JPH0788623B2 - Dust control mat lining composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for backing a dust control mat having excellent resistance to washing water.

(Prior Art) In a typical tufted carpet, which is a typical carpet at present, a pile of nylon, acrylic, vinylon, etc. is planted on the primary base cloth, and a lining treatment is performed to prevent the pile from falling off. Has been applied. For this backing treatment, an aqueous dispersion composition obtained by adding a filler, a dispersant, a thickener and the like to an aqueous dispersion of a high molecular weight polymer such as synthetic rubber latex as needed is used.

In recent years, there has been a strong demand for such carpets to have good washing resistance, and particularly in so-called dust control mats, dimensional changes of mats even after many washings,
For example, there is little shrinkage, there is no curling (bending) phenomenon, there is little falling of pile and backing resin, etc.
Severe washing resistance is required.

In order to secure such washing resistance, various aqueous dispersion compositions have already been proposed. For example, JP-A-59-15465
The publication describes an aqueous dispersion composition obtained by blending a styrene-butadiene copolymer rubber latex with an epoxy compound and a compound having an aziridine ring. Also,
There is also known a composition in which a thermosetting resin such as methylol melamine or a vulcanizing agent is mixed in rubber latex alone or in combination, but the dimensional change of the mat after selection, the dropping of the lining resin, etc. Regarding the above, the need for improvement is still recognized.

(Problems to be Solved by the Invention) As a result of intensive studies for solving the above-mentioned problems in conventional dust control mat backing compositions, the present inventors have found that a polymer having a carboxyl group and / or a hydroxyl group is used. By blending the melamine resin with the blocked polyisocyanate in the aqueous dispersion of the above, it has far superior washing resistance as compared with the conventional composition of the same kind, and the dust control mat which can meet the above-mentioned severe requirements. The present invention has been accomplished by finding that a backing composition can be obtained.

(Means for Solving Problems) The composition for backing a dust control mat according to the present invention comprises 0.5 to 50 parts by weight of blocked polyisocyanate per 100 parts by weight of solid content of an aqueous dispersion of a polymer having a carboxyl group and / or a hydroxyl group. It is characterized by containing 1 to 10 parts by weight of a melamine resin together with 30 parts by weight.

The aqueous polymer dispersion used in the present invention includes styrene-butadiene rubber (SBR) latex, methylmethacrylate-butadiene rubber (MBR) latex, acrylonitrile-butadiene rubber (NBR) latex,
Natural rubber (NR) latex, vinyl chloride polymer latex, methyl methacrylate-styrene-butadiene rubber (MSBR) latex, ethylene-vinyl acetate latex, acrylic latex, etc. It has a group and / or a hydroxyl group.

The aspect in which these functional groups are contained in the high molecular weight polymer in the latex is not limited at all, but typically,
It can be obtained by copolymerizing a monomer component constituting the main polymer and a monomer component having the functional group in the side chain in the molecule.

For example, to introduce a carboxyl group into the latex,
As a monomer component in the above copolymer, acrylic acid,
Ethylenically unsaturated monocarboxylic acids such as methacrylic acid and crotonic acid, ethylenically unsaturated dicarboxylic acids such as fumaric acid, maleic acid and itaconic acid, and half esters of these ethylenically unsaturated dicarboxylic acids may be used. Also,
To introduce a hydroxyl group into the latex, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate and N- are used as monomer components in the above copolymerization. Methylol (meth) acrylamide or the like may be used.

Further, the polymerizable polymer compound having these functional groups thus obtained is copolymerized, or the polymer compound having these functional groups is used as a protective colloid of the polymer during the polymerization reaction, Alternatively, it can be added after the polymerization reaction.

The blocked polyisocyanate used in the present invention is an addition reaction of the free isocyanate group of the polyisocyanate to inactivate it, and heating and / or
Alternatively, it refers to an addition reaction product of a compound (hereinafter referred to as a blocking agent) that is easily dissociated by a catalyst to form a bond for regenerating a polyisocyanate having a free isocyanate group, and polyisocyanate. Such blocked polyisocyanates are already known and are described, for example, in JP-A-60-203685.

As the polyisocyanate for the blocked polyisocyanate compound, any conventionally known polyisocyanate is used.

Therefore, as such a polyisocyanate, for example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,4,4-or
2,2,4-trimethylhexamethylene diisocyanate,
Aliphatic diisocyanates such as methyl 2,6-diisocyanatocaproate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, methylcyclohexane −
Aliphatic diisocyanates such as 2,4- or 2,6-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3- or 1,4-diisocyanatocyclohexane, m- or p-phenylene diisocyanate, Diphenylmethane-4,4'-diisocyanate, 2,4- or 2,6
-Aromatic diisocyanates such as tolylene diisocyanate, aromatic aliphatic such as 1,3- or 1,4-bis (isocyanatomethyl) benzene, 1,3- or 1,4-bis (α-isocyanatoisopropyl) benzene Mention may be made of diisocyanates such as diisocyanates.

Also, as triisocyanate, triphenylmethane-4,4,4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 1,3,5-tris (isocyanatomethyl)
Cyclohexane, 1,3,5-tris (isocyanatomethyl) benzene, 2,6-diisocyanatocaproic acid-2-
Isocyanatoethyl etc. can be mentioned.

Furthermore, as the polyisocyanate that can be used in the present invention, for example, a polymerized polyisocyanate such as a dimer or trimer of diisocyanate, polymethylene polyphenylene polyisocyanate, and an excess of the above isocyanate compound, for example, ethylene glycol, propylene. Glycol, dipropylene glycol, diethylene glycol,
Triethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, cyclohexanediol, hydrogenated bisphenol A, xylylene glycol, glycerin, trimethylolethane, tri Methylolpropane, hexanetriol, pentaerythritol, sorbitol, sorbit, sucrose, castor oil, ethylenediamine, hexamethylenediamine, ethanolamine, diethanolamine, triethanolamine, water, ammonia, low molecular weight compounds containing active hydrogen, or various Reacted with active hydrogen-containing high molecular weight compounds such as polyether polyol, polyester polyol, polyurethane polyol, acrylic polyol, and epoxy polyol. Obtained Te polyisocyanate,
Or these allophanatized polyisocyanates,
Examples include biuretized polyisocyanate.

The above isocyanate compounds are used alone or as a mixture of two or more kinds.

As the blocking agent, any conventionally known blocking agent is used. Examples of such blocking agents include phenol-based blocking agents such as phenol, cresol, p-nonylphenol and hydroxybenzoic acid ester, lactam-based blocking agents such as ε-caprolactam and γ-butyrolactam, diethyl malonate, and the like.
Active methylene-based blocking agents such as methyl acetoacetate and acetylacetone, ethanol, isopropyl alcohol, t-butyl alcohol, lauryl alcohol, ethylene glycol monoethyl ether, benzyl alcohol, glycolic acid, glycolic acid ester, lactic acid, lactate ester, diacetone. Alcohol, alcoholic blocking agents such as ethylene chlorohydrin, butyl mercaptan, octyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiothiophenol and other mercapcan blocking agents, acetanilide, acetic acid amide, acrylamide, benzamide, etc. Acid amide-based blocking agents, succinimide, imide-based blocking agents such as phthalimide, diphenylamine, carbazole, aniline, dibutyl Amine block agent such as Ming, imidazole, 2-ethyl imidazole block agent such as imidazole, urea, thiourea, urea-based block agents such as ethylene thiourea, 2-oxazolidone, N
-Carbamic acid ester-based blocking agents such as phenylcarbamic acid phenyl, oxime-based blocking agents such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, diacetylmonooxime, cyclohexanone oxime, benzophenone oxime, or sulfite. Examples thereof include sulfite-based blocking agents such as sodium hydrogen and potassium hydrogen sulfite. These blocking agents may be used alone or in combination of two or more, but in the present invention, an oxime-based blocking agent is particularly preferable from the viewpoint of reactivity, safety and the like.

The blocked polyisocyanate can be obtained by reacting the polyisocyanate and the blocking agent in a conventional manner as described above. This reaction can be carried out in a solvent having no active hydrogen or in the absence of solvent. As the solvent having no active hydrogen, for example, ethyl acetate, butyl acetate, cellosolve acetate,
Carbitol acetate, ester type such as dimethyl ester of dibasic acid, ketone type such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene,
Aromatic solvents such as xylene, sorbetso # 100, sorbetso # 150 and the like can be mentioned. When a sulfite-based blocking agent is used as the blocking agent, it is often preferable to use water as the solvent.

As described above, the blocking reaction of polyisocyanate may be carried out by a conventional method, but more specifically, for example, polyisocyanate blocking agent and NCO / blocking agent (equivalent ratio) of about 0.9 to 1.1 are used. , Preferably about 0.95 to 1.0, by reacting the polyisocyanate and the blocking agent.
A method of reacting with an NCO / blocking agent (equivalent ratio) of about 1.1 to 3.0, preferably about 1.2 to 2.0, and then reacting with the above-mentioned active hydrogen-containing low molecular weight compound and / or active hydrogen-containing high molecular weight compound. , After reacting the polyisocyanate with the active hydrogen-containing low molecular weight compound and / or the active hydrogen-containing high molecular weight compound at an NCO / active hydrogen (equivalent ratio) of about 1.5 to 10.0, preferably about 2.0 to 7.0, and then, if necessary, A method of removing the polyisocyanate and then reacting it with a blocking agent may be used. However, it is not limited to these. In the blocking reaction of polyisocyanate, a conventionally known catalyst such as a tertiary amine or an organometallic compound may be used.

The blocked polyisocyanate thus obtained is usually preferably added to the aqueous dispersion of the polymer as an aqueous mixture such as an aqueous emulsion, an aqueous dispersion or an aqueous solution. As described above, in order to form the blocked polyisocyanate into an aqueous mixture, any conventionally known method can be used.For example, the blocked polyisocyanate is mechanically micronized and dispersed in water, If necessary, a method of stabilizing the dispersion with a surfactant, protective colloid, dispersant, etc., a method of emulsifying with a surfactant, protective colloid, etc., salt formation in part of the blocked polyisocyanate A hydrophilic group to form a salt, or a hydrophilic group to the blocked polyisocyanate itself to self-emulsify or water-solubilize, or a hydrophilic blocking agent. Examples include a method of imparting self-emulsifying property or water-solubility to the blocked polyisocyanate. A method combining two or more of these methods is also possible.

When a solvent is used when producing a blocked polyisocyanate, it may be subjected to treatment such as emulsification in water while containing the solvent, dispersion, and dissolution, or treatment after removing the solvent in advance. Good. For a product which has been emulsified in water, dispersed, dissolved or the like while containing the solvent, the solvent can be removed by a method such as evaporation or liquid separation thereafter. It is also possible to add a conventionally known isocyanate reaction catalyst such as a tertiary amine or an organometallic compound or a dissociation catalyst for blocked polyisocyanate to the blocked polyisocyanate, and then to prepare an aqueous mixture.

In the composition according to the present invention, the mixing ratio of the aqueous polymer dispersion and the blocked polyisocyanate depends on the performance required for the backing resin formed from the composition and the properties of each component. Usually, the blending amount of the blocked polyisocyanate is in the range of 0.5 to 30 parts by weight based on 100 parts by weight of the solid content of the aqueous polymer dispersion. In the composition, if the blended amount of the blocked polyisocyanate is less than 0.5 parts by weight, the washing resistance as described above is not sufficient, while if it is more than 30 parts by weight, the composition is formed from the composition. The backing resin is hard and brittle, and the resin is prone to cracking or falling off. Further, since the blocked polyisocyanate is usually more expensive than the aqueous dispersion of the high molecular weight polymer, it is disadvantageous from the economical point of view to blend the polyisocyanate in an amount exceeding the required performance. . From the above, the blended amount of the blocked polyisocyanate in the composition is particularly preferably in the range of 1 to 20 parts by weight.

In order to obtain a mixture of the polymer dispersion and the blocked polyisocyanate, usually, these may be mixed as they are, if necessary, a surfactant, a dispersant, the addition of a thickener, or pH It is also possible to obtain a more stable mixture by adjustment or the like.

In the present invention, the blocked polyisocyanate may be partially replaced with an epoxy compound. Epoxy compounds that can be preferably used in the present invention include bisphenol type, resorcinol type, alicyclic epoxy resins having two or more epoxy groups per molecule on average, ethylene glycol, propylene glycol, glycerin, hexanetriol, Examples include reaction products of aliphatic polyhydric alcohols such as trimethylolpropane and polyethylene glycol with epichlorohydrin. These epoxy compounds may be water-soluble or water-insoluble, and depending on their solubility in water, they are added as an aqueous solution or by emulsification and dispersion, and then mixed into an aqueous dispersion of polymer combination.

When an epoxy compound is blended with a blocked polyisocyanate in an aqueous dispersion of a high molecular weight polymer, shrinkage and curling after washing of a carpet, dropping of a resin, etc. are small, though the pot life is shortened. A backing resin with improved washability is formed. However, blending a large amount of the epoxy compound extremely shortens the pot life, so from the viewpoint of the balance between performance and usability, the blending amount of the epoxy resin in the composition of the present invention is 1 part by solid content based on 100 parts by weight of solid content of the aqueous dispersion of
It is 0 parts by weight or less.

The composition according to the invention contains a melamine resin together with the blocked polyisocyanate.

The melamine resin used in the present invention, as well known, methylol melamine obtained by reacting melamine and formaldehyde under basic conditions,
Methylated or butylated methylolmelamine obtained by further reacting this with methanol or butanol can be mentioned. When the melamine resin is water-soluble, when the melamine resin is water-soluble, it may be mixed with the aqueous mixture as it is, but when it is water-insoluble, it is similar to the blocked polyisocyanate. To
It may be added as an aqueous emulsion or dispersion.

In the composition according to the present invention, the blending amount of the melamine resin is 1 to 10 per 100 parts by weight of the solid content of the aqueous dispersion of the polymer having a carboxyl group and / or a hydroxyl group.
The range is parts by weight. Particularly, from the viewpoint of performance balance, the range of 2 to 7 parts by weight is preferable.

When the composition contains such a melamine resin, such a composition is applied to the back surface of the pile-imbedded base fabric,
After drying, by heating, the blocking agent is liberated from the blocked polyisocyanate, polyisocyanate having a free isocyanate group is regenerated, and the polyisocyanate is a high molecular polymer and a melamine resin, respectively. To form a three-dimensional crosslinked structure,
Dust control mat It exhibits excellent washing resistance as a backing resin.

Further, the dust control mat backing composition according to the present invention may contain a vulcanizing agent when the aqueous dispersion of the high molecular polymer is an aqueous dispersion of a diene rubber.

Vulcanizing agents used in the present invention include sulfur or compounds that release sulfur upon heating, as well as metal oxides such as zinc oxide. Examples of sulfur include crystalline or non-crystalline powdered sulfur and colloidal sulfur. Examples of the compound that releases sulfur by heating include thiuram polysulfide, dithiodimorpholine, thioplast and the like. This vulcanizing agent is usually added in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the polymer dispersion. In order for the composition to form a backing resin having particularly excellent wash resistance and blocking resistance,
A range of 1-5 parts by weight is preferred.

In the present invention, the vulcanizing agent is preferably used in combination with a vulcanization accelerator, a vulcanization acceleration aid and the like. Examples of such vulcanization accelerators include dithiocarbamate-based, thiourea, guanidine-based, xanthate-based, thiuram-based, aldehydeamine-based, thiozole-based, and the like.
Examples of the vulcanization acceleration aid include zinc oxide, zinc carbonate, zinc stearate, stearic acid, oleic acid and the like.

When the composition according to the invention contains such a vulcanizing agent,
As described above, when the polyisocyanate having a free isocyanate group is regenerated, not only this polyisocyanate undergoes a crosslinking reaction with the diene rubber, but the vulcanizing agent also crosslinks the diene rubber to form a three-dimensional crosslinked structure. Therefore, the formed resin exhibits excellent washing resistance as a dust control mat backing resin.

Thus, when the composition according to the present invention contains a vulcanizing agent together with the melamine resin, the effects of the melamine resin and the vulcanizing agent described above are combined, and the resin formed is well balanced, Has excellent wash resistance.

Dust control mat backing composition according to the present invention, if necessary, in addition to the above components, a filler, a dispersant,
It may contain an ordinary compounding agent such as an antioxidant, a thickener and a colorant, a dissociation catalyst for blocked polyisocyanate, a reaction catalyst for isocyanate, a curing catalyst for melamine resin and the like. As the filler, for example, calcium carbonate, aluminum hydroxide, clay, talc, etc. are usually used. The blending amount is the solid content of the aqueous polymer dispersion.
About 100 parts by weight is usually 100 parts by weight or less. 100
It is not preferable to mix a large amount of the compound in excess of parts by weight, because the washing resistance may decrease.

The composition according to the present invention is applied to the back surface of a dust control mat, dried, and then heated to a temperature of about 110 to 200 ° C to form a backing resin having excellent washing resistance.

(Effect of the Invention) The aqueous composition for backing a dust control mat according to the present invention contains a melamine resin together with a blocked polyisocyanate in an aqueous dispersion of a polymer having a carboxyl group and / or a hydroxyl group, and has the same composition as that of a conventional composition. The pot life is significantly longer than that of the product, and no problem occurs even after a long period of time from the production of the composition to its use. Further, as described above, in the backing resin to be formed, the high molecular polymer and the polyisocyanate are crosslinked by the melamine resin and are tough, so that the dust control mat having such a backing resin is harsh as described above. Has wash resistance.

Furthermore, the composition for backing a dust control mat according to the present invention can contain a vulcanizing agent together with a melamine resin when the aqueous dispersion of the polymer is an aqueous dispersion of a diene rubber. According to such a composition, in the formed backing resin, the high molecular polymer and the polyisocyanate are crosslinked by the melamine resin, and the vulcanizing agent crosslinks the diene rubber to form a three-dimensional crosslinked structure. As formed, the layered resin exhibits excellent wash resistance.

The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

EXAMPLE Acrylonitrile-butadiene rubber (NBR) latex or acrylic latex was added to 100 parts by weight of solids at the blending amounts shown in Table 1 to produce blocked polyisocyanate, water-soluble melamine resin and / or vulcanizing agent, and ground calcium carbonate. Is added, and the viscosity is increased to 10000 with carboxymethyl cellulose.
A composition prepared by adjusting to ± 1000 cps was prepared.

The above composition is uniformly applied to the back surface of a polyester base cloth in which a pile made of polyamide is implanted at a rate of 1.0 kg / m ² , pre-dried at 120 ° C for 15 minutes, and then hot-air dried at 150 ° C for 10 minutes. did.

The dust control mat thus obtained was washed in a washing machine with a bath ratio of 1:30, a detergent concentration of 0.14% and a washing water temperature of 40 ° C. for 7 minutes, and cold water was overflowed for 10 minutes for rinsing and then at a temperature of 100. After 30 cycles of washing with one cycle of complete drying at ℃, the dimensional change of the mat was measured, and the back surface of the mat and the curling state were observed. The results are shown in Table 1.

As can be seen in Comparative Examples 1 and 3, the composition obtained by blending the latex with the melamine resin and the vulcanizing agent, or the melamine resin alone has not only the remarkable shrinkage ratio and curling after washing, but also the peeling of the resin. Is recognized, and the performance as a dust control mat backing composition is inferior. Also,
Comparative Example 2 is a composition in which only the blocked polyisocyanate is blended in the latex, and although the shrinkage ratio is somewhat improved, it is particularly inferior in the yarn removal strength and the blocking resistance, and similarly, the dust control mat Poor performance as a backing composition.

On the other hand, as seen in Examples 1 to 3 and Example 14, according to the composition of the present invention in which the melamine resin is added to the latex together with the blocked polyisocyanate, the shrinkage ratio is remarkably improved. Not only that, but the state of the back side is also excellent.

Further, as seen in Examples 4 to 13 and Example 15, according to the composition of the present invention, the latex is mixed with a blocked polyisocyanate, a melamine resin and a vulcanizing agent.
The shrinkage rate is remarkably small, and it is also excellent in all aspects of washing resistance such as curling, back surface condition and yarn removal strength.

Continuation of front page (56) References JP-A-54-2499 (JP, A) JP-A-52-134660 (JP, A) JP-B-59-9667 (JP, B2)

Claims (2)

[Claims] 1. Containing 1 to 10 parts by weight of a melamine resin together with 0.5 to 30 parts by weight of blocked polyisocyanate per 100 parts by weight of solid content of an aqueous dispersion of a polymer having a carboxyl group and / or a hydroxyl group. A composition for lining a dust control mat, characterized by: 2. A composition for backing a dust control mat according to claim 1, wherein the aqueous dispersion of the high molecular polymer is an aqueous dispersion of a diene rubber and further contains 0.5 to 10 parts by weight of a vulcanizing agent. object.