JP2014166765A - Foreign odor suppressive resin laminate and foreign odor suppression method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide means of avoiding contact of a resin such as epoxy resin with halogen, suppressing generation of various halogenated phenols thereby, and reducing foreign odor due to halogenated phenol and halogenated anisole generated therefrom; and also means of suppressing bleeding of a halogenated compound from the resin and/or volatilization from the resin surface into the atmosphere in the case that those halogenated compounds have already generated in the resin.SOLUTION: A resin layer comprising an acrylic urethane resin or a silicone resin is formed on a layer comprising a resin such as epoxy resin.

Description

The present invention suppresses the generation of off-flavor substances due to contact between a resin such as an epoxy resin and residual chlorine, and / or off-flavor suppression that suppresses bleeding and / or volatilization of off-flavor substances from resins that already have off-flavor substances. The present invention relates to a resin laminate, and a method for suppressing off-flavor using the off-flavor suppressing resin laminate. The present invention also relates to a resin film forming composition for forming the laminate.

In recent years, troubles of off-flavor and odor caused by chlorophenols have been reported for foods. For example, it has been reported that agrochemicals sprayed during vegetable cultivation remain and decompose to produce dichlorophenol having a chemical-like odor (see, for example, Non-Patent Document 1). In addition, phenol and residual chlorine contained in water react to produce dichlorophenol (DCP).
In addition, troubles that produce trichlorophenol (TCP) and contaminate foods have been reported (for example, see Non-Patent Document 2).

In addition, residual chlorine derived from sodium hypochlorite, etc. sprayed on wood products for the purpose of sterilization and bleaching, and lignin and its decomposition products in wood react to produce dichlorophenol and trichlorophenol. Have also been reported (for example, see Non-Patent Document 3). In addition, it is known that the produced trichlorophenol is converted to trichloroanisole (TCA) having a very low functional threshold by the converting bacterium, and the flavor of food is impaired by trichloroanisole. Furthermore, it has been reported that trichlorophenol sprayed on wood products as an antifungal agent is converted into trichloroanisole by the conversion bacteria, and the odor of the generated trichloroanisole contaminates the food, causing a major problem such as food recovery. (For example, refer nonpatent literature 4).

In general, epoxy resin is glossy, has excellent mechanical properties such as strength, has excellent resistance to chemicals, emits less volatile components during curing, and has good adhesion For this reason, it is widely used for civil engineering and building applications such as flooring, paints, and adhesives. In particular, epoxy resins are frequently used as flooring materials in food manufacturing plants, food processing plants, hospitals, and the like that require cleanliness.

However, the odor derived from the epoxy resin-based building material has not been studied so far, and the reduction of the solvent odor has been studied. For example, JP-A-2005-48118
The issue describes that the environment used for building work is improved by changing the solvent used to dissolve the raw materials and improve the workability to a solvent having a lower odor. Thus, conventionally,
Regarding the epoxy resin, studies have been made to reduce the solvent odor at the time of construction or immediately after the construction, but sufficient studies have not been made on the odor generated from the cured epoxy resin.

JP 2005-48118 A

“Food complaint handling cases at the Yokohama City Institute of Public Health-complaints about chemical odors”, published on February 28, 2008, the Yokohama City website (http://www.city.yokohama.jp/me/kenkou/ eiken /) Tsutomu Sugawara et al. “Griefed case of sweet natto using chlorophenols as a causative substance of odor”, Tokyo Metropolitan Institute of Health and Safety, 54, 227-230 (2003) Die Weinwirtschaft Technik, 13, 9, 276-279 (1985) Journal of Japan Packaging Society, Vol. 3, No. 1, 35 (1994)

Under such circumstances, the present inventor has added a phenolic compound added as a curing accelerator for an epoxy resin used as a building material such as a flooring material or a phenolic compound present as an impurity in the epoxy resin such as chlorine. It has been found that various halogenated phenols such as dichlorophenol and trichlorophenol are produced when they come into contact with other halogens, causing a bad odor. Furthermore, the present inventor has produced dichlorophenol and trichlorophenol,
It was found that the sensory threshold was extremely low and that it was converted by microorganisms into trichloroanisole, which caused the musty odor, causing a strange odor.

Particularly in manufacturing sites and hospitals where cleanliness is required, chemicals containing chlorine are used for the purpose of cleaning, sterilization, etc., and there are relatively many opportunities for building materials such as flooring to come into contact with chlorine in the chemicals.
For example, after the food is manufactured, the production line may be cleaned using a chemical containing chlorine or an aqueous solution thereof, but the waste liquid may come into contact with a flooring made of an epoxy resin composition.
Moreover, the chemical | medical agent containing chlorine and its aqueous solution may be sprayed directly on an epoxy resin-type building material for the purpose of disinfection and disinfection.

Therefore, when epoxy resin building materials come into contact with residual chlorine, dichlorophenol (
Various chlorinated phenols such as DCP) and trichlorophenol (TCP) are produced, and further, trichloroanisole (TCA) is produced by microorganisms, which may cause troubles of strange odor. For example, these off-flavor substances volatilize in the environment and give off off-flavors,
In addition, when off-flavor substances are produced in the food production process, the food is contaminated and the flavor of the food is impaired.

Furthermore, in recent years, the use of bromine-based fungicides instead of chlorine-based fungicides has expanded, but as in the case of chlorine-based agents, dibromophenol and tribromophenol are brought into contact with phenolic compounds and bromine-based agents. In addition, various brominated phenols such as the above may be generated, and tribromoanisole (TBA) may be generated by microorganisms, which may cause troubles of strange odor.

Also, epoxy resin-based building materials are generally made of a compound having a bisphenol skeleton. Bisphenol A, one of the compounds having a bisphenol skeleton, has been reported to produce chlorinated phenol in an aqueous sodium hypochlorite solution with 10 ppm residual chlorine (Takashi Ymamoto, et., Chemosphere, 46, 1215- 1223 (2002))
. Therefore, when an epoxy resin-based building material comes into contact with a chemical containing chlorine, the reaction between the phenolic compound added to the epoxy resin as a curing accelerator and / or the phenolic compound present in the epoxy resin as an impurity and residual chlorine. In addition to this, it is also conceivable that a reaction for producing chlorinated phenol by bisphenol A and residual chlorine in the epoxy resin occurs.

Furthermore, once the halogenated phenol, the halogenated anisole or the like as described above is generated in the epoxy resin, it is difficult to reduce off-flavors derived from the halogenated compound by washing the resin surface or the like.

The present inventor pays attention to such problems, avoids contact between epoxy resin (for example, flooring) used for building materials and halogens such as chlorine, thereby suppressing generation of various halogenated phenols, We studied to reduce off-flavors caused by halogenated phenols and halogenated anisole. In addition, when various halogenated phenols, halogenated anisole, etc. are already produced in the epoxy resin, the bleeding of those halogenated compounds from the resin and / or volatilization from the resin surface to the atmosphere is suppressed, and The reduction of off-flavors derived from the halogenated compounds was investigated. Furthermore, the applicability of such technology to other resins was also examined.

As a result of intensive studies to solve the above problems, the present inventors have formed a film using a specific resin on the surface of an epoxy resin (for example, a flooring material), whereby residual chlorine, an epoxy resin, and It was found that the contact of can be effectively avoided. In addition, by forming a coating containing a specific resin on the surface of an epoxy resin from which an off-flavor substance such as a halogenated phenol or anisole halide is formed, the off-flavor of the off-flavor substance from the resin and / or volatilization into the atmosphere It was found that can be effectively suppressed. Furthermore, it has been found that this technique can be applied not only to epoxy resins but also to other resins having a bisphenol skeleton, such as epoxy acrylate resins. Based on these findings, the present invention has been completed.

That is, the present invention relates to the following.
1. A strange odor-inhibiting resin laminate in which a second resin layer containing an acrylic urethane resin or a silicone resin is formed on one side or both sides of a first resin layer containing a cured epoxy resin or a cured epoxy acrylate resin.
2. 2. The laminate according to 1, wherein the first resin layer contains a cured bisphenol-based epoxy resin or a cured bisphenol-based epoxy acrylate resin.
3. The laminate according to 1, wherein the off-flavor is off-flavor caused by halogenated phenol or halogenated anisole.
4). Forming a second resin layer containing an acrylic urethane resin or a silicone resin on one side or both sides of a first resin layer containing an epoxy resin or an epoxy acrylate resin that is cured or curing, and a method for suppressing odor .
5. 5. The method for suppressing odor according to 4, wherein the odor is a odor caused by halogenated phenol or anisole.
6). A construction method comprising forming a second resin layer containing an acrylic urethane resin or a silicone resin on one side or both sides of a first resin layer containing an epoxy resin or an epoxy acrylate resin that has been cured or is being cured.
7). 7. The construction method according to 6, which is carried out to suppress off-flavors caused by halogenated phenol or halogenated anisole.
8). Including acrylic urethane resin or silicone resin material for coating on one or both sides of a layer comprising an epoxy resin or epoxy acrylate resin, cured or curing,
One-component type or two-component or more mixed-type resin film-forming composition.
9. 9. The composition according to 8, for suppressing off-flavors caused by halogenated phenols or halogenated anisole.

The resin laminate of the present invention can avoid contact between an epoxy resin or an epoxy acrylate resin and a halogen even when the resin laminate itself contacts with a halogen such as chlorine, and is produced in the epoxy resin or epoxy acrylate resin. Bleed from halogenated phenols and halogenated anisole resins and / or volatilization into the atmosphere is suppressed, and off-flavors derived from these halogenated compounds are reduced.

Therefore, it is useful to use the resin laminate as a building material such as a flooring material in place of the conventionally used epoxy resin or the like. In particular, the resin laminate is used as a building material for manufacturing sites that are required to prevent the generation of off-flavors, such as food processing sites and food manufacturing sites, or hospitals and research facilities that are relatively in contact with drugs. It can be used very suitably.

In the present invention, a second resin layer containing an acrylic urethane resin or a silicone resin is formed on one side or both sides of the first resin layer containing a cured or curing epoxy resin or epoxy acrylate resin. On the first resin layer, the material of the second resin layer may be applied and then cured, or a second resin layer that has been previously cured may be applied. In this way
A resin laminate in which the second resin layer is formed on one side or both sides of the cured first resin layer is obtained.
Moreover, the resin composition containing the material for producing | generating an acrylic urethane resin or a silicone resin has itself usefulness as a resin film formation composition for a 2nd resin layer.

(First resin layer)
The first resin layer is formed using an epoxy resin or an epoxy acrylate resin. For example, the resin may be applied to the floor or wall surface before curing to form a layer and then cured, or a pre-formed layer of cured resin may be applied to the floor or wall surface. Moreover, although a 1st resin layer may be newly formed, what was already used for a certain period as a construction material etc. may be used. For example, what is already used as a flooring and has been sterilized with halogen is dichlorophenol (
DCP), trichlorophenol (TCP), trichloroanisole (TCA) and the like may be generated, and such can also be the first resin layer of the present invention.

In the first resin layer, an epoxy resin or an epoxy acrylate resin may be used alone or in combination. In addition to these resins, the first resin layer contains other resins such as unsaturated polyester resin, polyurethane resin, methyl methacrylate resin, melamine resin, acrylic resin, polyester resin, fluororesin, phenol resin, furan resin. May be included. The content of the epoxy resin or epoxy acrylate resin in the first resin layer is not limited, but is typically about 20 to 60% by weight.

(Epoxy resin)
The term “epoxy resin” in the present specification has an ordinary meaning in the art, and typically has an epoxy group in a polymer and is cured by graft polymerization and its thermosetting resin. A cured product. In this specification, the term “epoxy resin” simply means a prepolymer before curing or a polymer after curing.

The epoxy resin that can be used in the present invention is not particularly limited in its structure,
Various epoxy resins can be used. For example, bisphenol A type epoxy resin which is bisphenol type epoxy resin, bisphenol F type epoxy resin, epoxy resin having biphenyl skeleton and naphthalene skeleton, alicyclic epoxy resin, brominated epoxy resin, aliphatic epoxy resin, multifunctional Various epoxy resins such as an epoxy resin can be used, and these may be used alone or as a mixture of two or more. Particularly preferable epoxy resins in the present invention include bisphenol type epoxy resins including bisphenol A type epoxy resins and bisphenol F type epoxy resins.

Commercially available products can be used as the bisphenol type epoxy resin as the prepolymer. For example, Epicoat 825, Epicoat 827, Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.), D.I. E. R. 331 (manufactured by Dow Chemical Company), Epicron 830, Epicron 840, Epicron 850 (Dainippon Ink Chemical Co., Ltd.), Adeka Resin EP-40
00, Adeka Resin EP-4100, Adeka Resin EP-4100G, Adeka Resin EP
-4901 (Asahi Denka), Epomic R110, Epomic R140 (Mitsui Chemicals)
Etc.

The molecular weight of the prepolymer epoxy resin used in the present invention is preferably 300 to
2000, more preferably 350 to 1000, particularly preferably 350 to 500.
When these molecular weight epoxy resins are used, physical properties suitable as a building material can be obtained. The properties of the prepolymer resin are not particularly limited, and liquid or solid materials can be used, but those that cure at room temperature are preferred.

The curing agent for curing the prepolymer epoxy resin is not particularly limited, and any curing agent such as an amine curing agent and a phenol curing agent may be used. However, in the present invention, since the generation of off-flavor substances can be suppressed by reducing the amount of phenols contained in the cured epoxy resin, various aliphatic polyamines and alicyclic polyamines that do not contain phenols. Amine-based curing agents such as aromatic polyamines, polyamidoamines, and epoxy adduct-modified polyamines are preferred. Among them, an epoxy adduct-modified polyamine is desirable because it has good finish and curability, has few residual phenol compounds, and effectively suppresses the generation of off-flavor substances. Moreover, in this invention, a hardening | curing agent may be used individually or in mixture of 2 or more types, and may contain water further.

The mixing ratio of the epoxy resin before curing and the curing agent is not particularly limited, and may be appropriately adjusted according to the use and workability of the epoxy resin.
With regard to the epoxy resin, a resin film forming composition containing a prepolymer and a curing agent is commercially available, and the first resin layer may be formed using them. Examples of such commercially available compositions include Chemicrete E (manufactured by ABC Corporation) and Chemicrete E.NP ((
Manufactured by ABC Shokai Co., Ltd.).

(Epoxy acrylate resin)
The term “epoxy acrylate resin” in the present specification has an ordinary meaning known in the art, and typically a resin in which acrylic acid or methacrylic acid is added to the epoxy group portion of the epoxy resin. Is diluted with styrene, a methyl methacrylate monomer, or a methyl methacrylate prepolymer, and the content of the epoxy acrylate resin is about 20 to 60%. A metal catalyst, an amine catalyst, and a peroxide are used. Used to mean a resin that is polymerized and cured by a radical reaction, and a cured product thereof. In this specification,
When simply referred to as “epoxy acrylate resin”, it means a prepolymer before curing or a polymer after curing.

In the present invention, the structure of the epoxy acrylate resin is not particularly limited, and various types can be used. However, an epoxy acrylate resin having a bisphenol skeleton, for example, a bisphenol-based vinyl ester resin or a bisphenol-based resin is preferable. They are a saturated polyester resin and a novolak type vinyl ester resin, and these can be used alone or as a mixture of two or more.

Commercially available products can be used as the bisphenol-type epoxy acrylate resin as the prepolymer, and examples include Lipoxy R-804 (manufactured by Showa Kogyo Co., Ltd.), Dicklight UE-5210 (manufactured by DIC), and the like. it can.

In order to cure the epoxy acrylate resin as a prepolymer, a metal catalyst or an amine catalyst and an organic peroxide are used in combination. However, it is not particularly limited, and any known catalyst and organic peroxide can be used. It may be used. Examples of typical metal catalysts include cobalt naphthenate and cobalt octenoate, and examples of amine catalysts include dimethylaniline, trimethylaniline and the like diluted with mineral spirits. Moreover, as an organic peroxide, what diluted benzoyl peroxide, methyl ethyl ketone peroxide, cumene acid peroxide, etc. with dioctyl phthalate, dimethyl phthalate, etc. is mentioned.

The blending ratio of the epoxy acrylate resin before curing, the catalyst and the organic peroxide is not particularly limited, and may be appropriately adjusted according to the use and workability of the resin.
In the present invention, a diluent can be used in forming the resin layer. By using a diluent, it is possible to adjust the raw resin and curing agent to an appropriate viscosity, and to improve the finish of the construction surface. The diluent is not particularly limited, and one type or two or more types of known diluents can be used in combination. Examples of the diluent include alcohols such as methanol, ethanol, propanol, butanol and benzyl alcohol; ketones such as acetone and methyl ethyl ketone; glycol solvents such as propylmethoxyacetate; ester solvents such as ethyl acetate and butyl acetate; Toluene, xylene, ethylbenzene, water and the like can be used.

In the present invention, a pigment can be used for the resin. As pigments, coloring pigments, extender pigments, functional pigments and the like can be blended depending on the purpose. The pigments are organic pigments, inorganic pigments,
Any of organic and inorganic composite pigments may be used, and one type or two or more types may be used in combination. For example, silica, talc, calcium carbonate, mica, clay, iron oxide, cyanine green,
Cyanine blue, carbon, etc. can be used.

In the present invention, an additive may be used for the resin. As the additive, generally known additives can be used depending on the purpose. For example, disinfectants, dispersants, wetting agents, leveling agents, anti-coloring agents, anti-settling agents, matting agents, slip agents, emulsifiers, preservatives, antifungal agents,
An ultraviolet absorber or the like can be used.
The content of the diluent, pigment, and additive can be appropriately set by those skilled in the art according to the purpose.

(Second resin layer and resin film forming composition therefor)
The resin used for the second resin layer in the present invention is preferably one that does not generate an off-flavor by itself and does not volatilize off-flavor substances in the atmosphere, and more preferably has excellent hypochlorous acid resistance. In the present invention, an acrylic urethane resin or a silicone resin is used as such a resin.

In the second resin layer, these may be used alone or in combination. Furthermore, in addition to these, the second resin layer may contain other resins such as acrylic resin, polyester polyol resin, and polyether polyol resin. The content of the acrylic urethane resin and silicone resin in the second resin layer is not limited, but in order to effectively exhibit the hypochlorite acid resistance and the effect of preventing the emission of off-flavor substances, these resins are used in the first resin layer. It is preferably the main component of the second resin layer, and typically the content thereof is preferably 10-80 respectively.
About 10% by weight, more preferably about 10 to 40% by weight. Moreover, application of the second resin layer is preferably from 0.05 to 0.5 / ^{m 2,} more preferably about between 0.1 and 0.3 kg /
m is ^2.

As the second resin layer, a desired cured resin may be applied on the first resin layer, or a coating composition containing the raw material is applied on the first resin layer and cured. The resin layer may be formed.

(Acrylic urethane resin)
The structure of the acrylic urethane resin that can be used in the present invention is not particularly limited, and various acrylic urethane resins can be used. For example, an acrylic urethane resin that forms a film by reacting an acrylic polyol having two or more active hydrogen-containing groups with an isocyanate compound having two or more isocyanate groups can be suitably used. Therefore, when the present invention is an acrylic resin film-forming composition, the composition is a one-component composition containing the acrylic polyol and an isocyanate compound, or two components separately containing both. The above-mentioned mixed composition at the time of use. Here, the composition at the time of use includes two or more separate liquids (for example, three liquids may be included), and these liquids are mixed when used for film formation. It means something like a kit. The same applies to the following.

Acrylic polyols are typically 2-hydroxyethyl (meth) acrylate, 4
-Copolymerizing one or more of hydroxyl group-containing acrylic monomers such as hydroxybutyl acrylate, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, caprolactone modified (meth) acrylate with other monomers It is obtained. Examples of other monomers combined with a hydroxyl group-containing acrylic monomer include aromatic vinyl monomers such as styrene, α-methylstyrene, p-tert-butylstyrene, vinyltoluene, methyl (meth) acrylate, and ethyl (meth) acrylate. , N-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (Meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate (Meth) acrylates such as relate or alkoxyalkyl (meth) acrylate, diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid and monohydric alcohols, vinyl acetate, vinyl benzoate, vinyl propionate, Examples thereof include vinyl esters such as vinyl laurate and vinyl acetate vinyl and vinyl ethers.

Moreover, the isocyanate compound should just be what can react with the hydroxyl group of acrylic polyol, and can be bridge | crosslinked and hardened, for example, can use aliphatic or aromatic isocyanate more than bivalence. Specifically, triresin isocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, or polyisocyanate obtained by adding these isocyanates to a polyol can be used.

A commercial item can be used as a composition for acrylic urethane resin film formation containing said acrylic polyol and an isocyanate compound. For example, keep coat AU (manufactured by ABC Shokai), keep coat AU aqueous VOC (manufactured by ABC Shokai), color top F top (manufactured by ABC Shokai), wall coat AU soft finish DX (( Inc., manufactured by ABC Shokai Co., Ltd.), Yucacrete AU (manufactured by Daido Paint Co., Ltd.), Hi Art (manufactured by Isamu Paint Co., Ltd.), and the like.

(Silicone resin)
The structure of the silicone resin that can be used in the present invention is not particularly limited, and various types can be used. For example, what gave the silicone characteristic to resin itself, silicone itself, etc. are mentioned.

Examples of the resin imparted with silicone characteristics include acrylic silicone and polyester silicone. For example, the acrylic silicone resin has two or more active hydrogen-containing groups obtained by introducing a silicone group into an acrylic polyol. Examples include a film obtained by reacting a silicone-modified acrylic polyol and an isocyanate compound having two or more isocyanate groups, and a film obtained by volatilizing a dispersion in which a silicone-modified resin is dispersed. As monomers used for modification, silicone monomers such as vinylethoxysilane and γ-methacryloxypropyltrimethoxysilane can be used. The isocyanate that can be used here may be any isocyanate that can react with the hydroxyl group of the acrylic polyol to be crosslinked and cured, as in the above-described isocyanates. For example, an aliphatic or aromatic isocyanate having a valence of 2 or more may be used. Can be used. Specifically, triresin isocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, or polyisocyanate obtained by adding these isocyanates to a polyol can be used.

Examples of silicone itself include alkoxysilanes and polysilazanes having a perhydrosilazane group or a silanol group, such as methyltrimethoxysilane, dimethyldimethoxysilane, and hexamethylsilazane. By mixing these with colloidal silica, Hydrolysis and polycondensation reactions of perhydrosilazane groups and silanol groups, which are reactive groups, occur to form a silicone resin film.

When the present invention is a composition for forming a silicone resin film, the composition is one liquid type or two liquids or more (for example, three liquids) containing the above-mentioned material for forming a silicone resin film. It may be a mixed composition at the time of use. For example, as a resin film forming composition, commercially available acrylic silicone resin film forming composition Protectite SU (manufactured by ABC Corporation), wall coat silicone top soft (manufactured by ABC Corporation), etc. Can be mentioned.

In the production of the second resin layer, a diluent can be used, and such a diluent can be included in the resin film forming composition for the resin layer. The diluent used is the same as that described above for the first resin layer. In the present invention, pigments and additives can also be used for the resin of the second resin layer. For example, these can be included in the composition for forming a resin film for the second resin layer. Such pigments and additives are the same as those described above for the first resin layer. In addition, as such an additive, a plasticizer (for example, a phthalic acid-based, adipic acid-based, or sebacic acid-based plasticizer) can also be used. The content of the diluent, pigment, and additive can be appropriately set by those skilled in the art according to the purpose.

(Apply)
The resin laminate formed by the resin described above may be manufactured at a construction site or may be manufactured in advance. Specifically, when the resin laminate of the present invention is manufactured at a construction site, a mode in which the material is applied at a construction site as a coating material is preferable. When the resin laminate is manufactured in advance, a sheet shape The aspect which manufactures a plate-shaped building material beforehand and applies it to a construction site is preferable. For example, in a preferred embodiment, the resin laminate in the present invention can be suitably used as a building material such as a flooring material, a waterproof material, an anticorrosive material, and a lining material. It can also be used as a covering material for concrete or as a reinforcing material for structures such as bridges. Furthermore, the resin laminate of the present invention can be suitably used not only outdoors but also indoors.

In addition, the present invention not only newly manufactures two resin layers, but also plans to form a second resin layer on the first resin layer that has been manufactured and used. For example, when the first resin layer is used as a building material for a certain period of time, the first resin layer is subjected to disinfection with repeated halogens, and is subjected to dichlorophenol (DCP), trichlorophenol (T
CP) and trichloroanisole (TCA) may be produced. Replacing such a building material with a new one is a considerable burden in terms of cost, but according to the present invention, the resin film forming composition is applied on the first resin layer. If the second layer is formed, it is possible to suppress the off-flavor caused by dichlorophenol (DCP), trichlorophenol (TCP), trichloroanisole (TCA), etc. Is also connected.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these. In the present specification, unless otherwise specified, the blending amount and others are based on weight, and the numerical range is described as including the end points.

Example 1
A film (second resin layer) is formed on the surface of the epoxy resin (undercoat material, first resin layer) using the resin composition for film formation of the present invention, and the effect of inhibiting the formation of chlorinated phenol and the film The discoloration was confirmed. The materials and test methods used are as follows.

(material)
Material 1 (used as a primer and film-forming composition)
・ Material A (undercoat)
Chemicrete E (manufactured by ABC Shokai Co., Ltd.): This is a two-component curable solventless epoxy resin comprising the following base A and curing agent A. A base A and a curing agent A are mixed at a weight ratio of 5: 1 and applied on an aluminum plate or a first resin layer to form a cured epoxy resin.
[Base A] “Chemcreat E base” (manufactured by ABC Corporation): an epoxy resin-based coating base material mainly composed of a bisphenol A type epoxy resin having a molecular weight of about 370.
[Curing Agent A] “Chemcreat E Curing Agent” (manufactured by ABC Corporation): a curing agent mainly composed of a modified aliphatic polyamine.

・ Material B (undercoat)
Chemicrete E.NP (manufactured by ABC Shokai Co., Ltd.): This is a two-component curable solventless epoxy resin comprising the following base B and curing agent B. Base B and curing agent B in a weight ratio of 6:
1 and mixed on an aluminum plate or a first resin layer to form a cured epoxy resin.

[Base B] “Chemcreat E / NP Base” (manufactured by ABC Corporation): containing 35-40 parts by weight of a bisphenol A type epoxy resin having a molecular weight of about 370 as a main component, and a non-phenolic diluent 5-15 A low-odor epoxy resin-based coating base comprising 40 parts by weight, filler (silica, barium sulfate) 40 to 50 parts by weight, calcium hydroxide 5 parts by weight, and color pigment 1 to 5 parts by weight.
[Curing agent B] “Chemcreat E · NP” curing agent (manufactured by ABC Corporation): a curing agent mainly composed of an epoxy adduct-modified amine curing agent.

Material 2 (Resin composition for film formation)
・ Material C (acrylic urethane resin)
Keep coat AU (manufactured by ABC Corporation): This is the following base C and curing agent C
Is a two-component curable solvent-based general-purpose acrylic urethane resin composition. Base C and curing agent C
Is mixed at a weight ratio of 4: 1, diluted by adding 20 to 40% by weight of a special diluent mainly composed of toluene to 100 parts by weight of the mixture, and applied onto the first resin layer, and then acrylic. A urethane resin is produced.

[Base C] 30-40 parts by weight of hard urethane-modified acrylic polyol, 30-40 solvent
A general-purpose acrylic urethane resin composition base comprising 20 parts by weight, inorganic powder and 20 to 30 parts by weight of pigment.
[Curing Agent C] Hexamethylene diisocyanate-based NCO-terminated prepolymer 30-40
A general-purpose acrylic urethane resin composition curing agent comprising parts by weight and 60 to 70 parts by weight of an organic solvent.

・ Material D (acrylic urethane resin)
Wall coat AU soft finishing material DX (manufactured by ABC Corporation): This is a two-component curable solvent-based elastic acrylic urethane resin composition comprising the following base D and curing agent D. The base D and the curing agent D are mixed at a weight ratio of 7: 1, and 100 wt parts of the mixture is diluted by adding 20 to 30 wt% of an exclusive diluent mainly composed of xylene. Apply on layer to produce acrylic urethane resin.

[Base D] Soft urethane-modified acrylic polyol 30-40 parts by weight, solvent 40-50
An elastic acrylic urethane resin composition base comprising parts by weight, inorganic powder and 20 to 30 parts by weight of pigment.
[Curing Agent D] Hexamethylene diisocyanate-based NCO-terminated prepolymer 30-40
An elastic acrylic urethane resin composition curing agent comprising parts by weight and 60 to 70 parts by weight of a solvent.

・ Material E (Polyurethane resin)
Color Top U (manufactured by ABC Shokai Co., Ltd.): This is a moisture-curable solvent-based polyurethane resin composition comprising the following base E and colorant E. The base E and the colorant E are mixed at a weight ratio of 1: 1 and applied onto the first resin layer to produce a polyurethane resin.

[Base E] A urethane resin composition base comprising 40 to 50 parts by weight of tolylene diisocyanate urethane prepolymer, 1 to 10 parts by weight of tolylene diisocyanate, and 50 to 60 parts by weight of a solvent.
[Colorant E] A colorant comprising 10 to 20 parts by weight of an acrylic resin, 15 to 25 parts by weight of a solvent, 60 to 70 parts by weight of an inorganic powder and a pigment.

・ Material F (silicone resin)
Protectito SU (manufactured by ABC Shokai Co., Ltd.): This is a two-component curable solvent-based silicone resin composition comprising the following base F and curing agent F. The base F and the curing agent F were mixed at a weight ratio of 9: 1, and 10 parts by weight of xylene was added to dilute 100 parts by weight of the mixture, and then applied onto the first resin layer. Generate.
[Base F] A silicone resin composition base comprising 20 to 30 parts by weight of a silicone-modified acrylic polyol, 40 to 50 parts by weight of a solvent, 30 to 40 parts by weight of an inorganic powder and a pigment.
[Curing agent F] Hexamethylene diisocyanate ("Takenate D170" manufactured by Mitsui Chemicals, Inc.)
N ") A silicone resin composition curing agent comprising 100 parts by weight.

・ Material G (acrylic resin)
Color Top H (manufactured by ABC Corporation): This is a lacquer type acrylic resin composition. An acrylic resin composition comprising 20 to 30 parts by weight of an acrylic resin, 40 to 50 parts by weight of a solvent, 20 to 30 parts by weight of an inorganic powder and a pigment. After dilution by adding 25% by weight of an exclusive diluent mainly composed of xylene, it is applied onto the first resin layer to produce a lacquer type acrylic resin.

(Test method)
Material A or B was used as the primer. Those bases and curing agents were mixed and stirred, and uniformly applied to an aluminum plate so as to be about 1 Kg / m ² . After confirming the curing, each component of the various film-forming resin compositions of materials C to G was mixed and stirred at a predetermined ratio, and about 0.1 kg / m ² per application on the epoxy resin cured coating film. It was applied twice evenly. In this way, a flooring was prepared. Dilution of various film-forming resin compositions was carried out at the maximum dilution of the standard specification.

The prepared flooring 25 cm ² is put in a petri dish of about φ9 cm, immersed in a hypochlorous acid aqueous solution (effective chlorine concentration 2000 ppm or 5000 ppm) to the extent that the flooring is sufficiently immersed, and allowed to stand at 35 ° C. for 24 hours or 72 hours. did. Thereafter, the immersion liquid was extracted into hexane with a steam distillation apparatus. The hexane extract was concentrated to 1 ml with a rotary evaporator and then analyzed with a gas chromatography-mass spectrometer to obtain 2,4,6-trichlorophenol (2
, 4,6-TCP) was measured.

The detection limit of 2,4,6-trichlorophenol (2,4,6-TCP) by this test method is 0.1 μg / m ² .
(Discoloration of film)
About the said flooring, the discoloration degree when immersed in the sodium hypochlorite aqueous solution for 24 hours or 72 hours was evaluated in three steps. The evaluation criteria are as follows.
1: No discoloration (good), 2: slightly discolored, 3: large discoloration

Table 1 shows the results. As this result shows, by forming a film using acrylic urethane resin (C, D), silicone resin (F), or acrylic resin (G) on the surface of the floor material using epoxy resin, the floor material And the amount of TCP produced when the residual chlorine comes into contact was significantly reduced. The coating using acrylic urethane resin, silicone resin, or acrylic resin avoids contact between the flooring material using epoxy resin and residual chlorine, and the reaction between epoxy resin and residual chlorine is suppressed. It can be said that the formation of compounds was suppressed.
However, a large discoloration was observed in the film using acrylic resin due to contact with residual chlorine. Therefore, it can be said that a film using an acrylic urethane resin or a silicone resin is particularly effective.

Example 2
2,6-dichlorophenol (2,6-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 2,4,6-trichloroanisole (2,4,6)
-TCA) added epoxy resin (undercoat material) film (first resin layer), another film (second resin layer) is formed on the surface, and volatilization of those chlorinated compounds The inhibitory effect was confirmed. The materials and test methods used are as follows.

(Quantification of migration amount of chlorinated compounds in epoxy resin)
In the primer A used in Example 1, 2,6-dichlorophenol (2,6-DCP), 2,
4,6-Trichlorophenol (2,4,6-TCP) and 2,4,6-trichloroanisole (2,4,6-TCA) were added to 1 ppm each, and the same as in Example 1 was performed. A first resin layer was formed on the aluminum plate. Next, in the same manner as in Example 1, a second resin layer was formed on the first resin layer using materials C to G, thereby creating a flooring material.

The experiment was performed in the same manner as in Example 1 except that the immersion liquid was changed. It was immersed in distilled water enough to immerse the flooring, and allowed to stand at 35 ° C. for 24 hours or 72 hours. Thereafter, the immersion liquid was extracted into hexane with a steam distillation apparatus. The hexane extract was concentrated to 1 ml with a rotary evaporator and then analyzed with a gas chromatography-mass spectrometer to measure the amount of chlorinated compound produced.

In addition, 2,6-dichlorophenol (2,6-DCP) 2,4,6- by this test method
The detection limit of the amount of trichlorophenol (2,4,6- (TCP) and 2,4,6-trichloroanisole (2,4,6-TCA) is 0.1 μg / m ² .

Table 2 shows the results. As this result shows, by forming a film using acrylic urethane resin, silicone resin, or acrylic resin on the surface of the flooring material using epoxy resin, the chlorinated compound in the epoxy resin moves out of the system. There wasn't. It can be said that bleed from the resin of the chlorinated compound and / or volatilization into the atmosphere could be suppressed by the coating using the acrylic urethane resin, the silicone resin, or the acrylic resin. However, in Example 1,
In view of the fact that the coating using acrylic resin has undergone significant discoloration due to contact with residual chlorine, in order to suppress bleeding of the chlorinated compound from the resin and / or volatilization into the atmosphere, especially acrylic urethane resin or It can be said that a film using a silicone resin is effective.

As described above, the acrylic urethane resin and the silicone resin, which are the off-flavor suppressing resins of the present invention, can suppress the formation of a chlorinated phenol compound due to the contact between a resin having a bisphenol skeleton such as an epoxy resin and residual chlorine. Further, in the present invention, such off-flavor-inhibiting resin contains bleed and / or chlorinated compounds already present in the resin.
Or in order to suppress volatilization to air | atmosphere, even if it constructs with respect to resin, such as a flooring which the off-flavor substance has already produced | generated, a stench can be suppressed. Therefore, by forming a coating film using the odor-inhibiting resin of the present invention, it is possible to avoid or suppress troubles that generate odors caused by floor materials using epoxy resin, etc., and into the manufacturing process and environment. The volatilization of pollutants derived from the flooring can be suppressed.

Claims (9)

A second resin layer containing an acrylic urethane resin or a silicone resin is formed on one or both sides of the first resin layer containing a cured epoxy resin or a cured epoxy acrylate resin.
Odor-inhibiting resin laminate. The laminate according to claim 1, wherein the first resin layer comprises a cured bisphenol-based epoxy resin or a cured bisphenol-based epoxy acrylate resin. The laminate according to claim 1, wherein the off-flavor is off-flavor caused by halogenated phenol or halogenated anisole. Forming a second resin layer containing an acrylic urethane resin or a silicone resin on one side or both sides of a first resin layer containing an epoxy resin or an epoxy acrylate resin that is cured or curing, and a method for suppressing odor . The method for suppressing odor according to claim 4, wherein the odor is a odor caused by halogenated phenol or anisole. A construction method comprising forming a second resin layer containing an acrylic urethane resin or a silicone resin on one side or both sides of a first resin layer containing an epoxy resin or an epoxy acrylate resin that has been cured or is being cured. The construction method according to claim 6, which is carried out in order to suppress a bad odor caused by a halogenated phenol or a halogenated anisole. A one-pack type or a two- or more-pack mixed type containing a material of an acrylic urethane resin or a silicone resin for coating on one or both sides of a layer containing an epoxy resin or an epoxy acrylate resin, which is cured or curing A resin film-forming composition. The composition according to claim 8, for suppressing off-flavors caused by halogenated phenols or halogenated anisole.