JP6221357B2 - Primer for structure surface layer, tunnel lining segment, tunnel, and method for manufacturing tunnel lining segment - Google Patents

Description

  The present invention relates to a primer for a surface layer of a structure, a tunnel lining segment including a primer layer composed of the primer, a tunnel in which a plurality of the segments are arranged, and a method for manufacturing the segment.

  In tunnels for water and sewage, rainwater, railways and motorways, electric power, gas, communications, and tunnels for these common grooves, etc., on the inner periphery of the tunnel formed by the shield method, A large number of arc-shaped plate-like segments are connected in the circumferential direction of the arc and the central axis direction of the circumference for coating. As this type of segment, a steel plate frame filled with concrete or mortar is known.

  By the way, such a segment is required to have sufficient water tightness and weather resistance depending on the type of tunnel to be covered, corrosion resistance against acid and alkali corrosion, as well as strength.

  In order to solve this problem, it has been proposed to apply a lining material to the surface of the segment body (see Patent Document 1). By the way, in order for the lining material to function effectively, it is necessary to apply the lining material to the surface of the segment until it reaches a predetermined thickness. However, from the viewpoint of workability, when the viscosity of the lining material is lowered, the lining material can only be applied thinly by one application, so in order to make the lining material function effectively, the lining material is applied to the segment surface, It is necessary to repeat the coating / drying operation of drying the lining material a plurality of times (about 3 to 5 times). However, particularly in winter, it takes about 4 to 5 hours from the application of the lining material to the segment surface until the lining material dries. In addition, since the lining material application operation is performed for many segments at the same time, it takes several days to repeat the application and drying of the lining material.

  On the other hand, if it is attempted to increase the viscosity of the lining material in order to shorten the work time, the lining material does not effectively penetrate into the irregularities on the surface of concrete or the like, and pinholes are generated in the lining material. And salt content, a water | moisture content, oxygen, etc. infiltrate from this pinhole, and waterproof performance may become inadequate.

  In order to effectively infiltrate the material with respect to the irregularities, first, a primer composition made of an epoxy resin composition is applied to the surface of the segment body, and the primer layer made of this primer composition is cured on the surface. It has been proposed to apply a conductive resin composition (lining material) (see Patent Document 2).

JP 2005-187780 A JP 2008-075033 A

  However, when the epoxy resin composition described in Patent Document 2 is used as a primer, it has excellent adhesion to concrete, but when an alkali component touches the coating film composed of the primer layer and the lining layer, the coating film swells, and this swelling causes The coating film can be broken. And salt content, moisture, oxygen, etc. infiltrate from this cracked part, and the steel material inside concrete may corrode. In this respect, the epoxy resin composition described in Patent Document 2 may have insufficient waterproof performance.

  This invention is made | formed in view of the said situation, The place made into the objective provides the primer for structure surface layers which can prevent the swelling of a coating film even if it exposes to an alkali component. That is.

  The present inventor has made extensive studies to solve the above-mentioned problems. As a result, a primer layer containing a polyurethane resin having at least one silanol group in the molecule is used, so that even if an alkali component touches, the primer layer The inventors have found that the coating film composed of the lining layer can be prevented from swelling, and have completed the present invention. Specifically, the present invention provides the following.

  (1) The present invention is a primer for a structure surface layer containing a polyurethane resin having at least one silanol group in the molecule.

  (2) Moreover, this invention is a primer for structure surface layers as described in (1) whose said polyurethane resin is a reaction material of a polyisocyanate component, a polyol component, and a hydrolysable silicon group containing compound. .

  (3) Moreover, this invention is a primer for structure surface layers as described in (2) whose said polyisocyanate component is alicyclic diisocyanate and whose said polyol component is a polyether-type polyol or a polyester-type polyol.

  (4) Moreover, this invention is a primer for structure surface layers in any one of (1) to (3) which further contains a strongly basic tertiary amine.

  (5) Further, in the present invention, a primer layer made of the primer for the structure surface layer according to any one of (1) to (4) is formed on at least a part of the tunnel lining segment body, The tunnel lining segment has a lining layer made of a lining material formed on the surface.

  (6) Further, the present invention is a tunnel in which a plurality of tunnel lining segments described in (5) are arranged.

  (7) Moreover, this invention applies primer for structure surface layers in any one of (1) to (4) to at least one part of a tunnel lining segment main body, and forms primer layer which forms a primer layer And a lining layer forming step of forming a lining layer by applying a lining material having a viscosity at 23 ° C. of 5 Pa · s or more to the surface of the primer layer. .

  ADVANTAGE OF THE INVENTION According to this invention, even if it touches an alkali component, the primer for structure surface layers which can prevent the swelling of a coating film can be provided.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

<Primer for structure surface layer>
The primer of the present invention is aqueous. This primer contains a polyurethane resin having at least one silanol group in the molecule (hereinafter also referred to as “silanol group-containing polyurethane resin”).

  The primer of the present invention is suitable for the surface layer of a structure. In the present specification, the “structure” includes both a partial portion for making up one thing and a finished product obtained by combining these partial portions. For example, a tunnel lining segment for making a tunnel, Includes both tunnels combined with segments.

[Silanol group-containing polyurethane resin]
The polyurethane resin having at least one silanol group in the molecule is obtained by, for example, reacting a hydrolyzable silicon group-containing compound having at least one active hydrogen group in the molecule with a polyurethane prepolymer, and It can be formed by dispersing or dissolving and hydrolyzing. The hydrolyzable silicon group refers to a group in which a hydrolyzable group that is hydrolyzed by moisture is bonded to a silicon atom. Specific examples of the hydrolyzable group include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, an amino group, an amide group, an aminooxy group, and a mercapto group. Of these, alkoxy groups are preferred because of their relatively low hydrolyzability and ease of handling. The hydrolyzable group is usually bonded to one silicon atom in the range of 1 to 3, but the reactivity, water resistance and solvent resistance of the hydrolyzable silicon group after coating are mentioned. To about 2 to 3 are preferable.

  Examples of the hydrolyzable silicon group-containing compound having at least one active hydrogen group in the molecule include γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ- (2-aminoethyl) aminopropyl. Triethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, γ- (2-aminoethyl) aminopropyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-amino Examples include propyldimethoxysilane, γ-aminopropyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropyldiethoxysilane. Effective by formation In that contributing, it is desirable to introduce silanol groups between molecules constituting a polyurethane resin, hydrolyzable silicon group-containing compound having two or more active hydrogen groups are preferred.

  The content of silanol groups or siloxane bonds is 0.1 to 10% by mass in terms of silicon with respect to the total solid content of the polyurethane resin in order to give the polyurethane resin excellent crosslinking reactivity and performance. If the amount is less than 0.1% by mass, the effect is low because it does not appropriately contribute to the crosslinking reaction, and if it exceeds 10% by mass, the effect is saturated and the stability of the primer for the structure surface layer decreases. Preferably it is 0.5-5 mass%.

  The polyurethane prepolymer can be obtained by reacting a compound having at least two active hydrogen groups per molecule with a polyisocyanate compound having at least two isocyanate groups per molecule.

  Examples of the compound having at least two active hydrogen groups per molecule constituting the polyurethane prepolymer include compounds having an amino group, a hydroxyl group and a mercapto group as the compound having an active hydrogen group. In view of the reactivity, a compound having a hydroxyl group is preferable because the reaction rate is high. Examples of the compound having at least two active hydrogen groups per molecule include polycarbonate polyol, polyester polyol, polyether polyol, polyester amide polyol, acrylic polyol, polyurethane polyol, and mixtures thereof. Among these, polycarbonate polyols, polyester polyols, and polyether polyols are preferable from the viewpoint of alkali resistance and the ability to contribute to the improvement of the crack followability of the lining material applied to the primer surface layer for the structure surface layer.

  Examples of the compound having at least two isocyanate groups per molecule include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2 Aliphatic isocyanates such as 1,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, For example, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate Tomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,2-bis (isocyanatomethyl) ) Cycloaliphatic diisocyanates such as cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, for example, m-xylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tri-isocyanate Aromatic diisocyanates such as diisocyanate, 4,4′-toluidine diisocyanate, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, and the like, for example, ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′- Aroaliphatic diisocyanates such as diisocyanate-1,4-dimethylbenzene and ω, ω′-diisocyanate-1,4-diethylbenzene, for example, triphenylmethane-4,4′-4 ″ -triisocyanate, 1,3 , 5-triisocyanatebenzene, 2,4,6-triisocyanate toluene and the like, for example, tetraisocyanate such as 4,4'-diphenyldimethylmethane-2,2 ', 5,5'-tetraisocyanate Containing polyisocyanate And polyisocyanate derivatives obtained from dimer, trimer, burette, allophanate or carbodiimide derived from the above polyisocyanate monomer and the above polyisocyanate monomer, such as ethylene glycol, propylene glycol, butylene glycol, etc. Adduct of the low molecular weight polyol having a molecular weight of less than 200 to the polyisocyanate monomer, and the polyisocyanate monomer such as polyester polyol, polyether polyol, polycarbonate polyol, polyester amide polyol, acrylic polyol, polyurethane polyol, etc. Examples include adducts.

  Moreover, in order to disperse the polyurethane resin in water, a hydrophilic group is introduced into the polyurethane prepolymer. In order to introduce a hydrophilic group, for example, the molecule has at least one active hydrogen group and contains a hydrophilic group such as a carboxyl group, a sulfonic acid group, a sulfonate group, or a polyoxyethylene group. What is necessary is just to copolymerize at least 1 sort (s) or more of a compound at the time of the said polyurethane prepolymer manufacture. Examples of the hydrophilic group-containing compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3, Carboxyl group-containing compounds such as 4-diaminobenzoic acid or derivatives thereof, or polyester polyols obtained by copolymerization thereof, maleic anhydride, phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Carboxyl group-containing compounds obtained by reacting a compound having an anhydride group with a compound having an active hydrogen group or derivatives thereof such as 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfo Sulfonic acid-containing compounds such as isophthalic acid and sulfanilic acid or these Derivatives, or these copolymerized polyester polyols obtained by the like.

[Neutralizer]
In the polyurethane resin, a neutralizing agent may be used in order to dissolve or disperse well in water. Examples of neutralizing agents that can be used in neutralization include tertiary amines such as ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine, and dimethylethanolamine, sodium hydroxide, potassium hydroxide, and calcium hydroxide. Basic substances such as alkali metal and alkaline earth metal hydroxides can be mentioned. From the viewpoint of weldability, solvent resistance, and odor during welding, tertiary amines having a boiling point of 120 ° C. or higher are used. preferable. These neutralizing agents may be used alone or in admixture of two or more. As a method for adding the neutralizing agent, the neutralizing agent may be added directly to the polyurethane prepolymer, or may be added to water when dissolved or dispersed in water. The addition amount of the neutralizing agent is 0.1 to 2.0 equivalents, more preferably 0.3 to 1.3 equivalents with respect to the carboxyl group.

[Surfactant]
In order to further improve the water solubility or dispersibility of the polyurethane prepolymer containing the carboxyl group, a surfactant may be used. Examples of such surfactants include nonionic surfactants such as polyoxyethylene nonylphenyl ether and polyoxyethylene-oxypropylene block copolymers, or anions such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate. A surfactant is used. However, in view of performance such as water resistance and solvent resistance, a soap-free type containing no surfactant is preferable.

[Organic solvent]
Moreover, when synthesizing the polyurethane prepolymer, an organic solvent can be used. When using an organic solvent, those having a relatively high solubility in water are preferred. Specific examples of such an organic solvent include acetone, ethyl methyl ketone, acetonitrile, N-methylpyrrolidone, and the like.

[Curing catalyst]
Further, a curing catalyst may be added to promote the formation of silanol group siloxane bonds of the polyurethane resin of the present invention. In the polyurethane resin according to the present invention, the strongly basic tertiary amine acts as a catalyst specifically for forming a siloxane bond without deteriorating water resistance and solvent resistance when the polyurethane resin is formed into a film. This makes it possible to efficiently introduce a crosslinked structure. This strongly basic tertiary amine is characterized by a pKa of 11 or more, in particular 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or 1,6-diazabicyclo [3. 4.0] Nonene-5 is preferably used. The strongly basic tertiary amine as the curing catalyst can be added during the synthesis of the polyurethane prepolymer, after the synthesis of the polyurethane prepolymer, or after the polyurethane prepolymer is dispersed or dissolved in water.

  Examples of the silanol group-containing polyurethane resin include Takelac (registered trademark) WS-6021, WS-5000, WS-5100, WS-4000 (all manufactured by Mitsui Chemicals).

[Dispersion stabilizer]
Moreover, in this invention, you may use various dispersion stabilizers in the range which does not inhibit the effect of this invention. Examples of the dispersion stabilizer include polyvinyl alcohol, fiber ether, starch, maleated polybutadiene, maleated alkyd resin, water-soluble polyester resin, water-soluble polyamide resin, water-soluble polyurethane resin, water-soluble acrylic resin, etc. Or can be used in combination of two or more. These may be added and used during the production of the polyurethane resin, or may be mixed after completion of the reaction.

[filler]
Moreover, in order to strengthen the primer layer obtained, to reduce the adhesiveness of the primer layer surface, and to improve the workability, a filler can be added to the primer composition for the structure surface layer. The blending amount of the filler is preferably 300 parts by weight or less, and preferably about 100 parts by weight with respect to 100 parts by weight of the silanol group-containing polyurethane resin (solid content). When the blending amount of the filler exceeds 300 parts by weight, adhesion of the primer layer to the concrete, elongation, and waterproof function may be impaired. Specific examples of the filler include cinnabar, talc, calcium carbonate, kaolin, gypsum, diatomaceous earth, titanium oxide, and one or more cements such as various Portland cement, blast furnace cement, and alumina cement. In addition, when mix | blending cement as a filler, the compounding quantity has preferable about 30 weight part with respect to 100 weight part of silanol group containing polyurethane resin (solid content). Further, if necessary, a surfactant, a viscosity stabilizer and the like up to about 5 parts by weight can be blended with 100 parts by weight of the silanol group-containing polyurethane resin (solid content).

[Flame retarding agent]
In order to impart flame retardancy to the primer layer, a vinylidene chloride polymer and / or a vinylidene chloride copolymer may be blended, or a compound having a triazine ring may be blended.

[Defoamer]
Furthermore, in this invention, it is preferable to mix | blend an antifoamer with the primer for structure surface layers, since the primer layer obtained can be used as a favorable primer layer without a pinhole and a bubble. The blending ratio of the antifoaming agent is preferably 0.1 to 1 part by weight, more preferably about 0.3 part by weight with respect to 100 parts by weight of the primer for the structure surface layer. Specific examples of the antifoaming agent include polyoxyalkylene fatty acid ester and polyether-modified siloxane.

[Method for producing primer]
In the production of the primer, the reaction sequence of these compounds and the addition timing of the strongly basic tertiary amine as a curing catalyst are not particularly limited, and examples thereof include the following production methods.

  A polyurethane prepolymer is produced by reacting an active hydrogen group-containing compound, a polyisocyanate compound, and a compound having a hydrophilic group in the molecule and having at least one active hydrogen group. Next, the hydrophilic group in the polyurethane prepolymer is neutralized with a neutralizing agent, a strong base tertiary amine is added as a curing catalyst, and the neutralizing agent and the polyurethane to which the strong basic tertiary amine is added. An aqueous composition of a polyurethane resin can be produced by dissolving or dispersing the prepolymer in water in which the hydrolyzable silicon group-containing compound and other chain extenders are dissolved.

<Tunnel lining segment>
In the tunnel lining segment of the present invention, a primer layer composed of the primer for the structure surface layer is formed on at least a part of the tunnel lining segment body, and a lining layer composed of a lining material is formed on the surface of the primer layer. The

[Lining layer]
The lining layer is made of a lining material. The type of the lining material is not particularly limited, and examples thereof include a modified silicone composition, a modified silicone / epoxy resin composition, and a polyurethane composition.

[Modified silicone composition]
The modified silicone composition used in the present invention refers to a curable composition containing a modified silicone as an essential component.

  As this modified silicone, JP-B-58-41291, page 3, column 6, line 29 to page 11, column 11, line 2, JP-A-52-73998, JP-A-58-10418, JP-A-58-10418 As disclosed in JP-A-62-230822 and JP-A-63-12777, organosilicon compounds having at least two silicon atoms bonded with hydrolyzable groups in the molecule, and JP-A-60- A composition comprising an oxyalkylene polymer having a silicon group and a (meth) acrylate (co) polymer having a silicon group, which has been proposed in JP-A Nos. 228516, 63-112642 and 1-131271 There is something like this.

  In particular, as disclosed in JP-A-63-112642, (a) an acrylic acid alkyl ester having a reactive silicon group and having a molecular chain substantially having (1) an alkyl group having 1 to 8 carbon atoms. A body unit and / or a methacrylic acid alkyl ester monomer unit, and (2) an acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms and / or a methacrylic acid alkyl ester monomer unit. And (b) a curable composition comprising an oxyalkylene polymer having a crosslinkable silicon group, an adhesive having excellent adhesive properties (such as tack range) can be obtained.

Here, the crosslinkable silicon group is a silicon-containing functional group that can be cross-linked by forming a siloxane bond, and a typical example is represented by the following general formula (1).

In Formula (1), R ¹ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ¹ _3. A triorganosiloxy group represented by SiO— (wherein R ¹ is the same as described above) is present, and when two or more R ¹ are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different. d represents 0, 1, 2, or 3, and e represents 0, 1, or 2, respectively. Further, p in the following general formula (2) need not be the same. p shows the integer of 0-19. However, d + (sum of e) ≧ 1 is satisfied.

  The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and d + (sum of e) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.

  The number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.

  As the crosslinkable silicon group, a crosslinkable silicon group represented by the following general formula (3) is preferable because it is easily available.

In formula (3), R ¹ and X are the same as above. d is an integer of 1, 2 or 3.

Specific examples of R ¹ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

  It does not specifically limit as a hydrolysable group shown by said X, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group, an amide group, and an aminooxy group are more preferable. An alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity increases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.

  In the case of the crosslinkable silicon group represented by the above formula (3), d is preferably 2 or more in consideration of curability. Usually, when d is 3, the curing rate is higher than when d is 2.

Specific structures of the crosslinkable silicon group include trialkoxysilyl groups [—Si (OR) ₃ ] such as trimethoxysilyl group and triethoxysilyl group, and dialkyl such as methyldimethoxysilyl group and methyldiethoxysilyl group. alkoxysilyl group ^[-SiR 1 _{(OR) 2]} and the like. Here, R is an alkyl group, preferably an alkyl group having 10 or less carbon atoms, and more preferably a methyl group or an ethyl group.

  Further, the crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group may be present in the main chain, the side chain, or both. It is preferable that a crosslinkable silicon group is present at the end of the molecular chain from the viewpoint of excellent cured product properties such as tensile properties of the cured product.

  The number of silicon atoms forming the crosslinkable silicon group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less.

  Among these polymers, tackifiers such as vinyl compounds such as vinyl chloride (co) polymers, phenol resin compounds, petroleum resins, terpene-phenol resins, rosin ester resins, etc., are proposed in JP-A-63-291918. Such a pre-reacted epoxy resin, a (meth) acrylate compound such as a butyl acrylate (co) polymer, or the like may be added as necessary.

[Modified silicone / epoxy composition]
The modified silicone / epoxy composition used in the present invention refers to a curable composition containing an epoxy resin and an amine as essential components in addition to the above-described modified silicone.

  This epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, etc., hydrogenated epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, urethane modified epoxy resin, nitrogen-containing epoxy resin , Epoxy resins derived from alcohols, polybutadiene, NBR, rubber-modified epoxy resins derived from terminal carboxyl groups NBR, flame retardant epoxy resins containing bromine, alicyclic epoxy resins, etc. It is not limited to this, and any epoxy resin that is generally known can be used.

  Moreover, the mixture with a monoepoxy compound for reducing the viscosity of the mixture of an epoxy resin and an epoxy resin can also be used.

  Examples of amines used in the present invention include primary amines, secondary amines, tertiary amines, polyamide amines, ketimines that generate amines upon encountering moisture, and enamines, but are not limited thereto. In addition, any generally known room temperature curing agent can be used. Moreover, what is necessary is just to use 1 type or in combination of 2 or more types as needed, and when hardening by heating, latent hardeners, such as a high melting point active hydrogen compound, can also be used.

  Primary amines include aliphatic diamines such as polymethylenediamine, polyetherdiamine, trimethylhexamethylenediamine, diethylaminopropylamine, aminoethylethanolamine, tri (methylamino) hexane, tetraethylenepentamine, bis (hexamethylene) triamine. Aliphatic polyamines such as mensene diamine, isophorone diamine, cyclic aliphatic polyamines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5,5] undecane, metaxylenediamine And aliphatic aromatic amines such as xylylenediamine, and aromatic diamines such as diaminodiethyldiphenylmethane and metaphenylenediamine.

  Examples of secondary amines include N-methylpiperazine, hydroxyethylpiperazine, piperidine, pyrrolidine, morpholine and the like.

  Tertiary amines include pendyldimethylamine, 2- (dimethylaminomethyl) phenol (DMP-10), 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30), triethanolamine, tetramethyl. Guanidine, pyridine, picoline, 1,8-diazabiscyclo (5,4,0) undecene-7 (DBU), N-methylmorpholine, triethylamine, N, N, N ′, N′-tetramethylpropanediamine, bis (2 -Dimethyldiaminoethyl) ether and the like.

  The polyamidoamine is typically produced by the reaction of a dimer acid (dimeric fatty acid) obtained by thermal polymerization of a refined vegetable oil fatty acid from drying oil, semi-drying oil, tall oil, etc. and an aliphatic polyamine. Any structure can be used as long as the functional group is an amide and an amine and the terminal is a primary amine or a secondary amine.

Any ketimine having at least one structure of the following formula (4) can be used as the ketimine.

In Formula (4), R ² and R ³ are hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

Any enamine can be used as long as it has at least one structure of the following formula (5).
-CH = N- (5)

  Examples of the high melting point active hydrogen compound of the latent curing agent include organic acid hydrazides such as dicyandiamide and adipic acid dihydrazide, diaminomaleonitrile, and melamine.

  In particular, when a latent curing agent such as ketimine, enamine, high melting point active hydrogen compound or the like is used, one solution can be obtained.

  If necessary, a diluent, a filler, an adhesion-imparting agent, a condensation catalyst, a thixotropic agent, a stabilizer, a moisture absorbent, a foaming agent, and the like can be blended with the above composition.

  Diluents include dibutyl phthalate and dioctyl phthalate, adipic acid esters such as di-2-ethylhexyl adipate, alkyl benzyl phthalates such as butyl benzyl phthalate, trimellitic acid ester, phosphoric acid ester, benzoic acid Examples thereof include plasticizers such as ester, phthalate polyester, adipic acid polyester, and epoxidized soybean oil, solvents such as methanol, ethanol, and toluene, high-boiling solvents, and reactive diluents.

  Examples of the filler include heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, kaolin, talc, silica, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, carbon black, glass balloon, and plastic balloon.

  Examples of the adhesion-imparting agent include various titanate or silashi coupling agents (aminosilane, epoxysilane, etc.), reaction products of coupling agents and isocyanate compounds, and reaction products of two or more types of coupling agents (for example, , Reaction products of various aminosilanes and epoxysilanes, condensation reaction products of two or more coupling agent alkoxy groups), and the like. These can be used alone or in combination.

[Polyurethane composition]
The polyurethane-based composition used in the present invention refers to a curable composition containing an active polyisocyanate and an isocyanate group-containing urethane prepolymer as essential components.

  These active polyisocyanates and isocyanate group-containing urethane prepolymers can be used as long as they are generally known, and are not particularly limited.

  Examples of the polyhydroxyl compound that is one production raw material of the polyurethane prepolymer include various polyether polyols, polyester polyols, polymer polyols, and the like that are generally used for the production of urethane compounds.

  The polyether polyol is, for example, a product obtained by addition polymerization of one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran to a compound having two or more active hydrogens. Here, examples of the compound having two or more active hydrogens include polyhydric alcohols, amines, alkanolamines, and polyhydric phenols.

  Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, and trimethylolpropane. Examples of the amines include ethylenediamine and hexamethylenediamine. Examples of the alkanolamines include ethanolamine and propanolamine. Moreover, resorcinol, bisphenols, etc. are mentioned as polyhydric phenols.

  Polyester polyol is a polyhydric alcohol and polybasic carboxylic acid condensate, a hydroxy carboxylic acid and polyhydric alcohol condensate, a lactone polymer, and the like. Examples of the polybasic carboxylic acids that have been exemplified above in the section of polyether polyol include adipic acid, glutaric acid, azelaic acid, fumaric acid, maleic acid, terephthalic acid, and dimer acid.

  Further, castor oil and a reaction product of castor oil and ethylene glycol are also useful as a condensate of hydroxycarboxylic acid and polyhydric alcohol.

  The lactone polymer is a product obtained by ring-opening polymerization of ε-caprolactone, α-methyl-ε-caprolactone or the like with an appropriate polymerization initiator.

  The polymer polyol is, for example, a polyether polyol or polyester polyol obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl (meth) acrylate, 1,2- or 1,4-polybutadiene polyol, Or these hydrogenated substances are said.

  Examples of the polyhydroxyl compound that is a raw material for producing the polyurethane prepolymer include those described above, and may be used alone or in combination of two or more, preferably those having a weight average molecular weight of about 100 to 10,000, More preferably about 5000. Examples of the polyisocyanate compound which is the other raw material for producing the polyurethane prepolymer include various compounds used for the production of ordinary polyurethane resins.

  Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, naphthylene-1,5-diisocyanate, and hydrogenating them. Compounds, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorazine isocyanate, triphenylmethane triisocyanate and the like.

  These polyisocyanate compounds may be used alone or in combination of two or more.

  Moreover, the manufacturing conditions of a polyurethane prepolymer are not specifically limited, The normal manufacturing conditions of a polyurethane prepolymer may be sufficient. That is, the reaction may be performed at a reaction temperature of about 50 to 100 ° C. under normal pressure.

  As a condensation catalyst, tertiary amines such as N-methylmorpholine, triethylamine, N, N, N ′, N′-tetramethylpropanediamine, bis (2-dimethylaminoethyl) ether are used for urethane prepolymer. And organic metal compounds such as lead octoate, lead naphthenate, tin octoate and dibutyltin dilaurate are used alone or in combination.

  For modified silicones, for example, organotin compounds, acidic phosphate esters, reaction products of acidic phosphate esters with amines, saturated or unsaturated polyvalent carboxylic acids, or acid anhydrides thereof, aluminum chelate compounds, organic Well-known silanol condensation catalysts, such as a titanate compound, are mentioned, What is necessary is just to use 1 type (s) or 2 or more types as needed.

  Specific examples of the organic tin compound include, for example, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanate (Dioctyltin diversate), dioctyltin oxide, reaction product of dioctyltin salt and normal ethyl silicate, tetravalent tin compound such as reaction product of dibutyltin oxide and phthalate ester, tin octylate, tin naphthenate, stearic acid Examples thereof include divalent tin compounds such as tin and tin dineodecanoate (tin versatate).

  Examples of the organic titanate compound include titanic acid esters such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate.

  Examples of the thixotropic agent include colloidal silica, hydrogenated castor oil, organic bentonite, tribenzylidene sorbitol, surface-treated precipitated calcium carbonate, and the like.

  Examples of the stabilizer include, for example, trade names of Irganox 1010 and 1076 (manufactured by Ciba Geigy), position hindered phenols such as Yoshinox BHT and BB, benzotriazoles such as Tinuvin 327 and 328 (Ciba Geigy), Sanol LS- Position-disordered amines such as 770 and 744 (manufactured by Ciba Geigy) and benzophenones such as Tomisap 800 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) are used.

  As the water absorbent, any active polyisocyanate and isocyanate group-containing urethane prepolymer, modified silicone storage stabilizer can be used, and any water absorbent that absorbs water such as a silane compound can be used. Possible and not particularly limited.

  In addition to these, active polyisocyanates and isocyanate group-containing urethane prepolymers, epoxy resins, modified silicones, amines, or those having the function of known inert inhibitors for condensation catalysts, etc., as necessary Can be used.

  As for the blending ratio of each component described above, the blending amount of 10 to 1000 parts of epoxy resin and 10 to 1000 parts of modified silicone can be applied independently to 100 parts of active polyisocyanate and isocyanate group-containing urethane prepolymer.

  The condensation catalyst mainly acts on active polyisocyanates and isocyanate group-containing urethane prepolymers or modified silicones, but may also act on epoxy resins depending on the type. The blending amount is preferably about 0 to 10 parts, and the blending amount varies depending on the type and combination of the cured compositions. Therefore, a preferable blending amount may be determined by confirming the performance each time.

  Amines may act as curing agents, curing aids, or curing accelerators, and in some cases as adhesion promoters.

  The blending amount varies depending on the type, the function, and the combination of the cured compositions. Therefore, a preferable blending amount may be determined by confirming the performance each time.

  Each of the active polyisocyanate and isocyanate group-containing urethane prepolymer, epoxy resin, modified silicone, amine, or condensation catalyst can be used independently or in combination of two or more types. Alternatively, it may be determined after confirming the performance.

[Film thickness]
The thickness of the lining layer after drying is preferably 0.20 to 1.00 mm. When the film thickness of the lining layer is less than 0.20 mm, it is not preferable because sufficient waterproof performance may not be obtained. On the other hand, if the film thickness of the lining layer exceeds 1.00 mm, it is not preferable because the labor of coating becomes complicated and the raw material cost of the coating material increases.

〔viscosity〕
The viscosity of the lining material is not particularly limited, but the viscosity at 23 ° C. is preferably 5 Pa · s or more, and more preferably 10 Pa · s or more. By being 5 Pa · s or more, the thickness of the lining layer can be set to a suitable thickness even if the number of times of applying the lining material is small (even once or twice). The manufacturing time of the engineering segment can be shortened.

  The upper limit of the viscosity at 23 ° C. is not particularly limited, but it is preferably 30 Pa · s or less because it tends to be applied with a roller brush, a trowel, or the like that is assumed as a lining material coating tool, More preferably, it is 20 Pa · s or less.

[Gas barrier properties]
In addition, since the lining layer has excellent gas barrier properties, it has a blocking property such as chlorine ions, an oxygen gas permeation preventing property, a water vapor permeation preventing property, and a carbon dioxide gas permeation preventing property.

<Method for manufacturing tunnel lining segment>
In the production method of the present invention, the primer for the structure surface layer is applied to at least a part of the tunnel lining segment body, the primer layer forming step for forming the primer layer, and the lining material is applied to the surface of the primer layer. Lining layer forming step of forming a lining layer.

  Since the primer applied in the primer layer forming step is the above-described primer for the structure surface layer, it is possible to prevent swelling of the coating film composed of the primer layer and the lining layer even if the primer is touched with an alkali component. Even if the viscosity of the lining material is high, the structure surface layer primer penetrates into the irregularities of the tunnel lining segment main body, so that the occurrence of pinholes in the lining material is suppressed, and the lining layer forming process continues with high viscosity. Even if this lining material is used, salt, moisture, oxygen, etc. can be prevented from entering from the pinhole.

The coating amount of the primer layer (DRY) ^is preferably ^{5g / m 2 ~50g / m 2} , more preferably ^{5g / m 2 ~30g / m 2} . When the coating amount (DRY) is less than 5 g / m ^2, it is not preferable in that the primer layer is inferior in environmental barrier properties. When the coating amount (DRY) exceeds 50 g / m ² , it is not preferable because it takes time and effort to apply the primer to the tunnel lining segment body, and the amount of the primer used becomes large.

  The viscosity of the primer is not particularly limited, but the viscosity at 23 ° C. is preferably 5 mPa · s to 250 mPa · s, and more preferably 15 mPa · s to 200 mPa · s. If the viscosity of the primer is too low, an effective coating thickness may not be ensured, which is not preferable. If the viscosity of the primer is too high, the primer does not penetrate into the irregularities on the surface of concrete or the like, and when a lining material is applied to the primer layer and dried, pinholes may be generated in the lining material, which is not preferable.

  The structure surface layer primer is dried in about 1 hour after coating even in winter. And in this invention, since it protected suitably using the primer for structure surface layers, even if it uses a highly viscous lining material, generation | occurrence | production of a pinhole can be suppressed and it has sufficient waterproof performance. Therefore, according to the present invention, the manufacturing time of the tunnel lining segment can be greatly shortened.

<Tunnel>
The tunnel of the present invention is obtained by arranging a plurality of the tunnel lining segments.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention does not receive a restriction | limiting at all by these description.

<Primer for structure surface layer>

In Table 1, examples and comparative examples are as follows.
Example 1: An aqueous dispersion of a polyurethane resin having at least one silanol group in the molecule (product name: Takelac WS-6021, solid content: about 30%, viscosity: 160 mPa · s (23 ° C.), Mitsui Chemicals, Inc. Made)
Example 2: A polyurethane resin diluted with the same volume of water (viscosity: 17.5 mPa · s (23 ° C.))
Comparative Example 1: One-part acrylic water-based sealer (Product name: Jolipat undercoat material JS-500, viscosity: 1570 mPa · s (23 ° C.), manufactured by Aika Kogyo)
Comparative Example 2: One-part aqueous multifunctional cationic sealer (product name: Miraxeal Eco, viscosity: 60 mPa · s (23 ° C.), manufactured by SK Kaken Co., Ltd.)
Comparative Example 3: Aqueous elastic sealer (product name: elastic sealer clear, viscosity: 30 mPa · s (23 ° C.), manufactured by SK Kaken Co., Ltd.)
Comparative Example 4: One-pack type epoxy-modified acrylic water-based sealer (product name: Super E, viscosity: 590 mPa · s (23 ° C.), manufactured by Kikusui Chemical Co., Ltd.)
Comparative Example 5: Epoxy resin emulsion two-component primer (Product name: EP primer EM, viscosity: 30 mPa · s (23 ° C.), manufactured by Cemedine)
Comparative Example 6: Water dispersion of polyurethane resin having no silanol group (Product name: Hydran HW-112, Viscosity: 150 mPa · s (23 ° C.), manufactured by DIC)

<Lining material>
[Synthesis of Polymer P1]
A methanol solution of sodium methoxide (NaOMe) was added to polyoxypropylene diol to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group to an allyl group. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added and reacted with methyldimethoxysilane, and the number average molecular weight in terms of PPG (polypropylene glycol) is about 38000, 2.0 per molecule. A polyoxypropylene polymer P1 having a terminal methyldimethoxysilyl group was obtained.

[Preparation of lining material]

In Table 2, various materials are as follows.
-Polymer P1: Polymer obtained by the above [Synthesis of polymer P1]-Fatty acid surface-treated calcium carbonate (product name: Calfine 200, manufactured by Maruo Calcium Co., Ltd.)
・ Heavy calcium carbonate (Product name: Whiteon SB, manufactured by Shiroishi Kogyo Co., Ltd.)
・ Coloring agent for urethane resin (Product name: FTR5570 Black, manufactured by Dainichi Seika Co., Ltd.)
・ Tetraethoxysilane (Product name: Ethyl silicate 28, manufactured by Colcoat Co.)
・ 3-Glycidoxypropyltrimethoxysilane (Product name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
A reaction product of MIBK (methyl isobutyl ketone) and 3-aminopropyltrimethoxysilane (product name: X12-812H, manufactured by Shin-Etsu Chemical Co., Ltd.)
-Reaction product of dioctyltin salt and normal ethyl silicate (Product name: Neostan S-1, manufactured by Nitto Kasei Co., Ltd.)

  Polymer P1, fatty acid surface-treated calcium carbonate, heavy calcium carbonate, and colorant for urethane resin were charged in the amounts shown in Table 2 and mixed and stirred. The mixture was heated to 100 ° C. and kneaded and dehydrated by mixing under reduced pressure for 2 hours. After cooling to room temperature, tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, a reaction product of MIBK (methyl isobutyl ketone) and 3-aminopropyltrimethoxysilane, and a reaction product of dioctyltin salt and normal ethyl silicate A lining material was obtained by charging the product in the amount shown in Table 2 and mixing and stirring. When the viscosity of the lining material at 23 ° C. was measured using a viscometer, it was 13 Pa · s.

[Conditions for alkali resistance test]
[Test place]
The test place (test room) is according to JIS K 5600-1-1: 1999 3.1.

[Test plate]
(1) Material and dimensions of test plate The test plate is a cement mortar plate prepared according to JIS R 5201: 1997, 10.4, and the size is 150 mm × 70 mm × 20 mm.
(2) Pretreatment of test plate Using a water-resistant abrasive paper No. 150 specified in JIS R 6253: 2006, the surface used for the test is sufficiently removed of fragile materials and powdered materials and wiped with a soft clean cloth. At this time, it is confirmed that the surface moisture content index is 10% or less.

[Preparation of test piece]
The test plate, primer, and lining material are placed in the test chamber and adjusted until they are not affected by temperature fluctuations before application.
And the said primer was apply | coated to one side of the said test board so that application quantity (DRY) might be 15 g / m < ² >, and it dried at 23 degreeC50% RH for 24 hours, and formed the primer layer.
Subsequently, the lining material was applied onto the primer layer so that the thickness after drying was 0.27 mm, and dried at 23 ° C. and 50% RH for 1 week to form a lining layer. Three test pieces were prepared.

[Alkali resistance test]
After the test piece was cured in a curing room for 7 days, it was placed in a calcium hydroxide saturated solution (23 ± 2 ° C.) prepared using calcium hydroxide as defined in JIS K 8575: 1994 (calcium hydroxide (reagent)). Soaked for 30 days. The test method is in accordance with JIS K 5600-6-1: 1999, paragraph 7. The case where there was no bulge was designated as “◯”, the case where there was a minute bulge having a diameter less than 3 mm was designated as “Δ”, and the case where there was a large bulge having a diameter of 3 mm or more was designated as “X”. The results are shown in Table 3.

  When a primer for a structural surface layer containing a polyurethane resin having at least one silanol group in the molecule is used, swelling of the coating film can be suitably prevented even when exposed to an alkali component (Examples 1 and 2).

  On the other hand, when a composition different from a polyurethane resin having at least one silanol group in the molecule is used as a primer, the coating film swells when the coating film is exposed to an alkali component, and the lining material may be cracked by this swelling. And salt content, a water | moisture content, oxygen, etc. infiltrate from this cracked part, and the steel materials inside concrete may corrode (Comparative Examples 1-6).

[Crack following test]
Moreover, the crack followable | trackability was evaluated using the primer which concerns on Example 2, and the said lining material. The evaluation of the crack followability was performed according to the JSCE-K 532-2010 method (crack followability test method for surface coating material) described in the Standard Specification for Concrete (Edited by Japan Society of Civil Engineers). The application amount and curing period of the primer layer and the lining layer are the same as the above [Conditions for Alkali Resistance Test]. The crack followability when using the primer described in Example 2 was 0.64 mm. Therefore, when the primer described in the Example was used, good crack followability was obtained, and as a result, it was confirmed that it was suitable for a tunnel lining segment.

Claims (5)

  A tunnel lining segment primer containing a polyurethane resin having at least one silanol group in the molecule and a strongly basic tertiary amine.   The tunnel lining segment primer according to claim 1, wherein the polyurethane resin is a reaction product of a polyisocyanate component, a polyol component, and a hydrolyzable silicon group-containing compound.   The tunnel lining segment primer according to claim 2, wherein the polyisocyanate component is an alicyclic diisocyanate, and the polyol component is a polyether polyol or a polyester polyol. A primer layer made of the tunnel lining segment primer according to any one of claims 1 to 3 is formed on at least a part of the tunnel lining segment body, and a lining layer made of a lining material is formed on the surface of the primer layer. Tunnel lining segment that has been. Applying the tunnel lining segment primer according to any one of claims 1 to 3 to at least a part of the tunnel lining segment body, a primer layer forming step of forming a primer layer;
A lining layer forming step of forming a lining layer by applying a lining material having a viscosity at 23 ° C. of 5 Pa · s or more to the surface of the primer layer;
A method for manufacturing a tunnel lining segment, comprising: