JPH05155646A - Hydraulic-material formed body - Google Patents

Abstract

PURPOSE:To improve the breaking strength by forming the thin film of a silane compd. shown by a specified formula on the surface of a polyolefin into which a reactive functional group is introduced by irradiation of radioactive rays, etc. CONSTITUTION:A reactive functional group is partially introduced into the surface of polyolefin by irradiation of radioactive rays, corona discharge, etc. The modified polyolefin is then treated with a 100-0.01wt.% soln. of a silane compd. shown by formula I (n=0 to 2, R<1> is a 1-6C hydrocarbon, a 1-6C org. group contg. amino, mercapto, epoxy, methacryloxyl, alkoxyl and halogen and H, and R<2> is 1-6C hydrocarbon, acyl and H), and a silane thin film is formed. A silica coating film is formed by using 0.01-100 pts.wt. of the partial hydrolyzate of alkoxysilane shown by formula II (n=0.1 and R<3> is a 1-6C hydrocarbon) or 0.01-100 pts.wt. of silica sol. The obtained material is cut, the cuttings are added with a hydraulic material, cast into a die and cured, thus the objective reinforced hydraulic-material formed body is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydraulic material molded product having a high moldability such as bending strength.

[0002]

2. Description of the Related Art A large number of fibers are used as a reinforcing material for a hydraulic material molded product. When classified by material, steel fibers and the like are used for metals, and glass fibers, carbon fibers, rock wool, and inorganic fibers for metals. Asbestos is known. Also, as an organic system,
Aramid, polypropylene, polyethylene, acrylic,
Polyvinyl alcohol and the like are known.

Asbestos is widely used in asbestos slates, asbestos pipes, high-pressure asbestos pipes, pulp cement boards, asbestos products (textile products, joint sheets, asbestos paper, friction materials, etc.), vinyl tiles and the like, and among them, building materials in particular. Used extensively in related products. Various building material products are usually manufactured by a papermaking method, an extrusion method, or the like. Also, asbestos is used in the field to improve the workability of plastering mortar. Asbestos is used in large amounts in the construction material field because it has excellent miscibility regardless of the dry method or the wet method and is economically inexpensive. In addition, asbestos is highly compatible with and miscible with hydraulic substances such as water and cement, and its products are not only lighter in weight than products without asbestos, but also have improved fracture strength and significantly brittleness. It is a reinforcing material for an improved hydraulic material molded body.

However, in recent years, asbestos is said to be extremely harmful to human health, and in Japan, construction materials, construction, and cement product manufacturing fields are subject to administrative guidance from relevant government agencies and voluntary regulations of asbestos cement manufacturers (Slate Association). There was a policy not to use asbestos in. In addition, there is a problem of exhaustion of asbestos resources, and it has become necessary to develop a reinforcing material for a hydraulic material molded body that replaces asbestos. Organic synthetic fibers, inorganic fibers, natural fibers and the like have been proposed as reinforcing materials to replace asbestos, but each has its advantages and disadvantages, and there are problems with reinforcing materials to replace asbestos.

[0005]

Polyolefin is a hydrophobic substance due to its small polarity and high surface energy. Even when the polyolefin used as a reinforcing material is used as it is when producing a reinforced hydraulic substance molded body. The manufacturability is poor and the adhesive force with the hydraulic material is weak, so a sufficient effect as a reinforcing material cannot be expected. The present invention, when producing a reinforced molded article, has excellent alkali resistance, does not have rusting properties, improves the hydrophilicity of an inexpensive polyolefin, and improves the adhesiveness with a hydraulic substance, by using a polyolefin. It is intended to produce a reinforced hydraulic material molded body.

[0006]

Among the organic substances, the present inventors have paid attention to polyolefins which are excellent in heat resistance, chemically stable, and inexpensive. However, since polyolefin is hydrophobic and has poor adhesion to hydraulic substances, a sufficient reinforcing effect cannot be expected. Therefore, the present inventors have found that the polyolefin is hydrophilic,
The inventors focused on improving the adhesion to hydraulic substances and using it as a reinforcing material in a reinforced hydraulic substance molded body.

The method is to partially introduce a reactive functional group into the surface of the polyolefin by irradiation treatment, corona discharge treatment, etc., and partially react the silane compound represented by the following general formula (1). A silane thin film is formed by a solution prepared by dissolving a solvent having a surface tension smaller than the critical surface tension of a polyolefin having a functional substituent introduced therein and adjusting the concentration to be 100 to 0.01 w%, or without a solvent. .. On the polyolefin on which the silane thin film is formed, the alkoxysilane represented by the following general formula (2) 0.01-
One or both of 100 parts by weight of the partial hydrolyzate and 0.01 to 100 parts by weight of silica sol may be used to form the silica thin film.

General formula (1) R ¹ _n Si (OR ² ) _(4-n) n = 0 to 2 (wherein R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, or an amino group, a mercapto group, Epoxy group, methacryloxy group,
1 to 1 carbon atoms including substituents such as alkoxy groups and halogens
6 is an organic group, or one or more bonding groups selected from hydrogen, R ² is a hydrocarbon group having 1 to 6 carbon atoms,
Alternatively, it is an acyl group having 1 to 6 carbon atoms or hydrogen. )

For example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2
-Methoxyethoxy) silane, vinyltriacetoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-
(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxymethyldimethoxysilane,
3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, trimethoxysilane, triethoxysilane, etc. can give.

General formula (2) H _n Si (OR ³ ) _(4-n) n = 0,1 (wherein R ³ is a hydrocarbon group having 1 to 6 carbon atoms)

Examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane and triphenoxysilane.

A polypropylene plate obtained by using the method according to the above was prepared. The created polypropylene plate is
Institute) Fiber adhesion test method (JCI-SF8) AS
An adhesion test piece was prepared using a cement mortar tensile test jig according to TM C190, and then measured by a tensile test. That is, a polypropylene plate is cut into a length of 35 mm (width 20 mm, thickness 1 mm), penetrates a gap of about 1 mm Teflon plate, and one side (pull-out side) is about 10 m.
m so that the other side (fixed side) is about 25 mm. This was made in one test piece at two locations and fixed in the center of the formwork, and then ordinary Portland cement (C), Toyoura standard sand (S) and water (W) were added at C: S: W = 1: 1. 7:
Mortar paste kneaded at a compounding ratio of 0.5 was poured into a mold, demolded the next day, and cured in a moist air for 6 days. The pull-out strength was measured by performing a tensile test at a loading speed of 0.5 mm / min on the 7th day from the date of preparation of the test piece. Shows the pull-out strength. In addition, the obtained polypropylene plate,
As a result of measuring the wetting index according to the wetting test method for polyethylene and polypropylene films (JIS K 6768), the untreated polypropylene plate was 31d.
While it was yn / cm or less, the polypropylene plate on which the silica thin film was formed showed a value of 54 dyn / cm or more. Further, the polypropylene plate on which only the silane thin film was formed had a pull-out strength about twice that of the untreated product and a wetting index of 33 dyn / cm.
When a silane thin film or a polyolefin fiber on which a silica thin film is formed after forming a silane thin film is used in place of asbestos in an aqueous slurry containing a hydraulic substance such as cement when forming a molded product by a papermaking method and an extrusion method, etc. Can easily and uniformly disperse without agglomerating and exert a reinforcing effect on cement products. It can also be used in the case of a premix mortar in which the raw materials are thoroughly stirred in a dry state in advance and water is poured during use.

[0013]

【Example】

(Example 1) Polypropylene 2D tow (37000D,
50 cm), an electron beam irradiation device (area beam type electron beam irradiation device, Curette manufactured by Nisshin High Voltage Co., Ltd.)
ron EBC-200-AA2) was used to irradiate an electron beam (accelerating voltage 150 keV, 10 Mrad). The irradiated polypropylene 2D tow was heated in a 1 wt% 1,2-dimethoxyethane solution of 3-aminopropyltriethoxysilane at 60 ° C. for 30 minutes. After the reaction was completed, it was taken out from the reaction solution and dried at 100 ° C. for 1 hour to form a silane thin film. Polypropylene on which silane thin film is formed 2
The D tow was cut into 5 mm. Mortar paste having the composition shown in Table 1 was kneaded, poured into a mold, demolded the next day, and cured in a moist air for 6 days. Loading speed 2 on the 7th day of test piece creation
A bending strength test was performed at mm / min.

Comparative Example 1 A molded product was obtained in the same manner as in Example 1 except that polypropylene 2D tow was mixed without treatment.
A bending strength test was performed. Table 1 shows the results of the bending strength tests of Example 1 and Comparative Example 1.

[0015]

[Table 1]

(Example 2) Polypropylene 2D tow (3
7000D, 50 cm) was irradiated with an electron beam (accelerating voltage: 150 keV, 10 Mrad) using an electron beam irradiation device (area beam type electron beam irradiation device, Curetron EBC-200-AA2 manufactured by Nisshin High Voltage Co., Ltd.). After leaving the electron beam-irradiated polypropylene 2D tow in the air, it was placed in a 1% by weight solution of 3-aminopropyltriethoxysilane in 1,2-dimethoxyethane at 60 ° C.
Heated for 30 minutes. After completion of the reaction, remove from the reaction solution, 1
It was dried at 00 ° C for 1 hour to form a first coating. Polypropylene 2D tow on which a silane thin film was formed was added to a solution prepared by dissolving 10 parts by weight of tetraethoxysilane and 2 parts by weight of 0.1N sodium hydroxide aqueous solution in 100 parts by weight of ethanol, and heated at 80 ° C. for 2 hours. After the reaction was completed, it was dried at 100 ° C. for 4 hours to form a silica thin film. The polypropylene 2D tow treated as described above was cut into 5 mm. The slurry was adjusted so that the solid content concentration was 10% at the compounding ratio shown in Table 2, and after the paper was made with a wire mesh of 50 mesh, 50 kg /
Pressed at cm ² . 1 day of natural curing after pressing and then 1
Autoclave curing was performed at 70 ° C. for 5 hours. A bending strength test was performed on the prepared plate according to JIS A 1408.

Comparative Example 2 A molded product was obtained in the same manner as in Example 2 except that polypropylene 2D tow was not treated, and a bending strength test was performed. Table 2 shows the results of the bending strength tests of Example 2 and Comparative Example 2.

[0018]

[Table 2]

As shown in Examples 1 and 2 and Comparative Examples 1 and 2, the bending strength of the product of the present invention was improved as compared with the comparative product. Further, when the sample was prepared, the product of the present invention had better moldability than the comparative product, and the superiority of Example 2 over Example 1 was remarkable.

[0020]

EFFECTS OF THE INVENTION A reinforcing material in which a thin film is formed on a surface of a polyolefin which is inexpensive with a silane compound or a silica thin film is formed after forming a thin film with a silane compound, has a significantly improved affinity for a hydraulic substance and is further formed. By having a chemical bond between the thin film and a hydraulic substance such as cement, the adhesiveness is remarkably improved as compared with the conventional mixed substance. By using the above reinforcing material, the dispersibility of the reinforcing material in mortar or the like is greatly improved, and the productivity of the molded product can be maintained high. As a result, due to the strength of the synthetic fiber as the reinforcing material, the affinity with the hydraulic material matrix of the formed thin film, and the adhesiveness, it is uniformly dispersed in the hydraulic material molded product, and its reinforcing effect is also obtained. You will be able to fully demonstrate it. A polyolefin in which a thin film is formed on the surface of a polyolefin with a silane compound or a silica thin film is formed after forming a thin film with a silane compound is excellent in hydrophilicity and adhesion to a hydraulic substance, and is industrially inexpensive. By using a thin film-formed polyolefin, it has become possible to provide an effectively reinforced hydraulic material molded body.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Norihide Arai 5-1 Ogimachi, Kawasaki-ku, Kanagawa Prefecture Kanagawa Prefecture Chemicals Research Laboratory (72) Inventor Kazuhiko Hiromoto 5 Ogimachi, Kawasaki-ku, Kawasaki-shi, Kanagawa No. 1 Showa Denko Co., Ltd. Chemicals Research Laboratory (72) Inventor Yoshimasa Ishimura 5-1 Ogimachi, Kawasaki-ku, Kawasaki-shi, Kanagawa Showa Denko Chemicals Research Laboratory

Claims (2)

[Claims] 1. A silane compound represented by the following general formula (1) in a solvent or without a solvent, in which a reactive functional group is partially introduced into the surface of a polyolefin by radiation irradiation treatment, corona discharge treatment, or the like. A molded product of a hydraulic material, characterized in that a polyolefin having a silane thin film formed thereon is added to a hydraulic material and molded. Formula _{^{(1) R 1 n Si (}} OR 2) (4-n) n = 0~2 ( wherein R ¹ is a hydrocarbon group having 1 to 6 carbon atoms or an amino group, a mercapto group, an epoxy group, Methacryloxy group,
1 to 1 carbon atoms including substituents such as alkoxy groups and halogens
6 is an organic group, or one or more bonding groups selected from hydrogen, R ² is a hydrocarbon group having 1 to 6 carbon atoms,
Alternatively, it is an acyl group having 1 to 6 carbon atoms or hydrogen. ) 2. A silane compound represented by the above general formula (1) in a solvent or without a solvent, in which a reactive functional group is partially introduced into the surface of a polyolefin by irradiation treatment, corona discharge treatment, or the like. A polyolefin having a silica thin film formed by forming a silane thin film and using one or both of a partial hydrolyzate of an alkoxysilane represented by the following general formula (2) or a silica sol was added to a hydraulic material to be molded. A hydraulic substance molded body characterized by the above. Formula _{(2) H n Si (OR} 3) (4-n) n = 0,1 ( wherein R ³ is a hydrocarbon group having 1 to 6 carbon atoms)