JP4507184B2 - Sheet lamination method - Google Patents

Description

  The present invention provides a sheet laminate capable of preventing deterioration of surface properties due to a plasticizer when a designable sheet is laminated on the surface of a base material containing a plasticizer such as a sealing material, a vinyl interior material, and a vinyl building material. It is about the method.

  In recent years, in the interior and exterior finishing of a building structure, for the purpose of simplifying construction and improving aesthetics, a method of attaching a design sheet with an adhesive has been performed. Since such a designable sheet is manufactured by printing, embossing, molding, precoating, and the like, various decorative layers having high designability can be provided. Moreover, since it finishes only by sticking using an adhesive agent at the time of construction, it has the characteristics that a curing process etc. can be simplified without requiring a skilled worker.

  In the case of such construction, when various building materials such as ceramics or metal are used on the surface of the building structure to be coated, the sealing material is used to provide waterproofness at the joint portion of the building material. Has been laid. When the designable sheet is applied to the entire surface to be coated including the joint portion of such building materials, the joint portion can be protected, and the overall design can be unified and the aesthetics can be enhanced.

  However, most of such sealants contain a plasticizer in their components. Therefore, when the designable sheet is applied directly on the surface of the sealing material, the plasticizer in the sealing material shifts to the designable sheet over time, and the designable sheet on the sealing material is plasticized and softened. In some cases, contaminants in the air adhere to the softened designable sheet portion and remarkably deteriorate the appearance.

On the other hand, in the interior of buildings, so-called vinyl-based materials such as wallpaper, ceiling materials, floor materials, etc., mainly composed of vinyl chloride resin, are preferred because they are relatively inexpensive and have good workability. However, there is a need for refurbishment when deterioration or contamination progresses over time or when there is a request for a change in design. Recently, as a method of refurbishing these, refurbishing with a design sheet has been attracting attention.
However, when a designable sheet is directly applied to the surface of such a vinyl-based material, the plasticizer contained in the vinyl-based material is transferred to the designable sheet as in the case of the sealing material described above. As a result, contaminants may adhere and impair the appearance.

In order to solve the problems as described above, for example, Patent Document 1 describes a method for providing a decorative sheet itself with a plasticizer migration preventing function.
However, as in Patent Document 1, when the plastic sheet migration prevention function is imparted to the decorative sheet itself, it has been necessary to take extra steps, costs, and the like for manufacturing the decorative sheet. Furthermore, the design properties of the decorative sheet may have to be limited.

JP-A-9-277460

  In order to solve these problems, the present inventor has intensively studied. As a result, the synthetic resin (A) and the hydrophilic group are contained in the base material including the plasticizer, and the temperature is 20 ° C. and the humidity is 65%. It has been found that by laminating a design sheet through an adhesive containing a hygroscopic powder (B) having a moisture absorption rate of 10% or more, the migration of the plasticizer can be prevented, and the present invention has been completed. It was.

  In the present invention, the details of the mechanism are not clear, but the effect of the hydrophilic group contained in the hygroscopic powder (B) and the effect of the hydrophilic layer formed by absorbing moisture in the air or in the base material This is considered to prevent migration of the plasticizer that is hydrophobic.

That is, the present invention has the following characteristics.
1. A sheet laminating method for laminating a designable sheet via an adhesive to a base material containing a plasticizer,
An adhesive material includes a synthetic resin (A) and a hygroscopic powder (B) containing a hydrophilic group and having a moisture absorption rate of 10% or more at a temperature of 20 ° C. and a humidity of 65%. Method 2. 1. The hydrophilic group is one or more selected from a carboxyl group, a hydroxyl group, an amino group, and an amide group. 2. Sheet lamination method according to 3. The adhesive contains 50 to 500 parts by weight of the component (B) with respect to 100 parts by weight of the solid content of the component (A). Or 2. Sheet lamination method according to

  According to the present invention, a synthetic resin (A) and an adhesive containing a hydrophilic group and containing a hygroscopic powder (B) having a hygroscopicity of 10% or more at a temperature of 20 ° C. and a humidity of 65% are used. Then, by laminating the designable sheet, the plasticizer can be prevented from moving.

  Hereinafter, the present invention will be described in detail based on the best mode for carrying out the invention.

  The adhesive of the present invention contains a synthetic resin (hereinafter also referred to as “component (A)”), a hydrophilic group, and a hygroscopic powder having a moisture absorption rate of 10% or more at a temperature of 20 ° C. and a humidity of 65%. (Hereinafter also referred to as “component (B)”).

((A) component)
(A) component in this invention should just select suitably considering the adhesiveness of the base material containing a plasticizer, and a designable sheet, For example, a water soluble type, a water dispersion type, a NAD type, a weak solvent Mold, solvent mold and the like. Examples of such component (A) include acrylic resin, urethane resin, epoxy resin, vinyl acetate resin, silicon resin, fluororesin, acrylic / vinyl acetate resin, acrylic / urethane resin, acrylic / silicone resin, and silicon-modified acrylic. Resin, resin solution or emulsion of ethylene / vinyl acetate / veova resin, ethylene / vinyl acetate resin, etc., synthetic rubber latex such as styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, butadiene rubber, natural rubber Latex and the like can be mentioned, and one or more of these may be used in combination.
In the present invention, it is preferable to use a water-soluble resin and / or a water-dispersed resin, and in particular, water-soluble acrylic resins, urethane resins, silicone resins, acrylic / urethane resins, acrylic / silicon resins, and silicone-modified acrylic resins. It is preferable to use a mold and / or a water-dispersed resin.

  Furthermore, it is preferable to use what has a reactive functional group as (A) component. When a synthetic resin having such a reactive functional group is used, it is combined with a synthetic resin having a functional group capable of reacting with the reactive functional group, or has a functional group capable of reacting with the reactive functional group. It is preferably used in combination with a crosslinking agent. By using the synthetic resin having a reactive functional group, in addition to the effect of improving the moisture absorption rate in the cured adhesive material, the adhesion strength can be improved and the migration of the plasticizer can be further prevented.

  Examples of combinations of reactive functional groups and functional groups capable of reacting with the reactive functional groups include, for example, carboxyl group and amino group, carboxyl group and metal ion, carboxyl group and carbodiimide group, carboxyl group and epoxy group, carboxyl group and Examples include an aziridine group, a carboxyl group and an oxazoline group, a carboxyl group and an alkoxyl group, a hydroxyl group and an isocyanate group, a carbonyl group and a hydrazide group, an acetoacetoxyl group and an amino group, an epoxy group and an amino group, and an alkoxyl group.

  The minimum film-forming temperature of the component (A) is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and further 40 ° C. or lower −50 ° C. or higher in consideration of workability and adhesiveness.

((B) component)
The component (B) of the present invention contains a hydrophilic group and has a moisture absorption rate of 10% or more, preferably 20% or more at a temperature of 20 ° C. and a humidity of 65%.
The hydrophilic group content is not particularly limited, but is preferably 1 mmol / g or more, preferably 3 mmol / g or more. Examples of such a hydrophilic group include a carboxyl group, a hydroxyl group, an amino group, an amide group, and the like, and a carboxyl group is preferably used.

  As the component (B) of the present invention, any organic powder, inorganic powder, etc. can be used without particular limitation as long as the above conditions are satisfied. However, from the viewpoint of many hydrophilic groups and excellent hygroscopicity. It is preferable to use organic powder.

  As organic powder, what can be manufactured with a well-known manufacturing method should just be used. The component constituting such organic powder is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, 2- Alkyl group-containing (meth) acrylic monomers such as ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate and benzyl (meth) acrylate; carboxyl group-containing (meth) acrylic such as (meth) acrylic acid Monomer: aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, Nt Butyrua Noethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate Amine-containing (meth) acrylic monomers such as N, N-dimethylaminopropyl (meth) acrylate and N, N-diethylaminopropyl (meth) acrylate; (meth) acrylamide, ethyl (meth) acrylamide, N-isopropyl ( Amide-containing (meth) acrylic monomers such as (meth) acrylamide, maleic acid amide, N-methylolacrylamide, N-methylolmethacrylamide, and diacetoneacrylamide; and nitrile group-containing (meth) acrylonitrile ) Acrylic monomer; Epoxy group-containing (meth) acrylic monomer such as glycidyl (meth) acrylate; diacetone (meth) acrylate, diacetone acrylamide, acrolein, vinyl methyl ketone, acetonyl acrylate, diacetone methacrylamide, vinyl ethyl ketone Carbonyl group-containing monomers such as vinyl isobutyl ketone, acryloxyalkyl propanals, methacryloxyalkyl propanals, 2-hydroxypropyl acrylate acetyl acetate, and butanediol acrylate acetyl acetate; 2-hydroxyethyl (meth) acrylate, hydroxy Hydroxy group-containing monomers such as propyl (meth) acrylate; N, N′-methylenebisacrylamide, ethylene glycol Di (meth) acrylic monomers such as dimethacrylate; isocyanate group-containing monomers such as methacryloyl isocyanate; hydrazino group-containing monomers such as propylene-1,3-dihydrazine and butylene-1,4-dihydrazine; styrene, methylstyrene, Aromatic hydrocarbon vinyl monomers such as chlorostyrene, vinyl toluene and divinylbenzene; vinyl monomers containing sulfonic acids such as styrene sulfonic acid and vinyl sulfonic acid; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl pivalate And vinylidene halides such as vinylidene chloride and vinylidene fluoride, ethylene, propylene, isoprene, butadiene, vinyl pyrrolidone, vinyl chloride and the like. These monomers can be used alone or in combination of two or more.

  Moreover, compounds other than the ethylenically unsaturated monomer mentioned above can also be contained. Examples of compounds other than the ethylenically unsaturated monomer include epoxy group-containing compounds such as allyl glycidyl ether, polyethylene glycol diglycidyl ether, polyhydroxyalkane polyglycidyl ether, diglycerol polyglycidyl ether, and sorbitol polyglycidyl ether; Carboxylic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, isocrotonic acid, salicylic acid and other carboxyl group-containing compounds; hydrazine and other hydrazino group-containing compounds; oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide , Adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide Hexadecandiohydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydrazide, 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N '-Hexamethylene bissemicarbazide, itaconic acid dihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, citric acid trihydrazide, 1,2,3-benzenetrihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, nitriloacetic acid trihydrazide, Hydrazide group-containing compounds such as cyclohexanetricarboxylic acid trihydrazide and pyromellitic acid tetrahydrazide; 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline Oxazoline group-containing compounds such as 2-vinyl-5-methyl-2-oxazoline and 2-isopropynyl-2-oxazoline; 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1, 6-hexamethylenediethyleneurea, diphenylmethane-bis-4,4′-N, N′-diethyleneurea, acryloylaziridine, methacryloylaziridine, acrylic acid-2-aziridinylethyl, methacrylate-2-aziridinylethyl methacrylate, etc. And aziridine group-containing compounds. These compounds can be used alone or in combination of two or more.

  The organic powder can be produced by mixing and polymerizing a component having a hydrophilic group among the above components, or by introducing the hydrophilic group after some treatment.

  For example, as a method of introducing a carboxyl group, the carboxyl group-containing (meth) acrylic monomer, a method of copolymerizing a carboxyl group-containing compound with another monomer that can be homopolymerized or copolymerized, an alkene, an alkyl halide, Examples of the method include oxidation and hydrolysis of alcohols and aldehydes. In the present invention, a method of subjecting a polymer obtained by copolymerizing a cyano group-containing monomer such as (meth) acrylonitrile to a hydrolysis treatment is preferably used.

  Furthermore, from the viewpoint of improving hygroscopicity, the component (B) preferably has a crosslinked structure. Such a crosslinked structure can be formed by a method such as introduction of a crosslinkable monomer in the polymerization stage, introduction of a crosslinkable compound after polymerization. As the crosslinkable monomer, divinylbenzene, ethylene glycol di (meth) acrylate, methylenebisacrylamide and the like can be suitably used, and as the crosslinkable compound, a hydrazine-based compound can be suitably used.

  Examples of the inorganic powder include hydrophilized products such as silica or talc, calcium carbonate, clay, kaolin, barium sulfate, and diatomaceous earth.

Such component (B) may be in the form of a powder, or may be in the form of a dispersion in which the powder is dispersed in a solvent. The solvent is not particularly limited, but water; alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and glycerin; acetone, methyl ethyl ketone Ketones such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, etc. Can be mentioned. These solvents can be used alone or in combination of two or more.
In the present invention, it is particularly preferable to use an aqueous dispersion dispersed in water.

The moisture absorption rate at a temperature of 20 ° C. and a humidity of 65% is when the component (B) is dried at 120 ° C. for 1 hour and then absorbed by a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 65% for 24 hours. It is a value obtained from the weight change. That is,
Moisture absorption rate (%) = {(weight after moisture absorption−weight after drying) / weight after drying} × 100
It is.
However, as the component (B), when the hygroscopic powder is a dispersion dispersed in a solvent, the moisture absorption rate may be measured after the dispersion is previously dried to form a powder.

Although the particle diameter of (B) component of this invention is not specifically limited, 0.1-100 micrometers, Preferably about 0.2-50 micrometers can be used.
The particle diameter can be measured with a scanning electron microscope (“SEM JSM5301LV” manufactured by JEOL Ltd.).

  (B) The compounding quantity of a component becomes like this. Preferably it is 50-500 weight part with respect to 100 weight part of solid content of (A) component, More preferably, it is 100-300 weight part. When the amount is less than 50 parts by weight, the formation of the hydrophilic layer may be insufficient and the migration of the plasticizer may not be prevented. When the amount exceeds 500 parts by weight, the water resistance and the adhesive strength are insufficient.

  The adhesive of the present invention is mainly composed of the components (A) and (B), but water, solvent, coloring material and extender pigment to the extent that the effects of the present invention are not impaired. Commonly used additives such as dispersants, viscosity modifiers, antifoaming agents, antifungal agents, preservatives, and algaeproofing agents can be added as appropriate.

In this invention, a designable sheet | seat is laminated | stacked through the said adhesive material with respect to the base material containing a plasticizer.
The form of the adhesive is not particularly limited, such as a liquid application type adhesive, a gel application type adhesive tape, a solid adhesive, and the like.

  The laminating method is not particularly limited, and the adhesive may be applied or pasted on the base material side and / or the design sheet side including the plasticizer and laminated. In such a method, workability is excellent, curing and the like can be simplified, and finishing can be performed very easily.

Examples of the base material containing the plasticizer include commonly used sealing materials, vinyl-based interior materials, vinyl-based building materials, etc., and these and metal steel plates such as aluminum steel plates, galvanized steel plates, stainless steel plates, copper steel plates, and wood. , Concrete, mortar, plaster board, fiber mixed cement board, calcium silicate board, slate board, slag cement perlite board, asbestos cement board, ALC board, siding board, extrusion board, plastic board, ceramics, glass, fired tile, porcelain It may be a composite of general substrates such as tiles.
As such a base material, a material having moisture permeability is preferable. By having moisture permeability, the adhesive can easily absorb water vapor from the substrate side, and the migration of the plasticizer can be further prevented.

Examples of the plasticizer include phthalic acid derivatives such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), di-2-ethylhexyl phthalate, dibenzyl phthalate and diisodecyl phthalate, phosphate esters such as tributyl phosphate, and oleic acid. Examples include fatty acid esters such as butyl and di-2-ethylhexyl adipate, alcohol esters such as diethylene glycol benzoate, and chlorinated paraffins.
Such a plasticizer is generally hydrophobic, and it is considered that migration can be prevented by a hydrophilic group contained in the adhesive of the present invention or a hydrophilic layer formed by moisture absorption.

  The design sheet is not particularly limited, and it is characterized by being able to be laminated on any design sheet such as a natural stone tone, wood grain tone, wood tone, metallic tone, embossed building material sheet, wallpaper sheet, Japanese paper sheet, etc. .

  As the building material sheet, for example, a synthetic resin and a coloring material are used as main components, and for example, a building material sheet coating material containing the synthetic resin and the coloring material is poured into a mold, cured, and demolded. Moreover, what laminated | stacked the reinforcement sheet | seat etc. may be used.

  Synthetic resins used for building material sheets include acrylic resin, silicone resin, acrylic silicone resin, polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, fluororesin, vinyl resin, vinyl chloride resin, Examples thereof include solvent-soluble types such as ethylene resin, vinyl acetate resin, polycarbonate resin, ABS resin, AS resin, cellulose, and polyvinyl alcohol, NAD type, water-soluble type, water-dispersed type, and solventless type.

  Coloring materials include titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, molybdate orange, permanent red, permanent carmine, anthraquinone red. , Perylene red, quinacridone red, ferric oxide, yellow iron oxide, titanium yellow, first yellow, chrome green, ocher, ultramarine, bitumen, cobalt green, cobalt blue and other inorganic color pigments, azo, naphthol, pyrazolone , Anthraquinone, perylene, quinacridone, benzimidazole, phthalocyanine, disazo, isoindolinone, quinophthalone and other organic color pigments, pearl pigments, aluminum pigments, metals or gold Glass flakes or resin films coated with oxides, brilliant pigments such as hologram pigments, cholesteric crystal polymer pigments, natural stones such as marble, granite, serpentinite, granite, fluorite, cryolite, feldspar, quartzite, quartz sand, And those pulverized products, ceramic pulverized products, ceramic pulverized products, glass pulverized products, resin pulverized products, metal particles, etc., and those whose surfaces are colored and coated.

In addition, for paints for building material sheets, commonly used solvents, extender pigments, thickeners, film-forming aids, leveling agents, plasticizers, antifreezing agents, pH adjusters, antiseptics, antifungal agents, and algae Additives such as an agent, an antibacterial agent, a dispersant, an antifoaming agent, an ultraviolet absorber, an antioxidant, a fiber, a catalyst, a photocatalyst, and a crosslinking agent can also be blended.
Examples of extender pigments include heavy calcium carbonate, light calcium carbonate, clay, kaolin, porcelain clay, china clay, talc, precipitated barium sulfate, barium carbonate, white carbon, and diatomaceous earth.
Examples of the wallpaper sheet include those containing the above synthetic resin, those containing synthetic fibers, natural fibers, and the like.
The wallpaper sheet and the Japanese paper sheet may be ones that have been designed by printing, painting, embossing, or the like.

In the present invention, the effect can be particularly effectively exerted on a sheet containing a resin or paper, in which the plasticizer easily migrates. Furthermore, if the designable sheet has moisture permeability, the adhesive can easily absorb moisture in the atmosphere, and the migration of the plasticizer can be further prevented.
Specifically, the water vapor permeability according to JIS K5400: 1990 8.17 is 10 g / m ² · 24 h or more, further 20 g / m ² · 24 h or more, further 20 g / m ² · 24 h or more and 2000 g / m ² · 24 h or less. Furthermore, it is preferably 30 g / m ² · 24 h or more and 1500 g / m ² · 24 h or less.

  Furthermore, after laminating the designable sheet, a known top coat material can be applied. The top coating material is not particularly limited as long as it does not interfere with the effects of the present invention, and a top coating material imparted with moisture permeability, water resistance, water repellency, antifouling property, chemical resistance and the like is preferable.

  Examples and Comparative Examples are shown below to clarify the features of the present invention.

Example 1
The raw materials shown in Table 1 were mixed in the paint formulation shown in Table 2 to produce an adhesive. The prepared adhesive sheet 1 was laminated on the surfaces of the base material 1 and the base material 2 shown below so that the applied amount was 500 g / m ² .
Substrate 1: A PVC cloth (containing 12% by weight of a phthalate ester plasticizer) with an average film thickness of 0.5 mm on a 300 mm × 300 mm slate plate Substrate 2: 300 mm × 300 mm slate Moisture curable urethane-based sealing material (containing 30% by weight of phthalate ester plasticizer) coated on a plate with a dry film thickness of 2 mm. Design sheet 1: Pattern Japanese paper sheet (water vapor permeability: 1000 g) / ^m 2 · 24h)

The moisture absorption rate of the powders 1 to 4 is that the temperature is 20 ° C. and the humidity 65%, and the powders 1 to 4 are each dried at 120 ° C. for 1 hour, and then the constant temperature and humidity chamber of the temperature 20 ° C. and the humidity 65%. It is a value calculated | required from the weight change when making it absorb moisture for 24 hours. That is,
Moisture absorption rate (%) = {(weight after moisture absorption−weight after drying) / weight after drying} × 100
It is.

(Plasticizer migration prevention test)
The prepared specimen was allowed to stand at a temperature of 80 ° C. and a humidity of 65% for 8 hours, and then colored silica sand (black) was sprinkled on the surface of the specimen, and the plasticizer migration prevention property was evaluated from the area where the colored silica sand adhered.
The evaluation was as follows: ◎: no colored silica sand adhered, ○: little colored silica sand adhered, △: colored silica sand partially adhered, x: colored silica sand adhered. The results are shown in Table 3.

(Examples 2-7, Comparative Examples 1-2)
Except for the raw materials shown in Table 1 and the formulation shown in Table 2, an adhesive was prepared in the same manner as in Example 1, and a plasticizer migration prevention test was performed. The results are shown in Table 3.

Claims (3)

A sheet laminating method for laminating a designable sheet via an adhesive to a base material containing a plasticizer,
An adhesive material includes a synthetic resin (A) and a hygroscopic powder (B) containing a hydrophilic group and having a moisture absorption rate of 10% or more at a temperature of 20 ° C. and a humidity of 65%. Method   The sheet lamination method according to claim 1, wherein the hydrophilic group is at least one selected from a carboxyl group, a hydroxyl group, an amino group, and an amide group. The sheet laminating method according to claim 1 or 2, wherein the adhesive contains 50 to 500 parts by weight of the component (B) with respect to 100 parts by weight of the solid content of the component (A).