JP4299817B2 - Composition and surface protective material using the same - Google Patents

Description

The present invention relates to an adhesive composition that cures at a low temperature and provides a hardened body with high flexibility, and in particular, a composition suitable for protecting the surface of a tension material such as a steel rod inside a sheath tube in a prestressed concrete structure. And a surface protection material using the same.

In the prestressed concrete structure, a tension material is used. For the purpose of preventing rust, a filler, for example, an inorganic material such as cement milk is used in the sheath tube (for example, see Non-Patent Document 1 and Patent Document 1). ).
Published by Japan Society of Civil Engineers "2002 Standard Specification for Concrete [Construction]", P190-230 JP-A-9-96052

However, especially when prestressed concrete structures are constructed by the precast segment method, the sheath tube may be deformed or fluctuated. When inorganic materials such as conventional cement milk are used as the filler for the sheath tube, it hardens below freezing point. In addition, even when cured, the sheath tube cannot follow the deformation and fluctuation of the sheath tube, and in severe cases, the filler is destroyed and the purpose of rust-proofing the internal tension material is lost. was there.

Therefore, the use of urethane resin as a filler has been studied with the intention of protecting and rust-proofing the surface by firmly adhering to the tension material surface while following deformation and fluctuation of the sheath tube (patent) Reference 2).
Japanese Patent Laid-Open No. 10-238697

However, urethane resin is not practical because it has a problem that it does not harden or takes a long time to harden during construction in a cold region, especially during winter.

In view of the state of the prior art, the present inventor develops a practical filler that solidifies in a short time even in winter construction in a cold region, and is excellent in filling workability into the sheath tube. As a result of various studies as much as possible, the inventors have obtained the knowledge that the problems of the prior art can be solved by using a composition having a specific composition, and have reached the present invention.

That is, the present invention provides (A) at least one molecule in one or two of the group consisting of 4 mol modified acrylate of nonylphenol (ethylene oxide) and 2.5 mol modified propylene oxide (propylene oxide). 100 mass parts of a mixture comprising 40 to 90 parts by mass of an acrylic ester compound containing a phenyl group, and (B) 10 to 90 parts by mass of a (meth) acrylic acid ester monomer containing at least one hydroxyl group in the molecule. Part (C) cumene hydroperoxide is 0.2 to 8.0 parts by mass, (D) one of the group consisting of cobalt octenoate, manganese octenoate, nickel octenoate and copper octenoate or It is characterized in that the metal soaps of two or more is 0.01 to 1.0 parts by containing metal basis It is a composition.

The present invention further contains at least one of (E) a powdery polymer compound and (F) an inorganic filler, and the total amount of (E) component and (F) component is (A ) with respect to 100 parts by weight of component ~ (D) the total amount of components, the compositions der to equal to or less than 200 parts by weight is, the paraffin, the (a) component (B) to combined composition 100 parts by weight of Ru composition der characterized in that it contains 0.2 to 5 parts by weight.

Moreover, this invention is a hardening body of the said composition, A glass transition temperature is 0 degrees C or less, A compression elastic modulus is 0.01-1.0 N / mm <2>, It is a hardening body characterized by the above-mentioned. .

Furthermore, the present invention is Ri surface protector der characterized by comprising the aforementioned composition, a filler sheath tube, characterized by comprising the said composition, said composition, 0 ℃ under temperatures below that Ru construction method der, characterized in that formed by filling the sheath tube of prestressed concrete structures by post-tensioning method.

The present invention is applicable to winter construction in a cold region, specifically 0 ° C. or less, more preferably construction at a temperature of −15 ° C. to 0 ° C. It has the effect of providing coalescence. Moreover, in a preferred embodiment, the present invention is characterized by providing a polymer having a glass transition point of 0 ° C. or lower and having a compression elastic modulus of 0.01 to 1.0 N / mm ² , for example, When applied to the filler in the sheath tube of a prestressed concrete structure by the post-tension method of the unbond method using the precast segment method, even if the sheath tube and the tension material in the sheath tube fluctuate, follow those changes. And can rust the tension material. In addition, the surface protective material of the present invention is extremely useful for protecting the surface of, for example, an in-sheath tension material, because it has excellent adhesiveness and flexibility at low temperatures.

Component (A) used in the present invention is an acrylate ester containing at least one phenyl group in the molecule, and preferably provides a polymer having a glass transition temperature of 0 ° C. or less. Or an oligomer. Examples of the component (A) include phenol (ethylene oxide) 2 mol modified acrylate, phenol (ethylene oxide) 4 mol modified acrylate, nonylphenol (ethylene oxide) 4 mol modified acrylate, and nonylphenol (propylene oxide) 2.5 mol modified. Examples include acrylate. These may be used alone for the purpose of adjusting the properties of the cured product, or may be used in combination of two or more.

The component (B) used in the present invention is (meth) acrylic acid esters containing at least one hydroxyl group in the molecule. Examples of the component (B) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and the like. These may be used alone for the purpose of adjusting the properties of the cured product, or may be used in combination of two or more.

In the present invention, by using both the component (A) and the component (B), the adhesive property with a tension material made of steel or the like is flexible even at low temperatures and has a low compression modulus. Is obtained.

In the present invention, the blending ratio of the component (A) and the component (B) is 40 to 90 parts by mass for the component (A) and 10 to 10 parts for the component (B) according to the results of the study by the present inventors. 90 parts by mass is preferable.

In the present invention, (C) cumene hydroperoxide has a small natural decomposability, and (D) causes a redox reaction with a metal soap (so-called redox reaction). This is a radical polymerization of (meth) acrylic acid esters,
Positioned as a radical polymerization initiator.

(C) It is preferable to use 0.5-8 mass parts with respect to 100 mass parts of the composition which match | combined (A) component and (B) component.

Examples of the metal soap (D) used in the present invention include cobalt naphthenate, cobalt octenoate, manganese naphthenate, manganese octenoate, nickel naphthenate, nickel octenoate, vanadium naphthenate, and copper octenoate. These metal soaps having a metal content in the range of about 1 to 20% by mass are generally commercially available. These may be used alone or in combination of two or more.

(D) It is preferable to use 0.01-1 mass part in conversion of a contained metal with respect to 100 mass parts of the composition which match | combined (A) component and (B) component.

The component (E) used in the present invention is a powdery polymer compound. Examples of the component (E) include low density polyethylene, high density polyethylene, polypropylene, and polystyrene.

As the component (F) used in the present invention, commercially available inorganic fillers can be used. Examples of the component (F) include silica sand, silica, calcium carbonate, and alumina.

The component (E) and the component (F) contain the component (E) and the component (F) with respect to 100 parts by mass of the composition composed of the components (A) to (D) for the purpose of adjusting the viscosity of the composition. It is preferable to use 200 parts by mass or less in total. At this time, the component (E) or the component (F) may be used alone, or the component (E) and the component (F) may be mixed and used.

Solid paraffin can be added to the composition of the present invention in order for the (meth) acrylic acid esters to undergo polymerization inhibition by oxygen, that is, to reduce anaerobic properties. The melting point of the solid paraffin is preferably 40 ° C. or higher, particularly preferably 42 to 70 ° C. The solid paraffin is preferably used in an amount of 0.2 to 5 parts by mass with respect to 100 parts by mass of the combined composition of the component (A) and the component (B).

Moreover, additives, such as a silane coupling agent, dye, a pigment, a ultraviolet absorber, a rust preventive agent, can be added to the composition of this invention as needed.

The compositions of the present invention, in the preferred embodiments thereof, the compression modulus gives polymer of 0.01~1.0N / mm ^2. When the compression elastic modulus is in the above range, for example, when used as a filler in a sheath tube of a prestressed concrete structure by a post-tension method using an unbond method using a precast segment method, the sheath tube and the tension material in the sheath tube Even if it fluctuates, it is preferable because the surface of the tendon can be protected and rust prevented by following those fluctuations.

(Example 1) As acrylic esters containing at least one phenyl group in the molecule, 80 g of Aronix M-113 (manufactured by Toagosei Co., Ltd., nonylphenol (ethylene oxide) 4 mol modified acrylate), As a (meth) acrylic acid ester containing at least one hydroxyl group, 20 g of GE-610 (Mitsubishi Gas Chemical Co., Ltd., 2-hydroxyethyl methacrylate) was mixed.

Next, 1 g of PARAFFIN WAX115 (manufactured by Nippon Seiwa Co., Ltd., melting point 55 ° C. solid paraffin) is added to the above monomer mixture, heated to 65 ° C. with stirring to dissolve the solid paraffin, and then stirred to 30 ° C. Cooled down.

To the above mixture, 1.5 g of Parkmill H80 (manufactured by NOF Corporation, 80% cumene hydroperoxide) as a radical polymerization initiator was added, stirred and mixed to obtain composition (1).

100 g of the composition (1) was weighed, Hi-Zex2100JPD (Mitsui Chemicals, powdered polyethylene) 50 g as a powdery polymer compound, and calcium carbonate (Nitto Flour Industry Co., Ltd.) as an inorganic filler. 30 g was added and stirred and mixed to obtain composition (2).

180 g of composition (2) is weighed in an atmosphere of 20 ° C., 1 g of Octlife Co12 (manufactured by Shinto Fine Co., Ltd., metal content: 12% by mass cobalt octenoate) is added and mixed by stirring to obtain composition (3). It was. The composition (3) was cured 30 minutes after adding and mixing Octlife Co12 to form a polymer.

When the composition (3) was used as a rust preventive filler for the tension material in the sheath pipe in the prestressed concrete structure by the post-tension method of the unbond method using the precast segment method, the atmosphere at an outside temperature of -5 ° C Even underneath, it cured in about 20 hours and could be used without problems.

Further, 90 g of the composition (2) is weighed, 0.5 g of Octolife Co12 is added, and the composition obtained by stirring and mixing is poured into a silicon rubber mold of 14 × 14 × 40 mm and cured. A compression test was carried out in the length direction of 40 mm with a universal testing machine using the polymer obtained. As a result of performing the test at a test speed of 10 mm / min, the initial elastic modulus was 0.5 N / mm ² .

Moreover, it was -10 degreeC when the glass transition point was measured by DSC method about the said polymer using the differential scanning calorimeter.

(Example 2) As acrylic esters containing at least one phenyl group in the molecule, 80 g of Aronics M-113 and (meth) acrylic ester containing at least one hydroxyl group in the molecule As a class, 20 g of GE-610 was weighed and mixed.

Next, 0.5 g of PARAFFIN WAX115 was added to the above monomer mixture, and 20 g of N / B linseed oil (manufactured by J-Oil Mills, linseed oil) was further added to the mixture and heated to 65 ° C. with stirring. The paraffin was dissolved and then cooled to 30 ° C. with stirring.

1 g of park mill H80 was added to this mixed liquid as a radical polymerization initiator, stirred and mixed to obtain composition (4).

100 g of the composition (4) is weighed, 50 g of Hi-Zex2100JPD is added as a powdery polymer compound, and 30 g of calcium carbonate is added as an inorganic filler, followed by stirring and mixing to obtain the composition (5). It was.

Octlife Co12 1g and Octlife Mn 8% (manufactured by Shinto Fine Co., Ltd., metal content 8 mass% manganese octenoate) were stirred and mixed to obtain a composition (6). 1.4 g of this was weighed and added to 180 g of the composition (5) in an atmosphere of 20 ° C. and mixed to obtain a composition (7). The composition (7) was cured after 4 hours from the addition and mixing of Octolife Co12 to form a polymer.

The composition (7) was used as a filler for rust prevention of the tension material in the sheath pipe in the prestressed concrete structure by the post-tension method of the unbond method using the precast segment method. It cured in about 6 hours and could be used without problems.

Moreover, when the compression test and the measurement of the glass transition point were performed on the polymer of the composition (7) in the same manner as in Example 1, the initial elastic modulus was 0.2 N / mm ² and the glass transition point was −20 ° C. Met.

(Example 3) 100 g of the composition (1) described in Example 1 was weighed, and 1.4 g of the composition (6) described in Example 2 was added thereto and mixed to obtain the composition (8). It was.

The composition (8) was used as a filler for rust prevention of the tension material in the sheath pipe in the pre-stressed concrete structure by the post-tension method of the unbond method using the precast segment method. It cured in about 10 hours to become a polymer and could be used without problems.

The polymer of composition (8) was measured for compression test and glass transition point in the same manner as in Example 1. As a result, the initial elastic modulus was 0.2 N / mm ² and the glass transition point was −10 ° C. Met.

(Comparative Example 1) Cement milk having a water / cement ratio of 30% by mass was used as a filler for a sheath pipe in a prestressed concrete structure by a post-tension method using an unbond method using a precast segment method. When the temperature was 0 ° C. or lower, the water was frozen and could not be used.

(Comparative Example 2) When the outside air temperature was 0 ° C or higher, cement milk was used as a filler for the sheath tube as in Comparative Example 1, but the cured product of cement milk could not follow the fluctuation of the sheath tube and cracked. As a result, the antirust performance of the tendon has been impaired.

(Comparative Example 3) Urethane resin was used as a filler for a sheath tube in a prestressed concrete structure by a post-tension method using an unbonded construction method using a precast segment method. It took time and the construction period was long.

Even if the sheath tube of the prestressed concrete structure by the post-tension method of the unbonding method using the precast segment method fluctuates, the composition of the present invention loses the function of rust-proofing the internal tension material following the change. Since it is possible to form an unfilled packed layer, it is suitable as a surface protective material for tendons, but the composition is used for other purposes such as surface protection (rust prevention) of deformed steel plates in addition to the above applications. The present invention is also extremely useful in industry.

Claims (7)

(A) Nonylphenol (ethylene oxide) 4 mol-modified acrylate and nonylphenol (propylene oxide) 2.5 mol-modified acrylate contains at least one phenyl group in one or two kinds of molecules With respect to 100 parts by mass of a mixture of 40 to 90 parts by mass of the acrylate compound and 10 to 90 parts by mass of (meth) acrylate monomer containing at least one hydroxyl group in the molecule (B) ( C) 0.2 to 8.0 parts by mass of cumene hydroperoxide, (D) a metal consisting of one or more of the group consisting of cobalt octenoate, manganese octenoate, nickel octenoate and copper octenoate A composition containing 0.01 to 1.0 parts by mass of soap in terms of contained metal. Furthermore, it contains any one or more of (E) powdery polymer compound and (F) inorganic filler, and the total amount of (E) component and (F) component is (A) component to ( The composition according to claim 1, which is 200 parts by mass or less with respect to 100 parts by mass of the total amount of component D). Furthermore, 0.2-5 mass parts is contained with respect to 100 mass parts of compositions which combined (A) component and (B) component with paraffin, The composition of Claim 1 or Claim 2 characterized by the above-mentioned. . It is a hardening body of the composition of any one of Claims 1 thru | or 3, Glass transition temperature is 0 degrees C or less, and a compressive elasticity modulus is 0.01-1.0 N / mm < ² >. Hardened body. A surface protective material comprising the composition according to any one of claims 1 to 3. A filler for a sheath tube, comprising the composition according to any one of claims 1 to 3. A construction method comprising filling the sheath tube of a prestressed concrete structure by a post-tension method at a temperature of 0 ° C. or less with the composition according to claim 1.