JP2002322602A - Pavement material of floor material and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pavement material or a floor material as a means for promoting material recycling of FRP formed articles, which is little fuzzing, gives elasticity to heighten the cushioning performance, improves walking feeling, and has superior bending strength, elasticity, tough and sliding resistance. SOLUTION: This pavement material or floor material is formed by mixing crushed material A of thermosetting resin mold and rubber chips B at a mixing ratio A:B=98 to 2:2 to 98 (wt. ratio), and using urethane resin as binder to be formed like a block or plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a block-like product obtained by forming a basic mixture of a crushed product of a used unsaturated polyester resin molded product (A) and a rubber chip (B) and bonding the mixture with a urethane resin binder. Also, the present invention relates to a pavement material or a floor material excellent in plate-like bending strength, elasticity, walking feeling, touch, and slip resistance.

[0002]

2. Description of the Related Art Most of used plastics are collected as municipal or industrial waste, and then single-piece, clean products are recycled or reused. However, at present, composite materials are finally disposed of by incineration or landfill without being recycled or reused. In particular, it is difficult to reuse thermosetting resin products, and most of them are landfilled. In addition, as a partial use of waste in paving materials, etc., incineration ash is used,
In addition, most products are made of stones, crushed ceramics, etc. as aggregate. In this way, it is becoming increasingly important to consider the preservation of the global environment from various directions and build a sustainable development by forming a recycling-based society.

However, used thermosetting resin molded products,
In particular, radically curable resin molded products such as unsaturated polyester resins and FRP molded products for unit baths, system kitchens, wall and floor materials, and the like have not been sufficiently utilized. These unsaturated polyester resin molded products have been landfilled because recycling is difficult from the viewpoint of technical or industrial profitability. For this reason, it is strongly desired to promote the material recycling of used molded articles.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a used thermosetting resin molded article, especially a radical curable resin molded article, to form a sustainable curable society.
The purpose of the present invention is to develop a pavement material and a floor material excellent in bending strength, elasticity, walking feeling, touch, and slip resistance as a method of effectively using an RP molded product.

[0005]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies and have completed the present invention. That is, in the present invention, the mixing ratio of the crushed thermosetting resin molded product (A) and the rubber chip (B) is
(A): (B) = 98-2: 2-98 (weight ratio), pavement material or floor material characterized by being formed into a block shape or a plate shape using a urethane resin as a binder, The mixing ratio of the crushed thermosetting resin molded product (A) and the rubber chip (B) is (A) :( B) = 98-2: 2.
To 98 (weight ratio), filling a block-shaped or plate-shaped mold with a urethane resin as a binder, and hot-press molding the mixture to provide a method for producing a pavement material or a floor material. Things.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin molded product of the crushed product (A) used in the present invention is, for example, an unsaturated polyester resin, vinyl ester resin, phenol resin, melamine resin, epoxy resin as waste. And a molded article of a thermosetting resin such as an acrylic resin. Preferably, it is a crushed product of a molded product of a radical-curable unsaturated resin selected from an unsaturated polyester resin, a vinyl ester resin, and an acrylic resin, and a fiber-reinforced molded product thereof. The fiber-reinforced molded product as referred to herein is a molded product (hereinafter referred to as an FRP molded product) obtained by mixing and containing a glass fiber reinforcing material in a radical-curable unsaturated resin, and curing the mixture. Particularly preferred is an unsaturated polyester resin glass fiber reinforced molded product. This waste includes not only the collected material but also the molding failure waste during molding.

The crushed thermosetting resin molded product (A) used in the pavement material or flooring material of the present invention is crushed pieces or crushed pieces of various sizes obtained by crushing the thermosetting resin molded product. This is a crushed material selected from powders according to the required characteristics.

[0008] The method of crushing may be any method, but it is preferable to use a less expensive crushed piece that can be crushed by a commonly used crusher. At that time, it is not necessary to separate a composite such as glass fiber. The particle size of the crushed product is preferably 0.05 to 15 mm, and the thickness is 0.0
5 to 15 mm. Average diameter is preferably 2 to 9 mm
And more preferably 4 to 7 mm. The particle size distribution area may have any distribution within the range of 0.05 to 15 mm at the minimum. Minimum side (0.05-1
mm) is 20% by weight or more of the whole, the appearance becomes fine, and if it is less than 20% by weight, the appearance becomes slightly coarse, but there is no problem as a pavement material. As a crushing method, for example, a crusher provided with a screen having an aperture of 12 to 15 mm may be used. It is not preferable to use a screen of less than 12 mm because the efficiency of crushing is low.
The crushed unsaturated polyester resin can be crushed, finely divided, fibrous, or granulated depending on the used product or the crusher used. For example, SMC products such as bathtubs and helmets are relatively thin molded products, and the glass fibers used are long, which is suitable for obtaining fibrous crushed products. On the other hand, a BMC molded product is suitable for obtaining a granular or powdery crushed product because the glass fiber used is short. The crushed and crushed material here means 2 to 2 with a sieve of a crusher.
It refers to a material that passes through a 10 mm mesh and has an average length (diameter) of 1 to 15 mm. Further, the fine crushed material refers to one having an average length (diameter) of less than 1 mm. 0.01-0.5mm
Finer crushed material of a degree can be obtained by secondary crushing.

The molded article in the thermosetting resin molded article used for the pavement material or floor material of the present invention is, for example, a house such as a bathtub, a bathroom panel, a waterproof pan, a vanity table, a washbasin, a kitchen counter, and a septic tank. Members, industrial members such as pipes and water tanks, various electric parts, ships, small boats, automobile members, helmets, mannequins, chairs and the like. Molded products are widely used so-called SMC or BM
It is a C molded product, and for example, a system kitchen, a unit bath, a helmet, and the like can be easily obtained and used. Various crushers can be used for crushing, and crushed products of various particle sizes can be obtained by combining and selecting the shape of the teeth, the number of rotations, the mesh, and the like. The obtained crushed material can be selected according to the required items such as the density and thickness of the target pavement material and the final product of the flooring material, or mechanical properties and elasticity. It is also possible to mix crushed materials having different particle sizes which have been crushed in advance in accordance with the purpose of density control or the like, and such mixing is effective for obtaining a uniform pavement material and floor material molded product.

The mixing ratio of the crushed material (A) and the rubber chips (B) varies depending on the size of both, the desired density of the pavement material, the density of the molded floor material, and the required items such as mechanical strength. The crushed material (A) is 98 to 2% by weight, the rubber chip (B) is 2 to 98% by weight, preferably the crushed material (A) is 75 to 25% by weight, and the rubber chip (B) is 25 to 25% by weight.
It can be selected in the range of 75% by weight. However, in order to further increase the elasticity of the pavement material and the floor material, it is desirable that the rubber chip (B) is 75% by weight or more.

The rubber chips (B) used in the pavement material or floor material of the present invention are not limited to waste tire rubber chips which can be easily obtained on the market.
Automobile parts such as wipers and car mats
An EPDM rubber material such as a roller or an insulating member of an electric device or a urethane rubber chip can also be used. Also,
The rubber chips are colored by using various colored rubber materials, or by adding a pigment to the mixture, paving material,
It is also possible to design and color the flooring. The particle size of the rubber chip (B) is preferably 1 to 8 mm. The particle size may be selected in accordance with the surface condition and functions such as water permeability, but is more preferably 1 to 4 m.
m has a stable particle size and is easy to use.

The rubber chip (B) used in the pavement or flooring material of the present invention may be made of polyethylene terephthalate resin (abbreviated as PET), acrylonitrile butadiene styrene resin (AB) for the purpose of density control or weight reduction.
S), a crushed product of a thermoplastic resin (C) selected from molded products such as a polycarbonate resin (abbreviated as PC), a crushed piece or a pellet alone or in combination with the crushed product (A) and a rubber chip. It can be mixed with the mixture of (B). The mixing ratio is preferably 30% by weight or less, more preferably 5 to 20% by weight, based on the mixture of the crushed material (A) and the rubber chips (B). The mixing has the effect of improving the elasticity and improving the homogeneity of the pavement and flooring molded products.

The pavement or flooring material of the present invention may contain an inorganic filler in order to increase the flame retardancy, surface hardness and slip resistance, or to obtain a more uniform pavement or flooring molding. Is preferred. Examples of the inorganic filler include granular or powdered glass, glass fiber pieces, glass wool, aluminum hydroxide, and calcium carbonate powder.
These can be mixed singly or in combination, and can be used for a mixture of crushed material (A) and rubber chip (B) or a mixture of crushed material (A), rubber chip (B) and thermoplastic resin (C). , Preferably 1 to 30% by weight,
More preferably, 5 to 20% by weight is mixed.

In the pavement material or flooring material of the present invention, it is effective means to increase the content of the rubber chip (B) in order to further increase the elasticity. However, the rubber chip (B) is bonded and solidified with a urethane resin binder. If it is used alone, disadvantages such as slippage due to rain or the like also occur. In order to improve this point, when selecting the mixing ratio of the crushed material (A) and the rubber chips (B), the object can be achieved to some extent by mixing a large amount of the crushed material (A). That is, only the rubber chip (B) is bonded and solidified with a urethane resin binder to form a core material layer, and a layer formed by bonding and solidifying a mixture of the crushed product (A) and the rubber chip (B) with a urethane resin binder is an upper layer or an upper layer. It is preferable to use a two-layer or three-layer structure as a lower layer. In this case, it is possible to laminate the layers separately formed, but it is more economical to fill a mold with a predetermined amount of each layer and press mold. In this case, the mixing ratio of the crushed material (A) and the rubber chip (B) in the upper layer or the upper layer and the lower layer is such that the crushed material (A) is 1 to 30% by weight, preferably 3 to 15% by weight, and the rubber chip (B) It is 70 to 99% by weight, preferably 97 to 85% by weight. Also, instead of the crushed material (A),
Alternatively, a glass fiber or a glass mat can be used together with the crushed material (A). In this case, the mixing amount of the crushed material (A) and the glass fiber is 1 to 30% by weight, preferably 3 to 20% by weight.

The urethane resin binder used in the pavement or flooring material of the present invention is preferably a moisture-curable urethane resin, and may be an organic polyisocyanate compound or
A polyol alone or a mixture thereof,
Preferably, an NCO / OH equivalent ratio of 1.5 or more, more preferably 1.5-20, is used, and a one-pack type of NCO group-containing prepolymer, which can be used, can be used. For example, water, a polyol, an amine compound, or the like can be used in combination as a curing agent. The mixing ratio of the urethane resin binder is determined by the size of the pavement material, the shape of the flooring material or the crushed material or rubber chip to be mixed, and the total amount of the crushed material (A), the rubber chip and (B) is: Preferably from 3 to 30% by weight, more preferably from 4 to 30% by weight.
20% by weight.

The method for producing a pavement material or flooring material of the present invention comprises:
Crushed thermosetting resin molded product (A) and rubber chip (B)
And the mixture ratio is (A) :( B) = 98-2: 2-98.
(Weight ratio), mixing with a mixing device such as a kneader, and then adding and mixing a urethane resin binder. The order of addition to the mixing device may be any order. It is also preferable to pre-treat the crushed product (A) and / or the rubber chips (B) with a polyol containing an acid compound or the like. This mixture is filled into a block-shaped or plate-shaped mold, and hot press-molded to produce a pavement material / floor material. Of course, the crushed material (A)
And press molding time and temperature are preferably 100 to 150 ° C., more preferably 110 to 145 ° C. for 5 to 30 minutes from the viewpoint of productivity and consideration that the burning of the urethane resin binder does not occur. , More preferably 10 to 25 minutes.

The pavement or flooring material of the present invention preferably has a block shape or a plate shape of 10 cm to 2 m.
(Width) × 10 cm to 2 m (length) × 1 to 80 mm (thickness), and larger ones can also be manufactured, and are manufactured by cutting small to large ones. It is also possible. This size can be manufactured in various sizes according to the purpose by selecting the size of the mold and the press die.

The pavement material / floor material of the present invention thus obtained preferably has a density of 0.8 to 1.3 and a hardness (Shore D) of 40 to 70, and crushes a thermosetting resin molded product. As compared with a molded article made of only a molded article, a molded article having excellent elasticity, excellent cushioning property, a very small amount of burrs of a crushed thermosetting resin molded article, a good touch feeling, and an excellent walking feeling can be obtained.

[0019]

EXAMPLES (Example 1) A unit bath made of SMC, which had been cut into about 50 cm square in advance so that it could be put into a crusher, was crushed to obtain crushed pieces that passed through a 4 mm mesh. The fiber length of the crushed pieces was 2 to 5 mm and was 60% by weight or more.
This crushed piece and tire rubber tip (average diameter about 2.5m
m) were mixed at a weight ratio of 50:50. To this mixture, 15 parts of Pandex TP-1950 (a terminal isocyanate group urethane resin manufactured by Dainippon Ink and Chemicals, Inc.) were added.
% Of water (5% by weight of water based on the urethane resin was added as a curing agent) and mixed with a Henschel mixer. The mixture is homogeneously filled in a mold and pressed at 140 ° C. for 15 minutes to form a 40 cm (width) × 50 cm.
A block-shaped pavement material / floor material molded product (length) × 2 cm (thickness) was obtained. The pavement / floor molded product had a uniform surface without burrs such as glass fibers and a smooth surface state. The density of the resulting molded article of pavement / floor material was 1.02 g / ml. 70mm (width) x 200mm (length) x 20m
When processed into a test piece of m (thickness) and subjected to a three-point bending strength test at a span of 16 cm, it was 7.2 MPa. The Shore D hardness was 54.

(Example 2) A helmet made of an unsaturated polyester resin (manufactured by Nichiei Plastics Co., Ltd.) was put into a crusher as it was, and a crushed material passed through a 6 mm mesh was prepared.
The fiber length of the crushed pieces was about 4 to 8 mm. The crushed pieces and the tire rubber chips (average diameter: about 6 mm) were mixed at a weight ratio of 50:
Mix at 50. An ABS helmet (manufactured by Niei Plastics Co., Ltd.) having an average diameter of about 2 to 3 mm prepared in advance with respect to this mixture, and an average diameter of 1 mm (center diameter:
Each glass powder having a particle size of less than 0.6 mm) was mixed in an amount of 5% by weight. That is, the final mixture ratio was crushed helmet (A): rubber chip (B): ABS piece (C): glass powder = 45: 45: 5: 5. To this final mixture, 15% by weight of a pandex TP-1950 (a terminal isocyanate group urethane resin manufactured by Dainippon Ink and Chemicals, Inc.) (adding 5% by weight of water to the urethane resin as a curing agent) is mixed. Then, the mixture was stirred and mixed with a Henschel mixer. 40cm (width) x 50cm (length) x 2cm by filling uniformly into a mold and pressing at 140 ° C for 15 minutes.
(Thickness) block-shaped pavement material / floor material molded product was obtained. Although the fiber length was longer than in Example 1, the surface portion was smooth with no fluff. The paving material obtained
The density of the molded floor material was 1.08 g / ml. A 70 mm (width) x 200 mm (length) x 20 mm (thickness) test piece was processed and subjected to a three-point bending strength test at a span of 16 cm. The elastic modulus was 133 MPa. The Shore D hardness was 60.

Example 3 10% by weight (based on urethane resin) of Pandex TP-1950 (terminal isocyanate group urethane resin manufactured by Dainippon Ink and Chemicals, Inc.) was added to a tire rubber chip (average diameter: about 2.5 mm). 5% by weight of water was added as a curing agent) and mixed with a Henschel mixer. Also, EPDM white rubber chips (average particle diameter 3 mm), crushed pieces of unsaturated polyester helmet (average fiber length: 4 to 8 mm) obtained by the method described in Example 2, and roving glass (cutting material) at the time of helmet production ( (Average fiber length: 20 mm) was mixed at a ratio of 95: 5 (weight ratio). The mixing ratio of the helmet crushed pieces and the roving glass was 90:10 (weight ratio). To this mixture, 10% by weight of pandex TP-1950 (a terminal isocyanate group urethane resin manufactured by Dainippon Ink and Chemicals, Inc.) and 5% by weight of water based on the urethane resin were added as a curing agent, and phthalocyanine green (a large amount of water). Nippon Ink Chemical Industries)
Was mixed with the resin in an amount of 1.0% by weight and stirred with a Hensiel mixer. A homogeneous green mixture was obtained. The mixture of the tire rubber chips and the urethane resin binder was filled in a mold, the surface thereof was made uniform, and then the rubber chip mixture colored green was filled on the upper surface. It is 40cm (width) x 50cm (length) x 2cm by molding with a press at 140 ° C for 15 minutes.
(Thickness) block-shaped pavement material and floor material molding were obtained. Of the thickness: 2 cm, the thickness of the lower layer tire rubber chip mixture was 1.5 cm. Its specific gravity is 1.04 g / m
l. This product was rich in elasticity and was less slippery than the pavement / floor material molded product of Example 1. 23
Slip resistance in wet condition at ℃
It was 72 (BPN) when measured according to.

[0022]

According to the present invention, by mixing a rubber chip and curing a crushed product of a thermosetting resin molded product with a urethane resin binder, fluff is hardly generated, elasticity is increased, cushioning is improved, and walking is improved. It is possible to provide a pavement material and a floor material which improve ease (feeling of walking) and have excellent bending strength, elasticity, touch, and slip resistance. In particular, when using a crushed product of an unsaturated polyester resin fiber reinforced molded product (FRP molded product), promote material recycling of the FRP molded product,
Used tire rubber chips and thermoplastics are also used to contribute to the promotion of a recycling-oriented society.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 55/02 C08L 55/02 63/10 63/10 67/02 67/02 67/06 67/06 69 / 00 69/00 75/04 75/04 101/00 101/00 E04F 15/10 104 E04F 15/10 104A // B29K 75:00 B29K 75:00 101: 10 101: 10 105: 16 105: 16 105 : 26 105: 26 B29L 7:00 B29L 7:00 31:10 31:10 (72) Inventor Shigeru Oda 4-32-13 Kugahara, Ota-ku, Tokyo F-term (reference) 2D051 AA08 AD07 AG03 AG11 AG13 AG15 AG16 AG17 AH02 DA02 DA11 DC09 4F204 AA36 AA45 AB11 AG02 AH43 AH48 FA01 FB01 4J002 AC13X BB15X BG00W BN154 CC03W CC18W CD00W CD20W CF064 CF21W CG014 CK02X CK02Y FD016 GL00

Claims (6)

[Claims] The mixing ratio of the crushed thermosetting resin molded product (A) and the rubber chip (B) is (A) :( B) = 98.
A pavement material or a floor material, which is mixed at a ratio of 2: 2 to 98 (weight ratio) and formed into a block or plate using a urethane resin as a binder. 2. A crushed thermosetting resin molded product (A)
The pavement material or floor material according to claim 1, which is a crushed product of a molded product of a radical curable resin selected from an unsaturated polyester resin, a vinyl ester resin, and an acrylic resin. 3. A crushed product of a thermoplastic resin (C) selected from a polyethylene terephthalate resin, an acrylonitrile butadiene styrene resin, a polycarbonate resin and the like is mixed, and the mixing ratio of the thermoplastic resin (C) is 2. The composition according to claim 1, wherein the content is 30% by weight or less.
3. The pavement material or flooring material according to any one of -2. 4. An inorganic filler is further mixed, and the mixing ratio thereof is 30% of the mixture of the crushed material (A) and the rubber chip (B).
% By weight or less.
Pavement or flooring as described. 5. A layer comprising a crushed thermosetting resin molded product (A), a rubber chip (B) and a urethane resin binder as an upper layer, or as an upper layer and a lower layer, wherein the core material layer is a rubber chip ( 2. The method according to claim 1, wherein B) is solidified with a urethane resin binder.
The pavement material or floor material according to any one of 2, 3, and 4. 6. The mixture ratio of the crushed thermosetting resin molded product (A) and the rubber chip (B) is (A) :( B) = 98.
２2: 2 to 98 (weight ratio), filled in a block or plate mold using urethane resin as a binder,
A method for producing a pavement material or flooring material, which is formed by hot press molding.