JPH1071661A - Execution of waterproof material and waterproof layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a waterproof material equipped with execution properties and walking propertires by forming the waterproof material from a hard surface layer consisting of a photro-setting resin compsn. and a fiber reinforcing material and a relatively soft rear surface layer. SOLUTION: Two kinds of photosetting resin compsns. 1, 2 are preliminarily prepared. These resin compsns. 1, 2 and chopped strands 5 obtained by cutting glass rovings 3 as a fiber reinforcing material by a chopper 4 are supplied to the gap between continuously taken-up lower and upper shading films 6, 7 in a predetermined ratio. Subsequently, the resin compsn. 1 for a soft rear surface layer and the resin compsn. 2 for a hard surface layer are infiltrated into the chopped strands 5 by a compression roller 8 to obtain a waterproof material 9.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel waterproofing material and a method for installing a waterproofing layer in civil engineering buildings. More specifically, it relates to a method for forming a waterproof layer in a short time by a simple laying operation and light irradiation, and a waterproof material which generates less odor of a polymerizable monomer during the operation and has less environmental pollution such as scattering of chips of a fiber reinforced material. Things.

[0002]

2. Description of the Related Art Conventionally, metal structures such as roofs of concrete structures such as condominiums and apartments, verandas of wooden structures such as verandas, detached houses and bridges, etc., are provided with asphalt-based waterproofing materials for the purpose of preventing water leakage. Waterproofing works using waterproofing materials described in JASS8 waterproofing work (published by the Architectural Institute of Japan) such as polymer sheet waterproofing material or paint film waterproofing material represented by polyurethane resin. Have been done. By the way, the above-mentioned various waterproofing materials have excellent waterproofing performance, but in the waterproofing material and the waterproofing layer, not only waterproofness but also walking property, corrosion resistance, heat insulation, sound insulation, workability and design, and Since various performances such as economy are required, they are properly used depending on purposes and applications.

[0003] Asphalt waterproofing materials are most widely used because of their reliability due to their thickness and their low cost. However, it is not suitable for walking as an exposed waterproofing, and it is necessary to provide a hard protective layer like the holding mortar method, so it takes a lot of construction time and cost, and 120 kg /
Since a load close to m ² is applied, excessive frame strength is required. Synthetic polymer sheet waterproofing material is excellent in terms of short construction time and reliability of thickness from factory production. However, it has the drawback of requiring the smoothness of the groundwork at the time of construction, and because of its low surface hardness and poor adhesion to the groundwork, it is necessary to use an asphalt-based waterproofing material to form a waterproofing layer for walking. It is necessary to form a protective layer in the same manner as described above.

[0004] On the other hand, a waterproof coating material is an excellent waterproof material which is excellent in design properties and adaptability to a base material, and which can secure walking strength, surface hardness and adhesion even with exposure waterproofing by selecting a material type. A polyurethane resin waterproofing material is most widely used as the coating waterproofing material, but in recent years, an FRP waterproofing material having a higher walking performance comprising an unsaturated polyester resin and a glass fiber reinforced material has also become widespread. FRP waterproofing material is a waterproofing material suitable for forming a waterproofing layer for walking because it has excellent water resistance and corrosion resistance, and also has a large base adhesion, strength and high surface hardness (Japanese Patent Laid-Open No. 4-142323, etc.). ). However, since these coating waterproofing materials are of the in-situ reaction type, it is difficult to control the curing reaction due to the influence of the temperature and the like, and it is difficult to ensure uniformity of the thickness of the waterproofing layer. In the waterproofing operation using the FRP waterproofing material, the step of laminating the resin and the fiber reinforced material in the atmosphere is repeated a plurality of times, and the waterproofing layer is formed through the curing of the resin. At this time, there are problems of environmental pollution such as generation of odor of volatile solvents and monomers contained in resins, primers and the like, and scattering of chips of the fiber reinforcing material.
Further, the ability to follow the base crack is poor, and the zero-span tension generated at the crack causes a break in the waterproof layer, and there is a high risk of causing a water leakage trouble. JP-A-63-186744 discloses a light-curable resin-reinforced plastic prepreg sheet for these coating film waterproofing materials, and describes application to waterproofing applications. The prepreg sheet is an excellent material which has less environmental problems such as scattering of glass chips and odor of monomer and which is quick and easy to perform. However, FR that follows the crack
It has the drawback of P waterproofing material and breaks the waterproofing layer.

On the other hand, Japanese Patent Laid-Open No. 1-219242 discloses that
A composite construction method of an FRP layer and a polyurethane resin layer is disclosed. This is an excellent waterproofing method that combines the advantages of both waterproofing materials, but the difficulty of controlling the curing reaction of conventional waterproofing materials and the unevenness of the thickness of the waterproofing layer have not been eliminated. It has drawbacks such as a long construction period due to multiple layers.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a waterproofing material for civil engineering buildings and waterproofing construction, in which a waterproofing material such as water resistance, weather resistance, substrate adhesion, strength, and substrate crack following ability is used. It is an object of the present invention to provide a waterproof material which sufficiently satisfies the required performance, and also has a workability, a walkability, an improvement of a working environment, a design property, and the like, and a method of constructing the waterproof material.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, they have two layers composed of a photocurable resin composition and a fiber reinforcing material, and have different hardnesses during curing. Has been found to be effective. As a result of further studies, the present inventors have found that a waterproof material formed by a front layer made of a hard layer and a back layer made of a relatively soft layer is particularly effective. That is, these waterproofing materials have the advantages of FRP waterproofing materials such as high strength, surface hardness, adhesiveness to base and designability, and the advantage of the thickness reliability of the waterproof layer, which is the advantage of synthetic polymer sheet waterproofing materials. The present invention has been found that a multi-layer waterproofing material that is effective in achieving a short-time construction by light curing and has high base crack following properties is effective.

In the above-described light-curable sheet-shaped waterproof material of the present invention, the waterproof material formed by the front layer made of the hard layer and the back layer made of the soft layer is formed by the following technical concept. Things. First, a fiber reinforcement (B) is dispersed in one layer composed of two types of photo-curable thermosetting resin compositions A ₁ and A ₂ having the same or different viscosities, so that the hardness differs. A sheet-like waterproof material obtained by forming two layers. Second, a sheet-like waterproofing material obtained by integrating a plurality of hard photocurable fiber-reinforced thermosetting resin composition layers (C) and a soft synthetic polymer sheet layer (D). Third, a sheet-like waterproof material obtained by generating a density distribution of the fiber reinforcing material (B) in a thickness direction of a sheet formed of one type of photocurable thermosetting resin composition. The photocurable sheet-like waterproofing material of the present invention is a waterproofing material obtained by the above-described method, and a waterproofing material obtained by combining these forming methods is also included in the present invention.

That is, according to the present invention, a fiber reinforcing material (B) is dispersed in a resin composition (A) containing a thermosetting resin, a photopolymerization initiator, and a thickener, and the surface layer and the back layer are cured at the time of curing. A photocurable sheet-like waterproof material formed so as to have different hardness is provided. In the above-mentioned light-curable sheet-like waterproof material, it is preferable that the surface on the side which is brought into close contact with the application base is a soft layer, and the back surface on the opposite side is a hard layer. In this case, the relationship between the thickness (T ₁ ) of the soft layer and the thickness (T ₂ ) of the hard layer is 10% <(T ₂ ) / [(T ₁ )
+ (T ₂ )] <85%. Generally, the thermosetting resin is selected from the group consisting of unsaturated polyester resins, vinyl ester resins and vinyl urethane resins. The resin composition (A) is the viscosity of forming a soft layer (eta ₁₎ is 10 ² ~10 ⁵ Pa · s resin composition is (25 ℃) (A ₁₎
And the viscosity (η ₂ ) for forming the hard layer is 10 ³ to 10 ⁶ Pa · s (25
Preferably a ° C.) resin composition is (A _2). Further, according to the present invention, a fiber reinforcing material (B) is dispersed in a resin composition (A) containing a thermosetting resin, a photopolymerization initiator and a thickener to form a surface layer, and a synthetic polymer sheet ( A light-curable sheet-like waterproof material in which D) is formed as a soft layer and integrated into a plurality of layers is provided. The above-mentioned synthetic polymer sheet layer (D)
Is preferably a vulcanized rubber type, non-vulcanized rubber type, vinyl chloride resin type, ethylene vinyl acetate resin type or urethane rubber type sheet. This synthetic polymer sheet layer (D)
Is a perforated body, and the perforated area is preferably in the range of 2 to 80% with respect to the entire area of (D). Further, according to the present invention, a fiber reinforcement (B) is densely dispersed in a surface layer of a resin composition (A) containing a thermosetting resin, a photopolymerization initiator, and a thickener to form a hard layer, A light-curable sheet-like waterproof material is provided, in which a soft layer is formed by roughly dispersing the back layer. Further, according to the present invention, a fiber reinforcement (B) is dispersed in a resin composition (A) containing a thermosetting resin, a photopolymerization initiator, and a thickener, and the hardness of the front layer and the back layer during curing is increased. A hard layer that acts as a fiber-reinforced waterproof layer by laying and rolling a light-curable sheet-like waterproof material formed differently so that the side to be closely adhered and cured to the construction substrate is a soft surface, and light-cured in the adhered state. And forming a soft layer acting as a buffer layer at the same time.

According to the waterproofing material and the waterproofing construction method of the present invention, a high-performance waterproofing layer is formed on the surface of a civil engineering building in a short time of about 30 minutes and with a small number of man-hours without polluting the working environment. be able to. In addition, the waterproof layer itself has the performance originally required, that is, it has water resistance, weather resistance and adhesion to the substrate, and has a design property, and of course, it can walk on the waterproof layer at the time of construction due to its high surface hardness. And has excellent base crack followability.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, the viscosity (η) of the resin composition (A) means that the prepared resin composition is placed in a 500 ml-volume can and left at 40 ° C. for 24 hours for aging. After cooling, the composition was cooled to room temperature.
H-type) (Pa · s (25 ° C.)). (Meth) acrylic acid, (meth) acrylate, (meth)
Acrylonitrile means methacrylic acid, acrylic acid; methacrylate, acrylate; methacrylonitrile, and acrylonitrile, respectively.

Hereinafter, the present invention will be described in detail. I. First, various materials used in the present invention will be described. 1. Resin composition (A) The resin composition (A) contains a thermosetting resin (a), a photopolymerization initiator (b) and a thickener (c). (1) Thermosetting Resin (a) As the thermosetting resin (a), a radical polymerization type resin is preferable from the viewpoint of curing speed and physical properties of a formed waterproof layer. For example, unsaturated polyester resin, vinyl ester resin and Vinyl urethane resin; (i) The unsaturated polyester resin is produced by polycondensation of an α, β-unsaturated dibasic acid or an acid anhydride thereof with a glycol, and optionally an aromatic, aliphatic or alicyclic acid component. Unsaturated polyester 30 to be produced in combination with a saturated dibasic acid or their acid anhydride
The thermosetting resin composition is preferably composed of a liquid obtained by mixing 70 to 20 parts by weight of a polymerizable monomer with 80 parts by weight.

Here, the α, β-unsaturated dibasic acid or acid anhydride thereof includes maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid and esters thereof; Examples of dibasic acids or acid anhydrides thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and esters thereof; As aliphatic or alicyclic saturated dibasic acids or their anhydrides, oxalic acid, malonic acid, succinic acid,
Adipic acid, sebacic acid, azelaic acid, glutaric acid,
Examples include hexahydrophthalic anhydride and esters thereof. These may be used alone or in combination of two or more.

The glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-butanediol,
Neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-
Hexanediol, bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct,
Hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl)
And propane. These may be used alone or in combination of two or more. In addition to these, oxides such as ethylene oxide (EO) and propylene oxide (PO) can also be used. Polycondensates such as polyethylene terephthalate can also be used as a part of the glycols and acid components. Further, a resin obtained by reacting a terminal carboxyl group of an unsaturated alkyd resin synthesized from a glycol and an acid with a reactive monomer having a glycidyl group can also be used. A typical example of the reactive monomer having a glycidyl group is glycidyl (meth) acrylate.

(Ii) As the vinyl ester resin, the polymerizable monomer 70 is added to 30 to 80 parts by weight of an epoxy vinyl ester in which the terminal of an unsaturated polyester is vinyl-modified or 30 to 80 parts by weight of an epoxy vinyl ester in which the epoxy skeleton of the epoxy resin is vinyl-modified. It is preferable that the composition is a thermosetting resin composition composed of a liquid obtained by mixing up to 20 parts by weight. The vinyl ester referred to here is more specifically a bisphenol-type epoxy resin, a resin alone or a mixture of a novolak-type epoxy resin, and has an average epoxy equivalent of 150 to 450.
It refers to an epoxy vinyl ester obtained by reacting an epoxy resin in the g / eq range with an unsaturated monobasic acid in the presence of an esterification catalyst.

Here, the bisphenol type epoxy resin is a glycidyl ether type epoxy resin obtained by reacting epichlorohydrin with bisphenol A or bisphenol F and having substantially two or more epoxy groups in one molecule. A dimethylglycidyl ether type epoxy resin obtained by reacting methyl epichlorohydrin with bisphenol A or bisphenol F;
An epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methylepichlorohydrin may, for example, be mentioned. Examples of the novolak type epoxy resin include an epoxy resin obtained by reacting phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin. Representative examples of unsaturated monobasic acids include (meth) acrylic acid, cinnamic acid, crotonic acid, monomethylmalate, monopropylmalate, monobutylmalate, sorbic acid, and mono (2-ethylhexyl) malate. There is. These may be used alone or in combination of two or more.

(Iii) The vinyl urethane resin includes a compound having an isocyanate group at a terminal obtained by adding a polyisocyanate compound to a terminal hydroxyl group of a polyether polyol and / or a polyester polyol, and a hydroxyl group in one molecule. It is preferable that the composition is a thermosetting resin composition comprising a liquid in which 70 to 20 parts by weight of a polymerizable monomer is mixed with 30 to 80 parts by weight of vinyl urethane obtained by reacting a compound having a double bond with a compound having a double bond. Here, as polyether polyols, number average molecular weight 400 ~
4,000 polypropylene glycols, polyethylene glycols, etc .; Polyester polyols include maleic acid, fumaric acid, adipic acid, dibasic acid and other dibasic acids alone or in combination with ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, etc. Polyester polyol having a hydroxyl group at a terminal obtained by reaction with a glycol alone or as a mixture; as polyisocyanate compounds, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, Hexamethylene diisocyanate; Examples of the compound having a hydroxyl group and a double bond in one molecule include hydroxyethyl acrylate and hydroxyethyl methacrylate.

(Iv) The polymerizable monomers in the radically polymerizable resins exemplified above include styrene, vinyl toluene, α-methyl styrene, chlorostyrene, dichlorostyrene, vinyl naphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl (meth) ) Vinyl compounds such as acrylate, ethyl (meth) acrylate and (meth) acrylonitrile; allyl compounds such as diallyl phthalate, diallyl fumarate, diallyl succinate, triallyl cyanurate; crosslinkable with unsaturated polyester, vinyl ester or vinyl urethane Vinyl oligomers and the like. Of these, styrene is generally used. These may be used alone or in combination of two or more.

(2) Photopolymerization initiator (b) (i) As the photopolymerization initiator (b), benzophenone compounds: benzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-methylbenzophenone, 4-methyl Benzophenone, β-naphthylphenylketone, 2-benzoylthiophenone, methyl methyl orthobenzoylbenzoate, 2-benzoylpyridine, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc., benzyl compounds: benzyl, 4 Xanthone compounds such as -chlorobenzyl and 4-methylbenzyl: xanthone, 2-chloroxanthone, 2-
Thioxanthone compounds such as isopropylxanthone:
Anthraquinone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone: anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 1-chloroanthraquinone, 9-fluorene, etc., acetophenone-based compounds: acetophenone, 4-methylacetophenone, 4-isopropylacetophenone, 4-chloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2,2,2-trichloro-4'-tert-butylacetophenone, Oxime compounds such as 2,2-dichloro-4'-phenyloxyacetophenone: 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1-phenyl-
Acylphosphine oxide compounds such as 1,2-propanedione-2- (o-ethoxycarbonyl) oxime: 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,
Examples include 4,6-trimethylbenzoyl-phenyl-phosphinic acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, bisacylphosphine oxide, and the like, and mixtures thereof.

(Ii) The amount of the photopolymerization initiator (b) used is as follows:
0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, per 100 parts by weight of the thermosetting resin (a) can be used. If the amount is less than 0.1 part by weight, the resin composition will not be sufficiently cured, and if it exceeds 10 parts by weight, the strength of the cured product and the gel fraction (standard of reaction) will be reduced, which is not preferable in terms of physical properties.

(3) Thickener (c) (i) As the thickener (c), inorganic compounds such as magnesium oxide, magnesium hydroxide and calcium oxide; xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, etc. Isocyanate compounds; aluminum chelates such as ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetonate) Compounds. (ii) The amount of the thickener (c) is generally 0.5 to 2 parts by weight based on 100 parts by weight of the thermosetting resin (a).
Is not necessarily limited to this amount, since the thickening characteristics vary depending on the type of the resin.

2. Fiber Reinforcing Agent (B) Examples of the fiber reinforcing material (B) include glass fibers; organic fibers such as amide, aramid, vinylon, polyester, and phenol; carbon fibers, metal fibers, and ceramic fibers or a combination thereof. Considering workability and economical efficiency, glass fibers or organic fibers are preferred. The fiber form of the fiber reinforcing material (B) is plain weave, satin weave, non-woven fabric, mat shape, etc. Among them, the mat shape is preferable from the viewpoint of the construction method, the maintenance of the thickness and the like. Alternatively, the glass roving may be cut to a length of 20 to 100 mm and used as a chopped strand. Further, a mat and a chopped strand can be used together.

3. Polymerization diluent, filler, etc. In the present invention, in addition to the above-mentioned resin composition (A) and fiber reinforcing material (B), known polymerization diluents, fillers and the like can be used as necessary.

(1) As a polymerization diluent, vinyl compounds such as styrene, vinyltoluene, vinylpyrrolidone, vinylcaprolactam and divinylbenzene; butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofuran Furyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy EO-modified (meth) acrylate, phenoxy PO-modified (meth) acrylate, nonylphenoxy EO or P
Mono (meth) acrylate compounds such as O-modified (meth) acrylate; 1,6-hexanediol diacrylate;
Polyvalent (meth) acrylate compounds such as trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate; (meth) acrylates modified with ethylene oxide and propylene oxide; and (meth) acrylates of polyethylene glycol and polypropylene glycol. Can be The amount used is preferably from 0 to 30 parts by weight based on 100 parts by weight of the thermosetting resin (a), and if it exceeds 30 parts by weight, it becomes difficult to adjust the viscosity.

(2) As the filler, aluminum hydroxide, calcium carbonate, calcium hydroxide, glass powder,
Glass beads and the like can be mentioned. In order to facilitate the photocuring reaction, among these, those having high transparency are preferable, and the amount used is 0 to 150 parts by weight per 100 parts by weight of the thermosetting resin (a).
Parts by weight are preferred. If the amount exceeds 150 parts by weight, it becomes difficult to integrate with the fiber reinforcing material, and the tensile strength is greatly reduced.

II. Secondly, a waterproofing material according to the present invention, a method for manufacturing the same, and a waterproofing method using the same will be described.

II-1. Waterproofing material (X) (1) As one typical waterproofing material in the present invention, a photocurable sheet-like waterproofing material comprising a resin composition (A) and a fiber reinforced material (B) will be described. Specifically, 50 to 97 parts by weight of a resin composition (A) containing a thermosetting resin (a), a photopolymerization initiator (b) and a thickener (c) and 50 to 3 parts by weight of a fiber reinforcing material (B) Is formed into a sheet of a photocurable fiber-reinforced thermosetting resin composition (C) (hereinafter sometimes abbreviated as resin composition (C)), which has a total thickness of 0.5.
5.05.0 mm, preferably 1.0-5.0 mm.

With respect to the composition of the resin composition (A) and the fiber reinforced material (B), a waterproof material obtained when the fiber reinforced material (B) is less than 3 parts by weight with respect to 100 parts by weight of the thermosetting resin (a). There is a danger that cracks will occur in the waterproof layer due to large curing shrinkage, and if it exceeds 50 parts by weight, the surface of the waterproof layer has a glass grain, which is not preferable in appearance. On the other hand, if the thickness of the entire sheet is less than 0.5 mm, it is difficult to obtain the strength that can withstand the intended walking, and if it exceeds 5.0 mm, the curing by light irradiation becomes insufficient, so that the inside of the sheet does not completely cure,
There is a disadvantage that the sheet itself is warped due to curing shrinkage, which is not preferable.

By the way, the waterproofing material of the present invention has two contradictory properties, namely softness and hardness, which directly lead to the adhesion to the waterproofing base, that is, the workability for riding, especially when the construction work is taken into consideration. There is a need. Here, the riding workability means that when laying a waterproofing material on a base and rolling it, the operator rides directly on the uncured waterproofing material, at which time footprints are left on the waterproofing material surface. This refers to the performance of a waterproof material that does not cause appearance defects such as transfer of the shape of a rolling jig such as a roller.

Therefore, one typical waterproofing material in the present invention comprises two layers derived from two kinds of resin compositions (A ₁ ) and (A ₂ ) having the same or different viscosities as follows. Is done. That is, the viscosity (η ₁ ) of the resin composition (A ₁ ) constituting the soft layer in contact with the substrate side is 10 ² to 10 ⁵ Pa · s.
(25 ° C.), and the viscosity (η ₂ ) of the resin composition (A ₂ ) constituting the hard layer coming to the atmosphere side is preferably in the range of 10 ³ to 10 ⁶ Pa · s (25 ° C.). Here, the resin composition and the viscosity of _{(A 1) (η 1)} , viscosity of the resin composition (A ₂₎ (η ₂₎ is
Preferably, both are in the range of 10 ³ to 10 ⁵ Pa · s (25 ° C.) (provided that η ₁ ≦ η ₂ ). The thickness occupied by the hard layer in the waterproof material is preferably in the range of 10% <hard layer / (soft layer + hard layer) <85%.

In the present invention, if the viscosity (η ₁ ) of the resin composition (A ₁ ) is less than 10 ² Pa · s, the releasability of the light-shielding film becomes extremely poor, and if it exceeds 10 ⁵ Pa · s, the waterproofing material and the substrate Adhesion with the side significantly decreases. On the other hand, when the viscosity (η ₂ ) of the resin composition (A ₂ ) is less than 10 ³ Pa · s, the riding workability during waterproofing is deteriorated, and when the viscosity exceeds 10 ⁶ Pa · s, the rolling pressure during the rolling work is increased. However, it is difficult to reach between the waterproof material and the substrate side, so that the adhesion tends to be insufficient. In addition, when the construction surface of the base is poor in smoothness, the waterproof material cannot follow the shape of the base, and an unbonded portion is easily generated between the waterproof material and the base.
Further, even when η ₁ and η ₂ are in the range of 10 ³ to 10 ⁵ Pa · s, when η ₁ > η ₂ , wrinkles are likely to be generated on the surface after curing of the resin composition, which is not preferable in appearance.

(2) Method for Producing Waterproofing Material A typical method for producing a waterproofing material in the present invention is to use a sheet molding compound (hereinafter abbreviated as SMC) impregnating machine. FIG.
It will be described according to. As described above, 2 having a predetermined viscosity
A resin composition (A ₁ ) 1 and a resin composition (A ₂ ) 2 are prepared in advance. These resin composition (A ₁ ) 1, resin composition (A ₂ ) 2 and chopped strand 5 obtained by cutting glass roving 3 with chopper 4 as fiber reinforcing material (B) are continuously wound at a predetermined ratio. Is supplied between the lower light-shielding film 6 and the upper light-shielding film 7. Next, the resin composition (A ₁ ) 1 and the resin composition (A ₂ ) 2 are impregnated into the chopped strand 5 with the compression roller 8,
Waterproof material 9 having a two-layer structure in a sheet shape having a predetermined thickness
Get. The total thickness of the waterproof material 9, that is, the thickness of the soft layer (derived from the resin composition (A ₁ )) and the thickness of the hard layer (derived from the resin composition (A ₂ )) are each It is adjusted by the blade 10 and the doctor blade 11.
The waterproofing material of the present invention obtained as described above is in the form of a two-layer sheet, and it is preferable that both outer surfaces of the waterproofing material are protected by light-shielding films 6 and 7.

(3) Waterproofing Method A waterproofing method using the waterproofing material will be described with reference to FIGS. That is, only the light-shielding film 6 of the soft layer of the waterproof material (the one in contact with the substrate side) is peeled off, and this surface is directly placed on the substrate 15 or the primer layer 14.
And roll it with rollers or the like. Next, the light-shielding film of another hard layer (the one that comes to the atmosphere side) of the waterproof material is peeled off, cured with sunlight or the like, and a waterproof layer is formed on the base. Here, as the primer layer 14, a known primer such as a one-component moisture-curable urethane resin, a two-component urethane resin, an epoxy resin, and an unsaturated polyester resin can be used. The structure formed after the application is the same as the primer layer 1 if there is a primer layer on the base 15.
4, a buffer layer 13 derived from the soft layer is formed,
It has a structure in which a waterproof layer 12 derived from a hard layer is formed thereon.

Since the waterproofing material of the present invention is a photo-curing type, the sheet layer of the resin composition (C) can be formed by a known light irradiation at the time of construction.
For example, it can be cured by using sunlight, ultraviolet light or visible light of 200 to 800 nm, or the like. In the case of sunlight, it cures in a short time of about 30 minutes and can form a waterproof layer.
During curing, it is hardly affected by temperature and weather (solar radiation)
For example, even in sunlight having a temperature of about 10 to 30 ° C. and an insolation of about 10 watt / m ² (when cloudy), the inside of the waterproof material can be completely cured in about the same time. Incidentally, since the conventional FRP waterproofing material is a thermosetting type, the curing time is greatly affected by the temperature. For example, when the temperature is 10 ° C. and 30 ° C., the curing speed changes nearly ten times. In the waterproofing material of the present invention, it is preferable that both outer surfaces are protected by a light-shielding film so that the photopolymerization reaction does not start until waterproofing is performed.

In the waterproofing work of the present invention, when the waterproofing material is laid and compacted, the volatilization of the solvent and the polymerizable monomer in the waterproofing material is largely suppressed by the remaining air-side light-shielding film, and the light-shielding film is peeled off. Since the hardening from the surface layer of the waterproofing material is fast even after this, the volatilization of the polymerizable monomer is extremely reduced. In order to further suppress volatilization of the polymerizable monomer, another film that can transmit sunlight or the like is provided between the waterproof material and the light-shielding film on the atmosphere side, and the light-transmissive film is left when cured by sunlight or the like. Alternatively, a method of peeling the film after curing may be adopted. Further, since the waterproofing material of the present invention contains a fiber reinforced material in advance, unlike the general construction method in which the fiber reinforced material is cut and layered on the resin layer while cutting the fiber reinforced material, the chipping in the waterproofing work is performed. Needless to say, the problem of scattering of air does not occur. In addition, in the case of ordinary synthetic polymer sheet, at the time of construction, there is a distinct step at the joint part of the sheet, whereas in the case of the waterproof material of the present invention, the wrap disappears due to the rolling work,
It has a flat finish like waterproof coating. That is, the present invention is also excellent in design.

II-2. Waterproofing material (Y) Next, as another typical waterproofing material in the present invention, a photocurable fiber-reinforced thermosetting resin composition (C) and a synthetic polymer-based sheet layer (D) were integrated in multiple layers. A waterproof material, a method of manufacturing the waterproof material, and a waterproof construction method using the waterproof material will be described. As the resin composition (C), those having substantially the same quality as the resin composition (A ₂ ) in the waterproofing material are generally adopted. In the description of the waterproofing material described with reference to FIG. It corresponds to a hard layer of a photocurable sheet-like waterproofing material comprising a resin composition (A) formed by a method lacking (A ₁ ) and a fiber reinforced material (B).

(1) Waterproofing Material The material of the synthetic polymer sheet layer (D) of the present invention is JIS
Preferred are a homogeneous sheet and a composite sheet conforming to A-6008 (synthetic polymer-based roofing sheet), but the thickness of the sheet is not limited. In this standard, vulcanized rubber system includes butyl rubber, ethylene propylene rubber, chlorosulfonated polyethylene, etc .; vinyl chloride resin system includes vinyl chloride resin and vinyl chloride copolymer; ethylene vinyl acetate resin system includes ethylene vinyl acetate Sheets such as copolymers can be used. As a sheet other than the above, a urethane rubber-based sheet is suitable, and any sheet having a tensile elongation of 100% or more can be used.

The synthetic polymer sheet layer (D) is porous.
You. Perforated area is the total area of synthetic polymer sheet layer (D)
Is usually 2 to 80%, preferably 10 to 50%. Yes
If the hole area is less than 2%, the adhesion to the substrate will be insufficient.
There is a risk of the waterproof layer peeling off due to wind pressure, etc., exceeding 80%
However, there is a tendency that the ability to follow the ground cracks is insufficient. Also hole-shaped
There is no particular restriction on the shape, but per sheet per unit area
Is 10 for the whole perforated part^-Four-10^-1Hole with area of rule
It is preferable that it is empty. This is 10^-FourSmaller
In other words, the rolling pressure is not easily transmitted to the interface with the substrate,
Peeling due to insufficient adhesion between polymer sheet layer and substrate
Risk of ^-1If larger than
On the other hand, there is a danger that the waterproof layer is locally broken. here
If the arrangement of the holes is regular, it is excellent in ventilation effect, which is preferable,
Irregularities do not lose their effect.

The thickness of the synthetic polymer sheet layer (D) is 0.1
-5.0 mm, preferably 0.5-2.5 mm. This thickness is 0.
If the thickness is less than 1 mm, there is a risk of breaking due to a tensile load during construction or a cut due to a protrusion on the ground, and if it is more than 5.0 mm, it is not possible to follow the shape of the ground and the waterproof layer is wrinkled.

(2) Manufacturing method of the waterproofing material A typical manufacturing method of the waterproofing material uses an SMC impregnating machine. An example of the method will be described with reference to FIGS. A resin composition (A ₂ ) 16 prepared in advance and glass roving 17 as a fiber reinforcing material were chopper 1
The chopped strand 19 cut at 8 is supplied at a predetermined ratio between the lower light-shielding film 20 and the synthetic polymer sheet 22 and the upper light-shielding film 21 which are continuously wound. Next, the chopped strand is impregnated with the resin composition (A ₂ ) by the compression roller 23 to obtain a sheet-like waterproof material 24 having a predetermined thickness and a two-layer structure. The overall thickness of the waterproof material is adjusted by the thickness of the synthetic polymer sheet and the doctor blade 25. The thus obtained waterproofing material of the present invention is in the form of a two-layer sheet, and both outer surfaces thereof are protected by light-shielding films.

Further, it is manufactured by laminating a sheet layer of the photo-curable fiber-reinforced thermosetting resin composition (C) prepared in advance and a synthetic highly polymerizable sheet layer (D) and integrating them into a multilayer structure. You can also. At this time, it is necessary to protect both surfaces of the obtained waterproof material with a light-shielding film or a light-shielding case so that a photo-curing reaction does not start until waterproofing.

(3) Method of Waterproofing A method of waterproofing using the waterproofing material of the present invention manufactured as described above will be described with reference to FIGS. Light-shielding film 21 on synthetic polymer-based sheet layer (D) side
Is peeled off and laid directly on the waterproof base (substrate) 30 or through a primer layer so that the surface of the synthetic polymer sheet layer (D) faces down, and the light-shielding film 20 is peeled off and photopolymerized. By a series of steps of starting the reaction, a waterproof layer can be formed in a short time. As the primer layer, known materials such as a one-component moisture-curable urethane resin, a two-component urethane resin, an epoxy resin, and an unsaturated polyester resin can be used. In the structure formed after the application, a ventilation layer 28 and a buffer layer 27 derived from the synthetic polymer sheet layer (D) are formed on the base 30 via the primer layer 29 if a primer layer is provided. , On which a waterproof layer 26 derived from a hard layer is formed.

The waterproof layer thus formed has not only the waterproof layer's inherent performance such as water resistance, corrosion resistance, weather resistance, substrate adhesion, and substrate crack followability, but also has a high surface hardness. It is also possible to walk on top. Furthermore, the unbonded portion between the synthetic polymer sheet layer (D) and the base surface is used as a ventilation layer, and a degassing tower is provided at a part of the waterproof layer, thereby generating the gas from the base. A deaeration function of removing water vapor can also be added. In addition, in the case of ordinary synthetic polymer sheets, a step is clearly formed at the joint portion of the sheet at the time of construction, whereas in the case of the waterproofing material of the present invention, the wrap disappears due to the rolling work, and the flatness such as the coating film waterproofing. The finish is excellent and the design is excellent.

II-3. Waterproofing material (Z) (1) Another typical waterproofing material in the present invention is a thermosetting resin (a), a photopolymerization initiator (b) and a thickener.
The resin composition (A) containing (c) is mixed with a fiber reinforcing material (B).
Is hardly formed by densely dispersing on the front surface layer, and coarsely dispersed on the back surface layer to form a soft layer. As a specific method of dispersing the fiber reinforcing material (B) densely in the front surface layer and coarsely dispersing the back surface layer, any means can be used, but one method that can be easily embodied is to include the fiber reinforcing material (B). Producing a photo-curable fiber-reinforced thermoplastic resin sheet having different ratios, and appropriately setting the sheet in which the fiber reinforcement (B) is densely dispersed in the surface layer and the sheet in which the fiber reinforcement (B) is coarsely dispersed in the back layer as appropriate. Can be obtained by laminating and integrating the number of layers. In this method, the fiber reinforcement (B) may be in any form, but is preferably in the form of a nonwoven fabric or a mat.

Here, the sheet-like waterproof material composed of at least two or more laminated layers of the photocurable fiber-reinforced thermosetting resin composition layers (C) having different contents of the fiber-reinforced material (B) is as follows:
The difference in physical properties between the hard layer and the soft layer is likely to be small, and it is difficult for the waterproof layer to follow the cracks in the underlayer after waterproofing. Therefore, preferably, (1) two types of photocurable thermosetting resin compositions (A
₁ and A ₂ ) and a sheet-like waterproofing material composed of two layers derived from the fiber reinforced material (B), and (2) a photocurable fiber reinforced thermosetting resin composition layer (C) and a synthetic polymer sheet It is a sheet-like waterproof material in which the layer (D) is integrated in multiple layers.

[0046]

EXAMPLES The present invention will be described in detail with reference to Production Examples, Examples, Reference Examples and Comparative Examples, which do not limit the present invention. In the following, “parts” are by weight unless otherwise specified.

[Test Methods] The waterproof materials or test pieces obtained in Examples and Comparative Examples were evaluated by the following test methods. The results are shown in [Table 2] to [Table 6]. (1) Adhesive strength: A specimen having a waterproof layer provided on a concrete flat plate of dimensions (300 mm x 300 mm x 60 mm) specified in JIS-A-5304 (paving concrete flat plate) was prepared, and the relative humidity was set at 20 ° C. It was left for one week in an atmosphere of 65%, cut, and a stainless steel jig (40 mm × 40 mm) was adhered with an epoxy adhesive. Thereafter, a test was performed at 20 ° C. at a loading speed of about 1 kgf / cm ² / sec using an adhesion research machine of the Building Research Institute, and the adhesive strength (kgf / cm ² ) was measured.

(2) Fatigue test: Using a test specimen, a building construction standard specification and the same description JASS 8 waterproofing work (hereinafter, JASS 8)
8). The specimen was an A-shaped specimen, and the testing machine was a hydraulic servo building finishing material fatigue tester (manufactured by Sagimiya Seisakusho).
Step 5 (movement 2.5 ← 5.0 mm) to Step 3 (movement 2.5 ← 5.0 mm). The test results are displayed in the following categories.

(3) Surface hardness: The surface hardness of the test piece having the highest value was determined using a Shore hardness tester.

(4) Indentation resistance: According to the indentation test of JASS 8, a load of 30 kg was applied at an ambient temperature of 40 ° C., and it was examined whether or not the waterproof layer of the specimen was broken.

(5) Impact resistance: A steel ball of 5 kg was dropped from a height of 1.5 m at an ambient temperature of 40 ° C. in accordance with the impact test of JASS8 to determine whether the waterproof layer of the test piece was broken. Was examined.

(6) Construction time: The time from the start of waterproofing with the waterproof material to the time when the surface hardness of the obtained specimen reaches the maximum value was measured and defined as the construction time. In Examples 1 to 6 and Comparative Examples 1 to 7, this application time substantially corresponds to a so-called curing time.

(7) Riding workability: During the operation from the waterproof material to the test piece, a metal cone (weight 5 kg, bottom area 20 cm ² ) was allowed to stand on the surface of the waterproof layer for 30 seconds before being cured by sunlight. After removing it, the surface dent depth (mm) was measured and evaluated in the following three steps. ○: less than 0.05mm, △: 0.05 to 0.10mm, ×: more than 0.10mm

(8) Styrene volatilization concentration: The styrene concentration (ppm) showing the highest value at a height of 10 cm on the substrate using a Kitagawa type gas detector tube until the test piece is prepared from the waterproof material.
Was determined as the styrene volatilization concentration.

(9) Surface appearance: The surface appearance of the obtained specimen was visually observed.

(10) Underground crack resistance: A test piece having a waterproof layer provided on an asbestos slate plate was prepared in accordance with the test method of a coating film waterproof material (KMK method: Housing and Urban Development Corporation), and a Shimadzu Autograph ( AG-10TD, manufactured by Shimadzu Corporation), the elongation, the strength and the peel width were measured.

(11) Swelling resistance: Measured in accordance with the swelling test of JASS8, using a test body provided with a waterproof layer on a sidewalk concrete flat plate specified by JIS. The test results are displayed in the following categories. Category blistering ^{1: 10.0kPa (0.102kgf / cm 2} ) pressure abnormality occurred before 10 minutes blisters ^{2: 20.0kPa (0.204kgf / cm 2} ) pressure abnormality blistering up to 10 minutes of 3: 50.0kPa (0.510 Abnormality occurs by 10 minutes at pressure of kgf / cm ² ) Swelling 4: No abnormality occurs at pressure of 50.0 kPa (0.510 kgf / cm ² )

(12) Bierbum scratch hardness The waterproof material is cured by a predetermined method (exposed to sunlight for 30 minutes) (by measuring both surfaces) to obtain a hardness H _{S1 of the} surface derived from the soft layer. The hardness H _H1 of the surface of the layer derived from the hard layer was measured by the Bierbum scratch hardness test method.
In addition, each layer is cut from both sides so that it is half,
The hardness H _S2 of the layer from the soft layer and the hardness H _H2 from the hard layer were measured (by measuring both sides).

Production Example 1 Preparation of Resin Composition (A-1) Unsaturated polyester resin (Ester WP260: trade name,
Mitsui Toatsu Chemical Co., Ltd.) 100 parts, 2-hydroxy-2-methyl-1-
A mixture of phenylpropan-1-one and bisacylphosphine oxide (photopolymerization initiator Irgacure 1700: trade name, manufactured by Nippon Ciba Geigy Co., Ltd.) and 1.0 part of a thickener (magnesium oxide) are stirred with a disper so as to be uniform. Then, a resin composition (A-1) was prepared. Table 1 shows the composition of each component and the measured viscosity (Pa · s (25 ° C.)) of the resin composition.

Preparation Examples 2-6 Preparation of resin compositions (A-2) to (A-6) As shown in Table 1, the amounts of the thickener (magnesium oxide) and the filler (aluminum hydroxide) were Except for the change, the same operation as in Production Example 1 was performed, and the five types of resin compositions (A-
2) to (A-6) were prepared. The measured viscosity (Pa · s (25 ° C.)) of the resin composition is shown in [Table 1].

[0061]

[Table 1]

Example 1 Production of Waterproof Material Using a SMC impregnator (with a doctor blade for thickness adjustment, manufactured by Tsukishima Kikai Co., Ltd.), the resin composition (A) obtained in the above production example was used.
-3) 28 parts, resin composition (A-4) 57 parts and fiber reinforcing material (glass roving: cut length 50 mm, manufactured by Asahi Fiber Glass Co., Ltd.) 15 parts, two light-shielding films (polyester laminated aluminum foil, (Manufactured by Hosokawa Yoko Co., Ltd.) to produce a sheet-like two-layer waterproof material. The thickness of the waterproof material is 0.5 mm for the soft layer derived from (A-3), and (A-4)
Is 1.0 mm, and the total thickness is 1.5 mm. Also, both sides of the waterproof material are protected by light-shielding films. Thereafter, the waterproofing material was allowed to stand in a constant temperature room (40 ° C.) for 24 hours to be aged. Next, peel off the light-shielding film on the soft layer side of the waterproof material,
This surface was laid on a substrate (concrete flat plate or asbestos slate plate) and rolled with a roller. Thereafter, the light-shielding film on the hard layer side was peeled off and cured with sunlight to obtain a test body having a waterproof layer provided on a substrate.

Examples 2 to 6 Production of Waterproofing Material As shown in Table 2, the viscosity and thickness of the soft layer and the hard layer of the resin composition obtained in the above production example and the amount of the fiber reinforcing material were adjusted to predetermined values. The same operation as in Example 1 was carried out except that it was changed within the range, to obtain a waterproof material and a test body, which were subjected to the test. As a result, as shown in [Table 2], the adhesive strength was good, the surface hardness was high, the application time was short, the overcoating workability was good, and the styrene diffusion concentration was low, so there was little odor, and A waterproof layer having a good appearance was obtained.

REFERENCE EXAMPLE 1 In the case where the thickness of the hard layer was set to 7.0 mm, which is larger than the preferable predetermined thickness. As shown in Table 3, the soft layer and the hard layer of the resin composition obtained in the above production example were The viscosity was as specified, the thickness of the soft layer was as specified, the thickness of the hard layer was 7.0 mm, which was larger than a predetermined value, and the same operation as in Example 1 was performed to obtain a waterproof material and a test body. Tested. As a result, the thickness of the hard layer is 7.
Since the thickness was 0 mm, which is larger than the predetermined value, curing by sunlight was insufficient, and the inside of the sheet was not completely cured. Due to curing shrinkage, the sheet surface was wrinkled and further warped. For that purpose, step 1 of the fatigue test (movement 0.
5 ← 1.0 mm), the waterproof layer was broken, and the performance as a waterproof layer could not be obtained.

Reference Example 2 In the case where a material having a viscosity lower than the preferred viscosity is used for the soft layer As shown in Table 3, a material having a viscosity lower than a predetermined value was used for the soft layer of the resin composition obtained in the above-mentioned production example. The same procedure as in Example 1 was carried out except that the hard layer had a predetermined viscosity and the thickness and the amount of the fiber reinforcing material were within the predetermined ranges. did. As a result, since a material having a viscosity lower than a predetermined value was used for the soft layer of the resin composition, the light-shielding film could not be used because of poor peelability.

Reference Example 3 In the case where the thickness of the hard layer was 0.1 mm, which was smaller than the preferable thickness. As shown in Table 3, the soft layer and the hard layer of the resin composition obtained in the above Production Example were as specified. The thickness of the soft layer was set to a predetermined value, the thickness of the hard layer was set to 0.1 mm, which was smaller than a predetermined value, and the same operation as in Example 1 was performed to obtain a waterproof material and a test piece, which were subjected to a test. . As a result, since the thickness of the hard layer was thin, footprints were formed on the surface and the surface became uneven, and the appearance as a waterproof layer was poor.

REFERENCE EXAMPLE 4 In the case where a material having a higher viscosity than the preferable viscosity is used for the hard layer. As shown in Table 3, the soft layer of the resin composition obtained in the above production example is made of a material having a predetermined viscosity. The hard layer used was a material having a viscosity higher than a predetermined value. The same operation as in Example 1 was carried out except that the thickness and the amount of the fiber reinforced material were within the predetermined ranges, to obtain a waterproof material and a test body, which were subjected to the test. As a result, since a material having a viscosity higher than a predetermined value is used for the hard layer of the resin composition, the rolling pressure during the rolling work hardly reaches between the waterproof material and the substrate side, and the adhesive strength is 15 kgf / cm ² . And a non-adhered portion was formed between the waterproof material and the substrate.

Reference Example 5 In the case where a material having a lower viscosity than the preferable viscosity was used for the hard layer. As shown in Table 3, the soft layer of the resin composition obtained in the above-mentioned production example had a predetermined viscosity. For the layer, a material having a viscosity lower than a predetermined value was used. Except that the thickness and the amount of the fiber reinforcement were within predetermined ranges, the same operation as in Example 1 was performed,
A waterproof material and a test body were obtained and subjected to a test. As a result, since a material having a viscosity lower than a predetermined value was used for the hard layer of the resin composition, the riding workability at the time of waterproofing was deteriorated, and when a person got on the sheet surface, dents were formed, resulting in unevenness and poor surface appearance.

Reference Example 6 When the resin composition / fiber reinforced material (weight ratio) was larger than the preferred range. As shown in Table 4, the soft layer and the hard layer of the resin composition obtained in the above Production Example were The same viscosity and thickness as specified, the resin composition / fiber reinforced material (weight ratio) was set to 98/2 outside the predetermined range, and the same operation as in Example 1 was performed to obtain a waterproof material and a test body. Tested. As a result, the resin composition / fiber reinforced material (weight ratio) was 98/2, and the amount of the fiber reinforced material was less than the predetermined value of 3 parts by weight.

Reference Example 7 When the resin composition / fiber reinforced material (weight ratio) was smaller than the preferred range. As shown in Table 4, the soft layer and the hard layer of the resin composition obtained in the above Production Example were The same procedure as in Example 1 was carried out by setting the resin composition / fiber reinforced material (weight ratio) to 45/55 out of the predetermined range by setting the viscosity and the thickness to a predetermined value, to obtain a waterproof material and a test body. Was served. As a result, since the resin composition / fiber reinforced material (weight ratio) = 45/55 and the amount of the fiber reinforced material exceeded the predetermined value of 50 parts by weight, the surface of the waterproof layer had a glassy appearance and was not preferable in appearance. Was.

COMPARATIVE EXAMPLE 1 In the case of FRP coated waterproofing material, FMA was applied by the Remaster RB-1 method (Mitsui Toatsu Chemicals).
A test piece having an RP waterproofing material was prepared and subjected to a test. As a result, the construction time was increased to 4 hours due to the coating waterproofing at the site, the odor of styrene was strong, and the process 1 was performed in the fatigue test.
As a result, the waterproof layer was broken, and there was still room for improvement in performance.

Comparative Example 2 In the case of a vinyl chloride sheet waterproof material A test piece having a vinyl chloride sheet waterproof material was prepared and subjected to a test. As a result, as compared with Examples 1 to 5, the adhesion to the substrate was significantly lower at 10 kgf / cm ² and the surface hardness was 15
It is good for non-walking because of low (Shore-D),
It could not be used for walking.

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

Example 7 Production of Waterproofing Material (Composite Integrated) 100 parts of an unsaturated polyester resin (Ester WP260), 1.0 part of a photopolymerization initiator (Irgacure 1700) and 1.0 part of a thickener (magnesium oxide) are made uniform. As described above to prepare a resin composition. Next, using an SMC impregnating machine (manufactured by Tsukishima Kikai Co., Ltd.) to which a polyvinyl chloride resin sheet (manufactured by Tsutsuya Naka Waterproofing Co., Ltd., processed from Sunroid DN sheet, perforated area: 20%, thickness: 1.0 mm) was previously installed. 50mm
Glass roving (made by Asahi Fiberglass) (15 parts by weight) and the above resin composition (85 parts by weight)
Was used to produce a waterproof sheet. In the waterproof sheet, the resin composition (C) has a sheet thickness of 1.5 mm, and the entire waterproof sheet has a thickness of 2.5 mm. Further, both sides of the waterproof sheet were packaged with a light-shielding film (polyester laminated aluminum foil, manufactured by Hosokawa Yoko Co., Ltd.). Further, the light-shielding film on the vinyl chloride resin sheet (D) side of the waterproof sheet was peeled off, laid so that this surface was in contact with a substrate (concrete flat plate or asbestos slate plate), and rolled with a roller.
Thereafter, the remaining upper light-shielding film was peeled off, cured with sunlight, and a test piece having a waterproof layer provided on a substrate was obtained and subjected to a test. As a result, it was possible to obtain a waterproof layer which could be applied in a short time, had a high surface hardness, and had good adhesion to the substrate, swelling resistance, fatigue test, resistance to cracking of the substrate, and good surface appearance.

Example 8 When the vinyl chloride resin sheet was a vulcanized rubber sheet In the middle part of Example 7, the vinyl chloride resin sheet was a vulcanized rubber sheet (made by Tajima Roofing Co., Samsung Plus Sheet PS-15). A test specimen was obtained in the same manner as in Example 1 except that processing and perforated area were changed to 20% and thickness was 1.5 mm). As a result, a waterproofing layer which could be applied in a short time, had a high surface hardness, and had good adhesion to the base, swelling resistance, fatigue test, resistance to base cracking, and good surface appearance was obtained.

Example 9 When the thickness of the sheet layer of the resin composition (C) was changed from 1.5 mm to 3.0 mm In the middle part of Example 7, the thickness of the sheet layer of the resin composition (C) was changed from 1.5 mm to 3.0 mm. Except for the above, a test body was obtained in the same manner as in Example 1 and subjected to a test. As a result, it was possible to obtain a waterproof layer which could be applied in a short time, had a high surface hardness, and had good adhesion to the substrate, swelling resistance, fatigue test, resistance to cracking of the substrate, and good surface appearance.

Example 10 In the case where the perforated area of the vinyl chloride resin sheet was changed from 20% to 50% In the middle half of Example 7, except that the perforated area of the vinyl chloride resin sheet was changed from 50% to 50%. A specimen was obtained by the same operation as described above, and was subjected to the test. As a result, the work can be performed in a short time, the surface hardness is high, the adhesive strength with the base, the blister resistance,
A waterproof layer having good fatigue test, resistance to cracks on the substrate, and good surface appearance was obtained.

Example 11 In the case of applying a primer In the latter half of Example 7, 0.3 kg of a primer (San PC-F: trade name, one-part moisture-curable urethane resin, manufactured by Mitsui Toatsu Chemicals, Inc.) was previously coated on a substrate. A test specimen was obtained in the same manner as in Example 1 except that the test piece was applied at / m ² and cured. As a result, it was possible to obtain a waterproof layer which could be applied in a short time, had a high surface hardness, and had good adhesion to the substrate, swelling resistance, fatigue test, resistance to cracking of the substrate, and good surface appearance.

REFERENCE EXAMPLE 8 When the thickness of the sheet layer of the resin composition (C) is larger than the preferable thickness. In the middle half of Example 7, the thickness of the sheet layer of the resin composition (C) is changed from 1.5 mm to 5.5 mm. Except for the above, the same procedure as in Example 1 was carried out to obtain a test body, which was subjected to the test. As a result, it can be applied in a short time, has high surface hardness, and has good adhesion to the base, blister resistance, fatigue test, and base crack resistance.
The surface appearance was wrinkled, and an unsuitable waterproof layer was obtained.

REFERENCE EXAMPLE 9 A case where the perforated area of the vinyl chloride resin sheet was larger than the preferred area. In the middle half of Example 7, the perforated area of the vinyl chloride resin sheet was changed from 20% to 90%. A specimen was obtained by the same operation as described above, and was subjected to the test. As a result, the work can be performed in a short time, the surface hardness is high, and the adhesive strength with the base and the swelling resistance are good, but the fatigue test becomes poor with A2, the base is cracked in the resistance, and is unsuitable as a waterproof layer. Things were obtained.

Comparative Example 3 In the case of a urethane-coated waterproofing material A test piece having a urethane waterproofing material was prepared by the Sansilal B-1 method (manufactured by Mitsui Toatsu Chemicals, Inc.) and subjected to a test.
As a result, the construction time was long, the swelling was as poor as 2, and the dent resistance and the impact resistance were broken, and a waterproof layer still having room for improvement was obtained.

Comparative Example 4 In the case of FRP-coated waterproofing material: Remaster RB-1 method (manufactured by Mitsui Toatsu Chemicals, Inc.)
A test piece having an RP waterproofing material was prepared and subjected to a test. As a result, the surface hardness was high, and the adhesion to the substrate and the swelling resistance were good, but the construction time was as long as 4 hours, the fatigue test was poor at A1, and it was broken in the substrate crack resistance test, and the waterproof layer was broken. As a result, there is still room for improvement.

Comparative Example 5 In the case of a vinyl chloride sheet waterproof material A test piece having a vinyl chloride sheet waterproof material was prepared and subjected to a test. As a result, the surface hardness was low, the adhesive strength to the base was low, the blistering resistance was 3, and the fatigue test was also A3. Thus, an unsuitable waterproof layer was obtained.

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

According to the waterproofing material and the waterproofing construction method of the present invention, a high-performance waterproofing layer can be formed on the surface of a civil engineering building without polluting the working environment in a short time of about 30 minutes and with a small number of man-hours. Can be formed. In addition, the waterproof layer itself has the performance originally required, that is, water resistance, weather resistance and adhesion to the base, not only having design properties, but also can walk on the waterproof layer due to its high surface hardness, and It is an excellent material with high underground crack followability.

[Brief description of the drawings]

FIG. 1 is a typical method for producing a waterproof material of the present invention (SMC
FIG. 4 is a schematic process diagram illustrating the use of an impregnating machine).

FIG. 2 is a perspective view showing a waterproofing material of the present invention according to the manufacturing method of FIG.

FIG. 3 is a cross-sectional view illustrating an example of the structure after the waterproof material is installed according to the present invention.

FIG. 4 is a schematic process chart showing another typical method for producing a waterproof material (using an SMC impregnating machine) of the present invention.

FIG. 5 is a perspective view showing a waterproof material of the present invention according to the manufacturing method of FIG. 4;

FIG. 6 is a cross-sectional view illustrating an example of the structure after the waterproof material is installed according to the present invention.

[Explanation of symbols]

1: resin composition (A ₁ ) 2: resin composition (A ₂ ) 3: glass roving 4: chopper 5: chopped strand 6, 7, light shielding film 8: compression roller 9: waterproof material 10, 11, doctor blade 12 : Hard layer｝ derived from resin composition (A ₂ ) ： 13: Soft layer｝ derived from resin composition (A ₁ )｝ 14: Primer layer 15: Base material 16: Resin composition (A ₂ ) 17 : Glass roving 18: Chopper 19: Chopped strand 20, 21: Light shielding film 22: Synthetic polymer sheet (D) 23: Compression roller 24: Waterproof material 25: Doctor blade 26: Waterproof layer consisting of hard layer 27: Synthetic height Buffer layer made of molecular sheet 28: Vent layer 29: Primer layer 30: Base

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication E04D 5/10 E04D 5/10 D (72) Inventor Yoshikazu Ishida 3-2 Kasumigaseki, Chiyoda-ku, Tokyo No. 5 Mitsui Toatsu Chemicals Co., Ltd.

Claims (10)

[Claims] 1. A fibrous reinforcing material (B) is dispersed in a resin composition (A) containing a thermosetting resin, a photopolymerization initiator and a thickener, and the hardness of the surface layer and the back layer during curing is increased. Light curable sheet-like waterproof material formed differently. 2. The waterproofing material according to claim 1, wherein the surface on the side to be hardened in close contact with the construction substrate is a soft layer and the surface on the opposite side is a hard layer, and a light-shielding film is laminated on the surfaces of the soft layer and the hard layer. . 3. The relationship between the thickness of the soft layer (T ₁ ) and the thickness of the hard layer (T ₂ ) is 10% <(T ₂ ) / [(T ₁ ) +
(T ₂ )] <85%. 4. The waterproofing material according to claim 1, wherein the thermosetting resin is one selected from the group consisting of an unsaturated polyester resin, a vinyl ester resin and a vinyl urethane resin. 5. A resin composition (A) is the viscosity of forming a soft layer (eta ₁₎ is 10 ² ~10 ⁵ Pa · s resin composition is (25 ° C.) and (A _1), a rigid layer The formed viscosity (η ₂ ) is 10 ³ to 10 ⁶ Pa
The waterproof material according to claim ₂ , comprising a resin composition (A2) having a s (25 ° C). 6. A resin composition (A) containing a thermosetting resin, a photopolymerization initiator and a thickener, a fiber reinforcing material (B) dispersed therein to form a surface layer, and a synthetic polymer sheet ( D)
The waterproofing material according to claim 2, wherein a plurality of layers are integrated as a soft layer. 7. The waterproofing according to claim 6, wherein the synthetic polymer sheet layer (D) is a vulcanized rubber-based, non-vulcanized rubber-based, vinyl chloride resin-based, ethylene vinyl acetate resin-based or urethane rubber-based sheet. Wood. 8. The waterproofing material according to claim 6, wherein the synthetic polymer sheet layer (D) is a perforated body, and the perforated area is in the range of 2 to 80% of the total area. 9. A fiber reinforced material (B) is added to a resin composition (A) containing a thermosetting resin, a photopolymerization initiator and a thickener,
A light-curable sheet-like waterproofing material in which a hard layer is formed by being densely dispersed on the surface layer, and a soft layer is formed by being coarsely dispersed on the back layer. 10. A fibrous reinforcing material (B) is dispersed in a resin composition (A) containing a thermosetting resin, a photopolymerization initiator and a thickener, and the hardness at the time of curing of the surface layer and the back layer is increased. A hard layer that acts as a fiber-reinforced waterproof layer by laying and rolling a light-curable sheet-like waterproof material formed differently so that the side to be closely adhered and cured to the construction substrate is a soft surface, and light-cured in the adhered state. And forming a soft layer acting as a buffer layer at the same time.