JP2001342228A - Unsaturated polyester resin for waterproofing frp and usage thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin for waterproofing FRP capable of effectively using a recovered PET while holding performance equivalent to a conventional PET and the usage of the same. SOLUTION: In the unsaturated polyester for waterproofing FRP, the unsaturated polyester is obtained from a raw material consisting of a recycled polyethylene terephthalate together with an acid component at least containing an α,β-unsaturated polybasic acid or its anhydride, and a glycol component. A FRP- waterproofing material for construction and building comprises the unsaturated polyester resin and a fiber reinforcing material, a waterproofing sheet for construction and building is produced by forming and curing the FRP-waterproofing material into a sheet, and a structure of construction and building is produced by integrating a FRP layer made of a cured body of the FRP waterproofing material or the waterproofing sheet as at least a part of the structure, or by forming the top coat resin layer with the unsaturated polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester resin for FRP waterproofing applied to concrete and mortar structures, and an FR for civil engineering and construction using the same.
TECHNICAL FIELD The present invention relates to a P waterproof material, a waterproof sheet for civil engineering construction, and a civil engineering building structure.

[0002]

2. Description of the Related Art Polyethylene terephthalate (hereinafter referred to as PET) has been conventionally produced by a condensation reaction of terephthalic acid and ethylene glycol or a transesterification reaction. Widely used for applications such as adhesives, molding materials, paints, plasticizers, etc. In recent years, from the standpoint of resource saving and environmental protection, PET products and
Waste generated during the production of the next processed product or used PE
There are many attempts to re-dissolve wastes of T products and recycle them into fibers and various industrial products.

[0003] When recycling recovered PET into fibers or various industrial products, complicated processes such as heat melting and pelletization are required, and thus there is a problem that the cost of producing recycled products by recycling is increased. Further, there is also a problem in that the recycled product made by using the recovered PET is often inferior in performance to the conventional product. For this reason, at present, attempts to recycle recovered PET into fibers, various industrial products, and the like have not been practically used. However, nevertheless, in recent years,
The collection of used PET bottles is being promoted by local governments, and the collected PET is difficult to dispose of without being reused.
The volume is expected to continue to increase.

[0004]

Therefore, the present inventor has proposed:
The above-mentioned attempt of the recovered PET recycling was reexamined.
As a result, it has been found that the recovered PET can be applied to an unsaturated polyester resin for FRP waterproofing for civil engineering if the recycling method is devised. Therefore, an object of the present invention is to provide an unsaturated polyester resin for waterproofing of FRP, which has the same performance as that of the conventional unsaturated polyester resin for waterproofing of FRP and which can effectively utilize the recovered PET and contribute to its consumption. An object of the present invention is to provide a used FRP waterproof material for civil engineering, a waterproof sheet for civil engineering, and a civil engineering building.

[0005]

Means for Solving the Problems The inventor of the present invention has intensively studied a method of recycling the recovered PET in order to solve the above problems. As a result, the recovered PET is decomposed by the glycol component, which is one of the unsaturated polyester raw materials,
By using the decomposed product as a raw material of an unsaturated polyester, it has been found that an unsaturated polyester having various physical properties required for waterproofing can be synthesized, and the present invention has been completed. That is, the unsaturated polyester resin for waterproofing of FRP of the present invention is an unsaturated polyester resin for waterproofing FRP comprising an unsaturated polyester (a) and a polymerizable monomer (a ′), wherein the unsaturated polyester resin is (A)
It is characterized in that it is obtained by using recovered polyethylene terephthalate as a raw material together with an acid component and a glycol component containing at least an α, β-unsaturated polybasic acid or an acid anhydride thereof.

[0006] The FRP waterproofing material for civil engineering and construction of the present invention comprises the unsaturated polyester resin (A) for FRP waterproofing and the fiber reinforced material (B). The waterproofing sheet for civil engineering and construction of the present invention is an FRP comprising the unsaturated polyester resin (A) for waterproofing FRP and the fiber reinforced material (B).
The waterproof material is formed into a sheet and cured. The civil engineering building structure of the present invention is an FRP comprising the FRP waterproof unsaturated polyester resin (A) and the fiber reinforced material (B).
An FRP layer formed by curing a waterproof material is included at least as a part.

Further, the civil engineering building structure of the present invention is characterized in that
At least a part of a waterproof sheet obtained by molding and hardening an FRP waterproof material containing an unsaturated polyester resin for RP waterproofing (A) and a fiber reinforcing material (B) into a sheet shape is included. Further, the civil engineering building structure of the present invention has an FR composed of at least an unsaturated polyester resin and a fiber reinforcing material.
A civil construction structure including a P waterproof layer and a top coat resin layer laminated on the FRP waterproof layer, wherein the top coat resin layer is formed of the unsaturated polyester resin. And

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION (Unsaturated polyester resin for FRP waterproofing) The unsaturated polyester resin for FRP waterproofing of the present invention comprises an unsaturated polyester (a) and a polymerizable monomer (a ').
It is important that the unsaturated polyester (a) is obtained from recovered PET as a raw material together with an acid component and a glycol component. Thereby, while exhibiting the same performance as the conventional unsaturated polyester resin for FRP waterproofing, the recovered PET can be effectively utilized to contribute to its consumption.

The unsaturated polyester resin for FRP waterproofing of the present invention can be obtained by first reacting the recovered PET with the glycol component to decompose the glycol, and then reacting with the acid component to perform esterification. it can.
Therefore, the unsaturated polyester resin for waterproofing of FRP of the present invention which is inevitably obtained is terephthalic acid as a saturated acid,
It contains ethylene glycol as the glycol component. The acid component may be any one containing at least an α, β-unsaturated polybasic acid or an acid anhydride thereof.
In addition to these, for example, a saturated polybasic acid or an acid anhydride thereof may be used in combination.

Examples of the α, β-unsaturated polybasic acid or its acid anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid and the like. Further, these derivatives, for example, dicyclopentadienyl maleate, which is a reaction product of dicyclopentadiene and maleic acid, or dicyclopentadienyl fumarate, which is a rearrangement compound thereof, can also be used. Dicyclopentadienyl maleate and dicyclopentadienyl fumarate can be obtained by a conventionally known method.For example, maleic anhydride is reacted with an equivalent amount of water at 60 to 100 ° C. to obtain maleic acid. Is reacted with dicyclopentadiene at 120 to 140 ° C.

It is preferable that the content of the α, β-unsaturated polybasic acid or its anhydride is 5 to 30% by weight based on the total amount of the unsaturated polyester (a). 30% by weight
If it exceeds, the flexibility at the time of curing the unsaturated polyester resin is impaired, and the ability to follow the underlayer in a waterproof sheet, a civil engineering building structure, or the like is reduced. 5
If it is less than the weight percentage, the curability will be poor. When dicyclopentadienyl maleate and / or dicyclopentadienyl fumarate is used, the content is preferably 30% by weight or less based on the total amount of the unsaturated polyester (a). . If it exceeds 30% by weight,
The flexibility when the unsaturated polyester resin is cured is impaired, and the ability to follow the underlayer of a waterproof sheet or a civil engineering building structure is reduced.

Examples of the saturated polybasic acid or its acid anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetraphthalic anhydride,
Hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, 1,12-docandioic acid, dimer acid, 2,6- Examples include naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid, and the like. In addition to these, trimellitic acid, pyromellitic acid and the like can also be used. In the present invention, among the above examples, it is preferable to use a linear saturated polybasic acid as a part of the acid component from the viewpoint of flexibility. Particularly, a linear saturated polybasic acid having 6 to 32 carbon atoms is preferable.

When an acid component other than the α, β-unsaturated polybasic acid or its acid anhydride is used, its content is preferably 5 to 40% by weight based on the total amount of the unsaturated polyester (a). preferable. In addition, as an acid component, you may use only 1 type and may use 2 or more types together. Examples of the glycol component include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and glycols containing ether groups such as polyethylene glycol and polypropylene glycol.
In the present invention, it is preferable from the viewpoint of flexibility that at least a part of the glycol component is an ether group-containing glycol.

It is preferable that the ether group-containing glycol accounts for 5% by weight or more of the total amount of the unsaturated polyester (a). More preferably, it is 5 to 50% by weight.
If the content is less than 5% by weight, the flexibility when the unsaturated polyester resin is cured is impaired, and the ability to follow the base is reduced. Also, if introduced over 50% by weight,
This leads to a decrease in the amount of recovered PET, which departs from the object of the present invention. When the obtained unsaturated polyester (a) is used as a top coat resin layer in a civil engineering construction structure described later, the ether group-containing glycol may not be contained, and may be contained.
The content is preferably 0% by weight or less. If introduced beyond this, the water resistance, weather resistance, and abrasion resistance, which are the objectives of the protective layer, will be reduced.

As the glycol component, besides the ether group-containing glycol, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol,
1,4-cyclohexanedimethanol, 2-methylpropane-1,3-diol, hydrogenated bisphenol A, adducts of bisphenol A with alkylene oxides such as propylene oxide and ethylene oxide, and trimethylolpropane can also be used. . In addition, as the glycol component, only one kind may be used, or two or more kinds may be used in combination.

In the present invention, the recovered PET is PET.
It refers to scrap and waste generated in the manufacturing process, the manufacturing process of the PET product, or the manufacturing process of the secondary processed product, and the collected product of the used product. Specifically, scrap such as scrap, drain, and coarsely pulverized material in the PET manufacturing process; discharged yarn scrap, undrawn material, cut waste, nonstandard waste in the spinning manufacturing process; cut waste in the film manufacturing process; molding material Waste products such as defective products and defective products in the manufacturing process; collected containers and packaging materials for drinking water and the like;
These collected PETs are preferably used in a crushed state, if necessary, after passing through steps such as washing, removal of dust such as labels, washing, dehydration, and sorting, but are not limited thereto. For example, it may be used in a cut state. In the present invention, the recovered PET
Can be used by omitting a conventional recycling process such as heat melting and pelletization.

The amount of the recovered PET is preferably 1 to 60% by weight, more preferably 5 to 50% by weight, based on the total amount of the unsaturated polyester (a). If the amount is less than 1% by weight, the consumption of recovered PET is reduced, which departs from the object of the present invention. On the other hand, when the content exceeds 60% by weight, the curability when the unsaturated polyester resin is cured is impaired, and the ability to follow the underlayer of a waterproof sheet, a civil engineering structure, or the like is reduced. In the present invention, the recovered PET is decomposed and esterified by the glycol component, which is a raw material of the unsaturated polyester (a). The glycol decomposing method at this time includes, for example, an inert gas atmosphere. The reaction may be performed at a temperature of 190 to 270 ° C. under normal pressure or under pressure, if necessary, in the presence of a catalyst such as manganese, cobalt, zinc, tin, and titanium. The glycol component and the recovered PET may be charged and heated at the same time, or the recovered PET may be put into the glycol component and heated. The glycol component may be added at a time when the recovered PET is decomposed into glycol, or may be separately charged during the decomposition and during the esterification after the decomposition.

The unsaturated polyester (a) is obtained by condensing the acid component, the glycol component, and the recovered PET.
There is no particular limitation on the reaction method used in the above, and the reaction may be performed by a conventionally known method. The mixing ratio of the acid component and the glycol component in the reaction is not particularly limited. The reaction temperature and reaction time during the reaction may be appropriately set so that the reaction is completed, and
The presence or absence of additives such as a catalyst and an antifoaming agent used for accelerating the condensation reaction, which are used as necessary in the reaction, and the amount of the additives are not particularly limited. The condensation reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or helium.

The unsaturated polyester (a) can be used by reacting a terminal hydroxyl group with a polyfunctional isocyanate. The polyfunctional isocyanate to be reacted in this case is not particularly limited and includes, for example, phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate,
Diisocyanates such as 4,4'-diphenylmethane diisocyanate and isophorone diisocyanate; triisocyanates such as triphenylmethane triisocyanate and 1,3,6-hexamethylene triisocyanate; and the like. Alternatively, they can be used in combination.

The amount of the polyfunctional isocyanate used is 0.1 to 10% by weight based on the unsaturated polyester (a),
Preferably, the content is 0.3 to 5.0% by weight. The reaction method for reacting the unsaturated polyester (a) with the polyfunctional isocyanate may be performed according to a known method. For example, in the presence of a polymerization inhibitor such as hydroquinone or oxygen and a urethanization catalyst such as a tin compound or a tertiary amine,
If necessary, a polymerizable monomer (a ′) described below is present,
The unsaturated polyester (a) may be reacted with the polyfunctional isocyanate at a room temperature of 130 ° C. or lower. The unsaturated polyester (a) also has a terminal carboxyl group,
It can also be used by reacting with a reactive monomer having a glycidyl group. The reactive monomer having a glycidyl group to be reacted is not particularly limited,
For example, glycidyl acrylate, glycidyl methacrylate and the like can be mentioned, and these can be used alone or in combination.

The reactive monomer having a glycidyl group is used in an amount of 0.5 to 2.0 mol%, preferably 0.1 to 2.0 mol%, based on the terminal carboxyl group of the unsaturated polyester (a).
The content is preferably 8 to 1.5 mol%. A reaction method for reacting the unsaturated polyester (a) with the reactive monomer having a glycidyl group may be performed according to a known method. For example, in the presence of a polymerization inhibitor such as hydroquinone or oxygen and a catalyst such as a zinc compound or a tertiary amine, a polymerizable monomer (a ′) described below may be present as necessary,
The unsaturated polyester (a) may be reacted with the reactive monomer having a glycidyl group at 0 to 130 ° C.

The unsaturated polyester resin for FRP waterproofing of the present invention comprises a polymerizable monomer (a ') together with the unsaturated polyester (a). Examples of the polymerizable monomer (a ′) include styrene, α-methylstyrene, divinylbenzene, vinyltoluene, p-methylstyrene, t-butylstyrene, methyl methacrylate, ethylene glycol di (meth) acrylate, and diethylene glycol. Di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc. Allyl compounds such as diallyl phthalate, diallyl fumarate, diallyl succinate and triallyl cyanurate;
And the like. Of these, styrene is particularly preferable because of its excellent curability and low cost, and it is preferable that styrene is essential. These may be used alone or in combination of two or more.

In the unsaturated polyester resin for waterproofing of FRP of the present invention, the mixing ratio of the unsaturated polyester (a) and the polymerizable monomer (a ′) is as follows: unsaturated polyester (a) / polymerizable monomer (A ') = 40 / 60- ~ 75 /
It is preferably 25 (weight ratio). When the amount of the polymerizable monomer (a ′) is less than the above ratio, the water resistance when cured tends to decrease. On the other hand, when the amount is more than the above ratio, the FRP waterproof material obtained by using the In the waterproof sheet, physical properties such as brittleness are deteriorated, which is not preferable. When obtaining the unsaturated polyester resin for waterproofing of FRP of the present invention, it is preferable to use a polymerization inhibitor for the purpose of preventing gelation and for adjusting the storage stability or curability of the resin. As polymerization inhibitors,
Although not particularly limited, for example, hydroquinone, methylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone,
Examples include p-benzoquinone, naphthoquinone, methoxyhydroquinone, hydroquinone monomethyl ether, trimethylhydroquinone, 2,5-di-t-butylhydroquinone, phenothiazine, copper naphthenate and the like. These may be used alone or in combination of two or more.

The unsaturated polyester resin for waterproofing of FRP of the present invention or the FRP waterproofing material described later is usually used after adding a curing agent. The curing agent is not particularly limited. For example, diisopropyl peroxydicarbonate, benzoyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxy-2
-Ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-
Organic peroxides such as amyl peroxy-2-ethylhexanoate, t-butyl hydroperoxide, t-butyl peroxy neodikenate, t-butyl peroxybenzoate, cumene hydroperoxide; azobisisobutyro Azo compounds such as nitrile and azobisdiethylvaleronitrile; and the like. The amount of these curing agents is 0.1 to 100 parts by weight of the unsaturated polyester resin.
It is preferably 5 to 5 parts by weight.

The unsaturated polyester resin for FRP waterproofing of the present invention or the FRP waterproofing material described below may also contain a curing accelerator. As a curing accelerator,
For example, cobalt naphthenate, cobalt octenoate, 2
Metal salts such as trivalent acetylacetone cobalt, trivalent acetylacetone cobalt, potassium octenoate, zirconium naphthenate, zirconium acetylacetonate, vanadium naphthenate, vanadium octenoate, vanadium acetonate, and lithium acetylacetonate are preferred. In addition, known curing accelerators such as amine compounds, phosphorus-containing compounds, and β-diketone compounds can be used. When a curing accelerator is used, its amount is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the unsaturated polyester resin.
More preferably, the content is 0.1 to 1 part by weight.

If necessary, a known thixotropic agent may be added to the unsaturated polyester resin for waterproofing of FRP of the present invention in order to impart thixotropic properties. Examples of the thixotropic agent include colloidal silica, fimed silica, silica airgel, organically modified clay, clay, silica powder, cellulose acetate and the like. Specifically, "Aerosil" manufactured by Nippon Aerosil Co., Ltd. , "Tixogel" manufactured by Yokohama Kasei Co., Ltd., "Dispalon" manufactured by Kusumoto Kasei Co., Ltd.,
Commercial products such as "Leo Seal" manufactured by Tokuyama Soda Co., Ltd. are exemplified. When a thixotropic agent is used, the amount thereof is 0.1 to 3 parts by weight based on 100 parts by weight of the unsaturated polyester resin.
It is preferable that the amount be 0.5 parts by weight, more preferably 0.5 to 1.5 parts by weight.

The unsaturated polyester resin for waterproofing of FRP of the present invention may contain various additives as required. As additives, for example, colorants such as dyes, extenders, ultraviolet absorbers, antioxidants, plasticizers,
Examples include a leveling agent, an antifoaming agent, a silane coupling agent, an antistatic agent, a flame retardant, a lubricant, a viscosity reducing agent, a low shrinkage agent, an inorganic filler, an organic filler, a drying agent, and a dispersant. (FRP waterproofing material for civil engineering construction) FR for civil engineering construction of the present invention
The P waterproofing material comprises the above-described unsaturated polyester resin for FRP waterproofing (A) of the present invention and the fiber reinforced material (B).

As the fiber reinforcing material (B), for example,
Glass fibers such as glass cloth, roving cloth and chopped strand mat; aramid fibers; organic fibers such as amide, vinylon, polyester and phenol; carbon fibers; metal fibers; ceramic fibers; Among these, glass fibers recycled from glass products collected on the market are particularly preferable from the viewpoint of resource saving. Examples of the form of these fibers include plain weave, satin weave, nonwoven fabric, and mat shape, and may be appropriately selected in consideration of workability, strength, flexibility, economy, and the like.

In the FRP waterproofing material of the present invention, the proportion occupied by the unsaturated polyester resin (A) is 40 to 9
5% by weight, and the proportion of the fiber reinforced material (B) is 5 to 6
It is preferably 0% by weight. If the proportion of the unsaturated polyester resin (A) is less than 40% by weight, impregnation is likely to occur and water leakage is likely. On the other hand, if it exceeds 95% by weight, strength tends to be insufficient. FRP of the present invention
The waterproof material can be produced by a conventionally known method, and can be easily obtained, for example, by impregnating or applying the unsaturated polyester resin (A) to the fiber reinforcement (B). .

(Waterproof sheet for civil engineering and construction) The waterproofing sheet for civil engineering and construction according to the present invention is an FRP waterproofing material comprising the above-mentioned unsaturated polyester resin (A) for FRP waterproofing of the present invention and a fiber reinforced material (B). Are formed into a sheet and cured. The content of the fiber reinforced material in the waterproofing sheet for civil engineering and construction of the present invention is suitably 60% by weight or less. However, in order to exhibit bending workability and flexibility while maintaining mechanical strength, crow cloth In the case of a roving cloth, the content is preferably 30 to 60% by weight, in the case of chopped strands and chopped strand mats, 10 to 30% by weight, and in the case of organic fibers, 5 to 15% by weight.

In the waterproof sheet for civil engineering and construction of the present invention, in addition to the unsaturated polyester resin (A) and the fiber reinforced material (B), for example, additives which are usually added to the unsaturated polyester resin are similarly used. Can be used for The civil engineering and construction waterproofing sheet of the present invention is a sheet in which the unsaturated polyester resin (A) is reinforced with the fiber reinforced material (B), and the width of the sheet is not particularly limited.
It is preferably 500 to 2000 mm, and more preferably 500 to 1200 mm in consideration of portability. Also, the thickness of the sheet is not particularly limited, but is preferably 0.5 to 5.0 mm, and 0.6 to 1.2 m.
m is more preferred.

The waterproofing sheet for civil engineering and construction of the present invention may be manufactured by a batch method by a conventionally known manufacturing method or by a continuous forming method (a so-called film forming method).
The continuous molding method is preferred in consideration of productivity and stability of quality. (Civil engineering building structure) The first civil engineering building structure of the present invention includes at least a part of the FRP layer obtained by curing the above-described FRP waterproof material of the present invention. The second civil engineering building structure of the present invention includes at least a part of the waterproof sheet of the present invention described above.

The third civil engineering building structure according to the present invention is:
An FRP waterproof layer comprising at least an unsaturated polyester resin and a fiber reinforcement, and a top coat resin layer laminated on the FRP waterproof layer, wherein the top coat resin layer is as described above. It is formed of the unsaturated polyester resin for waterproofing of FRP of the present invention.
In addition, the FRP waterproof layer in the third civil engineering building structure is not particularly limited, and a conventionally known FRP waterproof layer can be applied.
The FRP waterproofing layer using the FRP waterproofing material or waterproofing sheet of the present invention described above is the object of the present invention for recovering PET.
It is preferable from the point of consumption. In addition, it is preferable that the said FRP waterproof layer is normally formed in thickness of about 0.5-5.0 mm. If it is less than 0.5 mm, sufficient waterproofness may not be exhibited, while if it exceeds 5.0 mm, cracks tend to occur due to curing shrinkage.

The substrate which can be applied to the civil engineering building structure of the present invention is not particularly limited. For example, cement concrete, asphalt concrete, asbestos slate (JIS5403), ALC board, PC board, FR
C, plastics, woody materials, metals and the like alone or in combination. Also, the shape is not particularly limited, as long as it is the surface of the structure.
Any of a spherical surface, a curved surface, an extended surface, a flat surface, a vertical surface, a slope, a ceiling surface, etc. may be used. For a substrate having water absorption and permeability, such as cement concrete and asbestos slate, if the water content is high, swelling or peeling occurs due to moisture volatilized after construction, so that the substrate is dried so that the water content becomes 5% or less. It is desirable to construct later.

It is preferable that the substrate is previously subjected to a base treatment, a primer treatment, or the like, if necessary. As the primer, there are various primers such as urethane type, epoxy type and polyester type, and may be appropriately selected depending on workability, substrate condition and the like. The amount of the primer to be applied may be selected and applied in the range of 0.1 to 1 kg / m ² in consideration of the permeability of the material of the base. The method for constructing the first to third civil engineering building structures of the present invention is not particularly limited.For example, in the case of the first civil engineering building structure, first apply a primer on the substrate. After drying the primer, apply the FRP waterproofing unsaturated polyester resin or
Alternatively, the fiber reinforced material may be disposed on a substrate, and impregnated with the unsaturated polyester resin for FRP waterproofing by hand lay-up or spray-up. In the case of the second civil engineering building structure, for example, the waterproofing sheet for civil engineering construction may be attached using an adhesive or the like. As the adhesive, for example, an adhesive of a conventionally known liquid form such as a urethane type, an epoxy type, a silicon type, a vinyl ester type, an unsaturated polyester type, and an acrylic type may be used. In consideration of the above, an epoxy-based adhesive, a silicone-based adhesive, and a urethane-based adhesive having an isocyanate group are preferable.

When the third civil engineering building structure of the present invention is constructed, for example, the FRP waterproof layer of the present invention is formed on the FRP waterproof layer formed by the above-mentioned conventionally known construction method.
The unsaturated polyester resin for RP waterproofing is laminated as a top coat resin layer. At this time, the method for laminating the top coat resin layer is not particularly limited. For example, the FRP waterproofing unsaturated polyester resin may be applied by a roller or a spray and cured. In addition, the top coat resin layer is usually 0.00
It is preferable to form it to a thickness of about 5 to 1.0 mm.
If it is less than 0.005 mm, weather resistance and uniformity tend to be impaired, while if it exceeds 1.0 mm, cracks may occur.

[0037]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the examples. Various physical properties of the obtained unsaturated polyester resin and the like were evaluated by the following methods. In the Examples and Comparative Examples, “parts” indicates “parts by weight”. <Tensile strength and elongation of unsaturated polyester resin and FRP waterproofing material> Measured according to JIS-K7113. <Adhesive strength of civil engineering building structure sample> After leaving the obtained civil engineering building structure sample for one week, a cut was made, and a 40 × 40 mm steel jig was cut with an epoxy adhesive.
It adhered to the adhesion area of 6 cm ² . After the adhesive has cured,
9.8 N using a hydraulic adhesion tester (manufactured by Yamamoto Kojuki)
/ Sec, and the adhesive strength was calculated by the following equation.

Adhesive strength (N / cm ² ) = breaking load / adhesive area [Production of unsaturated polyester resin for FRP waterproofing] (Example 1) A thermometer, a stirrer, an inert gas blowing pipe and a reflux cooling pipe were provided. A 1 L four-necked flask was charged with 240 parts of the collected PET bottle pulverized material and 353 parts of diethylene glycol, and subjected to glycol decomposition under reflux for 8 hours. Thereafter, the temperature is lowered to 150 ° C. or less, and then
166 parts of phthalic anhydride, 125 parts of maleic anhydride, and 76 parts of adipic acid were charged, the reflux condenser was replaced with a fractionating tube, and a condensation reaction was performed at 210 ° C. for 10 hours while blowing nitrogen gas to obtain an unsaturated polyester.

To 60 parts of the obtained unsaturated polyester, 40 parts of styrene and 0.01 part of hydroquinone were added to obtain an unsaturated polyester resin (1) having an acid value of 10 and a viscosity of 4 poise. 8 parts were added to 100 parts of the obtained unsaturated polyester resin.
% Cobalt octenoate 0.3 part and methyl ethyl ketone peroxide 1.0 part were blended and vacuum degassed, and this was produced using two sheet glasses having a release film adhered to one surface and a 3 mm thick guide. Inject into the case, 3
A test plate having a thickness of mm was obtained, and various physical properties of the unsaturated polyester resin were measured. Table 1 shows the results.

(Example 2) In a flask similar to that in Example 1, 231 parts of the ground PET bottle collected, 66 parts of diethylene glycol, 23 parts of ethylene glycol, 208 parts of propylene glycol, and 0.06 part of tetrabutyl titanate were placed. The mixture was charged and refluxed at 200 ° C. for 1 hour to perform glycol decomposition. Thereafter, the temperature was lowered to 150 ° C. or lower, and then 125 parts of maleic anhydride and 34 parts of adipic acid were added.
After charging 7 parts, the reflux cooling pipe was changed to a fractionating pipe, and a condensation reaction was performed at 210 ° C. for 12 hours while blowing nitrogen gas to obtain an unsaturated polyester.

35 parts of styrene and 0.01 part of hydroquinone were added to 65 parts of the obtained unsaturated polyester to obtain an unsaturated polyester resin (2) having an acid value of 18 and a viscosity of 2.3 poise. A test plate was obtained in the same manner as in Example 1 using the obtained unsaturated polyester resin, and various physical properties of the unsaturated polyester resin were measured. Table 1 shows the results. (Example 3) Into the same flask as in Example 1, 450 parts of the collected pulverized PET bottle, 300 parts of triethylene glycol, and 0.06 part of tetrabutyl titanate were charged and refluxed at 220 ° C for 30 minutes. Decomposition was performed. Thereafter, the temperature was lowered to 150 ° C. or lower, and then 71 parts of maleic anhydride and 180 parts of adipic acid were charged. The reflux condenser was replaced with a fractionation tube, and nitrogen gas was blown into the mixture.
A condensation reaction was performed at 10 ° C. for 12 hours to obtain an unsaturated polyester.

To 65 parts of the resulting unsaturated polyester, 35 parts of styrene and 0.01 part of hydroquinone were added to obtain an unsaturated polyester resin (3) having an acid value of 10 and a viscosity of 4.5 poise. A test plate was obtained in the same manner as in Example 1 using the obtained unsaturated polyester resin, and various physical properties of the unsaturated polyester resin were measured. Table 1 shows the results. (Example 4) In the same flask as in Example 1, 80 parts of the collected pulverized PET bottle, diethylene glycol 2
53 parts, charged 0.06 parts of tetrabutyl titanate,
The mixture was refluxed at 220 ° C. for 30 minutes to perform glycol decomposition. Thereafter, the temperature was lowered to 150 ° C. or lower, and then 200 parts of diethylene glycol, 285 parts of maleic anhydride,
Adipic acid (182 parts) was charged, the reflux condenser was replaced with a fractionation tube, and a condensation reaction was performed at 210 ° C. for 12 hours while blowing nitrogen gas to obtain an unsaturated polyester.

35 parts of styrene and 0.01 part of hydroquinone were added to 65 parts of the obtained unsaturated polyester to obtain an unsaturated polyester resin (4) having an acid value of 10 and a viscosity of 7 poise. A test plate was obtained in the same manner as in Example 1 using the obtained unsaturated polyester resin, and various physical properties of the unsaturated polyester resin were measured. Table 1 shows the results. (Example 5) The same flask as in Example 1 was charged with 276 parts of the collected pulverized PET bottle and 339 parts of diethylene glycol, and subjected to glycol decomposition under reflux for 8 hours. Thereafter, the temperature was lowered to 150 ° C. or lower, and then 163 parts of maleic anhydride and 204 parts of adipic acid were charged.
The reflux condenser was replaced with a fractionation pipe, and a condensation reaction was performed at 210 ° C. for 10 hours while blowing nitrogen gas to obtain an unsaturated polyester.

To 60 parts of the obtained unsaturated polyester, 40 parts of styrene and 0.01 part of hydroquinone were added to obtain an unsaturated polyester resin (5) having an acid value of 10 and a viscosity of 4 poise. A test plate was obtained in the same manner as in Example 1 using the obtained unsaturated polyester resin, and various physical properties of the unsaturated polyester resin were measured. Table 1 shows the results. (Example 6) Into the same flask as in Example 1, 221 parts of the collected pulverized PET bottle, 510 parts of tetraethylene glycol, and 0.06 part of tetrabutyl titanate were charged, and refluxed at 200 ° C for 1 hour. Decomposition was performed. Thereafter, the temperature was lowered to 150 ° C. or lower, and then 194 parts of maleic anhydride and 68 parts of adipic acid were charged.
A condensation reaction was performed at 10 ° C. for 12 hours to obtain an unsaturated polyester.

To 65 parts of the resulting unsaturated polyester, 35 parts of styrene and 0.01 part of hydroquinone were added to obtain an unsaturated polyester resin (6) having an acid value of 18 and a viscosity of 2.3 poise. A test plate was obtained in the same manner as in Example 1 using the obtained unsaturated polyester resin, and various physical properties of the unsaturated polyester resin were measured. Table 1 shows the results. Example 7 The same flask as in Example 1 was charged with 401 parts of the collected PET bottle pulverized material, 318 parts of tetraethylene glycol, 31 parts of ethylene glycol, and 0.06 part of dibutyltin oxide. After refluxing for 1 minute, glycol decomposition was performed. Thereafter, the temperature was lowered to 150 ° C. or lower, and then 129 parts of maleic anhydride and 102 parts of adipic acid were charged, and the reflux condenser was replaced with a fractionation pipe.
A condensation reaction was performed at 210 ° C. for 12 hours while blowing nitrogen gas to obtain an unsaturated polyester.

To 65 parts of the obtained unsaturated polyester, 35 parts of styrene and 0.01 part of hydroquinone were added to obtain an unsaturated polyester resin (7) having an acid value of 10 and a viscosity of 4.5 poise. A test plate was obtained in the same manner as in Example 1 using the obtained unsaturated polyester resin, and various physical properties of the unsaturated polyester resin were measured. Table 1 shows the results. (Example 8) Into the same flask as in Example 1, 1000 parts of the unsaturated polyester resin obtained in Example 7, 10 parts of tolylene diisocyanate, and 0.02 part of zinc octenoate were charged and stirred at 85 ° C for 2 hours. After reacting and cooling, a urethane-modified unsaturated polyester resin having a viscosity of 6 poise (8)
I got

Using the obtained unsaturated polyester resin, a test plate was obtained in the same manner as in Example 1, and various physical properties of the unsaturated polyester resin were measured. Table 1 shows the results. [Production of Unsaturated Polyester Resin Used in General] (Comparative Example 1) 202 parts of terephthalic acid, 89 parts of adipic acid and 150 parts of phthalic anhydride were placed in the same flask as in Example 1.
Parts, 409 parts of diethylene glycol, 31 parts of propylene glycol, 0.03 part of dibutyltin oxide,
The condensation reaction was performed at 220 ° C. until the acid value reached 15 while blowing nitrogen gas. Thereafter, the temperature was lowered to 150 ° C. or lower, and then 119 parts of maleic anhydride was charged.
Further condensation reaction was performed at 12 ° C. for 12 hours to obtain an unsaturated polyester.

To 60 parts of the resulting unsaturated polyester, 40 parts of styrene and 0.01 part of hydroquinone were added to obtain a comparative unsaturated polyester resin having an acid value of 10 and a viscosity of 4 poise (Comparative 1). A test plate was obtained in the same manner as in Example 1 using the obtained unsaturated polyester resin, and various physical properties of the unsaturated polyester resin were measured. Table 1 shows the results. Comparative Example 2 In a flask similar to that in Example 1, 226 parts of terephthalic acid, 82 parts of adipic acid, and 172 parts of phthalic anhydride were added.
Parts, 408 parts of diethylene glycol, 21 parts of propylene glycol, 0.03 part of dibutyltin oxide,
The condensation reaction was performed at 220 ° C. until the acid value reached 15 while blowing nitrogen gas. Thereafter, the temperature was lowered to 150 ° C. or lower, then 90 parts of maleic anhydride was charged, the reflux condenser was replaced with a fractionating pipe, and 210 ° C. while blowing nitrogen gas.
For 12 hours to obtain an unsaturated polyester.

To 60 parts of the obtained unsaturated polyester, 40 parts of styrene and 0.01 part of hydroquinone were added to obtain an unsaturated polyester resin having an acid value of 10 and a viscosity of 4 poise (Comparative 2). A test plate was obtained in the same manner as in Example 1 using the obtained unsaturated polyester resin, and various physical properties of the unsaturated polyester resin were measured. Table 1 shows the results. [Production of FRP waterproofing material] (Examples 11 to 18 and Comparative Examples 11 and 12) 8% octene was added to each of 100 parts of the unsaturated polyester resin obtained in Examples 1 to 8 and Comparative Examples 1 and 2. 0.3 parts of cobalt oxide, 1.0 of methyl ethyl ketone peroxide
And a fiber reinforcing material (450 g / m ² glass mat, “CM-455F” manufactured by Asahi Fiberglass Co., Ltd.).
A "3 plies) to obtain an FRP waterproof material. In each case, the content of the fiber reinforced material was adjusted to be 30% by weight.

Table 1 shows the physical properties of the obtained FRP waterproofing materials.
Shown in [Manufacture of civil engineering building structure sample] (Examples 21 to 28 and Comparative Examples 21 and 22) JIS
On a concrete sidewalk board (300 × 300 × 70 mm), a one-component moisture-curable urethane resin (manufactured by NSC Japan, trade name “KBK-YP”) as a primer is 200 g / m.
A substrate coated ^{2 and} dried for 3 hours was prepared. A fiber reinforced material (450 g / m ² glass mat, 2 plies of “CM-455FA” manufactured by Asahi Fiber Glass Co., Ltd.) was placed thereon, and the fiber reinforcements obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were further placed. A resin composition obtained by blending 0.3 part of 8% cobalt octenoate and 1.0 part of methyl ethyl ketone peroxide into 100 parts of each of the saturated polyester resins is applied and impregnated, and a civil engineering building structure sample is obtained. Produced. In each case, the content of the fiber reinforced material was adjusted to be 25% by weight.

Table 1 shows the physical properties of the obtained civil engineering building structure samples.

[0052]

[Table 1]

As is evident from Table 1, it was found that the same physical properties as those obtained by using only the conventionally used unsaturated polyester resin for waterproofing of FRP were obtained by using the recovered PET as a raw material.

[0054]

According to the present invention, the recovered P has the same performance as that of the conventional unsaturated polyester resin for waterproofing FRP.
It is possible to provide an unsaturated polyester resin for waterproofing FRP, which can effectively contribute to the consumption of ET, and an FRP waterproofing material for civil engineering, a waterproofing sheet for civil engineering, and a civil engineering building using the same.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) E04D 7/00 E04D 7/00 G // C08L 67:06 C08L 67:06 (72) Inventor Toshiyuki Sugiura Aichi Aika Kogyo Co., Ltd., 24, Jinmeji-cho, Kaifu-gun, Aichi Prefecture, Japan (72) Inventor Shinsho Otsuki 5-8, Nishiobari-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. 5-8 Nishiburi-cho, Suita-shi Nippon Shokubai Co., Ltd.

Claims (10)

[Claims] An unsaturated polyester resin for FRP waterproofing comprising an unsaturated polyester (a) and a polymerizable monomer (a '), wherein the unsaturated polyester (a) is
An unsaturated polyester resin for FRP waterproofing, which is obtained by using recovered polyethylene terephthalate as a raw material together with an acid component and a glycol component containing at least an α, β-unsaturated polybasic acid or an acid anhydride thereof. 2. The recovered polyethylene terephthalate comprises:
2. The unsaturated polyester resin for FRP waterproofing according to claim 1, wherein the content of the unsaturated polyester (a) is 1 to 60% by weight based on all raw materials. 3. 3. The method according to claim 2, wherein at least a part of the glycol component is
3. The unsaturated polyester resin for FRP waterproofing according to claim 1, which is an ether group-containing glycol. 4. The unsaturated polyester resin for waterproofing of FRP according to claim 1, wherein a part of the acid component is a linear saturated polybasic acid. 5. An FRP waterproofing material for civil engineering and construction comprising the unsaturated polyester resin (A) according to any one of claims 1 to 4 and a fiber reinforcing material (B). 6. The civil engineering building according to claim 5, wherein the proportion of the unsaturated polyester resin (A) is 40 to 95% by weight, and the proportion of the fiber reinforced material (B) is 5 to 60% by weight. FRP waterproofing material. 7. An FRP waterproofing material comprising the unsaturated polyester resin (A) according to any one of claims 1 to 4 and a fiber reinforcing material (B) is formed into a sheet and cured. Tarpaulin for civil engineering and construction. 8. An FRP layer formed by curing an FRP waterproofing material comprising the unsaturated polyester resin (A) according to claim 1 and a fiber reinforcing material (B), at least in part. Civil and architectural structures, including as 9. A waterproof material obtained by molding an FRP waterproof material containing the unsaturated polyester resin (A) according to any one of claims 1 to 4 and a fiber reinforcing material (B) into a sheet shape and curing the FRP waterproof material. A civil engineering building structure comprising at least a sheet. 10. A civil engineering building structure comprising at least an FRP waterproof layer composed of at least an unsaturated polyester resin and a fiber reinforcing material, and a top coat resin layer laminated on the FRP waterproof layer. A civil engineering structure, wherein the top coat resin layer is formed of the unsaturated polyester resin according to any one of claims 1 to 4.