of the resulting building heat insulating material may be reduced. The appearance may be reduced.

  In addition to the flame retardant, a flame retardant aid such as cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane may be added.

  Examples of the foaming agent used in the expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material according to the present invention include aliphatic hydrocarbons having 5 or less carbon atoms that are used in the manufacture of general thermoplastic resin foams, such as n. -Butane, isobutane, n-pentane, isopentane, neopentane, etc. are mentioned.

  The content of the foaming agent is preferably in the range of 2 to 10% by mass, more preferably 3 to 9% by mass with respect to the polystyrene resin particles. When the content is less than 2% by mass, not only is it difficult to reduce the density, but the effect of increasing the secondary foaming power at the time of molding cannot be obtained, so that the appearance of the foamed molded product becomes inferior. On the other hand, if the content exceeds 10% by mass, the shrinkage during foam molding, the adjustment time of the residual gas in the pre-expanded particles is delayed, and the molding cycle becomes long, which is not preferable from the viewpoint of productivity.

  The expandable polystyrene-based colored resin particles for manufacturing heat insulating materials for buildings are used in the production of expandable polystyrene-based resin particles in the range that does not impair the physical properties, plasticizer, expanded cell nucleating agent, filling You may use an agent, a lubricant, etc. suitably as needed. In addition, if powdered metal soaps such as zinc stearate are applied to the surface of the expandable polystyrene colored resin particles for manufacturing a building heat insulating material, the expandable polystyrene colored resin particles for manufacturing a building heat insulating material In the pre-foaming step, it is preferable because the bonding between the pre-foamed particles can be reduced.

Since the expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material according to the present invention contain Solvent Blue 78 as a dye, a uniformly colored building heat insulating material can be easily manufactured without coloring unevenness.
In addition, Solvent Blue 78 can be colored beautifully and uniformly by combining a plurality of types of dyes of different colors and impregnating the surface of the polystyrene resin particles, so that variations in coloring can be increased.

  The expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material according to the present invention are obtained by placing polystyrene-based resin particles in a pressure-resistant container and further adding a dye and a foaming agent to the polystyrene-based resin particles. When producing expandable polystyrene colored resin particles for manufacturing heat insulating materials by impregnating with a flame retardant, a dye containing SolventBlue 78 is pre-dispersed in an aqueous medium, and expanded polystyrene for manufacturing heat insulating materials for buildings. It is manufactured by a method for obtaining colored resin particles.

In this production method, the polystyrene resin particles are preferably dispersed in an aqueous medium containing a dispersant.
Examples of the dispersant include poorly water-soluble inorganic compounds such as magnesium pyrophosphate and tricalcium phosphate, and water-soluble polymers such as polyvinyl alcohol, methyl cellulose, polyacrylamide, and polyvinyl pyrrolidone.

  As the surfactant used when dispersing the Solvent Blue 78 in an aqueous medium, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant may be used. It can be appropriately selected and used in consideration of dispersibility and the like.

  In this production method, polystyrene resin particles are placed in a pressure-resistant container together with an aqueous medium, the dye is added and the polystyrene resin particles absorb the dye, and then a foaming agent and a flame retardant are injected into the container. It is preferable that the inside of the container is heated to 60 ° C. or higher, and the polystyrene-based resin particles absorb the foaming agent and the flame retardant to produce expandable polystyrene-based colored resin particles for manufacturing a heat insulating material for buildings.

  The method for producing expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material according to the present invention, as described above, easily and inexpensively produces expandable polystyrene-based colored resin particles from which a beautifully-colored building heat insulating material can be obtained. can do.

The expandable polystyrene-based colored resin particles of the present invention are pre-foamed by heating with steam or the like using a well-known apparatus and method in the field of producing foamed resin moldings, and pre-foamed colored resin particles for manufacturing heat insulating materials for buildings (Hereinafter referred to as pre-expanded particles). The pre-expanded particles are pre-expanded so as to have a bulk density equivalent to that of the building heat insulating material to be manufactured. In the present invention, its bulk density is not limited, usually in the range of 0.010~0.10g / cm ^3, preferably in the range of 0.015~0.050g / cm ^3.

In the present invention, the bulk density of the pre-expanded particles refers to those measured in accordance with JIS K6911: 1995 “General Test Method for Thermosetting Plastics”.
<Bulk density of pre-expanded particles>
Fill the graduated cylinder with pre-expanded particles to a scale of 500 cm ³ . However, the graduated cylinder is visually observed from the horizontal direction, and if at least one pre-expanded particle reaches the scale of 500 cm ³ , the filling is finished. Next, the mass of the pre-expanded particles filled in the graduated cylinder is weighed with two significant figures after the decimal point, and the mass is defined as W (g). The bulk density of the pre-expanded particles is calculated by the following formula.
Bulk density (g / cm ³ ) = W / 500

<Bulk expansion ratio of pre-expanded particles>
Moreover, the bulk expansion ratio of the pre-expanded particles is a numerical value calculated by the following equation.
Bulk foaming factor = 1 / bulk density (g / cm ³ )

The pre-foamed particles are filled with the pre-foamed particles in a cavity of a mold using a well-known apparatus and technique in the field of foamed resin moldings, heated by steam heating or the like, and foam-molded in the mold. Manufacturing insulation materials.
Although the density of the building insulation material of the present invention is not particularly limited, usually in the range of 0.010~0.10g / cm ^3, preferably in the range of 0.015~0.050g / cm ³ .

In the present invention, the density of the heat insulating material for building refers to the density of the foam molded body measured by the method described in JIS K7122: 1999 “Measurement of foamed plastic and rubber-apparent density”.
<Density of foam molding>
A test piece of 50 cm ³ or more (100 cm ³ or more in the case of semi-rigid and soft materials) was cut so as not to change the original cell structure of the material, its mass was measured, and calculated by the following formula.
Density (g / cm ³ ) = Test piece mass (g) / Test piece volume (cm ³ )
Test piece condition adjustment and measurement test pieces were cut out from samples that had passed 72 hours or more after molding, and were subjected to atmospheric conditions of 23 ° C. ± 2 ° C. × 50% ± 5% or 27 ° C. ± 2 ° C. × 65% ± 5%. It has been left for more than an hour.

<Folding multiple of foamed molded product>
Further, the expansion factor of the foamed molded product is a numerical value calculated by the following equation.
Foaming factor = 1 / density (g / cm ³ )

  The shape and size of the architectural heat insulating material of the present invention are not particularly limited, and can be a fixed type such as a board shape or various other shapes. Moreover, in order to adapt to a construction location, you may perform secondary processes, such as cut | disconnecting and drilling | piercing, and you may provide an unevenness | corrugation in an edge part in order to arrange many in length and width.

  The heat insulating material for building of the present invention heats and expands the expandable polystyrene colored resin particles for manufacturing the heat insulating material for building, fills the obtained pre-expanded particles in the cavity of the mold and heats it. Since it is obtained by foam molding, there is no uneven coloring, and it has a beautifully colored appearance. Moreover, the heat insulating material for a building of the present invention has a thermal conductivity measured based on JIS A 9511 of 0.045 W / (m · K) or less, and the flammability standard described in JIS A 9511. It has flame resistance to satisfy. Therefore, the building heat insulating material of the present invention is extremely useful as a building heat insulating material.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, a following example is only the illustration of this invention and this invention is not limited to description of a following example.
In the following Examples and Comparative Examples, “parts by mass” is abbreviated as “parts”, and “mass%” is abbreviated as “%”.

[Example 1]
In an autoclave having an internal volume of 6 liters, 2200 parts of pure water as an aqueous medium, 5.0 parts of magnesium pyrophosphate, 1.2 parts of sodium dodecylbenzenesulfonate and 45 parts of cyclohexane as a plasticizer are stirred and suspended by a homomixer. A turbid liquid was prepared, 2100 parts of polystyrene resin particles (Mw: 300,000) were added to the liquid, stirred with a stirring blade (rotation speed: 250 rpm), and suspended in an aqueous medium at 30 ° C. .
Next, 2.5 parts of Solvent Blue 78 preliminarily dispersed in an aqueous medium of 100 g of pure water containing 0.2 g of sodium dodecylbenzenesulfonate was introduced into the autoclave, and then tetrabromocyclohexane as a flame retardant. Octane (trade name “Pyroguard FR-200S” 19 parts by Daiichi Kogyo Seiyaku Co., Ltd.) and 8 parts of dicumyl peroxide as a flame retardant aid were added.
Thereafter, 200 parts of butane was press-fitted as a foaming agent. Subsequently, the inside of the autoclave was heated to 90 ° C. and kept at this temperature for 5 hours. Then, it cooled to 25 degreeC and obtained the expandable polystyrene-type colored resin particle for heat insulation materials for buildings.
5 kg of the expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material thus obtained were put into a Ladige mixer M20 type (internal volume 20 liters) manufactured by Matsuzaka Trading Co., Ltd. Next, 2.5 g of zinc stearate, 2.5 g of 12-hydroxystearic acid triglyceride, and 2.5 g of stearic acid monoglyceride were sequentially added and stirred at 230 rpm for 3 minutes. Next, 2.5 g of polyethylene glycol having a weight average molecular weight of 300 was added and stirred at 230 rpm for 5 minutes to coat the resin particle surfaces.
After the coating, the expandable polystyrene-based colored resin particles for the production of heat insulating materials for construction are put into a small batch type pre-foaming machine having an internal volume of about 40 liters, heated under normal pressure with water vapor with a gauge pressure of 0.05 MPa, and a bulk expansion factor Pre-foaming was performed 50 times to obtain pre-foamed particles.
The obtained pre-expanded particles are left to stand at 20 ° C. for 24 hours, dried and matured, and then a mold having a cavity for manufacturing a heat insulating material for construction having an outer dimension of 300 × 400 × 25 mm is formed by attaching a surface pressure gauge. The pre-foamed particles were filled in the cavity, and in-mold foam molding was performed by steam heating. ACE-3SP manufactured by Sekisui Koki Seisakusho Co., Ltd. is used as the molding machine. In the QS molding mode, gauge pressure 0.7 kg / cm ² , mold heating 3 seconds, one heating 8 seconds, reverse one heating 1 second, double-side heating 10 seconds. Then, in-mold foam molding was performed under the conditions of water cooling for 5 seconds and a set extraction surface pressure of 0.02 MPa to produce a heat insulating material for construction (50 times the expansion ratio).
The obtained building heat insulating material was put in a drying room at 40 ° C. and dried for one day. The appearance was visually examined and evaluated based on the following <Measurement evaluation of uneven coloring>. The obtained heat insulating material for building was of a good quality with foam particles adhering well to each other, beautiful blue color and less uneven coloring. The results are shown in Table 1.

<Measurement evaluation of uneven coloring>
The heat insulating material for building was confirmed visually, and the number of foamed particles in which coloring unevenness occurred in the main surface (400 × 300 mm) was examined.
When the number of foamed particles in which uneven coloring occurs in the main surface is 3 or less and the color is uniform throughout, the coloring is not uneven (good (◯)) and the main surface is colored. When there were 3 or more foamed particles with unevenness, and those with color shading, color loss, etc., they were evaluated as having uneven coloring (defect (x)).

[Example 2]
A heat insulating material for building was manufactured in the same manner as in Example 1 except that the amount of Solvent Blue 78 was 0.1 part.
The obtained heat insulating material for building had a beautiful appearance in which the foamed particles were well fused with each other and were blue with little uneven coloring. The evaluation results of uneven coloring are shown in Table 1.

[Example 3]
A heat insulating material for building was produced in the same manner as in Example 1 except that the amount of Solvent Blue 78 was 8.5 parts.
The obtained heat insulating material for building had a beautiful appearance in which the foamed particles were well fused with each other and were blue with little uneven coloring. The evaluation results of uneven coloring are shown in Table 1.

[Example 4]
A heat insulating material for building was manufactured in the same manner as in Example 1 except that 2.7 parts of Solvent Blue 78 and 2.5 parts of Disperse Red 9 were used in combination.
The obtained heat insulating material for building had a beautiful appearance in which the foamed particles fused well to each other and were gray and had little uneven coloring. The evaluation results of uneven coloring are shown in Table 1.

[Comparative Example 1]
A heat insulating material for building was manufactured in the same manner as in Example 1 except that the same amount of an anthraquinone dye SolventBlue 87 which is not SolventBlue 78 was used.
The obtained heat insulating material for building was blue, but there were many uneven coloring, and the appearance was inferior. The evaluation results of uneven coloring are shown in Table 1.

[Comparative Example 2]
A heat insulating material for building was produced in the same manner as in Example 1 except that the same amount of an anthraquinone dye Solvent Blue 58 other than Solvent Blue 78 was used as the dye.
The obtained heat insulating material for building was blue, but there were many uneven coloring, and the appearance was inferior. The evaluation results of uneven coloring are shown in Table 1.

[Comparative Example 3]
A heat insulating material for building was manufactured in the same manner as in Example 1 except that 2.7 parts of SolventBlue 63, which is an anthraquinone dye other than SolventBlue 78, and 2.5 parts of DisperseRed9 were used in combination.
Although the obtained heat insulating material for construction was gray, there were many uneven colorings and the appearance was inferior. The evaluation results of uneven coloring are shown in Table 1.

From the results shown in Table 1, Examples 1 to 4 using Solvent Blue 78 as a dye were beautifully colored, and high-quality thermal insulation materials with little coloring unevenness were obtained.
On the other hand, the heat insulating materials for buildings obtained in Comparative Examples 1 to 3 using a dye different from Solvent Blue 78 had many coloring irregularities and were inferior in appearance.

[Measurement of thermal conductivity of Examples 1 to 4]
About the heat insulating material for buildings of Examples 1-4 manufactured as mentioned above, the heat conductivity was measured by the measuring method described in the following <thermal conductivity>.

<Thermal conductivity>
A rectangular parallelepiped test piece having a length of 200 mm, a width of 200 mm, and a thickness of 25 mm was cut out from the heat insulating material for building. Then, the thermal conductivity of this test piece was measured at a measurement temperature of 23 ° C. using a thermal conductivity meter (AUTO-Λ HC-072) manufactured by Eihiro Seiki Co., Ltd. according to JIS A1412.

  As a result, the thermal insulation materials for Examples 1 to 4 all had a thermal conductivity of 0.045 W (m · K) or less, and had practically sufficient thermal insulation properties as thermal insulation materials for architecture.

[Flame retardancy test of Examples 1 to 4]
About the heat insulating material for buildings of Examples 1-4 manufactured as mentioned above, the flame retardance was evaluated by the measurement evaluation method described in the following <flame retardance>.

<Flame retardance>
Five test pieces of rectangular parallelepiped shape 200mm long x 25mm wide x 10mm high are cut out from a building heat insulating material with a vertical cutter, cured in a 60 ° C oven for 1 day, and measured according to JIS A9511-2006 measurement method A. The average value of the five test pieces was obtained and used as the flame extinction time, and comprehensively evaluated based on the following criteria. In the JIS standard, the flame extinguishing time needs to be within 3 seconds, preferably within 2 seconds, and more preferably within 1 second.
Defective (x): The flame extinguishing time exceeds 3 seconds, or even one of the test pieces has residue, or burns beyond the combustion limit indicator line.
Good (O): The flame extinguishing time is within 3 seconds, and all five samples have no residue and do not burn beyond the combustion limit indicator line.
Extremely good (◎): Flame extinguishing time is within 1 second, and all five samples have no residue and do not burn beyond the combustion limit indicator line.

  As a result, all of the building thermal insulation materials of Examples 1 to 4 satisfied the JIS standard combustibility (flame extinguishing time within 3 seconds) and the flame retardancy was good (良好).

  The present invention relates to an expandable polystyrene-based colored resin particle for manufacturing a heat insulating material for building, which includes a foaming agent and is made of colored polystyrene-based resin particles, and a method for manufacturing the same. An expandable polystyrene-based colored resin particle for manufacturing a heat insulating material for building, a method for manufacturing the same, a colored resin pre-expanded particle for manufacturing a heat insulating material for building, and a heat insulating material for building are provided.

Claims (13)

In the foamable polystyrene-based colored resin particles for building heat insulation manufacturing colored with a dye,
An expandable polystyrene-based colored resin particle for manufacturing a building heat insulating material, characterized by containing SolventBlue 78 as a dye and a flame retardant.   2. The expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material according to claim 1, comprising Solvent Blue 78 in a range of 0.003 to 0.4 mass%.   The expandable polystyrene-based colored resin particle for manufacturing a heat insulating material for building according to claim 1 or 2, which contains a brominated flame retardant as a flame retardant.   4. One or more dyes selected from the group consisting of anthraquinone dyes other than blue, azo dyes, and quinoline dyes are used in combination with SolventBlue 78. 5. Expandable polystyrene-based colored resin particles for manufacturing building insulation materials.   The expandable polystyrene-based colored resin particles for manufacturing a heat insulating material for building according to any one of claims 1 to 4, wherein the expandable polystyrene-based colored resin particles contain a polyolefin-based resin. Put polystyrene resin particles in a pressure-resistant container, and then add dye, foaming agent and flame retardant, impregnate polystyrene resin particles with foaming agent, dye and flame retardant, and expand polystyrene coloring for manufacturing insulation materials for buildings. In the method for producing resin particles,
The method for producing expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material, wherein the dye contains Solvent Blue 78 and the dye is dispersed in an aqueous medium in advance.   The polystyrene resin particles are placed in a pressure-resistant container together with an aqueous medium, the dye is added and the polystyrene resin particles absorb the dye, and then a foaming agent and a flame retardant are injected into the container, and the container is filled with 60 The method for producing expandable polystyrene colored resin particles for manufacturing a heat insulating material for building according to claim 6, wherein the temperature is raised to at least ° C. and the polystyrene resin particles absorb the foaming agent and the flame retardant.   The content of Solvent Blue 78 in the expandable polystyrene-based colored resin particles is in the range of 0.003 to 0.4 mass%. The production of expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material according to claim 6 or 7. Method.   The manufacturing method of the expandable polystyrene-type colored resin particle for heat insulation materials for buildings of any one of Claims 6-8 containing a bromine-type flame retardant as a flame retardant.   The combined use with SolventBlue 78 contains one or more dyes selected from the group consisting of anthraquinone dyes other than blue, azo dyes, and quinoline dyes. Method for producing expandable polystyrene-based colored resin particles for manufacturing thermal insulation for buildings.   The method for producing expandable polystyrene-based colored resin particles for manufacturing a building heat insulating material according to any one of claims 6 to 10, wherein the expandable polystyrene-based colored resin particles contain a polyolefin resin.   Colored resin pre-expanded particles for manufacturing heat insulating materials for buildings obtained by heating and pre-expanding expandable polystyrene colored resin particles for manufacturing heat insulating materials for buildings according to any one of claims 1 to 5.   The thermal conductivity measured according to JIS A 9511, which is obtained by filling the pre-expanded colored resin particles for manufacturing a building heat insulating material according to claim 12 into a cavity of a molding die, heating and molding, and in-mold foam molding. Is a heat insulating material for building which is 0.045 W / (m · K) or less and satisfies the flammability standard described in JIS A 9511.