JPS63176531A - Patterned manhole cover - Google Patents

Abstract

PURPOSE:To raise the impact resistance and wear resistance of a patterned manhole cover by a method in which a nonsolvent-type chlorinated polyethylene- epoxy paste composed of specific components is packed into the recessed portion of the cover and hardened. CONSTITUTION:The 90-97wt.% mixture of a glycidyl compound of 300 or less molecular weight and liquid epoxy resin of 300-800 molecular weight is mixed with 10-3wt.% rubbery chlorinated polyethylene containing 25-50wt.% chlorine which is prepared by chlorinating a copolymer composed of polyethylene of a molecular weight of 10,000-100,000 or ethylene and another monomer, together with 0.1-20pts.wt. pigment and epoxy resin hardener on the basis of 100wt.% the mixture, to form a polyethylene-epoxy resin paste. The paste is cast into the recessed portions of the manhole cover and hardened by heating or at ordinary temperature to bond it to the cover. The impact resistance and wear resistance of the cover can thus be raised.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a patterned manhole cover.

(Prior Art) Conventionally, manhole covers have been coated or painted with a black tar epoxy paint for the purpose of corrosion prevention by coating or dipping. Recently, attempts have been made to color and add patterns to the concave parts of the lid's inner body, and this is being used to indicate aesthetics, waterway distinctions, purpose distinctions, etc. Conventionally, such coating materials have been relatively durable. Some epoxy or acrylic paints are used.

Manhole covers are generally installed in places with heavy traffic or in places that are particularly affected by the natural environment, such as being exposed to rain, seawater, sewage, sand, direct sunlight, etc., and are used under harsh conditions. The material has weather resistance, abrasion resistance, impact resistance, water resistance, and adhesion.

Performance such as cold and heat durability is required. In addition, the shape of the manhole cover itself is not constant, the pattern of the recess is complex, and the filling material is difficult to apply in solid form, and adhesives or adhesives must be used to bond it to the manhole base. Liquid epoxy resin has traditionally been considered the best material to handle harsh conditions.

(Problems to be solved by the invention) Epoxy resins have excellent adhesion to various base materials, water resistance, chemical resistance, physical strength, etc., and curing speed can be easily adjusted by selecting a curing agent. However, since the cohesive energy of the cured product is too strong, it has drawbacks such as cracks occurring when thick cast products are made at once, and insufficient impact resistance and compressive strain resistance. . In order to improve this drawback, there are methods to impart flexibility to epoxy resins, such as adding plasticizers, using curing agents that can impart flexibility, and using epoxy resins with flexible molecular structures. However, this can lead to a decrease in adhesive strength, a decrease in water resistance, chemical resistance, weather resistance, etc., and a significant decrease in physical properties. It is not necessarily something that should be satisfied.

(Means for Solving the Problem) The present applicant first dissolved a rubbery chlorinated ethylene polymer in a liquid epoxy resin to create an adhesive.

A solvent-free epoxy resin composition with excellent impact resistance was proposed (Japanese Unexamined Patent Publication No. 59-25835). The inventors
When this composition was applied as a filling material to a manhole cover, it was found that iron, which is the material of the cover, was applied.

Not only does it have good adhesion to FRP, concrete, etc.
It has been found that it has excellent impact resistance, abrasion resistance, weather resistance, compressive strength and bending strength, etc., which are the performance requirements for manhole covers, and is very effective as an agent for imparting patterns to manhole covers.

That is, in the present invention, (a) a glycidyl compound with a molecular m of less than 300 and a molecular weight of 300 to
90-97% by weight mixture with 800 liquid epoxy resin
and (b) chlorine content of 25 to 50% by weight, obtained by chlorinating a copolymer of polyethylene with a molecular weight of 10,000 to 100,000 or another monomer mainly composed of ethylene.
A solvent-free chlorinated polyethylene-epoxy system containing 0.1 to 20 parts by weight of a pigment and a curing agent as component (A) based on a total of 100 parts by weight of a rubbery chlorinated ethylene polymer of 10 to 3% by weight. This is a patterned manhole cover characterized by being filled with a paste agent and hardened.

The above-mentioned solvent-free chlorinated polyethylene-epoxy paste is made by dissolving a chlorinated ethylene polymer with rubber-like elasticity and a relatively large molecular weight in an epoxy mixture. Chlorinated ethylene polymer has a sea-island structure, and chlorinated ethylene polymer exists in the form of rubber spheres, which alleviates the cohesive energy of the epoxy resin itself and increases flexibility, abrasion resistance, impact resistance, and compression resistance. This improves permanent deformation and weather resistance.

The epoxy resin of component (a) constituting the solvent-free chlorinated polyethylene-epoxy paste used in the present invention is preferably a liquid one with a molecular weight of 300 to 800, particularly bisphenol A type or bisphenol F type epoxy resin. Especially when the SP value is 9.0~
A value in the range of 11.0 is optimal in terms of compatibility with the chlorinated ethylene polymer, workability as a paste agent, and physical properties of the cured product. Glycidyl compounds with a molecule i of less than 300 are -functional, difunctional, or trifunctional, such as butyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate, epichlorohydrin, phenyl glycidyl ether, butylphenyl glycidyl ether. , styrene oxide, diglycidyl ether, ethylene glycol diglycidyl ether, glycerin triglycidyl ether, C12
- C+a fatty acid glycidyl esters and C9 or less alkyl glycidyl ethers other than those mentioned above, etc., and these may be used alone or in combination of two or more.

If the glycidyl compound has a molecular weight of 300 or more, the diluting ability decreases, making it difficult to lower the viscosity of the paste. Moreover, the above glycidyl compound has an SP value of 8.8 to 11.
．． A value in the range of 0 is particularly preferred in terms of compatibility with the chlorinated ethylene polymer.

The mixing ratio of the glycidyl compound and liquid epoxy resin in component (a) is 5 to 25% by weight of the glycidyl compound.
The range is preferable from the viewpoint of the storage stability of the paste, the balance between the compatibility with the chlorinated ethylene polymer and the physical properties of the cured product, or the relationship with the paste viscosity.

Examples of the chlorinated ethylene polymer as the (oral) component constituting the paste agent of the present invention include molecules 1io and oo.

~100.000 polyethylene or a copolymer with other monomers having ethylene as the main component as raw material,
Chlorine content 25-5, chlorinated to eliminate crystals
0% by weight of rubbery polymer is used.

Such chlorination methods are already known. This rubbery polymer preferably has an SP value in the range of 9.2 to 10.6 in order to achieve the object of the present invention, and is also preferable in terms of compatibility with the epoxy mixture which is component (a). .

If the molecular weight of the polyethylene used as the raw material for the chlorinated ethylene polymer or the copolymer with other monomers containing ethylene as a main component is less than 10,000, the mechanical strength of the obtained chlorinated ethylene polymer will not be sufficient;
If raw materials exceeding 0.000 are used, the viscosity when made into a paste becomes abnormally high, resulting in poor workability and poor storage stability. In order to do this, the amount of chlorinated ethylene polymer must be extremely reduced, and the physical properties of the filled cured product cannot be sufficiently improved. Regarding the degree of chlorination of the chlorinated ethylene polymer, if it is less than 25% by weight, crystals of the raw material will remain and the solubility in the epoxy mixture will be poor, and insoluble matter will become bulky, impairing the appearance and impairing the physical properties. This causes a decrease in the temperature.

If the chlorine content exceeds 50% by weight, the solubility in the epoxy mixture is good, but the hardness of the cured product increases and flexibility, elongation, and thermal stability are reduced, which is not preferable. It is preferable that the residual crystals of the chlorinated ethylene polymer have a heat of crystal fusion (measured using a differential calorimeter at a heating rate of 10° C./min) of 0.5 Ca, fl/g or less by the DSC method. .

When the raw material for the chlorinated ethylene polymer is a copolymer, another seven-mer component is propylene.

Examples include butene, pentene, hexene, vinyl chloride, vinyl acetate, acrylic ester, etc., and the ethylene content in the copolymer is preferably 70% by weight or more, preferably 85% by weight or more.

The blending ratio of the epoxy mixture as the component (a) and the chlorinated ethylene polymer as the component (b) of the paste agent of the present invention is in the range of 90 to 97% by weight of the former and 10 to 3% by weight of the latter. It is desirable to have 100% by weight. (B)
If the component is less than 3% by weight, it is not sufficient to improve the rigidity of the epoxy resin, and if it exceeds 10% by weight, the viscosity becomes too high, making it difficult to form into a paste and also worsening storage stability. .

A pigment is added to the paste of the present invention for coloring.

As the pigment, known inorganic pigments and organic pigments can be used. Zinc white is an inorganic pigment.

White pigments such as antimony white, basic lead sulfate, basic lead carbonate, titanium white, and lithopone; black pigments such as carbon black, lamp black, graphite, and iron black; red pigments such as chrome vermilion and red iron; yellow lead; Yellow iron oxide, yellow pigments such as titanium yellow, zinc wire.

There are green pigments such as chromium green, cobalt green, and chromium oxide, and blue pigments such as ultramarine blue and deep blue. In addition, as organic pigments,
Red pigments such as Toluidine Red, Permanent Red, Lake Red, Hansa Scarlet, Hansa Red, Nitrochloraniline Red, Fire Red, Orange pigments such as Permanent Orange, Hansa Orange, Fast Yellow, Dalamar Yellow, Permanent Yellow, Chromophthalo Yellow Yellow pigments such as phthalocyanine green.

There are green pigments such as naphthol green, and blue pigments such as phthalocyanine blue, fast sky blue, and indane sprue. The amount of pigment blended is (a) and (b) above.
1 to 20 parts by weight are mixed with 100 parts of the component depending on the purpose of use.

The paste of the present invention contains a curing agent for curing component (A). As curing agents, there are conventionally known curing agents for epoxy resins, such as aliphatic amines, aromatic amines, modified amines thereof, carboxylic acids, polyamide resins, etc., and one or more of these can be added to the epoxy equivalent. It can be added accordingly.

In addition to the above-mentioned components, fillers may be added to the paste of the present invention for the purpose of viscosity adjustment or reinforcement. One such filler is calcium carbonate.

Barium sulfate, clay, talc, wrinkle strength, mica.

Examples include asbestos, alumina, and sand. These may be mixed into the paste agent in advance, or may be mixed immediately before use. As additional additives, appropriate amounts of antifoaming agents, antisettling agents, etc. can be added.

In preparing the paste, first, to mix and dissolve the chlorinated ethylene polymer (B) component in the epoxy mixture (A), the two are usually placed in a closed container equipped with a stirrer and heated to a temperature of 60 to 120°C. This is done by heating to C. The melting temperature can be adjusted appropriately depending on the type of component (a). Strong stirring is desirable, but a regular rotary blade stirrer for a long period of time is sufficient. It can also be dissolved by passing it several times through a triple roll heated to the above temperature.

Next, pigments and other optional components are added to the solution prepared above, and mixed and dispersed using a triple roll, ball mill, super mixer, etc. to form a paste.

The solvent-free chlorinated polyethylene-epoxy paste prepared in this manner is a paste-like material that is fluid at room temperature. The curing agent may be added and mixed at the time of use, and curing at room temperature or heating can be performed by selecting the curing agent.

Materials for manhole covers to which the paste of the present invention can be applied include iron, cast iron, concrete, FRP, etc., and it can be applied to any of these materials with high adhesion without priming.

Filling of the manhole cover can be carried out by pouring or pouring into the recess with an instrument or manually. The concave portion of the manhole cover itself can be formed in various patterns depending on its intended use. At the time of filling, the recessed portion of the lid may be filled in advance with metal powder or grains, glass spheres, ceramic grains, etc., and the paste of the present invention may be filled therein.

(Examples) Examples 1 to 2 Comparative Examples 1 to 4 Polyethylene with a molecular weight of 20.000 and 80.000 was treated with a chlorine content of 30% by weight and 45% by weight by an aqueous suspension chlorination method.
Weight 1%, DSC crystal heat of fusion 0.4ca, l! A chlorinated polyethylene of /g and Oca, Q/CI was obtained. These had SP values of 9.6 and 10.3, respectively.

As an epoxy mixture, bisphenol A type epoxy resin (Epicoat 828.2 manufactured by Yuka Shell Epoxy Co., Ltd.
molecule i 355. SP value 9.5) and a glycidyl compound (Neotote AE (fatty acid glycidyl ester type) 2 manufactured by Tobu Kasei Co., Ltd., molecular weight 230. SP value 9.4) were used.

Put the above chlorinated polyethylene and epoxy mixture in the proportions shown in Table 1 into a separable flask equipped with a stirrer and mix for 10 minutes.
Each resin solution was obtained by heating and stirring at 0° C. for 4 hours.

For 100 parts by weight of the above resin solution, 8 parts by weight of titanium oxide, 2 parts by weight of phthalocyanine blue, 50 parts by weight of barium sulfate, and an antifoaming agent (SN-Deft-mer).

0.3 parts by weight of San Nopco Co., Ltd. 1) was added, mixed, and passed through three rolls to form a colored paste. This was added with a modified aliphatic polyamine (ADEKA HARDNER EHX) as a hardening agent.
-225. (manufactured by Asahi Denka Kogyo Co., Ltd.) to prepare a paste.

Various physical property tests were conducted on the above paste agent, and the results are shown in Table 1.

The test method is as follows.

Hardness: Test piece 50x50x5mm, measured using durometer type D.

Impact resistance: Using a DuPont impact tester with a 1-inch diameter test piece, impact was applied to the test piece with a cylinder type of 500 (l), and the impact height was evaluated.

Tensile strength: test piece dumbbell type 2 (thickness 3mm),
Measured using a universal tensile tester at a tensile speed of 5 mm/min.

Bending strength: Measured using a universal testing machine with a test piece of 25 x 100 x 3 mm, a fulcrum width of 40 mm, and a loading rate of 20 mm/min.

Compressive strength: Test piece 12.5x 12.5x25mm, measured using a universal testing machine at a loading rate of 5mm/min.

In addition, in Examples 1 and 2 and Comparative Example 4 Therefore, compressive load and time (deformation amount) Figure 1 shows the relationship between

Abrasion resistance: Test piece thickness 1mm, toOmmφ, using a taper set abrasion tester, load 1000 (].

Measure the amount of wear after 1000 rotations with grindstone C3-10.

Comparative Example 1 is an example in which chlorinated polyethylene with a chlorine content of 40% by weight was chlorinated in the same manner as in the example using a raw material polyethylene whose molecular weight exceeds the range of the present invention (150,000). Although it was dissolved in an epoxy mixture at the blending ratio shown in Table 1, it only became gel-like and could not be made into a paste.

Comparative Example 2 and Comparative Example 3 are examples in which the chlorine content is 20% by weight (Comparative Example 2) and 55% by weight (Comparative Example 3), which are outside the range of the present invention, and were similarly dissolved in the epoxy mixture. but,
In Comparative Example 2, there were many undissolved parts, so-called lumps floating in the epoxy mixture in large numbers.We tried to make a paste by adding other additives in the same way as in the example, but it was not possible to form a uniform paste. As a result, the measured values for the physical property tests were too large. Furthermore, Comparative Example 3 had poor thermal stability during dissolution, and the solution itself turned blackish brown. The physical properties of the cured product were significantly worse than those of the Examples of the present invention, and the impact resistance and abrasion resistance were extremely low.

Comparative Example 4 is an example of only epoxy resin, and its physical properties are significantly inferior to those of the present invention in impact resistance and abrasion resistance, and as shown in Figure 1, it quickly deforms without deformation after compressive loading. Destruction is happening. In contrast, the product of the present invention can withstand a compressive load for a long time even though it is deformed.

Table 1 * Paste excluding curing agent + l for 0 OIffi parts Example 3 Comparative Example 5 Chlorine produced by aqueous suspension chlorination of an ethylene-ethyl acrylate copolymer of 160.000 molecules (ethyl acrylate content 6% by weight) Chlorinated ethylene polymer (S
P value 10.3> diglycidyl ether (SP value 10.9>10 parts by weight,
Epikote 82,870 parts by weight as epoxy resin A and Epikote 834 (molecular weight 470 parts as epoxy resin B)
．． SP value 10.3> In addition to 15 parts by weight of the epoxy mixture, the mixture was stirred and dissolved at 120° C. for 4 hours using the same apparatus as in Examples 1 and 2 to obtain a resin solution.

5 parts by weight of titanium oxide, 2 parts by weight of phthalocyanine green, 50 parts by weight of clay, and 0.1 part by weight of an antifoaming agent (KF-69, manufactured by Shin-Etsu Silicone Co., Ltd.) were mixed with 100 parts by weight of the above resin solution, and three-rolled. It was passed through to form a colored paste. A polyamide resin (ADEKA HARDNER E H-203) was added to this as a curing agent A.

As hardener B, modified aliphatic boriazine (ADEKA Hardener EH-259. manufactured by Asahi Denka Industries, Ltd.)
were added in the amounts shown in Table 2 to prepare a paste.

Degreased mild steel plate (150x 150x 2mm>2
After applying the above paste agent according to ASTMDI002-53T using two sheets, they are pasted together and fixed with clips for 3
It was cured for 10 days at 0°C.

As an adhesion test for the above specimen, tensile shear force and T-
Peeling strength was measured.

Instead of the above mild steel plate, use FRP plate (150x 150x 3
The same procedure was carried out for mm).

In addition, standard mortar plates (70x 70x
20 mm>, and apply the above paste agent on top of it by approximately 5 mm.
The adhesive force was measured using a Kenken-type tester after coating and curing to a thickness of mm.

The results of each of the above tests are shown in Table 2.

Next, a 1-inch nut was suspended in an 8 cm xiocm container so as to be centered in the container, and the paste was poured into the container and cured at about 15° C. for 48 hours and then at 25° C. for 14 days. Regarding this cured product, -20℃ x 6 hours + 1
00'Cx A cold/heat cycle test was conducted in which one cycle was 6 hours, and the number of times until abnormalities such as cracks and deformation occurred was investigated. The results are shown in Table 2.

As Comparative Example 5, a paste containing only an epoxy mixture as a resin component was prepared in the same manner as in Example 3, and the results are shown in Table 2.

Examples 4 to 6 Comparative Examples 6 to 7 Using the pastes prepared in Examples 1, 2.3 and Comparative Examples 4 and 5, the recesses (5
0x100x51T1m) 25 places were filled with the above paste using a syringe and cured at 30'C for 7 days.

The patterned manhole cover obtained above was exposed outdoors for two years, and the presence or absence of cracks, peeling, and discoloration was examined.
The results are shown in Table 3.

Table 3 (Effects of the Invention) In the patterned manhole cover of the present invention, the pattern material adheres firmly to the lid, and the pattern material itself has excellent mechanical properties such as impact resistance and abrasion resistance. Because it is weather resistant and flexible, it has unprecedented durability for manhole covers used in harsh environments. In addition, the pattern material itself is solvent-free during its manufacture, so there is no concern about environmental pollution, and even if it is poured into a thick layer at one time and hardened and molded, it will not cause cracks or deterioration.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between compressive load and time for the cured paste materials of Examples 1 and 2 and Comparative Example 4. The dotted line indicates that destruction has occurred.

Claims (1)

[Scope of Claims] A patterned manhole cover, characterized in that a concave portion of the manhole cover is filled with a solvent-free chlorinated polyethylene-epoxy paste consisting of the following ingredients and hardened. (a) Glycidyl compounds with a molecular weight of less than 300 and a molecular weight of 3
Mixture with liquid epoxy resin of 00-800 90-97
Weight% (b) Rubber-like chlorinated ethylene polymer with a chlorine content of 25 to 50% by weight, which is obtained by chlorinating polyethylene with a molecular weight of 10,000 to 100,000 or a copolymer with another monomer containing ethylene as a main component. 3% by weight above (
Pigment 0.1 per 100 parts by weight of the total amount of a) and (b)
A paste agent containing ~20 parts by weight and a curing agent of component (a)