JP5917009B2 - Flooring - Google Patents

Description

  The present invention relates to a flooring material that can easily peel off a floor surface material after construction and can rationalize a floor surface material pasting operation.

Conventionally, in the floor heating method in apartment houses such as condominiums and detached houses, when floor surface materials such as flooring are laid on the surface of hot water panels, hot water mats, discarded plywood, joists, etc., instead of nails Adhesives are often used, and adhesives are sometimes used in combination with nails. The method of using an adhesive has the advantage that it does not require skill and is easy to work, compared to a method of fixing a floor material only by nailing. However, the conventional method using an adhesive has the following drawbacks. In other words, once the adhesive has hardened, it becomes difficult to remove it. Therefore, when it becomes necessary to remove the flooring by re-installation or renovation, it cannot be easily modified. Sometimes the material is damaged. Development of a construction method that does not destroy the material is desired when the floor material once stretched is removed from the viewpoint of effective use of resources, construction, and cost.
In order to solve such problems, a construction method using a double-sided tape or a hook-and-loop tape instead of an adhesive has been proposed, but there are problems such as complicated work and insufficient adhesive force. . As adhesives to be used, polyurethane-based and modified silicone-based adhesives in which a specific amount of filler is blended with a resin component have been proposed (Patent Documents 1 and 2). However, in any technique, a large amount of filler is blended to cause the adhesive layer to break when peeling the flooring and prevent the flooring from being destroyed. In most parts where the coating was applied, peeling work with kelen or the like was necessary.

JP 2004-307788 A JP 2009-24095 A

  In view of the above-mentioned conventional problems, the present invention can be sufficiently fixed so that no warpage or gaps are generated in the flooring while it is used as a residence after laying the flooring. The present invention provides a floor material that can be peeled off at the interface between the adhesive and the base material without breaking the material when the floor material is peeled off.

As a result of research to solve the above-mentioned problems, the present invention was completed by covering the surface of the base material with a paint, and further providing an adhesive layer thereon to laminate and integrate the floor surface material. It came to do.
That is, this invention is shown to following (1)-(3).
(1) A base material, an acrylic resin-based coating layer, a one-component moisture-curable urethane resin-based adhesive layer containing a polyurethane-based high molecular weight plasticizer having a number average molecular weight of 1,000 or more, a floor surface material, The flooring is characterized by being laminated and integrated in this order.
(2) a base material, an acrylic resin-based coating layer, a one-component moisture-curable urethane resin-based adhesive layer containing a polyurethane-based high molecular weight plasticizer having a number average molecular weight of 1,000 or more, and a floor surface material Are laminated in this order and further integrated by nails.
(3) The flooring according to (1) or (2), wherein the content of the plasticizer is 10 to 200 parts by mass with respect to 100 parts by mass of the cured resin component in the urethane resin adhesive.

  According to the present invention, after laying the flooring material, it can be sufficiently fixed so as not to cause warping or gaps in the flooring material while being used as a residence, etc. The base material can be reused because it can be peeled off at the interface between the adhesive and the base material without destroying.

FIG. 1 is a side sectional view of a flooring material according to the first embodiment.

The present invention will be described in detail below.
As the adhesive for forming the adhesive layer in the present invention is a one-part moisture-curable urethane resin adhesive.
One-part moisture-curing urethane resin adhesive is an isocyanate group-containing urethane prepolymer obtained by reacting an organic polyisocyanate and an active hydrogen-containing compound with active hydrogen (group) in an excess of isocyanate groups. It will be.

Specific examples of the organic polyisocyanate include diphenylmethane diisocyanate (MDI) such as phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,4- Toluene diisocyanates, toluene diisocyanates (TDI) such as 2,6-toluene diisocyanate, aromatic diisocyanates such as diphenyl ether diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, etc. Aliphatic diisocyanate, cyclohexanediiso Alicyclic diisocyanates such as anate, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, and carbodiimide-modified, biuret-modified, allophanate-modified, dimer, trimer or polymethylene polyphenyl polyisocyanate of these diisocyanates ( (Crude MDI, polymeric MDI) and the like, and these can be used alone or in combination of two or more.
Of these, aromatic diisocyanates are preferred, and MDIs and polymethylene polyphenyl polyisocyanates are more preferred because of excellent tensile adhesion after curing.

Examples of the active hydrogen-containing compound include polymer polyols, amino alcohols, and polyamines.
Examples of the polymer polyol include polyester polyol, polycarbonate polyol, polyoxyalkylene polyol, polyolefin polyol, animal and plant polyol, copolyols thereof, and the like, or a mixture of two or more of these.
Examples of the polyester polyol include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, triphthalic acid, and the like. One or more of polycarboxylic acids such as merit acid, acid esters, or acid anhydrides, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9- Nonanediol, diethylene glycol, dipropylene glycol, , 4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, low molecular alcohols such as trimethylolpropane, glycerin and pentaerythritol, low molecular amines such as hexamethylenediamine, xylylenediamine and isophoronediamine Polyester polyol or polyester amide polyol obtained by a dehydration condensation reaction with one or more of low molecular amino alcohols such as monoethanolamine and diethanolamine.
Further, for example, lactone polyesters obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone, using low molecular alcohols, low molecular amines, and low molecular amino alcohols as initiators. A polyol is mentioned.
Examples of the polycarbonate polyol include dehydrochlorination reaction of low molecular alcohols and phosgene used in the synthesis of the polyester polyol described above, or esters of the low molecular alcohols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. What is obtained by an exchange reaction is mentioned.
Examples of polyoxyalkylene polyols include low molecular alcohols, low molecular amines, and low molecular amino alcohols used in the synthesis of the above-described polyester polyols as initiators, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and the like. Polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol, polytetramethylene ether polyol, (polyoxyethylene)-(polyoxypropylene) random or block copolymerized by ring-opening polymerization alone or in combination of two or more Polyols, (polyoxypropylene)-(polyoxybutylene) random or block copolymer polyols, and the aforementioned polyester polyols and polycarbonates A polyester polyol with a polyol and initiator. In addition, for modification of an isocyanate group-containing urethane prepolymer, polyoxyalkylene monool obtained by ring-opening polymerization of an epoxide such as propylene oxide using a monoalcohol such as methyl alcohol, ethyl alcohol, or propyl alcohol as an initiator Can be used.
Examples of the polyolefin polyol include hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene, and hydroxyl group-containing chlorinated polyethylene.
Examples of animal and plant-based polyols include castor oil-based diols.
These polymer polyols preferably have a number average molecular weight of 500 to 30,000, particularly 1,000 to 20,000.
As the active hydrogen-containing compound, a chain extender can be used in some cases, and the chain extender has a molecular weight of 500 among low molecular alcohols, low molecular amines, low molecular amino alcohols and the like used in the synthesis of the polyester polyol. The following are exemplified.
The compounds mentioned as the active hydrogen-containing compound can be used alone or in combination of two or more.
Among these, since the viscosity of the isocyanate group-containing urethane prepolymer can be lowered, the workability of the resulting adhesive becomes good, and the polymer polyol is excellent in that it has excellent rubber elastic properties and adhesiveness after curing. Polyoxyalkylene polyol is more preferable, and polyoxypropylene polyol is particularly preferable.
Further, it is preferable to use polyoxyalkylene diol and polyoxyalkylene triol in combination. Adhesives containing isocyanate group-terminated prepolymers using only polyoxyalkylene diols are capable of elongation of adhesives after curing at room temperature, but extreme deterioration of physical properties occurs due to heating, due to tacking noise and high-speed bending Generates sound. In addition, an adhesive containing an isocyanate group-terminated prepolymer using only polyoxyalkylenetriol exhibits a certain degree of adhesive strength after curing, but generates insufficient sound due to high-speed bending due to insufficient elongation. From such a point, the blending ratio of the polyol mixture is preferably polyoxyalkylene diol / polyoxyalkylene triol = 90% by mass / 10% by mass to 30% by mass / 70% by mass.

  The isocyanate group-containing urethane prepolymer needs to leave an isocyanate group in the molecule of the prepolymer. The equivalent ratio of isocyanate group / active hydrogen (group) of the isocyanate group of the organic polyisocyanate and the polymer polyol, and optionally the active hydrogen (group) of the chain extender is 1.1 to 20.0 / 1.0. 1.5 to 15 / 1.0 is more preferable. The isocyanate group-containing urethane prepolymer thus obtained preferably has an isocyanate group content of 0.1 to 20.0% by mass, more preferably 0.5 to 15.0% by mass. When the isocyanate group content is less than 0.1% by mass, the molecular weight becomes too large, the viscosity increases, and the workability decreases. Moreover, since there are few crosslinking points in a prepolymer, sufficient adhesiveness cannot be obtained. When the isocyanate group content exceeds 20.0% by mass, foaming due to carbon dioxide gas becomes severe, which is not preferable.

For the synthesis of isocyanate group-containing urethane prepolymers, metals such as stannous octylate and tin octenoate, such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese and iron, and octyl acid, octenoic acid and naphthenic acid A salt with an organic acid such as dibutyltin bis (acetylacetonate), a metal chelate compound such as zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), an organic metal such as dibutyltin dilaurate and dioctyltin dilaurate Known urethanization catalysts such as salts with organic acids, organic amines such as triethylenediamine, triethylamine, tri-n-butylamine, and salts thereof can be used. Salts with one of these metals organic acid salt or an organic metal and an organic acid is not preferable.

The urethane resin adhesive has a number average molecular weight of 1,000 because it is difficult to contaminate or deteriorate the adherend by curing after curing of the adhesive and has good compatibility with the isocyanate group-containing urethane prepolymer. The above polyurethane high molecular weight plasticizer is included .
As the polyurethane-based high molecular weight plasticizer, a reaction product of a polyoxyalkylene compound having active hydrogen and an isocyanate group-containing compound is preferable, and a polyurethane-based high molecular weight plasticizer containing substantially no hydroxyl group or isocyanate group is preferable. Specifically, polyoxyalkylene alcohol and organic isocyanate are suitably produced by reacting with an isocyanate group / hydroxyl group equivalent ratio of 0.9 to 1.1 / 1.0, most preferably 1/1. can do. When the equivalent ratio is less than 0.9 / 1.0, the hydroxyl group content increases, and when blended, the water resistance and storage stability of the adhesive deteriorate, and when it exceeds 1.1 / 1.0, an isocyanate group. This is not preferable because the content of is increased and the adverse effect on the physical properties of the rubber after curing cannot be ignored. The number average molecular weight is good Mashiku 1,000～60,000, more preferably from 2,000 to 20,000. Outside this range, it is difficult to achieve both the peeling effect when blended and the fact that there is very little bleeding.
Note that “substantially free of hydroxyl group or isocyanate group” means that a small amount of hydroxyl group or isocyanate group may remain in the polyurethane high molecular weight plasticizer depending on the selection of the reaction equivalent ratio. It means that there is no influence on the physical properties after curing, and there is no problem even if it is regarded as not containing.
The amount of the plasticizer is 10 to 200 parts by weight per 100 parts by weight cured resin component of the urethane resin in adhesives, that is more 20 to 80 parts by weight preferred.

The coating material for forming the paint coating layer in the present invention, the formation of high surface hardness coat layer is in terms possible, an acrylic resin paint, arbitrary paint composed mainly of polyisobutyl acrylate preferred.

  As a base material in the present invention, a floor heating structure incorporating a floor heating heating element and a heat storage body such as a hot water panel and mat used for floor heating, a heater, a lauan plywood, a softwood plywood, a hardwood plywood, a laminated wood, a particle A board, a mug board, an aluminum board, etc. can be used.

  Examples of the floor surface material in the present invention include a wood floor surface material such as a veneer of natural name wood, a veneer veneer, a decorative plywood, and a decorative laminated material, as well as wood-patterned decorative paper and a vinyl chloride sheet. .

Next, formation of the flooring of the present invention will be described.
The flooring material of the present invention is, for example, a hot water mat for floor heating or a dumping in which a paint coating layer is formed by coating and curing the surface on a joist that supports the floor surface or a discarded plywood fixed thereon. Place the back side of the base material, such as a laminated board, and fix it with an adhesive or screws. Apply the adhesive evenly to the surface of the paint coating layer of the base material to form an adhesive layer, and then apply the floor surface material on it. It can be formed by mounting and bonding.
In this case, nailing for further firmly fixing the floor surface material to the base material or joist and the small joist of the hot water mat may be performed.

Hereinafter, the present invention will be described in more detail with reference to examples and the like.
[Synthesis Example 1]
In a kneading and reaction vessel equipped with a stir bar, thermometer, nitrogen seal tube and heating / cooling device, polyoxypropylene diol (Asahi Glass Co., Ltd., Exenol 3021, number average molecular weight 3,200, molecular weight distribution (Mw / Mn) 1.1 To 1.2) 200 g and 150 g of polyoxypropylene triol (manufactured by Mitsui Chemicals, MN-4000, number average molecular weight 4,000, molecular weight distribution (Mw / Mn) 1.1 to 1.2) are charged and then stirred. However, 150 g of fatty acid surface-treated calcium carbonate (manufactured by Maruo Calcium Co., Calfine 200M) and 250 g of calcium carbonate were charged, kneaded, and uniformly dispersed. At this time, the water content by the Karl Fischer method before dehydration was 0.1% by mass. Next, 50 g of calcium oxide was added, and the mixture was stirred and heated at 90 to 110 ° C. for 1 hour to perform a dehydration operation, and then cooled to 40 to 50 ° C. to obtain a dehydrated mixture. The water content after dehydration was 0.01% by mass. Next, 100 g of 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MT, molecular weight 250) was charged with stirring while flowing nitrogen gas, and then heated and reacted at 70 to 75 ° C. for 1 hour. . After cooling to room temperature, 20 g of polymethylene polyphenyl polyisocyanate (manufactured by Nippon Polyurethane Industry, Millionate MR-200), 3 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), hindered Uniformly charged 5 g of phenolic antioxidant (Ciba Geigy, Irganox 1010) and 103 g of high molecular weight plasticizer (manufactured by Sanyo Chemical Industries, LBU-25, polyoxyalkylene urethane resin, number average molecular weight 6,200) The mixture was kneaded for 30 minutes, degassed under reduced pressure, filled in a container, and sealed to prepare a one-part moisture-curing urethane resin adhesive A (hereinafter referred to as adhesive A).
This adhesive A had a viscosity (using a B-type rotational viscometer) at 25 ° C. immediately after production of 138 Pa · s, and the appearance was a milky white paste.

[Synthesis Example 2]
In Synthesis Example 1, a one-component moisture-curing urethane resin adhesive B (hereinafter referred to as “adhesive B”) was prepared in the same manner except that 232 g of a high molecular weight plasticizer was used. This adhesive B had a viscosity (using a B-type rotational viscometer) at 25 ° C. immediately after production of 94 Pa · s, and the appearance was a milky white paste.

[Synthesis Example 3]
A one-component moisture-curable urethane resin adhesive C (hereinafter referred to as adhesive C) was prepared in the same manner as in Synthesis Example 1 except that 398 g of a high molecular weight plasticizer was used. This adhesive C had a viscosity (using a B-type rotational viscometer) at 25 ° C. immediately after production of 82 Pa · s, and the appearance was a milky white paste .

[Real Example 1]
Surface acrylic resin paint (manufactured by Fujikura Kasei Co., Ltd., Rezarikku TC-2) of lauan plywood (12 mm thick) as a base material a coating weight 100 g / m ² and uniformly applied so that, by 24 hours drying and curing at room temperature What formed the coating-coating layer was used. As the adhesive, the adhesive A obtained in Synthesis Example 1 was used at an application amount of 500 g / m ² . A single-layer flooring material (12 mm thickness, manufactured by Asahi Woodtech, EG-HOT) was used as a floor surface material. Using the base material, the adhesive, and the floor surface material, according to the test method described later, a specimen for a tensile shear test and a plane tensile test was cured and cured at 23 ° C. and 50% relative humidity for 7 days.

[Example 2]
A test specimen was manufactured in the same manner as in Example 1 except that the adhesive B obtained in Synthesis Example 2 was used instead of the adhesive A.

Example 3
A test body was manufactured in the same manner as in Example 1 except that the adhesive C obtained in Synthesis Example 3 was used instead of the adhesive A.

Example 4
A test specimen was produced in the same manner as in Example 1, except that a 30% solution of polyisobutyl acrylate in methyl ethyl ketone was used instead of the acrylic resin paint.

Example 5
In Example 2, a test specimen was produced in the same manner except that a 30% methyl ethyl ketone solution of polyisobutyl acrylate was used instead of the acrylic resin paint.

Example 6
In Example 3, a test specimen was produced in the same manner except that a 30% solution of polyisobutyl acrylate in methyl ethyl ketone was used instead of the acrylic resin paint .

[Ratio Comparative Examples 1]
A test body was manufactured in the same manner as in Example 1, except that the acrylic resin paint was not applied to the surface of the Lauan plywood (no paint coating layer).

[Comparative Example 2]
In Example 2, a test specimen was produced in the same manner except that the acrylic resin paint was not applied to the surface of the Lauan plywood (no paint coating layer).

[Comparative Example 3]
In Example 3, a test specimen was manufactured in the same manner except that the acrylic resin paint was not applied to the surface of the Lauan plywood (no paint coating layer) .

Using test specimens prepared in Examples 1-6 and Comparative Example 1 to 3 are shown in Tables 1 and 2 summarizes the results of testing by the test method described below.
〔performance test〕
<Tensile shear>
In accordance with JIS K6850: 1999 “Testing method for tensile shear bond strength of adhesive-rigid adherend”, the adhesive strength of the manufactured test specimen was measured and the state of fracture was observed.
The fracture position relative to the coating area is “the interface between the adhesive layer and the paint coating layer” based on the fracture status, and when there is no paint coating layer, the ratio of the area occupied by the “interface between the adhesive layer and the base material” ".
<Plane tension>
In accordance with JIS A5536: 2007 “Adhesive for Floor Finishing Materials”, 5.3.2 “Tensile Adhesive Strength”, the test specimen produced and the adhesive strength after heating this specimen at 80 ° C. for 1,500 hours The thickness was measured and the fracture condition was observed.
The fracture position relative to the coating area is “the interface between the adhesive layer and the paint coating layer” based on the fracture status, and when there is no paint coating layer, the ratio of the area occupied by the “interface between the adhesive layer and the base material” ".

[Example 7 ]
Acrylic resin paint (Fujikura Kasei Co., Ltd., Rezalic TC-2) is applied on the surface of Kokonota hot water mat (12mm thickness, high heat dissipation type, Osaka Gas Co., Ltd., 142L505) and the coating amount is 100 g / m ² . About 1.8m x about 1.8m lauan plywood (12mm thickness, JAS-accepted product) coated and dried at room temperature for 24 hours to form a paint coating layer with 303mm pitch with screws Fixed. On top of this, adhesive A is uniformly applied at a coating amount of 500 g / m ² to form an adhesive layer. Further, a 1 × 6 flooring material (12 mm thickness, manufactured by Asahi Woodtech Co., Ltd.) is used as a floor surface material. EG-HOT), and nails were driven in at a pitch of 303 mm from above, and cured at 23 ° C. and 50% relative humidity for 14 days to produce a floor heating flooring. The end (end in the longitudinal direction) was fixed by applying adhesive A so as to straddle the three nails and the flooring.

[Comparative Example 4 ]
In Example 7 , an acrylic resin paint was not applied to the surface of the lauan plywood (no paint coating layer), and a urethane resin adhesive containing no plasticizer instead of the adhesive A (manufactured by Auto Chemical Industries, Auton Adher) 8000) was used in the same manner to produce a floor heating flooring.

Table 3 summarizes the results of testing using the floor heating floor materials produced in Example 7 and Comparative Example 4 by the test method shown below.
〔performance test〕
<Thermal durability test>
Between the floor surface material (flooring material) at the side and end after continuously flowing hot water of 80 ° C for 1,100 hours to the heated floor mat of the manufactured floor heating floor material (initial stage) and this floor heating floor material The amount of gaps (interval of the joints of the flooring material) and the height of the step on the surface of the flooring material (the difference in height between the left and right surfaces at the joint of the flooring material) were measured. As a result, the gap when the flooring material was dried and shrunk by heating caused by insufficient fixing force of the adhesive, the level difference of the surface due to the warping of the flooring material, and the floor noise when walking on the flooring material were measured.
Those that were each below the reference value were considered acceptable.
<Peelability test>
After the endurance test, the flooring material was physically peeled off, and the peelability between the base material and the adhesive layer was evaluated according to the following criteria.
○: The base material was not destroyed and the base material was peeled off without any adhesive layer remaining.
Δ: The base material was not destroyed, and a part of the adhesive layer remained on the base material.
X: The base material was destroyed.

DESCRIPTION OF SYMBOLS 1 Base material 2 Floor surface material 3 Paint coating layer 4 Adhesive layer

Claims (3)

A base material, an acrylic resin paint coating layer, a one-part moisture-curing urethane resin adhesive layer containing a polyurethane high molecular weight plasticizer having a number average molecular weight of 1,000 or more, and a floor surface material, Floor material characterized by being laminated and integrated in order. A base material, an acrylic resin paint coating layer, a one-part moisture-curing urethane resin adhesive layer containing a polyurethane high molecular weight plasticizer having a number average molecular weight of 1,000 or more, and a floor surface material, A flooring characterized by being laminated in order and further integrated by nails.   The flooring according to claim 1 or 2, wherein the content of the plasticizer is 10 to 200 parts by mass with respect to 100 parts by mass of the cured resin component in the urethane resin adhesive.

Images