JP2006231664A - Laminate for building material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate for a building material which is excellent in barrier properties to a volatile organic compound. <P>SOLUTION: The laminate for the building material has at least one layer of a cured epoxy resin product. The product is formed by curing a composition containing an epoxy resin and an epoxy resin curing agent as main components, and at least 30 wt% of a xylilenediamine skeleton structure is contained in the layer of the cured epoxy resin product. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a laminate having barrier properties against volatile organic compounds. This laminated body can be used for wallpaper, a decorative board, and the like.

Conventionally, plastic films such as polyvinyl chloride and saponified ethylene vinyl acetate copolymer have been used as wallpaper for building interiors (see, for example, Patent Documents 1 and 2), but they do not always meet market demands. However, the current situation is not satisfied. For example, wallpaper made of a polyvinyl chloride film has poor barrier properties against volatile organic compounds generated from the interior building materials covered by the wallpaper, so that the volatile organic compounds pass through the wallpaper and are used indoors. It has been pointed out as a problem from the market that it causes sick house syndrome and that the components in the plasticizer of polyvinyl chloride bleed. A wallpaper made of a saponified ethylene vinyl acetate copolymer film is known to prevent bleeding of the plasticizer component (see Patent Documents 3 and 4), but has a sufficient barrier property against volatile organic compounds. I couldn't say that.
JP 58-23973 A Japanese Utility Model Publication No.59-172797 Japanese Patent Laid-Open No. 7-258889 JP 7-329253 A

The objective of this invention is providing the laminated body for building materials which is excellent in the barrier property of a volatile organic compound.

As a result of intensive studies to solve the above problems, the present inventors have found that a laminate using a cured product formed from a specific epoxy resin as a barrier layer has excellent barrier properties against volatile organic compounds. Invented. That is, the present invention is a laminate having at least one layer composed of a cured epoxy resin, and the cured product is formed by curing a composition mainly composed of an epoxy resin and an epoxy resin curing agent, And the laminated body for building materials which contains 30 weight% or more of frame | skeleton structures shown by Formula (1) in the layer which consists of this hardened | cured material, and the wallpaper, decorative board, and sheet | seat for building materials using this laminated body About.

According to the present invention, it is possible to produce a laminate having excellent barrier properties against volatile organic compounds. The laminate can be used for various building materials such as wallpaper and decorative boards.

The present invention is described in further detail below. The laminate for building materials of the present invention is a laminate having at least one layer composed of a cured epoxy resin. The layer made of the cured epoxy resin may be an adhesive layer or a coating layer.
There is no restriction | limiting in particular in layers other than the layer which consists of an epoxy resin hardened | cured material, According to the use of a laminated body, it can select arbitrarily. For example, wallpaper can be obtained by using papers such as flame retardant paper, non-woven fabric, glass fiber or the like as a base material and further laminating a polymer layer as necessary. Moreover, various building materials can be obtained by using a wood material as a base material and further laminating a polymer layer as required. Moreover, the sheet | seat for building materials used for various uses can be obtained by making a polymer into a base material and laminating | stacking a polymer layer further as needed.

The layer configuration of the laminate for building materials of the present invention can be arbitrarily selected depending on the application. Assuming that the layer made of the cured epoxy resin is (G), the base material layer is (S), and the polymer layer is (P), (S)-(G), (S)-(G)-(P), ( S)-(G)-(S)-(G)-(P), (S)-(G)-(P)-(G)-(P), (G)-(S)-(G) -(P), (G)-(S)-(G)-(P)-(G) and the like are exemplified, but the present invention is not limited to these layer structures.

The base material layer constituting the laminate for building materials of the present invention is formed from paper such as flame retardant paper, non-woven fabric, glass fiber, wood material, polyolefin resin, polyester resin, and the like, depending on the use of the laminate You can choose from these. For example, when used as wallpaper, it is applied to a base sheet for ordinary wallpaper, such as flame retardant paper, a non-woven fabric that has been rubbed with a resin binder and subjected to sealing treatment, or a woven fabric in which a resin layer is laminated. What is used can be used. Moreover, a decorative board can be obtained by using a plywood board, a fiber board or a particle board.

The polymer layer is formed of a normal foamed or non-foamed polymer such as a vinyl chloride resin, an acrylate resin, an olefin resin, a polyamide resin, a polyester resin, a polyurea resin, or a polyurethane resin. This foamed or non-foamed polymer includes organic fillers, antioxidants, heat stabilizers, light stabilizers, flame retardants, lubricants, inorganic or organic colorants, rust preventives, crosslinking agents, foams as necessary. Various additives such as an agent, a fluorescent agent, a surface smoothing agent, and a surface gloss improving agent can be used as long as the effects of the present invention are not impaired.

A layer made of a cured epoxy resin in the present invention (hereinafter referred to as a barrier layer) is formed by curing an epoxy resin composition mainly composed of an epoxy resin and an epoxy resin curing agent. It is preferable to contain 30% by weight or more of the skeleton structure represented by the formula (1). By setting the skeleton structure to 30% by weight or more, a good barrier property against a volatile organic compound is expressed. Here, the volatile organic compounds are mainly generated from building materials. For example, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, alcohols such as ethanol, and aldehydes such as formaldehyde. And ketones such as acetone. Further, when polyamines are used as a curing agent, carbonyl groups react with amino groups, so that it is possible to absorb aldehydes such as formaldehyde and ketones such as acetone in the air.

Below, an epoxy resin and an epoxy resin hardening | curing agent are demonstrated in detail.

The epoxy resin in the present invention may be any of a saturated or unsaturated aliphatic compound, alicyclic compound, aromatic compound, or heterocyclic compound. An epoxy resin containing a ring in the molecule is preferred. Specific examples include an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine, an epoxy resin having a glycidylamine moiety derived from 1,3-bis (aminomethyl) cyclohexane, and a glycidyl derived from diaminodiphenylmethane. Epoxy resin having amine moiety, epoxy resin having glycidylamine moiety derived from paraaminophenol, epoxy resin having glycidyl ether moiety derived from bisphenol A, epoxy resin having glycidyl ether moiety derived from bisphenol F, phenol Examples thereof include an epoxy resin having a glycidyl ether moiety derived from novolak and an epoxy resin having a glycidyl ether moiety derived from resorcinol. Among them, an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine, an epoxy resin having a glycidylamine moiety derived from 1,3-bis (aminomethyl) cyclohexane, and a glycidyl ether moiety derived from bisphenol F Epoxy resins and epoxy resins having a glycidyl ether moiety derived from resorcinol are preferred.

Further, it is more preferable to use an epoxy resin having a glycidyl ether moiety derived from bisphenol F or an epoxy resin having a glycidyl amine moiety derived from metaxylylenediamine as a main component, and derived from metaxylylenediamine. It is particularly preferable to use an epoxy resin having a glycidylamine moiety as a main component.

Furthermore, in order to improve various performances such as flexibility, impact resistance, and heat-and-moisture resistance, the above-mentioned various epoxy resins can be mixed and used at an appropriate ratio.

The epoxy resin in the present invention is obtained by reaction of various alcohols, phenols and amines with epihalohydrin. For example, an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine can be obtained by adding epichlorohydrin to metaxylylenediamine. Here, the glycidylamine moiety comprises a mono-, di-, tri- and / or tetra-glycidylamine moiety that can replace the four hydrogen atoms of the diamine in xylylenediamine. The ratio of mono-, di-, tri- and / or tetra-glycidylamine moieties can be varied by changing the reaction ratio of metaxylylenediamine to epichlorohydrin. For example, an epoxy resin mainly having a tetraglycidylamine moiety can be obtained by addition reaction of about 4 times mole of epichlorohydrin to metaxylylenediamine.

The epoxy resin in the present invention is an excess of epihalohydrin with respect to various alcohols, phenols and amines in the presence of alkali such as sodium hydroxide, 20 to 140 ° C., preferably 50 to 120 ° C. in the case of alcohols and phenols. In the case of amines, the reaction is carried out at a temperature of 20 to 70 ° C., and the produced alkali halide is separated. The number average molecular weight of the produced epoxy resin varies depending on the molar ratio of epihalohydrin to various alcohols, phenols and amines, but is about 80 to 4000, preferably about 200 to 1000, preferably about 200 to 500. It is more preferable.

As the epoxy resin curing agent in the present invention, generally usable epoxy resin curing agents such as polyamines, phenols, acid anhydrides or carboxylic acids can be used. These epoxy resin curing agents can be selected according to the use application of the laminate and the required performance in the application.

Specifically, polyamines include aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, aliphatic amines having an aromatic ring such as metaxylylenediamine and paraxylylenediamine, 1,3- Modification reaction products with alicyclic amines such as bis (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine, aromatic amines such as diaminodiphenylmethane, metaphenylenediamine, and epoxy resins or monoglycidyl compounds using these as raw materials, Modification reaction product with epichlorohydrin, modification reaction product with alkylene oxide having 2 to 4 carbon atoms and at least one acyl group capable of forming an amide group site and forming an oligomer by reaction with these polyamines A polyfunctional compound having at least one acyl group capable of forming an amide group site by forming a reaction product with the polyfunctional compound having the above, and reaction with these polyamines to form an oligomer; Reaction products with -8 monovalent carboxylic acids and / or derivatives thereof can be used.

Examples of phenols include multi-substituent monomers such as catechol, resorcinol and hydroquinone, and resole type phenol resins. Acid anhydrides or carboxylic acids include aliphatic acid anhydrides such as dodecenyl succinic anhydride and polyadipic acid anhydride, alicyclic acid anhydrides such as (methyl) tetrahydrophthalic anhydride, (methyl) hexahydrophthalic anhydride, and anhydrous Aromatic acid anhydrides such as phthalic acid, trimellitic anhydride, pyromellitic anhydride, and carboxylic acids thereof can be used.

In consideration of high barrier properties, it is preferable to use the following reaction products (A) and (B) or reaction products (A), (B) and (C) as the epoxy resin curing agent.
(A) polyamine (B) a polyfunctional compound having at least one acyl group capable of forming an amide group site by reaction with polyamine to form an oligomer (C) a monovalent carboxylic acid having 1 to 8 carbon atoms and / or Or its derivatives

Examples of the (A) polyamine include aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; aliphatic amines having an aromatic ring such as metaxylylenediamine and paraxylylenediamine; Alicyclic amines such as (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine, and aromatic amines such as diaminodiphenylmethane and metaphenylenediamine can be used, but metaxylylenediamine or paraxylylenediamine is particularly preferable.

Examples of the polyfunctional compound (B) include carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, succinic acid, malic acid, tartaric acid, adipic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and trimellitic acid. Examples include acids and derivatives thereof, such as esters, amides, acid anhydrides, acid chlorides, and acrylic acid, methacrylic acid and derivatives thereof are particularly preferable. In addition, the (C) monovalent carboxylic acid having 1 to 8 carbon atoms and / or a derivative thereof are monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, benzoic acid, and derivatives thereof. Examples thereof include esters, amides, acid anhydrides, acid chlorides and the like. These may be used in combination with the polyfunctional compound (B) to react with a polyamine.

The reaction molar ratio of (A) and (B) or (A) and (B) and (C) is the reactive functional group contained in (B) with respect to the number of amino groups contained in (A). Or the ratio of the total number of reactive functional groups contained in (B) and (C) to the number of amino groups contained in (A) ranges from 0.3 to 0.95. preferable. The amide group site introduced by the reaction has a high cohesive force, and higher barrier properties can be obtained by the presence of the amide group site in a high proportion in the epoxy resin curing agent. Furthermore, in order to improve various performances such as flexibility, impact resistance, and heat-and-moisture resistance, the above various epoxy resin curing agents can be mixed and used at an appropriate ratio.

In the present invention, the blending ratio of the epoxy resin and the epoxy resin curing agent that forms the barrier layer is generally a standard blending range in the case of producing an epoxy resin cured product by reaction of the epoxy resin and the epoxy resin curing agent. Good. Specifically, the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is in the range of 0.5 to 5.0, preferably 0.8 to 3.0.

In the present invention, the barrier layer is prepared by preparing a coating solution containing an epoxy resin composition composed of an epoxy resin and an epoxy resin curing agent as a coating film-forming component, and applying the coating solution to various materials constituting the laminate (hereinafter referred to as various materials). After application, it is formed by drying or heat treatment if necessary. The preparation of the coating solution is performed at a concentration of the epoxy resin composition sufficient to obtain the cured epoxy resin, but this may vary depending on the choice of starting material. That is, the concentration of the epoxy resin composition is about 5% by weight using a certain kind of appropriate organic solvent and / or water from the case where no solvent is used depending on the type and molar ratio of the selected material. It can take various states up to. Suitable organic solvents include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol Glycol ethers such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and other alcohols, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl Examples include aprotic polar solvents such as pyrrolidone and non-water-soluble solvents such as toluene, xylene, and ethyl acetate, but solvents having a relatively low boiling point such as methanol and ethyl acetate are more preferable.

In the case where the coating liquid is applied to various materials, a wetting agent such as silicon or an acrylic compound may be added to the coating liquid in order to help wet the surfaces of the various materials. Suitable wetting agents include BYK331, BYK333, BYK348, BYK381 available from Big Chemie. When adding these, the range of 0.01 weight%-2.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

In addition, in order to improve various properties such as barrier properties and impact resistance of the laminate of the present invention, inorganic fillers such as silica, alumina, mica, talc, aluminum flakes and glass flakes are added to the epoxy resin composition. You may do it. When adding these, the range of 0.01 weight%-10.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

In the epoxy resin composition of the present invention, a tackifier such as a xylene resin, a terpene resin, a phenol resin, or a rosin resin may be added as necessary in order to improve the adhesion to various materials immediately after coating. When adding these, the range of 0.01 weight%-5.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

Furthermore, a coupling agent such as a silane coupling agent or a titanium coupling agent may be added to the epoxy resin composition in the epoxy resin composition in order to improve adhesion to various materials. When adding these, the range of 0.01 weight%-5.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

In the present invention, any of commonly used coating formats such as roll coating, spray coating, air knife coating, dipping, and brush coating can be used as a coating format when applying the coating liquid to various materials. Among these, roll coating or spray coating is preferable. For example, common roll coat or spray techniques and equipment for applying curable paint components can be applied.

The thickness of the barrier layer after applying the coating liquid to various materials, drying and heat treatment is 0.1 to 100 μm, preferably 0.5 to 10 μm. If the thickness is less than 0.1 μm, sufficient barrier properties are hardly exhibited, while if it exceeds 100 μm, it is difficult to control the film thickness.

In the laminate of the present invention, the barrier layer can be formed on either the inner layer or the outer layer of the laminate.

When the barrier layer is formed on the inner layer of the laminate, a known laminating method such as dry lamination or extrusion lamination can be used. That is, in the case of the dry laminating method, after applying a coating liquid containing an epoxy resin composition serving as a barrier layer to a base sheet, the solvent is dried and a flexible polymer film or the like is immediately applied to the surface. A laminated body can be obtained by bonding. In this case, it is desirable to carry out post-curing for about 5 seconds to 2 days at room temperature to 140 ° C. as necessary after lamination.

In the case of the extrusion laminating method, after applying the coating solution to a base sheet or the like, the solvent material is dried and cured at room temperature to 140 ° C. to form a barrier layer, and then a polymer material melted by an extruder Can be laminated. These steps and other laminating methods can be combined as necessary, and the layer structure of the laminate can be changed depending on the application and form.

In the laminate of the present invention, a barrier layer may be provided on the outer layer of the laminate to form a coating layer. In addition, a barrier layer provided on the outer layer can be used as an adhesive layer when affixed to the structure, but an existing adhesive can be used separately from the barrier layer.

The building material using the laminate of the present invention is used for ceilings, walls, floors, etc. of ordinary houses, offices, restaurants, factories, laboratories, clinics, trains, automobiles, ships, airplanes and the like.

Examples of the present invention are introduced below, but the present invention is not limited to these examples.

<Epoxy resin curing agent A>
A reaction vessel was charged with 1 mol of metaxylylenediamine. The temperature was raised to 60 ° C. under a nitrogen stream, and 0.67 mol of methyl acrylate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 1 hour, and further heated to 180 ° C. in 3 hours while distilling off generated methanol. It cooled to 100 degreeC and the predetermined amount methanol was added so that solid content concentration might be 70 weight%, and the epoxy resin hardening | curing agent A was obtained.

<Epoxy resin curing agent B>
A reaction vessel was charged with 1 mol of metaxylylenediamine. The temperature was raised to 60 ° C. under a nitrogen stream, and 0.90 mol of methyl acrylate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 1 hour, and further heated to 180 ° C. in 3 hours while distilling off generated methanol. It cooled to 100 degreeC and the epoxy resin hardening | curing agent B was obtained.

<Epoxy resin curing agent C>
A reaction vessel was charged with 1 mol of metaxylylenediamine. The temperature was raised to 120 ° C. under a nitrogen stream, and 0.93 mol of methyl acrylate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 1 hour, and further heated to 180 ° C. in 3 hours while distilling off generated methanol. It cooled to 100 degreeC and the epoxy resin hardening | curing agent C was obtained.

Moreover, the evaluation method of the barrier property with respect to a volatile organic compound is as follows.
Toluene was placed in a 75 mmφ aluminum cup, covered with a test film for evaluation, and an adhesive was applied to the contact between the cup and the film, followed by sealing. It was measured by a gas phase method in which the film was not in direct contact with toluene. The mixture was allowed to stand for 500 hours in an environment of 60 ° C., and the toluene permeability (g / m ² · day) was determined from the change in weight. The toluene permeability coefficient of the barrier layer in the test film was calculated using the following formula. :
1 / R = 1 / Rn (n = 1, 2,...) + DFT / P
Here, R = toluene permeability of test film (g / m ² day)
Rn (n = 1, 2,...) = Toluene transmittance of each substrate film (g / m ² day)
DFT = barrier layer thickness (mm)
P = Toluene permeability coefficient of barrier layer (g · mm / m ² day)

<Example 1>
Methanol / ethyl acetate 1/1 containing 44 parts by weight of epoxy resin curing agent A and 50 parts by weight of epoxy resin having a glycidylamine moiety derived from metaxylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd .; TETRAD-X) A solution (solid content concentration: 30% by weight) was prepared, and 0.02 part by weight of an acrylic wetting agent (manufactured by Big Chemie; BYK381) was added thereto and stirred well to obtain a coating solution. This coating solution was applied to a high-density polyethylene (HDPE) having a thickness of 100 μm with a bar coater NO. 24, and after drying at 85 ° C. for 10 seconds, a polyethylene terephthalate film having a thickness of 100 μm was bonded by a nip roll and cured at 120 ° C. for 1 day to obtain a laminate. The thickness of the barrier layer was 10 μm. About the obtained laminated body, the toluene permeability coefficient of the barrier layer was measured. The results are shown in Table 1. The skeletal structure represented by the formula (1) contained in the barrier layer is 54.1% by weight.

<Example 2>
A laminate was prepared and evaluated in the same manner as in Example 1 except that 72 parts by weight of epoxy resin curing agent B was used instead of epoxy resin curing agent A. The skeletal structure represented by the formula (1) contained in the barrier layer is 56.5% by weight.

<Example 3>
A laminate was prepared and evaluated in the same manner as in Example 1 except that 78 parts by weight of epoxy resin curing agent C was used instead of epoxy resin curing agent A. The skeletal structure represented by the formula (1) contained in the barrier layer is 56.9% by weight.

<Comparative example>
As an application solution, an ethyl acetate solution (solid) containing 50 parts by weight of a polyether component (manufactured by Toyo Morton Co., Ltd.); TM-329) and 50 parts by weight of a polyisocyanate component (manufactured by Toyo Morton Co., Ltd .; CAT-8B). Partial concentration; 30% by weight). This coating solution was applied to a high-density polyethylene (HDPE) having a thickness of 100 μm with a bar coater NO. 24, and dried at 85 ° C. for 10 seconds. Then, an EVOH film having a thickness of 10 μm (ethylene content: 32 mol%, saponification degree: 99.6%) is bonded by a nip roll and cured at 120 ° C. for 1 day. As a result, a laminate was obtained. About the obtained laminated body, the toluene permeability coefficient of the EVOH layer was measured. The results are shown in Table 1.

Claims (9)

A laminate having at least one layer made of a cured epoxy resin, wherein the cured product is formed by curing a composition mainly composed of an epoxy resin and an epoxy resin curing agent, and the cured product. A layered product for building materials, comprising a skeleton structure represented by the formula (1) in a layer of 30% by weight or more.

The epoxy resin is an epoxy resin having a glycidylamine moiety derived from metaxylylenediamine, an epoxy resin having a glycidylamine moiety derived from 1,3-bis (aminomethyl) cyclohexane, or a glycidyl derived from diaminodiphenylmethane. Epoxy resin having amine moiety, epoxy resin having glycidylamine moiety derived from paraaminophenol, epoxy resin having glycidyl ether moiety derived from bisphenol A, epoxy resin having glycidyl ether moiety derived from bisphenol F, phenol A small amount selected from an epoxy resin having a glycidyl ether moiety derived from novolak and an epoxy resin having a glycidyl ether moiety derived from resorcinol. For construction laminate according to claim 1, characterized in that Kutomo is one resin. The epoxy resin curing agent is a reaction product of the following (A) and (B), or a reaction product of (A), (B) and (C). Laminate for building materials.
(A) polyamine (B) a polyfunctional compound having at least one acyl group capable of forming an amide group site by reaction with polyamine to form an oligomer (C) a monovalent carboxylic acid having 1 to 8 carbon atoms and / or Or its derivatives The laminate for building materials according to claim 1, comprising a base material layer made of paper, nonwoven fabric, or glass fiber. The building material laminate according to claim 1, comprising a base material layer made of a wood material. The building material laminate according to claim 1, comprising a base material layer made of a thermoplastic resin. The wallpaper which uses the laminated body for building materials of Claim 1. A decorative board using the laminate for building materials according to claim 1. A building material sheet using the building material laminate according to claim 1.