JPH08217515A - Production of thermoplastic cement formed material - Google Patents

Abstract

PURPOSE: To continuously obtain a lengthy thermoplastic cement formed material excellent in heat resistance, compressive strength and the like by extruding a specified forming material from an extruding die of a extruder immediately before passing it through a forming die to perform solidifying extrusion. CONSTITUTION: A forming material consisting of a thermoplastic cement composition is obtained by mixing 300-600 pts.wt. of hydraulic cement and/or non- hydraulic cement and 3-10 pts.wt. of hydrophilic cement with 100 pts.wt. of thermoplastic resin. The forming material is fed into a cylinder 2 of an extruder 1 through a hopper 5, and after while heated in heaters 4A-4D, it is melt and kneaded by an extruding screw 3, it is extruded in a specified shape from an extruding die 8 covered and formed over the whole inner surface with a skiddable material layer 14 of <=0.3 friction coefficient and >=50kg.f/10mm width tensile strength. Immediately after that, it is brought out to a forming die 9 covered and formed over the whole contact surface with the skiddable material layer 14 the same as the above and is subjected to solidifying extrusion, and then it is taken in by a take-in device 10.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a thermoplastic cement molding having intermediate properties between cement and a thermoplastic resin, and particularly to a long thermoplastic cement molding having high heat resistance and compressive strength. The present invention relates to a method for producing a thermoplastic cement molded product that can be continuously produced.

[0002]

2. Description of the Related Art Recently, although it is a cement composition, it possesses thermoplasticity, and while it is thermoplastically easy to process during molding, it loses thermoplasticity when it hardens due to water absorption, etc. A thermoplastic cement composition exhibiting the characteristics described above has been developed. For example, Japanese Patent Application No.
No. 149136 proposes a method for producing a thermoplastic cement composition and a cement molded product. This thermoplastic cement composition has thermoplastic resin, cement, and hydrophilic substance as basic components, and imparts hydrophilicity to the thermoplastic resin by polymer alloying or polymer blending the thermoplastic resin and the hydrophilic substance. , A composition in which cements added to the thermoplastic resin to which the hydrophilicity is imparted can be hydrated, and is different from the conventional composition in which cements are simply added to the resin. ing. The thermoplastic cement composition has both the moldability of a thermoplastic resin and the heat resistance of cement, and its application field is wide. Specifically, the thermoplastic cement composition is a thermoplastic resin 1
50 to 600 parts by weight of hydraulic cement and / or air-hardening cement, and 0.1 to 20 parts by weight of hydrophilic substance, relative to 00 parts by weight.
It is a composition obtained by mixing parts by weight, and various physical properties can be obtained by changing the mixing ratio.

The thermoplastic resin used in the above-mentioned thermoplastic cement composition may be any one that can be melted by heating during molding, and all kinds of thermoplastic resins can be applied. or,
Since mixed forms of different kinds of resins are not a problem, even waste resin materials can be used by roughly selecting only the thermosetting resin, and foreign materials accompanying the use of waste materials,
For example, even if thermosetting resin, dust, soil, sand, etc. are mixed in to some extent, they are captured by the binding force of cement and can be stably present as a filler in the molded product. For example,
Even a resin waste material to which soil or the like is attached, such as a polyvinyl chloride film or sheet used for an agricultural vinyl house, can be crushed and used as it is without removing the soil by washing or the like.

The utilization of the thermoplastic cement composition as described above is expected as a method for solving the environmental damage caused by waste resin, which has been a problem in recent years.

As a method for obtaining the above-mentioned thermoplastic cement molded product, various general methods such as injection molding, extrusion molding, calendering, compression molding, etc. are carried out depending on the melt index of the thermoplastic cement composition obtained by various compounding ratios. Various forming means are considered.

[0006]

However, when physical properties of the thermoplastic cement molded product are required to have particularly high heat resistance, compressive strength, dimensional stability, weather resistance, etc., the compounding amount of the thermoplastic cement composition Has a high cement content with respect to the thermoplastic resin, and the content of hydrophilic substances must be as low as possible. In a thermoplastic cement composition having such a composition, the melt index is low and the extrusion pressure is high, so that molding of a molded product by extrusion molding has been regarded as difficult. Therefore, it has been difficult to continuously manufacture a thermoplastic cement molded product that is required to have high heat resistance and the like as a long molded product.

In view of such manufacturing problems, the present invention has
Even long thermoplastic cement moldings with high heat resistance and compressive strength, etc. can be continuously manufactured using the extrusion molding technology, and thus can be manufactured as arbitrary long materials. It is an object of the present invention to provide a method for producing a thermoplastic cement molded product that enables the above.

[0008]

The present inventor has conducted various experiments and studies on the above-mentioned manufacturing problems, and as a result,
Even a thermoplastic cement composition having a high cement content and a low melt index as described above is extruded by using a solidification extrusion technique and coating a lubricant layer on the inner surface of the extrusion die and the forming die. Machine and extrusion die,
The present invention has been completed by finding that it becomes possible to mold a forming die without damaging it.

That is, the method for producing a thermoplastic cement molded article according to claim 1 of the present invention comprises a thermoplastic resin 100.
A thermoplastic cement composition obtained by mixing 300 to 600 parts by weight of hydraulic cement and / or air-hardening cement and 3 to 10 parts by weight of a hydrophilic substance with respect to parts by weight is used as a molding material, and the molding material is used. Immediately after being extruded into a predetermined shape from the extrusion die of the extrusion molding machine, solidification extrusion molding is conducted in which the molding die is connected to the forming die to form a solidified state.In the previous term, the entire contact surface between the extrusion die and the forming die inner surface with the molding material. Has a friction coefficient of 0.3 or less and a tensile strength of 50 kg.
The gist is that the solidification extrusion molding operation is performed under the condition that the lubricant layer having a width of f / (10 mm width) or more is formed by coating.

The invention according to claim 2 is characterized in that a speckled pattern is revealed by performing the solidification extrusion molding using a thermoplastic cement composition to which a coloring agent for pattern expression is added. The gist is the method for producing a thermoplastic cement molded article according to claim 1.

The method for producing a thermoplastic cement molded article according to claim 3 of the present invention is characterized in that the lubricant layer comprises a film or sheet having a tetrafluoroethylene resin as a lubricant. Its main point is solidification extrusion.

Each component of the thermoplastic cement composition used in the present invention, production conditions and the like will be described in detail below.

(Thermoplastic Resin) The thermoplastic resin used in the present invention may be any one as long as it can be melted by heating during molding, and all kinds of thermoplastic resins can be applied. Further, since mixed forms of different kinds of resins may be used, it is possible to use even a resin waste material by rough selection only by eliminating the thermosetting resin, and also foreign substances associated with the use of this waste material, for example, thermosetting resin, dust, Even if soil or sand is mixed in to some extent, it is captured by the binding force of the cement, and there is an advantage that it can stably exist as a filler in the molded product.

Specific examples of the thermoplastic resin applicable to the present invention include asphalt, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVA), ethylene-vinyl acetate copolymer (EVA), acrylonitrile. -Butadiene-styrene copolymer (AB
S), acrylonitrile-acrylic rubber-styrene copolymer (AAS), acrylonitrile-EPDM-styrene copolymer (AES), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS), methyl methacrylate-butadiene-styrene copolymer. Coalescence (MBS),
Ethylene vinyl chloride copolymer, polyvinylidene chloride, chlorinated olefin-budadiene copolymer, polyacetal (POM), polyamide (nylon), polyethylene terephthalate (PET), polycarbonate (PC),
Polystyrene (PS), polymethylmethacrylate (P
MMA), urethane type thermoplastic elastomer (TP
U), polybutylene terephthalate (PBT), polyphenylene ether (PPE), polyarylate (PA
R), liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), polyether ketone (PE
K), polyether ether ketone (PEEK), polyether sulfone (PES), styrene thermoplastic elastomer, olefin thermoplastic elastomer, polyester elastomer, polyamide elastomer,
Polybutadiene-based elastomers, vinyl chloride-based elastomers, and other rubber-based materials include natural rubber, styrene-butadiene rubber (SBR), butadiene rubber (BR) isoprene rubber (IR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR). ), Ethylene-propylene rubber (EPM), isobutylene-isoprene rubber (IIR) and the like.
Not only can new resins be used in combination with more than one species, but it is also possible to use resin waste materials.

(Cement) As the cement which can be used in the present invention, a general hydraulic cement is suitable, but a pneumatic cement which produces a hardened product by gas in the presence of water can also be used. And as the hydraulic cement, ordinary Portland cement, blast furnace cement, fly ash cement, other Portland cements such as white cement, ultra-high early strength cement of awin system, alumina cement, oxychloride cement, acid resistant cement, gypsum, and further It also includes active silica-calcium hydroxide, activated alumina-calcium hydroxide, and the like, which can form a hydraulic cement by reacting two or more components in the presence of water. As the air-hardening cement, in addition to limes and magnesia cement, a mixed system of carbonic acid source substances such as ethylene carbonate and ammonium carbonate and oxides and hydroxides of limes or magnesium, iron, zinc, etc., iron powder and zinc Examples thereof include a mixed system of a metal powder such as powder that is easily oxidized and an oxidizing agent such as peroxide or manganese dioxide.

These cements may be used alone,
It is also possible to use two or more types in combination.

The amount of the cement according to the present invention is 300 to 600 parts by weight of cement with respect to 100 parts by weight of the thermoplastic resin. Preferably, the blending amount is in the range of 400 to 500 parts by weight.

When the content of cement exceeds 600 parts by weight with respect to 100 parts by weight of the thermoplastic resin, it is difficult to impart desired thermoplasticity to the molded article regardless of the content of the hydrophilic substance. In addition, the melt index of the thermoplastic cement composition becomes too low, and a good molded product cannot be obtained even by the solidification extrusion molding according to the present invention. If the amount of cement is less than 300 parts by weight, the properties of the thermoplastic resin remain even after curing treatment such as hydration, and desired physical properties such as heat resistance cannot be obtained.

In order to facilitate water absorption of the cement, the cement may be optionally subjected to a pretreatment for improving the wettability of the surface. Specifically, the surface treatment may be performed with a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin or butadiol. Further, the surface treatment of cement can be performed using the following hydrophilic substances.

(Hydrophilic substance) The hydrophilic substance used in the present invention is a polymer blend or polymer alloy with a thermoplastic resin to impart hydrophilicity to the thermoplastic resin, and thus to cure the thermoplastic cement molded product. It has a function of efficiently spreading water over the entire thermoplastic cement molded product to bond and cure the cement. Specific examples thereof include polyether polyurethanes, polyolefin oxides, high molecular weight polyhydric alcohols, water-absorbing polymers, and the like, and reactive polyether polyurethanes having a blocked isocyanate group are particularly preferable. That is, this reactive polyether polyurethane is obtained by chain-extending a polyol by reaction with diisocyanate and blocking an isocyanate residue (usually 3 to 5%) with a blocking agent such as MEK oxime. By heating in a mixed form, the block of the isocyanate group dissociates and reacts with the thermoplastic resin, so that there is an advantage that good compatibility with the thermoplastic resin can be secured.

However, as the polyol component of the ether polyurethane, polyethylene oxide (PE
O), polyolefin oxides such as polypropylene oxide (PPO), polyvinyl alcohol (PV
A), high molecular weight polyhydric alcohols such as polyethylene glycol (PEG) and polypropylene glycol (PPG), copolymers thereof, urethane prepolymers containing a polyoxyalkylene structure, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, etc. Examples thereof include derivatives of polyether glycols belonging to nonionic surfactants, esters of other polyhydric alcohols, and the like. Further, as the diisocyanate, tolylene diisocyanate (TDI), diphenylmethane-4.4 '
Common diisocyanate compounds such as diisocyanates (MDI) are used.

Specific examples of the water-absorbent polymer include starch-acrylonitrile graft polymer, starch-acrylic acid graft polymer, starch-styrene sulfonic acid graft polymer, starch-vinyl sulfonic acid graft polymer, starch-acrylamide. Graft polymer, starch-polyvinyl ketone polymer, cellulose-acrylonitrile graft polymer, cellulose-styrene sulfonic acid graft polymer, other starch or cellulose derivatives, hiruaroic acid, agarose, chitosan, natural products such as colagen,
Also, synthetic polymer-based PVA cross-linked polymers, PVA elastomers, acrylate cross-linked polymers, acrylic acid ester-
Partial hydrolyzate of vinyl acetate copolymer, acrylate-
Vinyl alcohol copolymer, partial hydrolyzate of polyacrylonitrile polymer, hydroxyethyl methacrylate polymer, maleic anhydride-isobutylene copolymer salt,
Examples thereof include a vinylpyrrolidone copolymer or polymer, a polyethylene glycol-diacrylate copolymer, a polypropylene glycol-diacrylate copolymer, and a polyethyleneimine copolymer.

When these water-absorbent polymers are applied as hydrophilic substances to the thermoplastic resin, if the water-absorbent polymer and the thermoplastic resin are directly powder-mixed, the water-absorbent property is likely to be lowered, and the water-absorbent polymer and the thermoplastic resin are mixed. Since the water-absorbent polymer is poor in compatibility with the resin and is also insoluble in organic solvents, it is recommended to apply the method for synthesizing the water-absorbent polymer to synthesize the water-absorbent polymer in the thermoplastic resin. This synthetic method is one in which one of the synthetic raw materials is powder-mixed with a thermoplastic resin, the other is directly added to the thermoplastic resin or dissolved and added with a compatibilizing agent, and both thermoplastic resins are mixed and heated to melt and reacted. You can do it.

The above hydrophilic substances may be used alone,
Also, two or more kinds may be mixed and used.

The content of the above-mentioned hydrophilic substance is 3 to 10 parts by weight, preferably 4 to 8 parts by weight, based on 100 parts by weight of the thermoplastic resin. Is good. If the content of the hydrophilic substance exceeds 10 parts by weight, the tensile strength and bending strength of the obtained molded product will be remarkably reduced, and if the content of the hydrophilic substance is less than 3 parts by weight, it will be completely contained in the cement. It becomes difficult to cause a hardening reaction such as hydration.

When adding the above-mentioned hydrophilic substance to the thermoplastic resin, a compatibilizing agent may be used as an auxiliary agent for compatibilizing, if necessary. This compatibilizer is not only a compatibilizer for ordinary polymer alloys, but is well compatible with the above-mentioned hydrophilic substance, is also compatible with the thermoplastic resin, and is a substance exhibiting hydrophilicity and oil solubility which itself is also a hydrophilic substance, Examples thereof include polyvinyl ether, polyvinyl ketone, lecithin and the like. These can be used by polymerizing with a hydrophilic substance.

Alternatively, a commercially available macromonomer may be used as a compatibilizer, and this may be reacted with a hydrophilic substance to form a graft polymer, which may be blended with a thermoplastic resin. A method in which the terminal group of the macromonomer has a polar hydroxyl group or carboxyl group and is reacted with a hydrophilic substance is useful.

A reactive compatibilizing agent comprising a hydrophilic urethane, an aliphatic amine and a mono- or diglycidyl ether is also useful.

All of these are mixed with a roll or a kneader under heating.

(Colorant for pattern development) The colorant for pattern development is required when a speckled colored pattern is displayed on the surface of the thermoplastic cement molded product to obtain a beautiful appearance. The following specific examples can be given as the coloring agent for pattern expression.

Concrete Example 1 It is possible to use a thermoplastic resin or an elastomer which undergoes a crosslinking reaction with an organic peroxide, in which a dye / pigment and an organic peroxide are blended. With this composition, a spotted pattern is obtained.

In order to complete the appearance of the speckled pattern, it is preferable to employ a thermoplastic resin or elastomer that does not decompose and melt at the molding temperature of the thermoplastic cement.
Further, those having fluidity equivalent to or close to that of the thermoplastic resin used for the thermoplastic cement are suitable. The resin or elastomer for the colorant may be in the form of any of a homopolymer (homopolymer), a copolymer (copolymer) and a mixture thereof. As a typical one of them, L
DPE, LIDPE, HDPE, PP, EEA, EGM
Olefin resin such as A, SBS, SIS, SEBS,
Examples include elastomers such as SEPS and EPM and EPDM elastomers.

Examples of the organic peroxide to be blended with the colorant resin or elastomer as a crosslinking agent include ketone peroxides, alkyl peroxides, hydroperoxides, dialkyl peroxides, alkylaryl peroxides. , Peroxyketals, alkylperesters, peroxycarbonates and the like, but dicumyl peroxide and tributylbenzyl peroxide are particularly preferably used. The degree of crosslinking of the resin can be adjusted by the amount of the crosslinking agent used. The preferable ratio of the organic peroxide to the colorant resin or elastomer is 0.2 to 2.5%.

As the dye and pigment, those commercially available for resins can be used, and the amount thereof can be appropriately increased or decreased depending on the shade of the pattern to be obtained.

In the production of the above colorant, a method is used in which an organic peroxide and a dye / pigment are added to a coloring resin, the mixture is kneaded by using a heating roll, an extruder or the like, and then pulverized to 10 to 4000 μm. However, at that time, a dispersant, a stabilizer and the like can be added if necessary.

Example 2 As another example of the colorant, a crosslinked bead of the same kind as or close to the thermoplastic resin which is a component of the thermoplastic cement composition that does not flow at the extrusion processing temperature of the thermoplastic cement composition is used. You can also Typical examples are PMMA crosslinked beads and PS crosslinked beads. In the case of polystyrene resin, styrene, in the case of polymethylmethacrylate resin, methylmethacrylate etc. and a crosslinkable monomer such as divinylbenzene, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate etc. which undergoes cross-linking polymerization with these monomers. Polymer particles obtained by cross-linking polymerization. Such crosslinked beads are colored or dyed in advance, but the method of coloring or dyeing is not particularly limited. For example, if a coloring agent such as a pigment or dye is required, a method of adding the coloring agent in the polymerization bath in the presence of a dispersant or the like, and coloring the raw material,
A method of dyeing a crosslinked finely divided polymer with a heat-resistant dye such as a disperse dye by a known method can be adopted.

Specific Example 3 As another coloring agent for pattern appearance, a solid thermosetting resin having a softening point higher than the extrusion processing temperature of the thermoplastic cement composition and having excellent transparency and coloring property. Can be used. Examples thereof include epoxy resin, unsaturated polyester resin, melamine resin, acrylic resin and the like. This pattern-appearing colorant can be obtained as desired particles by pulverizing and classifying a molded product which has been hardened by adding additives such as a curing agent, a curing accelerator and various stabilizers according to a conventional method.

The colorants for pattern expression shown in the above specific examples 1 to 3 are used as powders, and the average particle size is 10 to 40.
It is desirable that the fine particles have a size of 00 μm. If it is less than 10 μm, it becomes a monochromatic system, and it is difficult to obtain the effect of developing a speckled pattern. On the other hand, when it exceeds 4000 μm, impact resistance is lowered. A preferred range is 100 to 1000 μm. The shape of the colorant may be spherical, scale-like, or the like.

SPECIFIC EXAMPLE 4 As another coloring agent for pattern expression, a fiber length of 0.1 to 1
A colored synthetic fiber powder having a diameter of 0 mm and a fiber diameter of 5 to 200 μm can also be used. Fiber length is less than 0.1 mm or fiber diameter is 5
If it is less than μm, it is difficult to obtain a molded product having a clear spot pattern, and if the fiber length exceeds 10 mm or the fiber diameter exceeds 200 μm, the impact resistance decreases. The fiber length is preferably 0.5 to 5 mm and the fiber diameter is 10 to 100 μm. As the synthetic fiber, one kind or two or more kinds of polyester fiber, polyamide fiber, aramid fiber, vinylon fiber and the like can be used. The synthetic fibers may be colored by a known method using a known dye and pigment. There is no limitation on the amount of the dye / pigment used, and it may be used within a range capable of coloring in a desired color.

The above colorants for pattern expression may be used alone or in combination of two or more kinds. The pattern-developing colorant according to the present invention may be added in an arbitrary blending amount depending on the desired appearance of the thermoplastic cement molded product.

(Other Additives) In the present invention, the above-mentioned thermoplastic resin, cement, hydrophilic substance, additive for pattern appearance,
In addition to the compatibilizer, various additives such as lubricants, aggregates, reinforcing materials composed of various fiber substances, cement dispersants, molding aids, resin stabilizers, etc. are added to the thermoplastic cement composition as required. Can be blended. In particular, the addition of a molding aid is suitable for ensuring good moldability during extrusion molding.

The molding aid is a plasticizer and a mineral oil, and is useful for reducing the melt viscosity of the thermoplastic cement composition and improving the moldability. Therefore, it is necessary to exhibit compatibility with the thermoplastic resin which is a component of the thermoplastic cement composition. Further, the molding aid is preferably a liquid one in order to wet the thermoplastic resin and adhere the cements so that a uniform mixture can be easily obtained.

Examples of the plasticizer to be used include phthalate ester-based ones such as DMP, DOP and DBP, and fatty acid (dibasic) ester-based ones such as DIOA and D.
BS, DOS, etc., and TOTM, etc. can be listed as a trimellitic acid ester type.

The mineral oil is a hydrocarbon liquid paraffin obtained by highly refining and separating a high-quality crude oil, and has a viscosity-specific gravity constant (V, G, C) of less than 0.9. It is preferably used.

The compounding amount of the molding aid can be appropriately added within a range that does not impair the performance of the thermoplastic cement molded product depending on the extrusion molding condition. Preferably the thermoplastic resin 100
The compounding amount of the molding aid is 0 to 100 parts by weight, preferably 60 parts by weight or less, based on parts by weight.

(Production Conditions) The production conditions of the thermoplastic cement molded product will be described below with reference to the drawings.

In molding, premixing is first performed. When the thermoplastic resin and the hydrophilic substance are easily compatibilized, all the components described above may be mixed at the same time. However, when it is difficult for the thermoplastic resin and the hydrophilic substance to be compatibilized with each other, it is recommended that the thermoplastic resin and the hydrophilic substance be polymer-blended in advance or polymer-alloyed and then mixed with cement or the like. .

Next, the mixture obtained by the above premixing operation is used as a molding material, and this is solidified and extruded into a predetermined cross-sectional shape by a solidification extruding apparatus. The solidification extrusion molding device used here is generally made of a polymer material such as a round bar or a plate,
It is used to extrude into a pipe or a shaped product, extruding while melting the thermoplastic cement composition in an extruder, and then distributing the melted thermoplastic cement composition to an extrusion die as needed. By cooling while passing through a forming die attached to the tip of the forming die, it is solidified and molded into a desired shape and size. The solidification extrusion method using such an apparatus can be suitably used for molding not only general resins but also materials having particularly high melt viscosity and poor fluidity, and materials with high filler filling. That is, since the molten material is solidified and extruded in the forming die, the pressure inside the die becomes extremely high. Therefore, it is possible to suppress the generation of voids and bubbles in the molded product, and obtain good quality. It has features.

Since the forming die of the solidification extruder used here needs to control the temperature depending on the type of the thermoplastic resin, it is preferable to equip it with a water-cooled or oil-cooled jacket, air-cooled fins, or the like.

A typical example of the solidification extrusion molding apparatus used in the present invention is shown in FIG. In the figure, (1) is the extruder body, (2) is its cylinder, (3) is the extrusion screw installed inside it, (4A).
(4B) (4C) (4D) are first to fourth heating devices of the cylinder (2), (5) is a material supply hopper, (6)
Is a driving device, (7) is a throttle portion at the tip of the cylinder (2), (8) is an extrusion die provided subsequently to it, (9)
Is a forming die with a water-cooling jacket (9a) connected in front of it, (10) is a device for picking up a molded product such as a rubber roll or a caterpillar, and (11) and (12) are the above-mentioned drawing part (7) and extrusion. The heating device for the die (8), and (13) are the measuring devices for the extrusion pressure at the end of the cylinder.

By the way, in the practice of the present invention, a specific sliding treatment is applied to the inner surfaces of the extrusion die (8) and the forming die (9) in contact with the extruded material to prevent the molding material from sticking. Must be given. This slipping treatment is indispensable to enable continuous extrusion molding for a long time while keeping the surface properties and the texture of the thermoplastic cement molded product constant and satisfactorily. Is 0.3 or less and the tensile strength is 50 kgf /
This is performed by applying the lubricant layer (14) having a width of 10 mm or more to the entire inner surfaces of the extrusion die (8) and the forming die (9) by sticking or the like. Attached lubricant layer (1
In the case of 4), when the friction coefficient exceeds 0.3, the extrusion pressure of the molding material increases, and it becomes impossible to maintain a preferable predetermined pressure described later, which makes molding practically difficult. A preferable friction coefficient is 0.15 or less.

The tensile strength is 50 kgf / (10 mm
If the width is less than (width), the sliding material layer (14) is damaged early due to the strong rubbing of the molding material during extrusion molding, the lubrication effect is lost, and the propulsive force is reduced, making continuous molding difficult. Become. Preferably, the tensile strength is 100 kgf / (10 mm
Width) or more is better.

The constituent material of the lubricant layer (14) is not particularly limited as long as it has the above-mentioned friction coefficient and tensile strength, but it is a fluorine-based material because of its low friction coefficient. It is preferable to use a resin as the sliding material. Among them, it is particularly preferable to use tetrafluoroethylene resin (PTFE). The required tensile strength may be imparted by increasing the thickness of the resin film or sheet used as the above-mentioned lubricant, but the required strength can be obtained while using a thin resin film itself as the lubricant. In order to provide it, it is advantageous to deal with it by forming a composite material by laminating the resin film on a core layer made of a tensile fiber such as glass fiber, Kevlar fiber or metal fiber.

In the solidification extrusion molding apparatus described above, the molding material is introduced from the hopper (5), is kneaded by the screw (3) while being melted and softened by being heated in the cylinder (2), and is drawn (7). And is extruded into a predetermined shape from the extrusion die (8). The extrudate extruded from the extrusion die is cooled by a water cooling jacket (9a) provided therein while passing through the forming die (9), shaped into a predetermined cross-sectional shape and solidified (A).
Is manufactured.

As other conditions, the pressure of the extruded resin in the cylinder throttle portion (7) is 50 kg / cm ^{2 to} 500 kg /
cm ^2, preferably should be operated within the range of ^{70kg / cm 2 ~400kg / cm 2} . Resin pressure is 50kg / cm
^If it is less than ² , cavities and the like are likely to occur and the quality of the thermoplastic cement molded product is deteriorated. ^{On the other hand} , if it exceeds 500 kg / cm ² , there is a mechanical limit, and there is a risk of damaging the extruder, the extrusion die, and the forming die.

The thermoplastic cement molded product produced by the above production method exhibits thermoplasticity in a state before curing and can be shaped into an arbitrary shape by heat treatment. Then, in actual use, when the cement is hardened by hydration curing treatment or air-hardening treatment, high heat resistance, compression resistance, weather resistance and dimensional accuracy similar to those of a cement molded product can be secured. Therefore, the application of the thermoplastic cement molding covers a very wide range of industrial fields. For example, substitute products for heat-resistant plastic products and flame-retardant plastic products, permanent formwork, secondary concrete products, sewer materials, road materials, rubbing prevention asphalt, civil engineering materials such as color paving materials, waterproof materials, floor materials, wall materials. , Building related materials such as putty. Also, when a coloring agent for pattern appearance is added, a beautiful pattern such as marble appears on the thermoplastic cement molded product, and therefore it is particularly suitable as a wall material that is particularly noticeable among construction-related materials. .

[0057]

【Example】

Examples 1 to 4 As a solidification extrusion molding apparatus, a full light type molding machine (caliber: 50 mm, L / D = 32, screw compression ratio: 2.5) as shown in FIG. 1 was used. In addition, the entire inner surface of the extrusion die (8) and the forming die (9) of the extrusion device,
In Examples 1 and 2, PT using a glass fiber woven fabric as the core material
Lubricant layer with FE (dynamic friction coefficient: 0.10, tensile strength 20
0 kg · f / (10 mm width)), and in Examples 3 and 4, a lubricant layer of PTFE having a bronze mesh as a core material (dynamic friction coefficient: 0.12, tensile strength 250 kg · f / (10 mm)
(Width)) was formed as a coating.

[0058]

[Table 1]

On the other hand, thermoplastic cement compositions having various compositions shown in Table 1 were used as molding materials. The contents of the abbreviations in the table are as follows.

"Resin" PVC ... Polyvinyl chloride PP ... Polypropylene ABS ... Acrylonitrile-butadiene-styrene copolymer

"Cement" NPC ...... Normal Portland cement SC ...... Blast furnace cement FC ...... Fly ash cement WC ...... White cement

"Hydrophilic substance" A1 ......... TDI compound of polyethylene glycol (PEG) having an average molecular weight of 6000 A2 ......... TDI compound of polyethylene glycol (PEG) having an average molecular weight of 20,000 A3 ......... Polyethylene oxide having an average molecular weight of 300,000 (PEO) TDI compound

"Plasticizer" DOP ... Di-2-ethylhexyl phthalate PMMA ... Polymethylmethacrylate

"Glued material, core material" PTFE ... Tetrafluoroethylene resin

The materials shown in Table 1 were put in a Henschel mixer at the compounding ratio shown on the right of each material and mixed for 10 minutes.

Then, after the mixture was charged into the hopper of the solidification extrusion molding machine, the extrusion die temperature was 180 ° C., the cooling temperature of the molded body by the forming die was 40 ° C., and the extrusion pressure was 37.
When it was solidified and extruded into a plate having a thickness of 10 mm and a width of 760 mm under the condition of 0 (kg / cm ² ), a thermoplastic cement molded product could be obtained in a good molded state.

Therefore, in order to cure the thermoplastic cement molded product, it was cured in water for 7 days, and the physical properties of the molded product before and after the curing were measured and compared. The results are also shown in Table 1.

Regarding the measurement of tensile strength, JI
Using the measurement method of SK-713, regarding the softening point, J
The Vicat softening point was measured using the measuring method of IS K-7206, and the hardness was measured using the measuring method of JIS K-7215.

As shown in Table 1, the physical properties of the thermoplastic cement molded product largely changed before and after curing, and the molded product after curing was
Most of the physical properties of the thermoplastic resin have disappeared, and the heat resistance, hardness and linear expansion coefficient have improved, and the physical properties approximate to those of cement molded products.

Examples 5 and 6 Next, in order to make a speckled pattern appear on the surface of the thermoplastic cement molded product, the same mixing method and extrusion conditions as in Example 1 were applied with the materials and formulations shown in Table 2 below. Solidification extrusion molding was performed. Here, the following were used as the coloring material for pattern appearance in the table.

"Colorant for Pattern Appearance" Colorant B1 ... As an elastomer, dicumyl peroxide is used as an elastomer against styrene-butadiene-styrene block copolymer (Shell Chemical Co., Ltd., Califlex TR1184). It is added so as to be 1.0% by weight, and 12% of pigments such as carbon black, titanium oxide and anthraquinone are mixed and heated by a roll at 180 to 220 ° C.
Colored particles having an average of 500 to 1000 μm, kneaded in, cooled and pulverized Colorant B2 ... Each fiber length 3 mm, fiber diameter 50 μm
1 / 1.5 / each of m, blue, red, and yellow polyester fibers
Mixed in a ratio of 2.0

[0072]

[Table 2]

As shown in the results in Table 2, when the coloring agent for pattern development was added, a speckled pattern appeared on the surface, and a plate-like thermoplastic cement molded product similar in appearance to marble was obtained. I was able to get it.

The molded products of Examples 5 and 6 were almost the same as the molded product of Example 1 in physical properties before and after curing.

Comparative Example 1 When a thermoplastic cement composition formulated by the same material, mixing ratio and mixing method as in Example 1 above was tried to be molded by an extruder using a T-die, the fluctuation of discharge was extremely large. However, stable dischargeability was not obtained, and a phenomenon such as roughening of the sheet or conspicuous unevenness of the sheet was generated, and a good plate-like molded product having shape retention could not be obtained.

Comparative Example 2 A thermoplastic cement composition having the same compounding ratio as in Example 1 was used for molding with an ordinary extrusion molding machine in which both the extrusion die and the forming die were not coated with a lubricant. Extrusion was stopped because the extrusion pressure of the extruder increased to 500 kg / cm ² .

[0077]

According to the present invention, the combination of the solidification extrusion method and the specific sliding treatment for the extrusion die and the forming die makes it possible to obtain a heat having a low melt index which has been conventionally difficult to form. A molded product having excellent heat resistance and the like formed of the plastic cement composition can be molded by the solidification extrusion molding method without any trouble. Therefore, an arbitrarily long thermoplastic cement molded product having a required cross-sectional shape can be efficiently manufactured. Further, since the waste resin can be easily used in the thermoplastic cement composition, if the use range of the thermoplastic cement molded product is expanded by the manufacturing method of the present invention, it will play a part in solving the waste resin treatment problem.

Further, by adding an appropriate colorant for pattern development, a high-quality product which shows a spotted pattern and has an appearance similar to that of natural marble and which is uniform in quality as a whole. You can get it.

Further, by forming a film or sheet of tetrafluoroethylene resin as the lubricant layer, a more efficient and high-quality thermoplastic cement molded product can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic vertical sectional view showing an example of a solidification extrusion molding apparatus used for an extrusion molding operation of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Extruder body 2 ... Cylinder 8 ... Extrusion die 9 ... Forming die 9a ... Water cooling jacket 14 ... Attached lubricant layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C04B 24/26 C04B 24/26 AZ // (C04B 28/02 24:26) 103: 46 ( 71) Applicant 000000240 Chichibu Onoda Co., Ltd. 2-14-1 Nishishimbashi, Minato-ku, Tokyo (71) Applicant 000210687 Chichibu Concrete Industry Co., Ltd. 4-8-17 Hongo, Bunkyo-ku, Tokyo (71) Applicant 000010065 Fukubi Chemical Industry Co., Ltd. 33-66, 33-shasha-cho, Fukui-shi, Fukui Prefecture (71) Applicant 000201582 Maesawa Kasei Co., Ltd. 3-2-9, Kyobashi, Chuo-ku, Tokyo (72) Inventor Kazuo Nakazato Fujiidera, Osaka 3-9-19-205 Fujieda, Ichi, Japan (72) Yasuhiro Kadota, 501-11 Harigayacho, Utsunomiya City, Tochigi Prefecture

Claims (3)

[Claims] 1. A thermoplastic cement composition comprising 100 parts by weight of a thermoplastic resin and 300-600 parts by weight of hydraulic cement and / or air-hardening cement and 3-10 parts by weight of a hydrophilic substance for molding. Used as a material, the molding material is subjected to solidification extrusion molding in which the molding material is molded into a solidified state by being conducted to a forming die immediately after being extruded into a predetermined shape from an extrusion die of an extrusion molding machine. The solidification extrusion molding operation is carried out under the condition that a lubricant layer having a friction coefficient of 0.3 or less and a tensile strength of 50 kgf / (10 mm width) or more is formed on the entire contact surface with the molding material by coating. A method for producing a thermoplastic cement molded article, comprising: 2. The thermoplastic resin composition according to claim 1, wherein a speckled pattern is revealed by performing the solidification extrusion molding using a thermoplastic cement composition to which a coloring agent for pattern appearance is added. Method for producing cement molded product. 3. The lubricant layer according to claim 1 or 2, wherein the lubricant layer is a film or sheet containing a tetrafluoroethylene resin as a lubricant.
A method for producing a thermoplastic cement molded product by the solidification extrusion molding as described.