JP2010138324A - Viscous primer composition for sheet lining and sheet lining method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a viscous primer composition for sheet lining, especially one for FRP sheet, capable of coated with uniform thickness without causing fluid dripping in the ceiling and wall direction, having good curability on a wet surface and excellent in chemical resistance. <P>SOLUTION: The viscous primer composition for sheet lining comprises a radically curable resin (a) comprising a polymerizable monomer and epoxy acrylate, and a filler (b), wherein a reactive monomer having one or more hydroxy is used as the polymerizable monomer, and the filler contains hydrophobic silica. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a viscous primer composition for sheet lining and a sheet lining method using the viscous primer composition for sheet lining. In particular, the present invention relates to a viscous primer composition as an adhesive or sealant used to reinforce the surface of concrete structures such as piers, tunnels and sewage treatment plants.

  Conventionally, it is known that the surface of a structure is sheet-lined for the waterproofing method of concrete and mortar structures, and for the seismic reinforcement of concrete structures, in order to suppress the corrosion and damage of concrete due to industrial wastewater, etc. ing.

  As the sheet used for the sheet lining, a soft prepreg type FRP sheet in which a glass fiber, a carbon fiber or the like is impregnated with a resin is used. In order to increase the adhesion of such FRP sheets to concrete or mortar structures, a low-viscosity base primer such as uretan resin, acrylic resin, epoxy resin, unsaturated polyester resin, epoxy acrylate resin, etc. is applied to the base beforehand and dried. A method is adopted in which a viscous primer is applied and a sheet is attached and cured.

  Viscous primer can be applied stably to the prescribed thickness required for adhesion to ensure stable adhesion between the FRP sheet and concrete or mortar structure, even when ceiling or wall surfaces are installed. In general, an epoxy resin, an unsaturated polyester resin, an epoxy acrylate fat or the like is added with a filler or a thixotropic agent to impart viscosity and thixotropy. However, when an epoxy resin is used, it takes 1 day or more to cure at room temperature. Particularly, when the temperature is 5 ° C. or less in winter, the curing becomes extremely slow, and the construction takes a long time. . Furthermore, epoxy resins generally have poor acid resistance, and may not be suitable as a viscous primer composition for sheet lining in repair applications such as sewage treatment plants that require high acid resistance.

  On the other hand, unsaturated polyester resins and epoxy acrylate resins have the disadvantage that if the substrate has moisture, curing at low temperature takes one day or longer, and if the substrate has a lot of moisture, it becomes uncured.

  In order to solve these problems, a lining composition containing an epoxy acrylate resin containing a curing agent containing an organic oxide and an inorganic persalt, a curing accelerator, an aggregate, cement, and water has been proposed. (See Patent Document 1 below). However, in this lining composition, since 300 to 800 parts by weight of aggregate and 50 to 200 parts by weight of cement are added to 100 parts by weight of resin, the viscosity of the lining composition becomes high and the viscosity increases. There is a drawback that the coating workability becomes very poor in a low temperature range. Further, since the aggregate is added, there is a problem that it is extremely difficult to apply uniformly as required for the viscous primer for FRP sheet lining.

JP-A-9-169898

  The present invention is a viscous primer composition used for sheet lining, and in particular, can be applied with a uniform thickness without dripping in the ceiling / wall direction, has good curability on a wet surface, and has good chemical resistance. An object is to provide an excellent viscous primer for an FRP sheet.

As a result of intensive studies to solve the above problems, the present inventors have used a reactive monomer having one or more hydroxyl groups as a polymerizable monomer of a radical curable resin, and further used a hydrophobic as a filler. It has been found that the above-mentioned problems can be solved by using porous silica, and the present invention has been completed.
That is, the present invention is the following [1] to [6]:

  [1] A viscous primer composition for sheet lining comprising a radical curable resin (a) composed of a polymerizable monomer and an epoxy acrylate, and a filler (b), having at least one hydroxyl group as the polymerizable monomer The viscous primer composition for sheet lining, wherein a reactive monomer is used, and the filler contains hydrophobic silica.

[2] The viscous primer composition for sheet lining according to [1], wherein the hydrophobic silica has a specific surface area of 200 m ² / g or less as measured by a BET method.

  [3] The sheet according to [1] or [2], wherein the content of the reactive monomer having a hydroxyl group is 5% by weight or more and 20% by weight or less with respect to the radical curable resin (a). Viscous primer composition for lining.

  [4] The sheet lining according to any one of [1] to [3], wherein the content of the hydrophobic silica is 5% by weight or more and 10% by weight or less with respect to the radical curable resin (a). Viscous primer composition.

  [5] Any of the above [1] to [4], wherein the radical curable resin (a) comprising the polymerizable monomer and the epoxy acrylate has a viscosity at 25 ° C. of 0.05 Pa · s to 0.5 Pa · s. A viscous primer composition for sheet lining according to claim 1.

  [6] In a method for lining a concrete structure using an FRP sheet, after applying the viscous primer composition for sheet lining according to any one of [1] to [5] above a base, A method for lining a concrete structure, wherein a layer comprising a reinforcing fiber sheet and a curable resin is formed and cured.

  In the viscous primer composition for sheet lining according to the present invention, a viscous primer composition for sheet lining containing a reactive monomer having one or more hydroxyl groups and a radical curable resin composed of epoxy acrylate and hydrophobic silica is used. By using it, compared with the conventional viscous primer composition, it can apply | coat uniformly and it becomes what was excellent in workability | operativity, without dripping in a ceiling and a wall direction. In addition, the viscous primer composition for sheet lining according to the present invention can provide a viscous primer for FRP sheet which has good curability on a wet surface and is excellent in chemical resistance.

  The epoxy acrylate constituting the viscous primer composition according to the present invention may be any known one, and is not particularly limited. For example, a reactive organism obtained by a reaction between an epoxy resin and an unsaturated monobasic acid, or saturated Preparation of polyester (meth) acrylate by reacting an epoxy compound containing an α, β-unsaturated dicarboxylic acid ester group with a terminal carboxyl group polyester obtained from dicarboxylic acid and / or unsaturated dicarboxylic acid and polyhydric alcohol In this case, a crosslinking polymerization monomer is blended.

  Examples of the epoxy resin used as the raw material include polyglycol glycidyl ethers such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Examples thereof include brominated bisphenol A type epoxy resins. Examples of glycidyl esters include phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, benzoic acid, and dimer acid glycidyl ester. Examples of the heterocyclic epoxy resin include 1,3-diglycidyl-5,5-dimethylhydantoin or triglycidyl isocyanate. Examples of alicyclic epoxy resins include naphthalene type epoxy resins. These epoxy resins may be used alone or in combination of two or more.

  Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbidic acid, acrylic acid dimer, monomethyl malate, monobutyl malate and the like. These unsaturated monobasic acids may be used alone or in combination of two or more.

  As the saturated dicarboxylic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid and the like can be used.

  As the unsaturated dicarboxylic acid, fumaric acid, maleic anhydride, maleic acid, itaconic acid and the like can be used.

  Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl- 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, and the like can be used.

  In the present invention, it is necessary to use a reactive monomer having at least one hydroxyl group as the polymerizable monomer.

  Examples of the reactive monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, and trimethylolethane mono (meth) acrylate. Examples include hydroxyalkyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and the like.

  Examples other than reactive monomers having a hydroxyl group include styrene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, Examples include neopentyl glycol dimethacrylate, isobornyl methacrylate, trimethylolpropane trimethacrylate, ethylene oxide adduct dimethacrylate of bisphenol A, diallyl phthalate, triallyl trimetate, and the like.

  The content of the reactive monomer having a hydroxyl group is preferably 5% by weight or more and 20% by weight or less with respect to the radical curable resin. If the content of the reactive group having a hydroxyl group exceeds 20%, the dryness of the surface is deteriorated and a problem of stickiness occurs, and further, chemical resistance performance, particularly acid resistance is deteriorated. On the other hand, when the content of the reactive substance having a hydroxyl group is less than 5%, the curing time is significantly delayed due to the influence of moisture, and in particular, there is a problem that the curing time in the low temperature region requires a time of 1 day or more.

  The radical curable resin preferably has a viscosity at 25 ° C. of 0.05 Pa · s to 0.5 Pa · s using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.). When the viscosity of the radical curable resin exceeds 0.5 Pa · s, the viscosity of the viscous primer composition after addition of the filler is increased, and workability in a low temperature range is significantly deteriorated. On the other hand, if the viscosity of the radical curable resin is less than 0.05 Pa · s, it is necessary to fill a large amount of hydrophobic silica in order to give thixotropy to the viscous primer composition, and there is a problem in that it is disadvantageous in terms of cost. The adhesiveness of the resin deteriorates and causes a decrease in strength.

Furthermore, it is necessary to contain hydrophobic silica as a filler in the present invention.
Here, as the hydrophobic silica, the surface of silica (fine silicon dioxide) is subjected to hydrophobic treatment, for example, treated with dimethyl silicone oil (product name: RY200 manufactured by Nippon Aerosil Co., Ltd.), treated with trimethylsilyl group. Examples include products (product name: RX200 manufactured by Nippon Aerosil Co., Ltd.) and those treated with octylsilane (product name: R805 manufactured by Nippon Aerosil Co., Ltd.).

It is preferable to use a hydrophobic silica having a specific surface area of 200 m ² / g or less by the BET method. When the specific surface area exceeds 200 m ² / g by the BET method, a large amount of addition is required to give thixotropy to the viscous primer composition. Sex worsens. Furthermore, the adhesiveness with the ground becomes worse and causes a decrease in strength.

  In the present invention, fillers other than hydrophobic silica can be added. As filler, quartz sand, cinnabar sand, cocoon powder, ceramic powder, barium sulfate, calcium sulfate, calcium carbonate, titanium oxide, aluminum hydroxide, talc, clay, mica, volcanic ash, shirasu, concrete powder, foamed concrete powder, glass Examples include flakes, fly ash, carbon black, and alumina. The blending amount is preferably 150 wt% or less with respect to the radical curable resin. In applications where high acid resistance is required, acid resistant fillers such as barium sulfate are preferably used.

  The radical curable resin used in the present invention is generally used by adding a curing accelerator, a polymerization inhibitor and the like in order to adjust curability. Examples of generally used curing accelerators for radical curable resins include metal soaps such as cobalt naphthenate, cobalt octenoate, vanadyl octenoate, copper naphthenate, and barium naphthenate. Metal chelate compounds include vanadyl There are acetyl acetate, cobalt acetyl acetate, and iron acetyl acetate. Examples of amines include dimethylaniline, Nn-diethylaniline, Nn-dimethylparatoluidine, N-ethyl-metatoluidine, triethanolamine, diethylenetriamine, metatoluidine, diethanolaniline and the like. These may be used alone or in combination of two or more.

  Examples of the polymerization inhibitor for the radical curable resin used in the present invention include hydroquinones, phenols, cresols, catechols, benzoquinones, and the like, for example, benzoquinone, p-benzoquinone, p-toluquinone, p-xyloquinone. , Naphthoquinone, 2,6-dichloroquinone, hydroquinone, trimethylhydroquinone, catechol, pt-butylcatechol, 2,5-di-t-butylhydroquinone, monomethylhydroquinone, p-methoxyphenol, 2,6-di-t Necessary amounts of -butyl-p-cresol, hydroquinone monomethyl ether and the like can be added.

  Examples of the curing agent for the radical curable resin used in the present invention include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and peroxycarbonates. Examples of the organic peroxide include methyl ethyl ketone peroxide, benzoyl peroxide, lauryl peroxide, dicumyl peroxide, cumene hydroperoxide, and the like.

Hereinafter, a sheet lining method using the primer composition according to the present invention will be described.
Apply base primer to the groundwork of ground-treated concrete or mortar structure as needed. As the base primer, urethane resin, acrylic resin, epoxy resin, unsaturated polyester resin, epoxy acrylate resin, or the like is used. The coating amount is usually about 200 g / m ² or less.

A curing agent is mixed and applied to the viscous primer composition for sheet lining according to the present invention.
Addition of ketone peroxide methyl ethyl ketone peroxide, diacyl peroxide benzoyl peroxide, etc. as a curing agent Apply primer.
The coating amount of the sheet lining for viscosity primer composition is a 500g / m ² ~1500g / m ² approximately, preferably ^{1000g / m 2 ~1300g / m 2} .
After the application, a layer composed of a reinforcing fiber sheet and a curable resin is formed and cured until the viscous primer gels.

  As a curing method, after a photocurable prepreg sheet formed by impregnating a photocurable resin and a photoinitiator into a reinforcing fiber sheet is pasted, a photocuring method, or after a reinforcing fiber sheet is pasted, There is a method of curing after impregnating with a photocurable resin or a thermosetting resin, but a method of applying a photocurable prepreg sheet and irradiating with UV light or the like is preferably used.

Hereinafter, the present invention will be specifically described with reference to non-limiting examples.
In the following Examples 1 to 5 and Comparative Examples 1 to 3, primer compositions were prepared, and performance was evaluated according to the following evaluation criteria.

Curability when mixed with water: Curing time at 20 ° C. when mixed with 2% of water, “O” within 4 hours, “Δ” within 8 hours, and “X” over 8 hours.

Applicability (uniformity) : “○” indicates that the base is uniformly applied and can be applied uniformly, “△” indicates that there is slight unevenness, and “×” indicates that the coating cannot be applied uniformly. did.

Surface stickiness : The stickiness of the primer surface after curing, with no stickiness, “◯”, with the stickiness on the surface being “Δ”, and with the surface layer being uncured, “×”.

Dripping: a sagging of the primer after the wall direction applied, "○" a thing without sagging, what slight sagging "△", and those sagging significant as "×".

Adhesive strength (MPa) : According to Kenken-type tensile test (JIS A 6909).

[Example 1]
90 g of a resin obtained by adding styrene monomer as a polymerizable monomer to an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, 10 g of 2-hydroxyethyl methacrylate as a reactive monomer having a hydroxyl group is mixed, and the viscosity is 0. 0.1 g of a radical curable resin adjusted to 15 Pa · s, 0.6 g of cobalt naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing accelerator, and a specific surface area of 100 m ² / g as hydrophobic silica by BET method Aerosil: 6 g of RY-200 (manufactured by Nippon Aerosil Co., Ltd.) and 50 g of barium sulfate W-6 (manufactured by Takehara Chemical Co., Ltd.) as a filler were added, followed by stirring and mixing for 30 minutes to obtain a viscous primer composition. Prepared.

  2% by weight of water and 2.0% by weight of methyl ethyl ketone peroxide Mepox D (manufactured by Kawaguchi Pharmaceutical Co., Ltd.) as a curing agent were added to the prepared viscous primer, and the curability (curing time) at 20 ° C. was evaluated. . The results are shown in Table 1 below.

  To the viscous primer, 1.5 g of methyl ethyl ketone peroxide: Mepox D (manufactured by Kawaguchi Pharmaceutical Co., Ltd.) was added as a curing agent, and the mixture was stirred and mixed for 1 minute.

  Evaluation of adhesion to a mortar pavement plate having a size of 300 × 300 × 60 mm was evaluated by a Kenken-type tensile test (JIS A 6909). Also, apply the viscous primer composition with a rubber spatula, apply the viscous primer (uniformity), observe the surface stickiness after curing the viscous primer, apply the viscous primer with the mortar pavement sideways, The situation was observed. The results at that time are also shown in Table 1 below.

[Example 2]
Aerosil having a specific surface area of 100 m ² / g by the BET method: RY-200 (manufactured by Nippon Aerosil Co., Ltd.) Aerosil having a specific surface area of 260 m ² / g by the BET method: R812 (manufactured by Nippon Aerosil Co., Ltd.) 6 g The same evaluation as in Example 1 was performed except that was added. The results are shown in Table 1 below.

[Example 3]
Radical curable resin is mixed with bisphenol A type epoxy resin with methacrylic acid added to epoxy acrylate resin and styrene monomer as polymerizable monomer is mixed with 97 g of resin and 3 g of 2-hydroxyethyl methacrylate is mixed to a viscosity of 0.15 Pa · s. Except that, the same viscous primer composition as in Example 1 was prepared and evaluated. The results are shown in Table 1 below.

[Example 4]
The radical curable resin is an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 78 g of a resin mixed with a styrene monomer as a polymerizable monomer is mixed with 22 g of 2-hydroxyethyl methacrylate to a viscosity of 0.15 Pa · s. Except that, the same viscous primer composition as in Example 1 was prepared and evaluated. The results are shown in Table 1 below.

[Example 5]
A viscous primer composition similar to that of Example 1 was prepared and evaluated, except that the amount of Aerosil: RY-200 (manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 100 m ² / g by the BET method was changed to 12 g. It was. The results are shown in Table 1 below.

[Comparative Example 1]
As a radical curable resin, without adding a reactive monomer having a hydroxyl group, a viscosity of 0.15 Pa is obtained by mixing a styrene monomer as a polymerizable monomer with an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin. -The same viscous primer composition as Example 1 was prepared and evaluated, except that 100 g of radical curable resin adjusted to s was used. The results are shown in Table 1 below.

[Comparative Example 2]
A viscous primer composition similar to that of Example 1 was prepared and evaluated without adding Aerosil: RY-200 (manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 100 m ² / g by the BET method. The results are shown in Table 1 below.

[Comparative Example 3]
Addition of barium sulfate W-6 (manufactured by Takehara Chemical Co., Ltd.) as a filler without adding Aerosil: RY-200 (manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 100 m ² / g by the BET method The same viscous primer composition as in Example 1 was prepared and evaluated, except that the amount was 200 g. The results are shown in Table 1 below.

Claims (6)

  A viscous primer composition for sheet lining comprising a radical curable resin (a) comprising a polymerizable monomer and an epoxy acrylate, and a filler (b), wherein the reactive monomer having one or more hydroxyl groups as the polymerizable monomer. The viscous primer composition for sheet lining according to claim 1, wherein a filler is used and the filler contains hydrophobic silica. The viscous primer composition for sheet lining according to claim 1, wherein a specific surface area of the hydrophobic silica is 200 m ² / g or less as measured by a BET method.   The viscous primer composition for sheet lining according to claim 1 or 2, wherein the content of the reactive monomer having a hydroxyl group is 5 wt% or more and 20 wt% or less with respect to the radical curable resin (a). .   The viscous primer composition for sheet lining according to any one of claims 1 to 3, wherein the content of the hydrophobic silica is 5 wt% or more and 10 wt% or less with respect to the radical curable resin (a). .   5. The viscosity of the radical curable resin (a) comprising the polymerizable monomer and epoxy acrylate is 0.05 Pa · s or more and 0.5 Pa · s or less at 25 ° C. 5. Viscous primer composition for seat lining.   In the sheet lining method of a concrete structure using an FRP sheet, after applying the viscous primer composition for sheet lining according to any one of claims 1 to 5 on a base, a reinforcing fiber sheet and A sheet lining method for a concrete structure, wherein a layer made of a curable resin is formed and cured.