JP2005068359A - Two-liquid mixing type resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-liquid mixing type resin composition which enables agents A and B to mix in a proper blend ratio even by eye measuring, cures at room temperature and after curing exhibits a tough dynamic strength and a proper flexibility capable of following up movement at a place required of stress dispersion such as a joint part. <P>SOLUTION: The two-liquid mixing type resin composition is composed of the agent A comprising a modified silicone resin, curing agent for an epoxy resin, colloidal precipitated calcium carbonate, whiting and plasticizer and the agent B comprising an epoxy resin, curing agent for a modified silicone resin, colloidal precipitated calcium carbonate, whiting, cement and organic solvent, wherein the absolute value of a specific gravity difference between the agents A and B is ≤0.1. The resin composition is applicable to civil engineering uses. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a two-component mixed resin composition suitably used particularly for civil engineering.

Conventionally, epoxy resin-based compositions such as epoxy resin-based adhesives have been widely used in the civil engineering field. For example, an epoxy resin-based primer and a polymer cement-based substrate-conditioning material on the primary lining surface of a tunnel In addition, the intermediate coating material of the same type as the above-mentioned top coating material mixed with the fiber reinforcing material is sequentially applied, and then an epoxy resin-based, vinyl ester resin-based or methyl methacrylate resin-based top coating material is applied. A next lining method is disclosed.
JP-A-10-202180

In addition, as an epoxy resin composition used for such applications, for example, a secondary lining coating comprising an agent A blended with a room temperature curing epoxy resin component and an agent B containing the curing agent component A liquid is disclosed.
JP-A-10-204373

  However, although a cured product of such an epoxy resin-based composition exhibits a tough mechanical strength, it is generally poor in flexibility, and therefore, stress distribution such as a joint portion (seal portion) in a tunnel is required. There is a problem in that the movement cannot follow the movement, and a crack (crack) or the like occurs to cause water leakage.

  In general, in the construction site of civil engineering, there are cases where a measuring instrument is not provided, so the A agent and the B agent are often mixed in an appropriate amount, but in that case, the specific gravity of the A agent and the B agent When the specific gravity is greatly different, there is a problem that the mixing ratio of the agent A and the agent B becomes inappropriate.

  In view of the above problems, the object of the present invention is to mix the A agent and the B agent at an appropriate mixing ratio even in a scale, and is cured at room temperature, and has a tough mechanical strength and joint after curing. An object of the present invention is to provide a two-component mixed resin composition that exhibits moderate flexibility that can follow the movement of a part such as a part where stress dispersion is required.

  The two-component mixed resin composition according to the invention of the present invention (the present invention) is an agent A comprising a modified silicone resin, a curing agent for epoxy resin, colloidal light calcium carbonate, heavy calcium carbonate and a plasticizer. And an epoxy resin, a curing agent for modified silicone resin, colloidal light calcium carbonate, heavy calcium carbonate, cement B and a B agent containing an organic solvent, and the specific gravity difference between the A agent and the B agent The absolute value of is not more than 0.1.

  Moreover, the two-component mixed resin composition according to the invention described in claim 2 is the modified silicone resin 100 in which the agent B is contained in the agent A in the two-component mixed resin composition according to claim 1. 30 to 70 parts by weight of epoxy resin, 0.5 to 5 parts by weight of curing agent for modified silicone resin, 30 to 120 parts by weight of colloidal light calcium carbonate, 10 to 100 parts by weight of heavy calcium carbonate, cement 1 It is contained so that it may become -50 weight part and 5-50 weight part of organic solvents.

  Furthermore, the two-component mixed resin composition according to the invention described in claim 3 is characterized in that the two-component mixed resin composition described in claim 1 or 2 is used for civil engineering.

  The agent A constituting the two-component mixed resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) contains a modified silicone resin as an essential component. The modified silicone resin referred to in the present invention means a modified silicone compound having at least one reactive silicon group in one molecule.

  By containing the modified silicone resin in the agent A, the cured product of the resin composition of the present invention exhibits appropriate flexibility that can follow the movement of a part that requires stress dispersion such as a joint part. To be.

  The reactive silicon group of the modified silicone resin is, for example, a silanol condensation having a hydrolyzable functional group such as an alkoxyl group, an oxime group, an alkenyloxy group, an acetoxy group, a halogen group, or a silicon atom to which a hydroxyl group is bonded. A group that can be cross-linked by reaction.

  Specific examples of the reactive silicon group are not particularly limited. For example, a methyldimethoxysilyl group, cyclohexyldimethoxysilyl group, methyldiethoxysilyl group, octyldimethoxysilyl group, vinyldiethoxysilyl group, chloro Methyl (diisopropoxy) silyl group, phenyldimethoxysilyl group, phenyldiethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, dimethoxypropylsilyl group, isobutyldimethoxysilyl group, octyldimethoxysilyl group, octadecyldimethoxysilyl group, Methyldiethoxysilyl group, ethyldiethoxysilyl group, isobutyldiethoxysilyl group, octyldiethoxysilyl group, vinyldimethoxysilyl group, vinyldiethoxysilyl group, allyldiethoxysilyl group, (3- Rolopropyl) dimethoxysilyl group, chloromethyldiethoxysilyl group, bis (2-methoxyethoxy) vinylsilyl group, 3-glycidoxypropyldimethoxysilyl group, diethoxy (3-glycidoxypropyl) silyl group, dimethoxy [2- ( 7-oxabicyclo [4,1,0] -hept-3-yl) ethyl] silyl group, chlorodimethoxysilyl group, chlorodiethoxysilyl group, chlorobis (1,3-dimethylbutoxy) -silyl group, chlorodiethoxy Silyl group, 3- (triethoxysilyl) -propionitrile group, 4- (triethoxysilyl) -butyronitrile group, 3- (triethoxysilyl) -propyl isocyanate group, 3- (triethoxysilyl) -propylthioisocyanate Group, phenyldimethoxysilyl group, phenyldie Xylsilyl group, trimethoxysilyl group, triethoxysilyl group, tripropoxysilyl group, tributoxysilyl group, 1,2-bis (methyldichlorosilyl), diacetoxydiphenylsilyl group, methyltris (ethylmethylketoxime) silyl group, Methyltris (N, N-diethylaminoxy) silyl group, bis (ethylmethylketoxime) methylisopropoxysilyl group, bis (ethylmethylketoxime) ethoxymethylsilyl group, 2- (3,4-epoxycyclohexylethyl) trimethylsilyl group , Tris (1-methylvinyloxy) vinylsilyl group, methyltriisopropenoxysilyl group, ethyltriacetoxysilyl group, methyltriacetoxysilyl group, diacetoxydimethylsilyl group, triacetoxyvinylsilyl group, tetra Examples include an acetoxysilyl group, a diacetoxymethylphenylsilyl group, a dimethoxyethylmethylketoximemethylsilyl group, and the like. These reactive silicon groups may be used alone or in combination of two or more.

  The modified silicone resin may have a functional group capable of reacting with an epoxy resin contained as an essential component in the agent B described later. Although it does not specifically limit as a functional group which can react with the said epoxy resin, For example, an amino group, a mercapto group, a carboxyl group etc. are mentioned. These functional groups capable of reacting with the epoxy resin may be used alone or in combination of two or more.

  Specific examples of the modified silicone resin are not particularly limited. For example, trade names “MS Polymer S-203”, “MS Polymer S-303”, “MS Polymer S” manufactured by Kaneka Chemical Co., Ltd. -903 "," MS polymer EPION "and other" MS polymer "series, trade names" Syryl 5B25 "," Syryl 5B30 "," Syryl SAT-200 "," Syryl MA-403 ", also manufactured by Kaneka Chemical Co., Ltd. "Cyrillic" series such as "Cyryl MA-447", "Cyrillic MA-903", trade names "EXCESTERS ESS-2410", "Excester ESS-2420", "Excester ESS-3630" manufactured by Asahi Glass Co., Ltd. Such as “Exstar” series, acetoxy-terminated polydimethylsiloxane manufactured by Chisso Corporation (trade name “PS363”) 5 "), dimethylamino terminated polydimethylsiloxane (trade name" PS383 "), ethoxy terminated polydimethylsiloxane (trade name" PS393 "), stearyloxy terminated polydimethylsiloxane (trade name" PS053.5 "), triethoxysilyl modified Poly (1,2-butadiene) (trade name “PS078.5”), (N-trimethoxysilylpropyl) polyazamide (trade name “PS075”), (N-trimethoxysilylpropyl) polyethyleneimine (trade name “PS076”) )), (N-trimethoxysilylpropyl) -O-polyethylene oxide urethane (trade name “PS077”) and the like. These modified silicone resins may be used alone or in combination of two or more.

  The agent A constituting the resin composition of the present invention contains an epoxy resin curing agent as an essential component. By containing the epoxy resin curing agent in the agent A, the epoxy resin contained as an essential component in the agent B constituting the resin composition of the present invention can be effectively cured.

  The epoxy resin curing agent is not particularly limited as long as it is a compound capable of reacting with an epoxy group (glycidyl group) in an epoxy resin, preferably at room temperature, and preferably curing the epoxy resin at room temperature. For example, polyethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine, 2,4,6-tris (dimethylaminomethyl) phenol and the like can be mentioned. These epoxy resin curing agents may be used alone or in combination of two or more.

  Agent A and Agent B constituting the resin composition of the present invention contain colloidal light calcium carbonate as an essential component. By containing colloidal light calcium carbonate in agent A and agent B, the mixture of agent A and agent B has an excellent structural viscosity.

  The colloidal light calcium carbonate is light calcium carbonate in a special dispersion state, and usually means an average particle diameter of 0.1 to 10 μm and an apparent specific gravity of about 0.2 g / ml. . These colloidal light calcium carbonates may be used alone or in combination of two or more.

  Agent A and Agent B constituting the resin composition of the present invention contain heavy calcium carbonate as an essential component. By containing heavy calcium carbonate in agent A and agent B, the mixture of agent A and agent B exhibits a tougher mechanical strength without causing a disadvantageous increase in viscosity. It becomes a thing.

  The above-mentioned heavy calcium carbonate is obtained by mechanically pulverizing and classifying, for example, excluding a colored portion of limestone. These heavy calcium carbonates may be surface-treated. Moreover, these heavy calcium carbonate may be used independently and 2 or more types may be used together.

  The agent A constituting the resin composition of the present invention contains a plasticizer (softener) as an essential component. By containing a plasticizer in the A agent, the viscosity of the A agent is reduced and the mixing property with the B agent is improved, and the cured product of the resin composition of the present invention exhibits more excellent flexibility. To be.

  The plasticizer is not particularly limited, and examples thereof include phthalic acid esters such as dibutyl phthalate, di-n-octyl phthalate and di-2-ethylhexyl phthalate, tributyl phosphate, and tri-phosphate. Phosphate esters such as 2-ethylhexyl and tricresyl phosphate, aliphatic monobasic esters such as butyl oleate and glycerol monooleate, and aliphatic dibasic esters such as butyl adipate and di-n-hexyl adipate And paraffin such as liquid paraffin and chlorinated paraffin. These plasticizers may be used alone or in combination of two or more.

  B agent which comprises the resin composition of this invention contains an epoxy resin as an essential component. By containing an epoxy resin in the agent B, the cured product of the resin composition of the present invention expresses tough mechanical strength.

  As the epoxy resin, an epoxy resin having at least two epoxy groups in one molecule is preferable considering reactivity with the curing agent for epoxy resin contained in the agent A, preferably reactivity at room temperature. Although not particularly limited, for example, the epoxy compound is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S Type epoxy resins, bisphenol type epoxy resins; phenol novolac type epoxy resins, cresol novolac type epoxy resins, etc. novolac type epoxy resins; trisphenol methane triglycidyl ether, etc., and aromatic epoxy trees such as hydrogenated products and halides thereof 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate, bis (3,4-epoxy Cyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3, 4-epoxy) cyclohexanone-meta-dioxane, alicyclic epoxy resins such as bis (2,3-epoxycyclopentyl) ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Glycerin trig Includes triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, polyoxyalkylene glycol having 2 to 9 carbon atoms, polytetramethylene ether glycol, etc. Aliphatic epoxy resins such as polyglycidyl ethers of long-chain polyols; diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl-p-oxybenzoic acid, glycidyl ether-glycidyl ester of salicylic acid , Glycidyl ester type epoxy resins such as dimer acid diglycidyl ester and hydrogenated products thereof; triglycidyl isocyanurate, cyclic N, N'-diglycidyl derivatives of alkylene urea, N, N, O-triglycidyl derivatives of p-aminophenol, N, N, O-triglycidyl derivatives of m-aminophenol, and glycidyl such as hydrogenated products thereof Amine type epoxy resin; polyester resin having at least two epoxy groups in one molecule; urethane modified epoxy resin in which urethane bond is introduced in the structure of the above various epoxy resins; polycaprolactone bond in the structure of the above various epoxy resins Examples include polycaprolactone modified epoxy resins that have been introduced. Among them, bisphenol-type epoxy resins are preferably used because they can be cured products with excellent reactivity at room temperature with the epoxy resin curing agent and excellent mechanical strength. It is done. These epoxy resins may be used independently and 2 or more types may be used together.

  B agent which comprises the resin composition of this invention contains the hardening | curing agent for modified silicone resins as an essential component. By containing the curing agent for modified silicone resin in agent B, the modified silicone resin contained as an essential component in agent A constituting the resin composition of the present invention can be effectively cured.

  The curing agent for the modified silicone resin is not particularly limited, and examples thereof include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin lauric acid) oxide, and dibutyltin bis. Examples thereof include organic tin catalysts such as acetylacetonate, dibutyltin bis (monoester malate), tin octylate, dibutyltin octoate, and dioctyltin oxide. These modified silicone resin curing agents may be used alone or in combination of two or more.

  As described above, the agent B constituting the resin composition of the present invention contains colloidal light calcium carbonate and heavy calcium carbonate as essential components.

  B agent which comprises the resin composition of this invention contains a cement as an essential component. By including cement in the agent B, the resin composition of the present invention expresses better adhesion (adhesion) to an adherend made of cement mortar, concrete, or the like, and is cured. The mechanical strength of the object is also improved. Further, even when the surface of the adherend made of cement mortar or concrete is a wet surface, moisture (humidity) absorbed in the resin composition can be captured by the hydration reaction of the cement. The physical property fall of the hardened | cured material resulting from can be prevented effectively.

  Although it does not specifically limit as said cement, For example, normal Portland cement; special Portland cements, such as early strong Portland cement and white Portland cement; mixed Portland cements, such as blast furnace slag mixing cement and fly ash cement, etc. Of these, ordinary portland cement is preferably used because of its excellent balance between performance and cost. These cements may be used alone or in combination of two or more.

  B agent which comprises the resin composition of this invention contains the organic solvent as an essential component. By including an organic solvent in the agent B, the mixing property of the agent A and the agent B of the resin composition of the present invention, particularly the mixing property at low temperatures, is improved, and the viscosity of the mixture of the agent A and the agent B is improved. In addition, the rate of change in viscosity due to temperature (temperature dependence of viscosity) is reduced, and application workability (including filling workability), especially mixing and application workability at construction sites in civil engineering applications, etc. improves.

  The organic solvent is not particularly limited as long as it can effectively dilute the B agent and thus the mixture of the A and B agents. For example, methyl cellosolve, ethyl cellosolve, propyl cellosolve, Examples include butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate and the like. These organic solvents may be used independently and 2 or more types may be used together.

  The two-component mixed resin composition of the present invention is composed of agent A and agent B each containing the above-mentioned essential components, and among them, the modified silicone resin in which agent B is contained in agent A 30 to 70 parts by weight of epoxy resin, 0.5 to 5 parts by weight of a curing agent for modified silicone resin, 30 to 120 parts by weight of colloidal light calcium carbonate, 10 to 100 parts by weight of heavy calcium carbonate, 100 parts by weight, cement It is preferable that it is a resin composition contained so that it may become 1-50 weight part and 5-50 weight part of organic solvents.

  When the content of the epoxy resin in the B agent is less than 30 parts by weight with respect to 100 parts by weight of the modified silicone resin in the A agent, the mechanical strength of the cured product of the resin composition may be insufficient. Conversely, if the content of the epoxy resin in the B agent exceeds 70 parts by weight with respect to 100 parts by weight of the modified silicone resin in the A agent, the flexibility of the cured product of the resin composition may be insufficient. .

  Further, if the content of the curing agent for the modified silicone resin in the agent B is less than 0.5 parts by weight based on 100 parts by weight of the modified silicone resin in the agent A, the modification contained as an essential component in the agent A If the silicone resin cannot be cured sufficiently, the content of the curing agent for the modified silicone resin in the B agent exceeds 5 parts by weight with respect to 100 parts by weight of the modified silicone resin in the A agent. Even though the effect of curing the modified silicone resin is no longer improved, an undesirable diluting action may occur.

  Further, when the content of colloidal light calcium carbonate in the agent B is less than 30 parts by weight with respect to 100 parts by weight of the modified silicone resin in the agent A, the structural viscosity of the mixture of the agent A and the agent B is insufficient. Thus, for example, when a decorative material such as a tile is attached to a vertical surface, the decorative material may be shifted downward, and conversely, the content of colloidal light calcium carbonate in the B agent is modified in the A agent. If it exceeds 120 parts by weight with respect to 100 parts by weight of the silicone resin, the structural viscosity of the mixture of the agent A and the agent B becomes too high, and the mixing operation itself becomes difficult or the mixture is applied (including filling). At this time, for example, the wiping workability may be deteriorated.

  Further, when the content of heavy calcium carbonate in the agent B is less than 10 parts by weight with respect to 100 parts by weight of the modified silicone resin in the agent A, the mechanical strength of the cured product of the resin composition is not sufficiently improved. On the contrary, if the content of heavy calcium carbonate in the B agent exceeds 100 parts by weight with respect to 100 parts by weight of the modified silicone resin in the A agent, the B agent and consequently the mixture of the A agent and the B agent The viscosity may become too high, making the mixing operation itself difficult, and, for example, applying the mixture may worsen the workability of glazing.

  Further, if the content of the cement in the B agent is less than 1 part by weight with respect to 100 parts by weight of the modified silicone resin in the A agent, the above-mentioned effect due to the cement being contained may not be sufficiently obtained. On the contrary, when the content of cement in the B agent exceeds 50 parts by weight with respect to 100 parts by weight of the modified silicone resin in the A agent, the specific gravity of the B agent becomes too high, and the specific gravity difference between the A agent and the B agent. May exceed 0.1, or cement may separate and settle during storage or transportation of agent B.

  Furthermore, when the content of the organic solvent in the B agent is less than 5 parts by weight with respect to 100 parts by weight of the modified silicone resin in the A agent, the above-described effect due to the inclusion of the organic solvent may not be sufficiently obtained. On the contrary, when the content of the organic solvent in the B agent exceeds 50 parts by weight with respect to 100 parts by weight of the modified silicone resin in the A agent, the viscosity of the B agent itself becomes too low, and the colloid in the B agent When inorganic materials such as light calcium carbonate, heavy calcium carbonate and cement cause sedimentation, or when a decorative material such as a tile is pasted on a vertical surface using a mixture of agent A and agent B, the decorative material is downward. It may slip off.

  In addition to the essential components of the modified silicone resin, epoxy resin curing agent, colloidal light calcium carbonate, heavy calcium carbonate and plasticizer, the agent A constituting the resin composition of the present invention achieves the object of the present invention. If necessary, for example, adhesive resin, adhesion-imparting agent, colloidal light calcium carbonate and fillers other than heavy calcium carbonate, specific gravity reducing agent, colorant, dehydrating agent, cement, antioxidant One kind or two or more kinds of various additives such as an agent (anti-aging agent), a heat stabilizer, a light stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent and an organic solvent may be contained.

  In addition to the B component constituting the resin composition of the present invention, in addition to the essential components epoxy resin, hardener for modified silicone resin, colloidal light calcium carbonate, heavy calcium carbonate, cement and organic solvent, As long as it does not hinder the achievement of the problem, for example, adhesive resin, adhesion imparting agent, colloidal light calcium carbonate and fillers other than heavy calcium carbonate, specific gravity reducing agent, colorant, dehydrating agent, One kind or two or more kinds of various additives such as a plasticizer, an antioxidant (anti-aging agent), a heat stabilizer, a light stabilizer, an ultraviolet absorber, a flame retardant, and an antistatic agent may be contained.

  The adhesive resin is not particularly limited. For example, rosin resin, modified rosin resin, terpene resin, modified terpene resin, terpene phenol resin, C5 or C9 petroleum Examples thereof include resins and coumarone indene resins. These adhesive resins may be used alone or in combination of two or more.

  The adhesiveness-imparting agent is not particularly limited. For example, glycidoxytrimethoxysilane, glycidoxypropylmethyldiethoxysilane, N- (aminoethyl) aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane And silane coupling agents, titanium coupling agents, aluminum coupling agents and the like. These adhesiveness imparting agents may be used alone or in combination of two or more.

  The filler other than colloidal light calcium carbonate and heavy calcium carbonate is not particularly limited, and examples thereof include magnesium carbonate, clay, talc, anhydrous silica, hydrous silica, and calcium silicate. These fillers other than colloidal light calcium carbonate and heavy calcium carbonate may be used alone or in combination of two or more.

  The specific gravity reducing agent is not particularly limited, and examples thereof include inorganic hollow particles such as glass balloons and shirasu balloons, hollow resin particles, and organic hollow particles such as thermally expanded microcapsules. These specific gravity reducing agents may be used alone or in combination of two or more.

  Although it does not specifically limit as a coloring agent, For example, a titanium oxide, a petite, carbon black etc. are mentioned. These colorants may be used alone or in combination of two or more.

  The dehydrating agent is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and the like. These dehydrating agents may be used alone or in combination of two or more.

  In the two-component mixed resin composition of the present invention, the absolute value of the specific gravity difference between the agent A and the agent B needs to be 0.1 or less. That is, the agent A and the agent B constituting the resin composition of the present invention are required to have a blended composition in which the absolute value of the specific gravity difference between the agent A and the agent B is 0.1 or less.

  When the absolute value of the specific gravity difference between the agent A and the agent B constituting the resin composition of the present invention exceeds 0.1, the agent A and the agent B in terms of scale at a construction site where a measuring instrument is not provided. It becomes difficult to mix the agent at an appropriate mixing ratio, the mixing ratio of the A agent and the B agent becomes inappropriate, and the mechanical strength and flexibility of the cured product become insufficient.

  The method for producing the agent A and the agent B constituting the resin composition of the present invention is not particularly limited. For example, using a normal kneader such as a kneader, a mixer, a roll, or an extruder, Under heating, if necessary, in an inert gas atmosphere such as nitrogen gas or in a vacuum dehydration atmosphere, each predetermined amount of each essential component to be contained in agent A or agent B and contained in agent A or agent B What is necessary is just to manufacture A agent and B agent separately by knead | mixing each predetermined amount of each component which may be sufficient.

  The mixing ratio of the agent A and the agent B constituting the resin composition of the present invention is such that the epoxy resin contained in the agent B is 30 parts by weight with respect to 100 parts by weight of the modified silicone resin contained in the agent A. ~ 70 parts by weight, hardener for modified silicone resin 0.5 to 5 parts by weight, colloidal light calcium carbonate 30 to 120 parts by weight, heavy calcium carbonate 10 to 100 parts by weight, cement 1 to 50 parts by weight and The proportion is preferably such that the organic solvent is 5 to 50 parts by weight.

  The method of using the resin composition of the present invention is not particularly limited. For example, the agent A and the agent B are uniformly mixed at a predetermined mixing ratio, and preferably within the pot life (pot life). Apply as soon as possible to the bonding surface of at least one adherend, then laminate the bonding surface of the other adherend and press if necessary, preferably cure at room temperature or heat cure if necessary By doing so, a desired joined body can be obtained. The application pattern at the time of application is not particularly limited, and may be, for example, full-surface application or partial application such as a bead shape, a spiral shape, or a dot shape.

  The application of the two-component mixed resin composition of the present invention is not particularly limited, and is preferably used for any application that requires room temperature curing. It is particularly preferably used for civil engineering.

  Specific examples of the civil engineering include, but are not limited to, joining, filling (sealing), lining, and the like of shield segments, joint grooves, ponds, fire prevention water tanks, and the like.

  The two-component mixed resin composition of the present invention comprises a modified silicone resin, a curing agent for epoxy resin, an agent A containing colloidal light calcium carbonate, heavy calcium carbonate and a plasticizer, and an epoxy resin and modified silicone resin. A hardener, colloidal light calcium carbonate, heavy calcium carbonate, B agent containing cement and an organic solvent, and the absolute value of the specific gravity difference between the A agent and the B agent is 0.1 or less Since it is made so that agent A and agent B can be mixed at an appropriate mixing ratio even at a scale, and cured at room temperature, after curing, such as tough mechanical strength and joint parts Appropriate flexibility that can follow the movement of the part where stress dispersion is required, and the applicability of the mixture of agent A and agent B and the mixture of agent A and agent B at room temperature (Including filling properties ) It is also excellent in workability at room temperature, such as.

  Moreover, the resin composition of this invention is 30-70 weight part of epoxy resins with respect to 100 weight part of modified silicone resins contained in A agent, 0.5 to 5 hardening agents for modified silicone resins. By containing 30 parts by weight, colloidal light calcium carbonate 30 to 120 parts by weight, heavy calcium carbonate 10 to 100 parts by weight, cement 1 to 50 parts by weight, and organic solvent 5 to 50 parts by weight. The above effects are more certain.

  Furthermore, since the resin composition of the present invention has the above-mentioned excellent performance, it is suitably used particularly for civil engineering on the premise of on-site construction.

  In order to describe the present invention in more detail, examples are given below, but the present invention is not limited to these examples.

(Example 1)
(1) Preparation of Agent A 50 parts by weight of the trade name “MS Polymer S-203” as the modified silicone resin, 50 parts by weight of the trade name “MS Polymer S-303” as the modified silicone resin, and 2, as the curing agent for the epoxy resin 4,6-tris (dimethylaminomethyl) phenol (trade name “DMP-30”, manufactured by Yuka Shell Epoxy Co., Ltd.), 5 parts by weight, as colloidal light calcium carbonate, trade name “Whiteon CCR” (manufactured by Shiraishi Kogyo Co., Ltd.) 80 Parts by weight, 20 parts by weight of a trade name “Whiteon SB” (manufactured by Shiroishi Kogyo Co., Ltd.) as heavy calcium carbonate, 15 parts by weight of di-n-octyl phthalate (DOP) as a plasticizer, and titanium oxide as a colorant (trade name) "Taipeku CR-90" (manufactured by Ishihara Sangyo Co., Ltd.) 10 parts by weight, 3 parts by weight of vinyltrimethoxysilane as a dehydrating agent, 3 parts by weight of Sidoxytrimethoxysilane, 1 part by weight of the trade name “Tinuvin 327” (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber, and 1 part by weight of the product name “Tinuvin 770” (manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber Part A was blended and kneaded uniformly for 60 minutes in a vacuum (reduced pressure) atmosphere using a planetary mixer to prepare agent A.

(2) Preparation of agent B Bisphenol A type epoxy resin (trade name “Epicoat 828”, manufactured by Yuka Shell Epoxy Co., Ltd.) 50 parts by weight as epoxy resin, trade name “Whiteon CCR” 35 parts by weight as colloidal light calcium carbonate, 70 parts by weight of “Whiteon SB” as heavy calcium carbonate, 30 parts by weight of ordinary Portland cement as cement, 15 parts by weight of glass balloon (trade name “Qcel-7040S”, manufactured by The PQ Corporation) as a specific gravity reducing agent 2 parts by weight of dibutyltin dilaurate as a curing agent for silicone resin, 1 part by weight of carbon black as a colorant, and 10 parts by weight of butyl cellosolve as an organic solvent, and uniform for 60 minutes in a vacuum (reduced pressure) atmosphere using a planetary mixer Kneaded to make B agent It was.

(Comparative Example 1)
As the A agent, the A agent prepared in Example 1 was used as it was. Moreover, B agent was produced like Example 1 except not having mix | blended normal Portland cement as cement.

(Comparative Example 2)
As the A agent, the A agent prepared in Example 1 was used as it was. Moreover, B agent was produced like the case of Example 1 except not having mix | blended the glass balloon "Qcel-7040S" as a specific gravity reducing agent.

(Comparative Example 3)
As the A agent, the A agent prepared in Example 1 was used as it was. Moreover, B agent was produced like Example 1 except not having mix | blended butyl cellosolve as an organic solvent, and having mix | blended DOP10 weight part as a plasticizer instead.

  Performances of the two-component mixed resin compositions obtained in Example 1 and Comparative Examples 1 to 3 (1. Specific gravity, 2. Low temperature mixing property, 3. Adhesion to concrete, 4. Mixing compatibility at a scale amount Property) was evaluated by the following method. The results are shown in Table 1.

1. Specific gravity The specific gravity of A agent and B agent was measured based on the specific gravity cup method of JIS K 6833 "General test method for adhesives". Moreover, the absolute value of the specific gravity difference of A agent and B agent was calculated | required.

2. Low temperature mixability After leaving agent A and agent B in an atmosphere of 5 ° C. for 24 hours in advance, 1 kg of agent A and 1 kg of B agent are mixed using a spatula in the same atmosphere. evaluated. [Criteria]
○ The resistance to the spatula was small and the low temperature mixing was good.
× …… The resistance to the spatula was large and the low temperature mixing was poor.

3. Adhesion to concrete Using concrete as an adherend, the H-type tensile properties of the cured resin composition were measured in accordance with JIS A 5758 “Building Sealant”, and the breaking strength (N / mm ² ) and The elongation at break (%) was determined. Moreover, the destruction state at the time of a fracture | rupture was observed visually, and it described in Table 1 with the following symbol.
(Abbreviation)
cf: cohesive failure of resin composition (cured product) af: interface failure between resin composition (cured product) and concrete sf: material failure of concrete

4). Mixing suitability in the amount of measure After taking out agent A and agent B in the amount of measure without using a measuring instrument, measure the actual weight of agent A and agent B and take the The weight ratio was determined, and the compatibility with the amount of scale was evaluated according to the following criteria.
[Criteria]
○ The weight ratio of agent A and agent B was 10% or less.
X ... The weight ratio of A agent and B agent exceeded 10%.

  As is clear from Table 1, the resin composition of Example 1 according to the present invention was excellent in both low temperature mixing and adhesion to concrete.

  On the other hand, in the resin composition of Comparative Example 1 in which cement was not contained in the agent B, 50% of the interface fracture between the resin composition (cured product) and the concrete was observed in the adhesion test for concrete. Adhesion to was poor. In addition, the resin composition of Comparative Example 2 in which the absolute value of the specific gravity difference between the A agent and the B agent exceeded 0.1 (0.16) was poor in mixing compatibility in terms of an amount. Furthermore, the resin composition of Comparative Example 3 in which the plasticizer (DOP) was contained instead of the organic solvent in the B agent had poor low temperature mixing properties of the A agent and the B agent.

  As described above, the two-component mixed resin composition of the present invention can mix the agent A and the agent B at an appropriate mixing ratio even with a scale amount, is cured at room temperature, and is tough after curing. High mechanical strength and moderate flexibility that can follow the movement of parts that require stress distribution such as joints, such as shield segments, joint grooves, ponds, fire tanks, etc. It is suitably used as an adhesive and a sealing agent for various uses, including an adhesive and a sealing agent for on-site construction in civil engineering applications such as joining, filling (sealing), and lining.

Claims (3)

  Modified silicone resin, epoxy resin curing agent, colloidal light calcium carbonate, heavy calcium carbonate and agent A containing plasticizer, epoxy resin, modified silicone resin curing agent, colloidal light calcium carbonate, heavy calcium carbonate A two-component mixed resin composition characterized by comprising a B agent containing cement and an organic solvent, and an absolute value of a specific gravity difference between the A agent and the B agent being 0.1 or less Stuff.   B agent is 30 to 70 parts by weight of epoxy resin, 0.5 to 5 parts by weight of curing agent for modified silicone resin, and 30 to 120 colloidal light calcium carbonate with respect to 100 parts by weight of modified silicone resin contained in agent A. The two-component mixed type according to claim 1, wherein the two-component mixed type is contained so as to be 10 parts by weight, 10 to 100 parts by weight of heavy calcium carbonate, 1 to 50 parts by weight of cement, and 5 to 50 parts by weight of an organic solvent. Resin composition.   The two-component mixed resin composition according to claim 1 or 2, which is used for civil engineering.