JPH09300421A - Extrusion resin molded object containing inorganic material and molding thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an extrusion resin molded object containing an inorg. material also excellent in shape holdability after combustion in addition to capacity such as the low water absorbability, high toughness or the like of a resin and capable of being widely used as a fireproof building material and a method for molding the same. SOLUTION: A molded object is obtained by the extrusion molding of a mixture of a resin and a specific inorg. material forming gap parts by the entanglement of primary particles with an aspect ratio of 5-500 and has voids of 5-60vol.%. This molded object is molded by a method wherein 30-230 pts.wt. of a specific ionorg. material constituting void parts by the entanglement of primary particles with an aspect ratio of 5-500 is added to 100 pts.wt. of a resin and water is further added thereto and all of them are uniformly mixed by a mixer and the resulting mixture is dried to be molded by a single-screw extrusion molding machine.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an extruded resin molding and a molding method thereof. More specifically, the present invention relates to an extruded resin molded body containing an inorganic material and excellent in shape retention during combustion, and a molding method thereof.

[0002]

2. Description of the Related Art Generally, a resin is a material having characteristics such as low water absorption and high toughness and is widely used in various fields.
On the other hand, the extrusion molding method is one of typical resin molding methods capable of efficiently molding a long product having a complicated cross-sectional shape, and resin extrusion moldings are now widely used in various fields.

However, since the resin is easily burnt, and the shape and the defect thereof are remarkably deformed by the burning, there is room for improvement in the fireproof property, so that the use thereof in the construction field where fireproof property is important is considerably limited. It is the current situation. As one of the methods for improving the fireproofness of the resin, there is a composite with an inorganic material, but if the addition rate of the inorganic material is increased, the characteristics of the resin are lost and extrusion molding becomes difficult, so conventionally,
It was difficult to obtain a fireproof extruded product that was sufficiently added with an inorganic material and was excellent in shape retention during combustion.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an extruded resin molded article containing a fireproof inorganic material which is excellent in shape retention during combustion, in addition to resin characteristics such as low water absorption and high toughness. It is to provide the forming method.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that when a resin and an inorganic material are compounded to obtain a molded article, a specific inorganic material is mixed and extruded. It has been found that the structure having a void formed by a molding machine has an improved shape retention during combustion and an excellent fire prevention property with an increase in the porosity, and has completed the present invention.

That is, one aspect of the present invention is a resin molding containing an inorganic material, wherein the inorganic material has an aspect ratio of 5 to 5.
No. 00 primary particles and having a bulky structure in which they are intertwined to form voids, and the content of the inorganic material is 30 to 230 parts by weight with respect to 100 parts by weight of the resin, and the voids are 5 to 60. An extruded resin molded body containing an inorganic material, which is characterized by being a volume%, and another aspect of the present invention is a method for molding an extruded resin molded body containing an inorganic material, wherein the inorganic material is A bulky structure in which primary particles have an aspect ratio of 5 to 500 and are entangled to form voids is used, and 100 parts by weight of the resin is mixed with the inorganic material 30.
˜230 parts by weight, and further add water, mix uniformly using a mixer, then dry the mixed material to remove water, and use the extruder to form the mixed material from which the water has been removed. A method for molding an extruded resin molded body containing an inorganic material, which comprises molding.

Hereinafter, the present invention will be described in detail. The resin used in the present invention is not particularly limited as long as it is a resin capable of extrusion molding, polyethylene, polypropylene, polystyrene, polyamide, styrene-butadiene copolymer,
Examples thereof include acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic copolymer, phenol resin and the like. These can be used alone or as a mixture of two or more kinds, but it is preferable to use a resin having high flame retardancy such as polyvinyl chloride or phenol resin.

The inorganic material used in the present invention has a primary particle morphology of an aspect ratio of 5 to 500, preferably 10 to 30.
0, more preferably 10 to 100 or more, that is, fibrous or needle-like, and they must be entangled to form a bulky higher-order structure containing voids inside, It is preferable that the powder has a shape-retaining property after a pressing operation such as pressing. When an inorganic material having an aspect ratio other than the above range is used, it is difficult to obtain an extruded resin molded article having excellent fire resistance.

Specific examples of the inorganic material used in the present invention include crystalline calcium silicate hydrates such as xonotlite and tobermorite, and relatively low crystalline calcium silicate hydrates called CSH-I and CSH-II. Examples thereof include wollastonite, basic magnesium sulfate, and the like. These may be used alone or in combination of two or more kinds.

The inorganic material used in the present invention is further required to be the primary particles of the above-mentioned aspect ratio and to form a bulky high-order structure containing voids inside by entanglement of the primary particles. A high-order structure has a particle size of 10 to 10
It is preferable that secondary particles of 0 μm are formed, and
More preferably, secondary particles having a size of -40 μm are formed.

The inorganic material used in the present invention may be a granular material in the form of powder or an aqueous slurry in which the particles are dispersed in water. In particular, calcium silicate hydrate such as xonotlite can be synthesized as an aqueous slurry, but in the present invention, this slurry can also be used as a raw material in a state where it is not dried. The content of the inorganic material in the extruded resin molded product of the present invention is 30 to 230 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the resin.
The amount is 0 to 200 parts by weight, more preferably 65 to 150 parts by weight. If the content of the inorganic material is too low, a molded article having excellent fire resistance cannot be obtained. On the other hand, if the content of the inorganic material is too high, extrusion molding becomes difficult, and a molded product having resin characteristics such as low water absorption and high toughness cannot be obtained.

In the extruded resin molded product of the present invention, instead of the inorganic material, a part of the inorganic material may be replaced with an inorganic fiber to be contained. Those containing inorganic fibers are effective in increasing the strength and further improving fire resistance. Examples of the inorganic fiber used in the present invention include glass fiber, carbon fiber, rock wool and the like, but the content of the extruded resin molding is preferably 40% by weight or less. More preferably, it is 20% by weight or less.

Even when the resin composition contains inorganic fibers, the resin content of the extruded resin molding is preferably at least 40% by weight. The term "voids" as used in the present invention means that there is a bulky higher-order structure in which primary particles of an inorganic material are entangled with each other in a resin, forming voids, and the voids communicate with the surface of the molded body. It is preferable that there is no void, that is, an independent void.

In the extruded resin molded product of the present invention, the ratio of voids (porosity) is required to be 5 to 60% by volume, more preferably 10 to 50% by volume,
In particular, it is preferably from 13 to 40% by volume. If the porosity is 5% by volume or less, a molded article excellent in shape retention during combustion cannot be obtained, and if it is 60% by volume or more, physical properties such as mechanical strength are unfavorable.

However, since the voids introduced by adding the foaming agent do not contribute to the improvement of the shape retention during combustion,
Voids introduced by the addition of the foaming agent are not included in the voids in the present invention. Further, the hollow portion when the extruded resin molded body has a hollow structure does not correspond to the void portion in the present invention. Since the extruded resin molded product of the present invention has a porosity, the shape retention during combustion is improved. The mechanism by which this shape retention is improved is not clear, but the higher the proportion of the higher-order structure of the inorganic material in the molded body, the higher the shape-retention during combustion, and the shape-retention is the void of the higher-order structure. It seems that there is a correlation with the existence ratio of.

The extruded resin molded product of the present invention has a high porosity due to the presence of many entangled structures of inorganic materials, and exhibits excellent shape retention during combustion, but conventional extruded products having a low porosity are Since the entangled structure of the inorganic material is destroyed during the mixing of the raw materials and the extrusion molding, the porosity is low and the shape retention during combustion is presumed to be poor. The term "porosity" as used in the present invention means the volume ratio of the voids in the extruded resin molded body, and is determined by the following method.

The molded body is crushed to 50 μm or less and the temperature is 20
Let stand in a desiccator whose temperature is controlled at ℃ and silica gel until the water content becomes constant. Then, using an air pycnometer (air-comparison specific gravity meter), determine the actual volume Vt, and
The weight Mt is obtained, and from this result, the true density ρt of the molded product is calculated by the following equation. ρt = Mt / Vt ... On the other hand, a 50 × 50 × 5 mm molded body was allowed to stand in a desiccator whose temperature was 20 ° C. and was regulated with silica gel until the moisture content became constant. The volume Va is obtained, and the bulk density ρa of the molded body is calculated by the following equation based on these.

Ρa = Ma / Va The porosity P (volume%) of the molded body is determined by the following equation. P = 1-([rho] a / [rho] t) Next, a method for molding an extruded resin molded body containing the inorganic material of the present invention will be described. First, the resin, the inorganic material, and water, and the respective raw materials such as inorganic fibers to be added if necessary, are mixed until uniform.

At this time, a dispersant, a surfactant or the like for promoting uniform mixing of the respective raw materials may be added if necessary. The rate of water addition cannot be decided unconditionally because it depends on the conditions such as the form of resin to be added, the mixing ratio of resin and inorganic material, and the mixing method, but each raw material can be uniformly mixed and left standing after mixing. However, it may be in the range where the separation of the raw materials does not occur. Specifically, concrete slump test method (J
The slump of the mixed raw material measured by IS 1101) is 5
It is preferable to set it in a range showing a value of 25 cm. More preferably, it is 10 to 20 cm.

The order of adding the raw materials and the mixing method are not particularly limited as long as they can uniformly mix the respective raw materials without significantly destroying the entangled structure of the inorganic materials to be added and used. It may be decided accordingly. As a suitable mixing method, a mixing method such as an all-purpose mixer, an Obert type mixer, an omni mixer, a paddle type mixer or the like, which does not take a relatively large share, can be exemplified.

The resin used in the present invention is preferably water-dispersible, and powder resin or resin emulsion is preferably used. When using powdered resin, the particle size is 5
It is preferably 0 μm or less, more preferably 30 μm or less. When a resin having a particle size of more than 50 μm is used, it becomes difficult to obtain a molded product in which the resin and the inorganic material are uniformly mixed.

By thus mixing the resin in a state where water is added, the resin and the inorganic material are mixed with each other without using a mixing method having a high share, that is, a mixing method that significantly destroys the entangled structure of the inorganic material. It is considered that the resin can be uniformly mixed, and an extruded resin molded product having a high porosity can be obtained. Conventionally, in the case of extrusion molding a mixed raw material of a resin and an inorganic material, first, in order to uniformly mix the resin and the inorganic material, once using a device such as a mixing roll or a twin-screw kneading extruder, a high share is required. There was mixing. Therefore, it is considered that the entangled structure formed by the inorganic material was destroyed, and a molded product having a high porosity, that is, a molded product excellent in shape retention after combustion could not be obtained.

The inorganic material used in the present invention has the above-mentioned aspect ratio, is granular, and has a particle size of 10 to 100 μm.
It is preferable that the particles have a higher order structure. More preferably, it is 20 to 40 μm. Here, the higher-order structure of the inorganic material refers to one having a strong structure in which a large number of primary particles are entangled and aggregated, and the aggregated state can be confirmed by SEM observation.

A calcium silicate hydrate such as xonotlite can be synthesized as an aqueous slurry, and in the present invention, this aqueous slurry can be used as a raw material by mixing it with a resin without being dried. The slurry of the mixed raw material of the resin and the inorganic material thus obtained is dried and then put into an extrusion molding machine to be extrusion molded.

As the extrusion molding machine, it is preferable to use an all-purpose extrusion molding machine or the like which has a relatively small share. The molding conditions may be the same as the molding conditions for the resin alone, but the heating temperature of the raw material in the molding machine is preferably slightly higher than that for the resin alone. As described above, in the method for molding an extruded resin molded body of the present invention, since the mixed raw material that has been dried and moisture is put into the extrusion molding machine, it is not necessary to carry out a drying treatment after extrusion molding, so that shrinkage etc. It is possible to form an extruded resin molded product having a hollow section and a complicated cross-sectional shape as shown in FIG. it can. In addition, it is possible to mold a long extruded resin molded body having no warp with the same precision as a molded body of resin alone.

The molding method of the extruded resin molding containing the inorganic material of the present invention has such advantages, and the molding obtained has properties such as low water absorption and high toughness which are the original characteristics of the resin. It also has excellent shape retention during combustion.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the used raw materials and the evaluation method are shown below. (1) Vinyl chloride resin Measure the particle size distribution with a laser light scattering type particle size distribution measuring device, and use powder (Shin-Etsu Polymer Co., Ltd., trade name, EX-206) with no particle size of 30 μm or more. I was there. (2) Vinyl chloride-acrylic copolymer emulsion An aqueous emulsion having a resin concentration of 50% and a minimum film forming temperature of 100 ° C. (3) Inorganic material It was confirmed by SEM that the primary particles have an aspect ratio of 10 or more, and that they are entangled with each other to form secondary particles having a bulky high-order structure of 20 to 40 μm and confirmed to be zonotolite powder. Was used. (3) Fire resistance test Using a building material flammability tester {manufactured by Toyo Seiki Seisakusho Co., Ltd.}, the flame resistance test class 1 of the interior test materials for buildings and the flammability test method of construction method (JIS A13421) is used. In accordance with the above, heating was performed on a 220 × 220 × 5 mm flat plate-shaped test body, and the deformation state of the test body after heating, such as warpage and cracking, was evaluated in the following three stages.

⊚: There is little warpage due to heating and no cracks reach the backside of heating. ◯: There is little warpage due to heating, but cracks reaching the backside of heating occur. ×: Warpage occurs remarkably due to heating. Cracks that split into

[0029]

Example 1 100 parts by weight of vinyl chloride resin powder, 67 parts by weight of xonotlite, and 120 parts by weight of water were added, and a universal mixer {trade name, ACM-3, manufactured by Kodaira Seisakusho Co., Ltd.
0 L} was used and mixed at a rotation speed of 200 rpm for 5 minutes to make it uniform. This mixed raw material is heated by a hot air dryer to produce 11
Water was completely removed by drying at 0 ° C. for 240 minutes.

The mixed raw material after drying was heated at a heating temperature of 190 ° C. and a screw rotation speed of 3 using a single-screw extruder (manufactured by Ono Seisakusho Co., Ltd., trade name, ONP-50B).
A flat plate having a width of 240 mm and a thickness of 5 mm was extruded at 0 rpm. The resulting extruded resin molded body has a porosity of 20.5.
% By volume. A 220 × 220 mm sample was taken from this flat plate and subjected to a fireproof test. Table 1 shows the results of the fire protection test.
It was shown to.

[0031]

Example 2 Example except that 200 parts by weight of vinyl chloride-acrylic copolymer emulsion (100 parts by weight of resin content), 150 parts by weight of xonotlite, 75 parts by weight of water, and the heating temperature of the raw material were 170 ° C. A flat plate was extruded in the same manner as in 1. The obtained flat plate had a porosity of 14.1% by volume. Table 1 shows the results of the fire resistance test for this flat plate.

[0032]

Example 3 200 parts by weight of vinyl chloride-acrylic copolymer emulsion (100 parts by weight of resin content), 85 parts by weight of xonotlite, and 10 parts by weight of glass fiber were mixed in the same manner as in Example 1 using a universal mixer. To make it uniform, and further use aluminum sulphate / 1 as a coagulant for the resin emulsion.
After adding 5 to 4 parts by weight of water 4 to 18 and mixing again with a universal mixer at a rotation speed of 200 rpm for 3 minutes, this was vacuum dried at 80 ° C.

A flat plate was extruded from the dried mixed raw material in the same manner as in Example 2 using a single-screw extruder. The obtained flat plate had a porosity of 17.3% by volume. Table 1 shows the results of the fire resistance test for this flat plate.

[0034]

Comparative Example 1 100 parts by weight of vinyl chloride resin powder and 67 parts by weight of xonotlite were mixed with a mixing roll having a roll temperature of 180 ° C. at a rotation speed of 50 rpm for 15 minutes to be uniform and dried. A flat plate was extruded from the mixed raw material in the same manner as in Example 1 using a single-screw extruder. The obtained flat plate had a porosity of 3.8% by volume.
Table 1 shows the results of the fire resistance test for this flat plate.

[0035]

Comparative Example 2 A flat plate having a porosity of 8.5 volume% was obtained in the same manner as in Example 1 except that the amount of xonotlite was 25 parts by weight and the amount of water added was 60 parts by weight. Table 1 shows the results of the fire resistance test for this flat plate.

[0036]

[Table 1]

[0037]

INDUSTRIAL APPLICABILITY The method for molding an extruded resin molded product containing the inorganic material of the present invention is capable of molding an extruded resin molded product having a complicated cross-sectional shape with high dimensional accuracy as compared with the conventional method. A long extruded resin molded body without warping can be molded. Extruded resin moldings containing this inorganic material, in addition to the characteristics of the resin such as low water absorption, high toughness,
It has excellent shape retention during combustion and is suitable for fireproof building materials.

[Brief description of drawings]

FIG. 1 shows an extruded resin molded body containing a conventional inorganic material,
Explanatory drawing of cross section schematically showing mixed state of inorganic material and resin

FIG. 2 is an explanatory view of a cross section schematically showing a mixed state of an inorganic material and a resin in an extruded resin molded body containing the inorganic material of the present invention.

FIG. 3 is a cross-sectional view showing an example of the cross-sectional shape of a long product of the extruded resin molding of the present invention.

[Explanation of symbols]

 1: Inorganic material 2: Resin 3: Void portion due to bulky secondary particles

Claims (2)

[Claims] 1. A resin molding containing an inorganic material, which has a bulky structure in which the inorganic material is primary particles having an aspect ratio of 5 to 500 and is entangled to form a void portion, and the content of the inorganic material is high. Is 30 to 230 parts by weight with respect to 100 parts by weight of the resin, and the void portion is 5 to 60% by volume.
An extruded resin molded product containing an inorganic material characterized in that 2. A method for molding an extruded resin molded body containing an inorganic material, wherein the inorganic material has a bulky structure in which primary particles have an aspect ratio of 5 to 500 and are entangled to form a void portion, and a resin 100 is used. After adding 30 to 230 parts by weight of the above inorganic material to parts by weight and further adding water,
An extruded resin containing an inorganic material, characterized by uniformly mixing using a mixer, then drying the mixed material to remove water, and molding the mixed material from which the water has been removed using an extruder. Molding method of molded body.