JP2002188072A - Polyurethane composition for forming adhesive for sticking plastic floor board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane composition for forming adhesive for sticking a plastic floor board, having excellent removability and resistance to contamination of groundwork, and further to provide an adhesive material obtained by applying the composition. SOLUTION: This heat-curable type or two-component curable type polyurethane composition for forming the adhesive for sticking the plastic floor board comprises a urethane prepolymer having isocyanate groups at the terminals and derived from a polyol comprising a polyol having 200-10,000 hydroxy equivalent, and excess of an organic polyisocyanate, and/or a blocked compound thereof, and a polyol comprising the polyol having 200-10,000 hydroxy equivalent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane composition for forming a pressure-sensitive adhesive on a plastic flooring material such as polyvinyl chloride, and a pressure-sensitive adhesive material and a plastic flooring material obtained by applying the same.

[0002]

2. Description of the Related Art Conventionally, when constructing a plastic flooring material such as polyvinyl chloride, a method of bonding the flooring material with a strong adhesive to prevent the flooring material from shifting due to walking during use has been adopted. There is a problem that the floor material cannot be peeled off at the time of changing the fixing place or at the time of renovation. On the other hand, in order to solve the above-mentioned problems, an adhesive for flooring (JP-A-2-219886) and a construction method (JP-A-3-17170) mainly having an acrylic pressure-sensitive adhesive and having a re-peeling function have been proposed.

[0003]

However, in the case of acrylic pressure-sensitive adhesives, plasticizers such as dioctyl phthalate contained in plastic flooring materials such as polyvinyl chloride migrate to the pressure-sensitive adhesive layer during long-term use, causing stickiness and adhesive strength. Becomes stronger,
There were drawbacks such as contamination of the groundwork and the inability to peel off the floor material during reforming.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on an adhesive which solves the above problems, and as a result, have reached the present invention.

[0005] That is, the present invention provides a hydroxyl equivalent of 200 to 1
An isocyanate group-terminated urethane prepolymer (A1) derived from a polyol (a) consisting of 3,000 polyol (a1) and an excess of an organic polyisocyanate (c) and / or a block (A2) thereof, and a hydroxyl equivalent of 200 A thermosetting or two-pack curable polyurethane composition for forming a plastic flooring adhesive, comprising a polyol (B) comprising up to 10,000 polyols (b1); a paper, plastic film or sheet; Adhesive for sticking plastic flooring, which is applied or impregnated and cured on a substrate selected from plastic foam and nonwoven fabric; and a plastic having an adhesive layer obtained by curing the composition on at least a part of the back surface It is flooring.

In the present invention, the hydroxyl equivalent is 200 to 10,
000 polyols (a1) include polyether polyols (a11) and polyester polyols (a1).
2), polydiene polyol (a13), castor oil-based polyol (a14), and a mixture of two or more of these. The hydroxyl equivalent (number average molecular weight per hydroxyl group by hydroxyl value measurement) of the (a1) is usually from 200 to
It is 10,000, preferably 500 to 5,000, more preferably 1,000 to 3,000. The (a)
The number of functional groups in 1) is preferably 2 to 8, more preferably 2 to 4, and particularly preferably 2 to 3.

Examples of the polyether polyol (a11) include compounds having a structure in which an alkylene oxide (hereinafter abbreviated as AO) is added to a compound containing an active hydrogen atom, and a mixture of two or more thereof.

Examples of the compound containing an active hydrogen atom include a polyhydric alcohol (a), a polyhydric phenol (b) and an amine (c).

As the polyhydric alcohol (a), dihydric alcohols [aliphatic dihydric alcohols having 2 to 20 carbon atoms (ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3-, 2,3- and 1,4
-Butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, etc.), a dihydric alcohol having an alicyclic group having 6 to 15 carbon atoms (cyclohexylene glycol, , 4-cyclohexanedimethanol, 4,
4'-dihydroxycyclohexylmethane, etc., C8 to C15 aromatic ring-containing dihydric alcohols (m- and p-
-Xylylene glycol, etc.); trihydric alcohols (3 to 15 carbon atoms, for example, glycerin, trimethylolpropane); 4 to 8 hydric alcohols (5 to 15 carbon atoms, for example, pentaerythritol, diglycerin, sorbitol)
, Dipentaerythritol, glucose, sucrose);
Tertiary amino group-containing polyhydric alcohol [trialkanolamine having 2 to 4 carbon atoms of hydroxyalkyl group (such as triethanolamine), N-alkyl (1 to 10 carbon atoms)
Dialkanolamines (such as N-methyldiethanolamine) and mixtures of two or more thereof.

As the polyhydric phenol (b), monocyclic polyhydric phenols (C6 to C12, for example, pyrogallol, catechol, hydroquinone) and bisphenols (C12 to C20, for example, bisphenol A, bisphenol F, bisphenol S) Is mentioned.

Examples of the amine (c) include ammonia; monoamines [aliphatic monoamines having 1 to 20 carbon atoms (such as butylamine and octylamine), alicyclic monoamines having 6 to 12 carbon atoms (such as cyclohexylamine), and 6 carbon atoms. ~
12 aromatic (aliphatic) monoamines (aniline, benzylamine, etc.)]; aliphatic polyamines having 2 to 18 carbon atoms (ethylenediamine, hexamethylenediamine, diethylenetriamine, etc.); alicyclic polyamines having 6 to 15 carbon atoms (4, 4'-diaminocyclohexylmethane, isophoronediamine, etc.); aroma (fat) having 6 to 15 carbon atoms
Group polyamines (tolylenediamine, xylylenediamine, 4,4'-diaminodiphenylmethane, etc.); and alkanolamines having 2 to 4 carbon atoms in a hydroxyalkyl group (monoethanolamine, diethanolamine, etc.).

AO to be added to the above-mentioned active hydrogen atom-containing polyfunctional compound is ethylene oxide (hereinafter referred to as EO).
Abbreviation), propylene oxide (hereinafter abbreviated as PO),
Examples thereof include 1,4-, 1,2-, 2,3- and 1,3-butylene oxide, styrene oxide, and α-olefin oxides having 5 to 10 or more carbon atoms.

AO may be used alone or in combination of two or more.
In the latter case, block addition, random addition, or a mixture of both may be used. Of these AOs, preferred are EO alone, PO alone, or a combination of PO and EO.

The addition of AO to the active hydrogen atom-containing polyfunctional compound can be carried out by a usual method, and can be carried out without a catalyst or in the presence of a catalyst (alkali catalyst, amine catalyst, acidic catalyst) (particularly in the latter half of AO addition). In one or more stages under normal pressure or under pressure.

Examples of the polyester polyol (a12) include the above-mentioned polyhydric alcohols (particularly, dihydric alcohols and trihydric alcohols).
And / or a condensed polyester polyol obtained by reacting a polyalkylene ether polyol having a molecular weight of 1,000 or less with a dicarboxylic acid; And a polylactone polyol obtained by ring-opening polymerization of lactone No. 12.

Examples of the polyalkylene ether polyol having a molecular weight of 1,000 or less include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, polyoxypropylene triol (eg, polyoxypropylene adduct of glycerin) and two or more of these. Mixtures are mentioned.

The dicarboxylic acid may have 4 to 20 carbon atoms.
Aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, etc.), aromatic dicarboxylic acids having 8 to 12 carbon atoms (terephthalic acid, isophthalic acid, phthalic acid, etc.), and ester forming properties of these dicarboxylic acids Derivatives [acid anhydride, lower alkyl (C 1-4) ester,
And mixtures of two or more of these. Further, as the lactone, ε-caprolactone,
γ-butyrolactone, γ-valerolactone and mixtures of two or more thereof.

The polyester polyol (a12) can be prepared by a conventional method, for example, by converting a di- or trihydric alcohol and / or a polyether polyol having a molecular weight of 1,000 or less with a dicarboxylic acid or an ester-forming derivative thereof, or an anhydride thereof and AO (for example, EO and / or P
O), or by ring-opening addition of a lactone to a di- or trihydric alcohol and / or a polyether polyol having a molecular weight of 1,000 or less.

These polyester polyols (a1
Specific examples of 2) include polyethylene adipate diol, polybutylene adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, polyethylene sebacate diol, polycaprolactone diol, and triol.

Examples of the polydiene polyol (a13) include polybutadiene polyol, polyisoprene polyol, and partially or completely hydrogenated products thereof. Preferred among these are polybutadiene polyols. As the polybutadiene polyol,
Those having a 1,2-vinyl structure, those having a 1,2-vinyl structure and a 1,4-trans structure, and 1,4-
Those having a trans structure are exemplified. The ratio between the 1,2-vinyl structure and the 1,4-trans structure can be variously changed, and is, for example, 100: 0 to 0: 100 in molar ratio. Polybutadiene polyols also include homopolymers and copolymers (styrene butadiene copolymer,
Acrylonitrile butadiene copolymer).

The castor oil-based polyol (a14) includes castor oil and modified castor oil (such as castor oil modified with a polyhydric alcohol such as trimethylolpropane and pentaerythritol).

Of the above (a1), preferred are polyether polyol (a11) and polydiene polyol (a13), more preferred are polyoxypropylene polyol and polybutadiene polyol, and particularly preferred are polyoxypropylene glycol. Polyoxypropylene triol and polybutadiene polyol.

In (a1) of the present invention, a low molecular polyol (a2) having a hydroxyl equivalent of less than 200 can be used in combination, if necessary. Examples of (a2) include a polyhydric alcohol, an AO adduct of the polyhydric alcohol, and an AO adduct of a polyhydric phenol. Examples of the polyhydric alcohol and polyhydric phenol include those exemplified as the starting material of the above (a11) (especially those having 2 to 3 valences).
When (a2) is used together, the amount used is (a1) and (a
Preferably it is 50 equivalent% or less based on the total of 2), More preferably, it is 30 equivalent% or less.

As the organic polyisocyanate (c) in the present invention, those conventionally used for producing polyurethane can be used. Such polyisocyanates include carbon numbers (excluding carbon in NCO groups, and so on)
6-20 aromatic polyisocyanate, 2-18 carbon atoms
Aliphatic polyisocyanate, alicyclic polyisocyanate having 4 to 15 carbon atoms, araliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, Modified compounds containing a burette group, a uretdione group, a uretimine group, an isocyanurate group, an oxazolidone group, etc.) and a mixture of two or more of these.

Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, ,
4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl -4,4'-diisocyanatodiphenylmethane, crude MDI [crude diaminodiphenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight)]
A mixture with a triamine or higher polyamine]: polyallyl polyisocyanate (PAPI)],
1,5-naphthylene diisocyanate, 4,4 ', 4 "
-Triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate.

Specific examples of the above aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (H
DI), dodecamethylene diisocyanate, 1,6,1
Examples thereof include 1-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.

Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate,
Methylcyclohexylene diisocyanate (hydrogenated TD
I) 1,3- and / or 1,4-diisocyanatomethylcyclohexane (hydrogenated XDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- And / or 2,6-norbornane diisocyanate.

Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI). Can be

Among these, preferred are aromatic diisocyanates, araliphatic polyisocyanates and modified products thereof, and particularly preferred are TDI,
MDI, TMXDI and their modified products (carbodiimide modified product, buret modified product, isocyanurate modified product).

The isocyanate group-terminated urethane polymer (A1) in the present invention usually has an equivalence ratio (NCO / OH ratio) of the isocyanate group (NCO) of (c) and the hydroxyl group (OH) of the polyol (a) of 1. It is obtained by reacting in the range of 1-3, preferably 1.5-2.2. Catalysts commonly used for polyurethanes to promote the reaction {for example, organotin compounds (dibutyltin dilaurate, stannas octoate, etc.); tertiary amines [triethylenediamine, trialkylamine having 1 to 8 carbon atoms in the alkyl group ( Triazylamine), diazabicycloalkenes (1,8-diazabicyclo- [5,4,
0] -undecene-7]; and a combination of two or more of these.

The urethane prepolymerization reaction is usually carried out in the absence of a solvent, but can be carried out in the presence of a solvent inert to isocyanate, if necessary. Examples of the solvent include aromatic hydrocarbon solvents (toluene, xylene, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ether solvents (cellosolve acetate, dioxane, tetrahydrofuran, etc.), ketone solvents (methyl ethyl ketone, methyl Isobutyl ketone) and a mixed solvent of two or more of these. The amount of the solvent to be used is generally 30% by weight or less, preferably 20% by weight or less, based on the weight of (A1). The reaction temperature is usually 50 to 120 ° C, preferably 60 to 110 ° C, and the reaction time is usually 3 to 10 hours, preferably 5 to 8 hours.

The isocyanate group equivalent (number average molecular weight per isocyanate group) of (A1) is usually from 300 to 3
It is preferably 10,000, preferably 500 to 10,000.

As the blocking agent constituting the block (A2) obtained by blocking part or all of the isocyanate group of (A1), a blocking agent composed of an oxime [having 3 to 10 carbon atoms, for example, Acetoxime, methyl ethyl ketoxime (MEK oxime), methyl isobutyl ketoxime (MIBK oxime), etc.], a blocking agent composed of a lactam (e.g., having 4 to 18 carbon atoms, such as ε-caprolactam, δ-valerolactam, γ-butyrolactam) and A mixture of two or more of these may be mentioned. Preferred among these are MEK oxime and ε-caprolactam, particularly preferred are MK oxime and ε-caprolactam.
EK oxime.

The blocking agent can be added at any stage of the urethane prepolymer reaction and allowed to react to obtain a block (A2) of (A1). As an addition method, there is a method of adding at the end of a predetermined urethane prepolymer reaction, adding at the beginning of the reaction, adding a part at the beginning of the reaction, and adding the remainder at the end of the reaction. Preferably, it is added at the end of the reaction. When the addition amount is at the end of the reaction, the urethane prepolymer (A
1 to 2 equivalents to the free isocyanate group of 1),
Preferably it is 1.05-1.5 equivalent. When the blocking agent is added at the beginning or in the middle of the reaction, the blocking agent is added from the equivalent of the isocyanate group of (c) to (a).
It is preferable to use an equivalent that is substantially the same as the equivalent obtained by subtracting the equivalent of the hydroxyl group. The reaction temperature when the blocking agent is added is usually 50 to 110 ° C. At the time of the reaction, it is possible to promote the reaction by adding the above-mentioned urethanization reaction catalyst.

Blocked urethane prepolymer (A2)
Apparent equivalent of blocked isocyanate group (number average molecular weight per blocked isocyanate group)
Is usually 300 to 30,000, preferably 500 to 1
It is 0000.

As the polyol (b1) in the present invention, polyether polyol (b11), polyester polyol (b12), polydiene polyol (b1)
3), polyurethane polyol (b14) and a mixture of two or more thereof.

Examples of the polyether polyol (b11) include those exemplified as the polyether polyol (a11).

Examples of the polyester polyol (b12) include those exemplified as the polyester polyol (a12).

Examples of the polydiene polyol (b13) include those exemplified as the polydiene polyol (a13).

Examples of the polyurethane polyol (b14) include those obtained by reacting the above (a1) or the polyol composed of (a1) and (a2) with the organic polyisocyanate exemplified in the above (c) in excess of the polyol. Can be The equivalent ratio (OH / NCO) of the hydroxyl group (OH) of the polyol to the isocyanate group (NCO) of the organic polyisocyanate is usually (1.2 to 20): 1, preferably (1.5 to 10): It is one.

The hydroxyl equivalent of (b1) is usually 200
It is from 10,000 to 10,000, preferably from 500 to 5,000, and more preferably from 1,000 to 3,000. If the hydroxyl equivalent is less than 200, the adhesive strength tends to be insufficient,
If it exceeds 000, the compatibility with (A1) or (A2) becomes poor and coating unevenness tends to occur. In addition, the (b1)
The number of functional groups is preferably from 1.5 to 8, more preferably from 2 to 6, particularly preferably from 2 to 3, from the viewpoints of stickiness (base stain resistance) and adhesive strength of the adhesive.

Of the above (b1), preferred are (b1)
1), (b13) and (b14), and more preferred are polyoxypropylene polyols (particularly polyoxypropylene glycol and polyoxypropylene triol), polybutadiene polyols, and those obtained by reacting these with organic polyisocyanates. It is a polyurethane polyol.

In (b1) of the present invention, a low molecular polyol (b2) having a hydroxyl equivalent of less than 200 can be used in combination, if necessary. As (b2), those exemplified as the above (a2) can be mentioned. The amount used when (b2) is used in combination is preferably 50 equivalent% or less, more preferably 30 equivalent%, based on the sum of (b1) and (b2).
It is as follows.

In the present invention, the equivalent ratio of the isocyanate group in (A1) and / or the blocked isocyanate group in (A2) to the hydroxyl group in (B) [(blocked)
NCO / OH ratio] is preferably (0.8 to 5) from the viewpoints of stickiness (base stain resistance) and adhesive strength of the adhesive.
1, more preferably (1-3): 1.

In the present invention, for the purpose of accelerating the reaction,
A urethanization promoting catalyst (C1) and / or a block dissociation catalyst (C2) can be used. (C1) includes a metal catalyst [tin-based catalyst [dibutyltin dilaurate,
Stannate octoate, etc.], lead-based catalysts [lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.]]; tertiary amines [triethylenediamine, alkyl group having 1 to 8 carbon atoms] (E.g., triethylamine), diazabicycloalkenes [1,8-diazabicyclo- [5,4,0] -undecene-7, etc.]; and a combination of two or more of these. Preferred among these are dibutyltin dilaurate, lead 2-ethylhexanoate and 1,8-diazabicyclo- [5,4,0] -undecene-7. Examples of (C2) include metal catalysts [tin-based catalysts [trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, stannasoctoate, dibutyltin maleate, etc.], lead-based catalysts [ Lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.],
Other metal catalysts (eg, naphthenate metal salts such as cobalt naphthenate); quaternary ammonium organic acid salts (eg, octylate of trimethylethylquaternary ammonium); and a combination of two or more of these. .
Of these, preferred are dibutyltin dilaurate, lead 2-ethylhexanoate and trimethylethyl4.
It is an octylate of quaternary ammonium. The amount of (C1) and / or (C2) added is usually 1% by weight or less, preferably 0.5% by weight or less, based on the weight of (A1) and / or (A2). When (C1) and / or (C2) are contained in advance, it is preferable to contain them in (B).

The polyurethane composition for forming an adhesive of the present invention may contain additives such as a tackifier, a plasticizer, an antioxidant, an ultraviolet absorber, a pigment, and a filler, if necessary. Examples of the tackifier include terpene-phenol resins, xylene resins, rosin resins, acrylic oligomers, alicyclic or aromatic petroleum resins, and the like. Examples of the plasticizer include phthalic acid esters [dioctyl phthalate etc.], phosphoric acid triesters [triphenyl phosphate etc.], aliphatic dibasic acid esters [di (2-ethylhexyl) adipate etc.], fatty acid ester [methyl] Acetyl ricinoleate], polyesters (eg, adipic acid-propylene glycol ester), polyhydric alcohols [eg, triethylene glycol dibenzoate], and citrate esters [eg, triethyl citrate].

As the antioxidant, phenolic [2,
6-di-t-butyl-p-cresol (BHT), butylated hydroxyanisole (BHA), etc.], and sulfur-based [dilauryl 3,3′-thiodipropionate (DLT)
DP)], phosphorus-based [triphenyl phosphite (T
PP) and the like, and amines [octylated diphenylamine and the like]. Examples of ultraviolet absorbers include benzotriazoles [such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole], benzophenones [such as 2-hydroxy-4-methoxybenzophenone], and salicylic acids [such as phenyl salicylate]. ,
Acrylate [2-ethylhexyl-2-cyano-
3,3'-diphenyl acrylate, etc.].

Examples of the pigment include inorganic pigments (titanium oxide, red iron oxide, graphite, cadmium pigment, ultramarine blue, etc.) and organic pigments (azo chelate type, monoazo type, disazo type, chelate azo type, benzimidazoline type, phthalocyanine type, quinacridone type, Dioxazine type, isoindolinone type,
Thioindigo, perylene, quinophthalone, anthraquinone and the like can be mentioned. Examples of the filler include calcium carbonate, talc, clay, silicic acid, silicate, asbestos, mica, glass fiber, glass balloon, carbon fiber, metal (such as aluminum) fiber, ceramic whisker, and titanium whisker.

The amount of the above additives is usually not more than 50%, preferably not more than 30%, based on the total weight of (A1) and / or (A2) and (B), plasticizer, pigment and The filler is usually 30% or less, preferably 15% or less, respectively, and the antioxidant and ultraviolet absorber are usually 5% or less, preferably 1% or less, respectively.

The composition for forming a pressure-sensitive adhesive of the present invention comprises (A1)
And / or (A2) and (B) are each weighed in a predetermined amount at the time of use, then mixed with a static mixer or a mechanical mixer, and applied to a substrate selected from paper, plastic film or sheet, plastic foam and nonwoven fabric. Impregnated and cured to form an adhesive.

In the pressure-sensitive adhesive forming composition of the present invention,
The gelation time of the combination of (A1) and (B) is usually 3 to 60 minutes, and the combination of (A2) and (B) is usually at 80 to 160 ° C. for about 1 to 20 minutes after application. A step of dissociating and regenerating the blocked isocyanate group by heating is required.

Examples of the plastic film or sheet to which the composition for forming a pressure-sensitive adhesive of the present invention is applied include polypropylene, polyethylene, polyester, polyacryl, polyvinyl chloride, polystyrene, nylon, ethylene-vinyl alcohol copolymer and polyvinyl alcohol. Each film or sheet, or a plastic film or sheet whose surface is subjected to a vapor deposition treatment with aluminum or silica or a coating treatment with polyvinylidene chloride is exemplified. In addition, the plastic film or sheet has a diameter of 10 to 1,000 μm.
A porous plastic film or sheet having holes on the entire surface may be used. As the plastic foam to which the pressure-sensitive adhesive forming composition of the present invention is applied, for example, polyethylene foam, polypropylene foam,
Polyurethane foam, polystyrene foam and the like can be mentioned. Examples of the material of the nonwoven fabric to which the composition for forming an adhesive of the present invention is applied include natural fibers, rayon, polypropylene, polyester, and nylon.

For application to a plastic film, a gravure coater, reverse roll coater, comma coater or the like is used. For application to paper, non-woven fabric, porous film or plastic foam, a method of coating and transferring to a release paper or release film or a method of impregnation is used. The coating amount (solid content) of the pressure-sensitive adhesive forming composition is usually 5 to 100 g / m ² . For coating on a plastic sheet, a comma coater, a die coater, a knife coater or the like is used. In this case, the coating amount (solid content) of the pressure-sensitive adhesive forming composition is usually 1
0 to 500 g / m ² .

After coating, the coating is usually carried out at 80 to 160 ° C., preferably 100 to 140 ° C., for usually 1 to 20 minutes, preferably 3 to 1
After curing by heating under the condition of 0 minutes, the temperature is from room temperature to 50 ° C for 1 minute.
After curing for about 4 days, an adhesive is formed.

The adhesive material of the present invention thus obtained does not deteriorate due to migration of the plasticizer even when used for a long period of time, and is particularly useful for bonding a plastic flooring material such as polyvinyl chloride to a base such as mortar. Then, the pressure-sensitive adhesive is stuck to at least a part of the back surface of the floor material to form a pressure-sensitive adhesive layer, which can be suitably used. In addition, the composition of the present invention may be directly coated on a plastic flooring material such as polyvinyl chloride and cured (thermosetting or two-liquid curing) to form an adhesive layer on at least a part of the back surface of the flooring material. . Further, the composition of the present invention is also suitably used for adhesive processing of, for example, plastic-made wallpaper for building interior such as soft or semi-rigid polyvinyl chloride.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.
Parts and% in the examples indicate parts by weight and% by weight, respectively.

[Preparation of Isocyanate Group-Terminated Urethane Prepolymer (A1-1)] Production Example 1 In a 2 L flask equipped with a stirrer, a thermometer, and a nitrogen gas introducing tube, polypropylene glycol (having a hydroxyl equivalent of 1,000
0, number of functional groups 2) 434 parts, propylene oxide adduct of glycerin (hydroxyl equivalent 1,300, number of functional groups 3)
434 parts and TDI 132 parts were charged under a nitrogen stream.
The reaction was carried out at 60 to 80 ° C. for 7 hours, the solid content was 100%, the viscosity was 4,500 mPa · s / 25 ° C., and the NCO group content was 3.2.
% Urethane prepolymer (A1-1) was obtained.

[Blocked urethane prepolymer (A2
Preparation of -1)] Production Example 2 In a reaction container similar to that of Production Example 1, (A) was obtained in Production Example 1.
1-1) Charge 1,000 parts, then add 69.6 parts of methyl ethyl ketoxime, and add 60 to 8 under a nitrogen stream.
After reacting at 0 ° C. for 3 hours, it was confirmed by infrared absorption spectrum that the absorption of isocyanate groups had disappeared. Thus, a solid content of 100% and a viscosity of 17,000 mP
As a / s / 25 ° C, a blocked urethane prepolymer (A2-1) having a blocked NCO content of 3.0% was obtained.

[Adhesive (X
Preparation of -1)] Production Example 3 Urethane prepolymer (A1-1) 10 obtained in Production Example 1
0 parts, polypropylene glycol (hydroxyl equivalent 1,50
0, the number of functional groups 2) (B-1) 115 parts and 0.25 parts of a lead 2-ethylhexanoate-containing catalyst [LL690D (manufactured by Sankyoki Synthetic Chemical Co., Ltd.)] are mixed, and an applicator is applied to a 25 μm-thick polyester film. , The film thickness after drying is 1
It was applied so as to be 00 μm. Next, after heat-curing in an oven at 130 ° C. for 10 minutes, release paper was attached to the application surface to form an adhesive layer. Further, a pressure-sensitive adhesive layer was similarly formed on the back surface of the film to obtain a pressure-sensitive adhesive material (X-1) for attaching a plastic flooring material having a pressure-sensitive adhesive layer on both sides of a polyester film.

Production Example 4 The blocked urethane prepolymer obtained in Production Example 2 (A2
-1) 100 parts, polypropylene glycol (hydroxyl equivalent: 1,500, functional group number: 2) (B-1) 110 parts and lead catalyst containing 2-ethylhexanoate [LL690D (manufactured by Sankyoki Synthetic Chemical Co., Ltd.)] 25 parts were mixed, and thereafter, in the same manner as in Production Example 3, an adhesive (X-
2) was obtained.

Example 1 The release paper on one side of (X-1) obtained in Production Example 3 was peeled off and stuck on a PVC floor tile ["Light Stone" homogenous vinyl floor tile HT manufactured by Tori Co., Ltd.] to weigh 5 kg. The pressure roller was reciprocated four times to obtain a floor tile with adhesive (Y-1). Peel off the release paper of (Y-1) and apply 5
A pressure roller of 4 kg is reciprocated four times, and after one month, it is peeled off, and the adhesive strength, re-peelability, and stain resistance to the ground (the state of the adhesive remaining on the concrete surface) are evaluated according to the following (test method). did. Table 1 shows the results.

Example 2 A test was conducted in the same manner as in Example 1 using (X-2) obtained in Production Example 4. Table 1 shows the results.

Example 3 The urethane prepolymer (A1-1) 10 obtained in Production Example 1
0 parts, polypropylene glycol (hydroxyl equivalent 1,50
0, the number of functional groups 2) (B-1) 115 parts and 0.25 part of a lead 2-ethylhexanoate-containing catalyst [LL690D (manufactured by Sankyoki Gosei Kagaku Co., Ltd.)] are mixed, and a PVC floor tile [Tori Co., Ltd. ) "Light Stone" Homogeneous Vinyl Floor Tile HT], and dried so as to have a film thickness of 150 μm. Was adhered four times back and forth, and peeled off after one month to examine the adhesive strength, re-peelability, and stain resistance (state of adhesive remaining on the concrete surface), and the results are shown in Table 1. .

Example 4 The blocked urethane prepolymer obtained in Production Example 2 (A2
-1) 100 parts, polypropylene glycol (hydroxyl equivalent: 1,500, functional group number: 2) (B-1) 110 parts and lead catalyst containing 2-ethylhexanoate [LL690D (manufactured by Sankyoki Synthetic Chemical Co., Ltd.)] 25 parts were mixed and tested in the same manner as in Example 3. The results are shown in Table 1.

COMPARATIVE EXAMPLE 1 An epoxy / urethane-based one-pack reactive vinyl floor tile adhesive [US Cement (manufactured by Tori Co., Ltd.)] was applied to a concrete surface so that the film thickness after drying would be 100 μm, and PVC was applied. A floor tile ["Light Stone" homogenous vinyl floor tile HT manufactured by Tori Co., Ltd.] was attached by reciprocating a 5 kg pressure roller four times, and the same test as in Example 3 was performed. Table 1 shows the results.

Comparative Example 2 Acrylic pressure-sensitive adhesive [Polysic 410-SA (manufactured by Sanyo Chemical Industries, Ltd.), evaporation residue 40%] 100 parts, TD
I trimethylolpropane adduct [Coronate L
(Manufactured by Nippon Polyurethane Industry Co., Ltd.), evaporation residue 75
%], And mixed with PVC floor tile [Toilei Co., Ltd. “Light Stone” homogeneous vinyl floor tile HT]
Was applied so that the film thickness after drying was 150 μm. Next, after thermosetting in an oven at 100 ° C. for 10 minutes, the same test as in Example 3 was conducted. Table 1 shows the results.

(Test Method) Adhesion: In the table, those having strength enough to withstand practical impacts were evaluated as good, ○ as good, Δ as slightly poor, and x as poor. Removability: When the floor tile can be peeled off from the concrete surface with a force that does not cause pain when the floor tile is peeled off, it is evaluated as good.
In the table, the mark is good, the mark is slightly bad, and the mark x is bad. Substrate contamination resistance: When the floor tile is peeled off from the concrete surface, the one that does not leave any adhesive on the concrete surface is regarded as good, the mark ○ is good, the mark △ is slightly poor (sparsely left),
X is described in the table as defective (remains entirely).

[0068]

[Table 1]

As is evident from Table 1, the plastic flooring material adhered to the substrate using the polyurethane composition for adhering plastic flooring material of the present invention was different from the conventional one (Comparative Examples 1 and 2). In comparison, they are superior in removability and resistance to ground contamination.

[0070]

The polyurethane composition of the present invention for forming an adhesive on a plastic flooring has the property of being cured by heat curing or two-part curing to form an adhesive, and has a sufficient adhesive force for practical use. Has peelability. In addition, when the plastic flooring to which the composition is applied is a polyvinyl chloride resin containing a plasticizer, it exhibits an effect of being superior in resistance to background contamination as compared with a conventional adhesive. Due to the above effects, the composition of the present invention can be suitably used for adhesion between a plastic flooring material such as polyvinyl chloride and a base such as mortar, and various industrial adhesive tapes or sheets (for example, electric and Adhesive tape for electronics, binding tape for vegetables, etc., masking film, wallpaper, automobile mold tape, etc.)
Is very useful because it can be suitably used.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 7/02 C09J 7/02 Z 11/00 11/00 // E04F 15/10 104 E04F 15/10 104A F term (reference) 4J004 AA14 AA17 AA18 AB01 CA01 CA02 CB01 CB02 CC02 FA08 4J034 CA03 CA04 CA05 CA12 CA13 CA14 CA15 CA16 CA19 CB02 CB03 CB04 CB07 CB08 CC03 CC08 CC10 CC12 CC26 CC45 CC52 CC61 CC62 CC01 DF21 DF21 DF21 DG03 DG04 DG05 DG06 DG23 DP02 DP06 DP19 EA12 HA01 HA02 HA06 HC07 HC12 HC13 HC33 HC34 HC35 HC61 HC64 HC67 HC71 HD04 HD12 JA42 KA01 KB02 KB04 KC17 KD02 KD04 KD11 JA EF12 EF051 EF051 EF051 EF051 JA13 JB09 KA17 KA26 KA29 KA31 KA35 KA42 MA09 MA10 PA23

Claims (10)

[Claims] 1. An isocyanate-terminated urethane prepolymer (A1) derived from a polyol (a) comprising a polyol (a1) having a hydroxyl equivalent of 200 to 10,000 and an excess of an organic polyisocyanate (c) and / or a block thereof. Body (A2) and a hydroxyl equivalent of 200 to 1
A thermosetting or two-component curable polyurethane composition for forming a plastic flooring adhesive applied to a pressure-sensitive adhesive, comprising a polyol (B) comprising 000 polyol (b1). 2. The composition according to claim 1, wherein (a1) and / or (b1) is a polyoxypropylene polyol and / or a polydiene polyol. 3. The isocyanate group equivalent of (A1) is 30.
3. The composition according to claim 1, wherein the composition is 0 to 30,000. 4. The method according to claim 1, wherein (A2) converts (A1) to an oxime and / or
4. The composition according to claim 1, wherein the composition is blocked with a lactam blocking agent. 5. The method according to claim 1, wherein the equivalent ratio of the (blocked) isocyanate group of (A1) and / or (A2) to the hydroxyl group of (B) is (0.8 to 5): 1. A composition as described. 6. The composition according to claim 1, further comprising a urethanization promoting catalyst (C1) and / or a block dissociation catalyst (C2). 7. The composition according to claim 1, further comprising a tackifier, a plasticizer, an antioxidant, an ultraviolet absorber, a pigment and / or a filler. 8. A method for applying a composition according to claim 1 to a base material selected from paper, plastic film or sheet, plastic foam and nonwoven fabric, or impregnating and curing the base material. Adhesive material. 9. A plastic flooring material having a pressure-sensitive adhesive layer obtained by curing the composition according to claim 1 on at least a part of the back surface. 10. A layer of a pressure-sensitive adhesive that cures the composition on the back of the plastic flooring or by applying or impregnating and curing a substrate selected from paper, plastic film or sheet, plastic foam and non-woven fabric. The plastic flooring material according to claim 9, which is a layer of an adhesive obtained by attaching an adhesive material.