JPH0726336B2 - Composition for lining textile products - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for backing a textile product, which is excellent in light resistance, blister resistance, and appearance of the back surface.

Pile fabrics such as tufted carpets, upholstery cloths, car seats, aircraft seats, artificial grass, etc. In addition to SBR latex, natural rubber latex, polymer aqueous dispersion such as polymer emulsion, inorganic fillers such as heavy calcium carbonate and aluminum hydroxide, and various additives such as thickeners were blended as necessary. The composition of the present invention, in which the composition is lined (backing), is used as the above-mentioned pile woven fabric, for lining a woven fabric.

[Conventional technology]

Of the above polymer aqueous dispersions, SBR latex, when using natural rubber latex as a backing agent, even though it is a backing agent, when the product is exposed to sunlight for a long time, the backing agent ages and its strength decreases, Alternatively, a change in texture or discoloration (yellowing) may occur, resulting in a marked decrease in commercial value.

On the other hand, in the drying process of the textile product coated with the backing agent, especially when the air volume is increased to improve the drying efficiency, when the water content in the applied adhesive evaporates,
Only the surface may dry rapidly to form a film, and the water remaining inside may break through the dry film on the surface, causing a blister phenomenon, and significantly impairing the appearance of the product. This phenomenon can be prevented by blending an organopolysiloxane compound in the composition when SBR latex, NBR latex, MBR latex, or natural rubber lax is used as the polymer aqueous dispersion, but it is not possible to use alkyl acrylate. When a polymer emulsion of a polymer or copolymer obtained by using an ethylenically unsaturated monomer such as ester, styrene or acrylonitrile as a main monomer is used, even if an organopolysiloxane compound is added, the blister phenomenon may occur. It is difficult to prevent. For example
As seen in No. 59-230075, by using a small amount of an ammonium compound together and taking measures such as drastically enhancing the effect of organopolysiloxane, even in a polymer dispersion mainly composed of acrylic acid ester, the blister phenomenon occurs. However, when an ammonium salt is used, the salt may recrystallize and precipitate when cooled from a humid or watery state, which may change the appearance of the back surface. Especially in winter, it is noticeable when the backing surface is colored black.

[Problems to be solved by the invention]

(1) The one using SBR latex, natural rubber latex or the like as the backing agent is easy to prevent blister but is inferior in light resistance. Further, a conventional one using a polymer emulsion as a backing material has excellent light resistance, but it is difficult to prevent blisters.

(2) When an organopolysiloxane and an ammonium salt are used in combination to improve the blister resistance of the polymer emulsion, the salt is recrystallized and the back surface appearance is impaired.

[Means for solving problems]

The present inventor has conducted extensive studies to develop a composition for backing a textile product which is excellent in light resistance, blister resistance, and back surface appearance, and as a result, 100 parts by weight of acrylic resin emulsion (solid content), inorganic filler 0 to A composition containing 500 parts by weight, 0.03 to 3 parts by weight of an organopolysiloxane compound, and 0.5 to 10 parts by weight of an amorphous salt of an alkanolamine and an acid is achieved to achieve the intended purpose. Heading, it came to complete the present invention.

[Action]

The acrylic resin emulsion used in the present invention is intended for pile fabrics such as tufted carpets, upholstery cloths, automobile seats, aircraft seats and artificial grass, adhesion of piles, adhesion of secondary base cloth, and dimensional stability. Used for. The main purpose of the filler is to be used as an extender for cost reduction, but it is also used to give the product a feeling of weight. Further, the organopolysiloxane compound is effective in preventing the occurrence of the blister phenomenon by using a non-crystalline salt composed of an alkanolamine and an acid in combination.

The acrylic resin emulsion of the present invention is a monomer having a functional group (for example, ethylenically unsaturated carboxylic acid, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, acrylamide, N-methylolacrylamide. ) Is preferably contained in the total monomer in an amount of 0.5 to 10% by weight. Within this range, excellent adhesive strength, filler dispersibility, viscosity stability over time, and water resistant polymerization stability can be obtained.

Examples of the constituent monomer of the acrylic resin emulsion include ethylenic unsaturated carboxylic acid alkyl ester (for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth)). Acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylenically unsaturated aromatic monomer (for example, styrene, α- Methylstyrene, divinylbenzene), ethylenically unsaturated carboxylic acids (eg acrylic acid, methacrylic acid, itaconic acid, maleic acid,
Fumaric acid, crotonic acid), and other vinyl monomers (eg atrilonitrile, (meth) acrylic acid-2-
It is a polymer emulsion composed of a homopolymer or a copolymer of hydroxyethyl, 2-hydroxypropyl (meth) acrylate, acrylamide, and N-methylolacrylamide. The acrel-based resin emulsion can be produced by emulsion polymerization in a water-based medium using an emulsifier, a polymerization initiator, a chelating agent, and a molecular weight modifier by a known method.

As the emulsifier used in the production of the acrylic resin emulsion used in the present invention, anionic and nonionic surfactants used in ordinary polymerization can be used. Examples of the anionic surfactant include sulfuric acid ester salts of higher alcohols, sodium alkylbenzene sulfonate, aliphatic sulfonates, and fatty acid soaps. Examples of the nonionic activator include ordinary polyethylene glycol alkyl ethers, alkyl esters, and alkyl phenyl ethers. However, since the composition of the present invention does not cause blister, it also has excellent strength and water resistance. The amount of the emulsifier used during the polymerization is preferably 1.5 parts by weight or less per 100 parts by weight of the solid content of the acrylic resin emulsion in order to maintain the above content.

Examples of the polymerization initiator include water-soluble initiators such as ammonium persulfate, sodium persulfate and potassium persulfate, oil-soluble initiators such as benzoyl peroxide, and redox-based initiators obtained by combining them with hydrogen peroxide / ferrous sulfate. Either can be used.

As the molecular weight regulator, chelating agent, inorganic salt and the like, those known in emulsion polymerization can be used.

As the filler used in the present invention, calcium carbonate, aluminum hydroxide, clay, talc, etc. may be used alone or in combination. The amount used is 0 to 500 parts by weight per 100 parts by weight of the solid content of the polymer dispersion. If the white color of the backing layer due to the filler is disliked, the filler may not be used, but generally, it is recognized that the blister resistance tends to be better when the amount of the filler is increased,
The preferred amount used is 100 to 400 parts by weight. If it exceeds 500 parts by weight, satisfactory physical properties cannot be obtained.

The substance having a blister prevention effect used in the present invention comprises a combination of an organopolysiloxane compound, a salt of an alkanolamine and an acid, and it is difficult to prevent blisters even when used alone. Organopolysiloxane compounds, Japanese Patent Publication No. 40-21427, Japanese Patent Publication No. 47-19604,
JP-A-50-24336, U.S. Pat.Nos. 3,246,339, 325,514
No. 0, described in British Patent No. 1141867, for example, _{HO-C 4 H 8 O-} CH 2 (CH 3) 2 SiO (CH 3) 2 SiO 10 Si (CH 3
O-C ₄ H ₈ OH (HO-CH ₂ CH _{2 2} N-CH ₂ -Si (CH _{3 2} O-Si
A dimethylpolysiloxane-alkylene oxide copolymer such as (CH ₃ ) ₂ —CH ₂ —N (CH ₂ CH _{2 2} OH) is preferably used, and as a commercially available product, for example, TP
A4380, TPA4390 (Toshiba Silicon Co. product) can be mentioned.

The amount used is 10% solids of acrylic resin emulsion.
0.03 to 3.0 parts by weight per 0 parts by weight. If the amount is less than 0.03 part by weight, it becomes impossible to prevent the blister property, and if the amount is more than 3.0 parts by weight, the effect of preventing the blister property is not obtained.

As the salt used in combination with the organopolysiloxane compound,
It must be an amorphous salt of an alkanolamine and an acid. When an ammonium salt of an acid having crystallinity is cooled from a state of being moist or wet, the salt may be precipitated as crystals to impair the appearance of the back surface.

As the alkanolamine, primary, secondary and tertiary ethanolamine, propanolamine and the like can be used. Examples of the acid include oxalic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid, and oxalic acid such as formic acid, acetic acid, fumaric acid, maleic anhydride, oxalic acid and citric acid. These salts also have a catalytic action for the crosslinking reaction when using a carboxylic acid monomer in the emulsion and a monomer having self-crosslinking property such as N-methylolacrylamide. As a preferable salt, for example, a monoethanolamine hydrochloride or the like can be mentioned. The amount of salt added is 0.5 to 100 parts by weight of the solid content of the polymer emulsion.
10 parts by weight. If it is less than 0.5 part by weight, the blister prevention effect is weak, and if it is more than 10 parts by weight, strength and water resistance are deteriorated, which is not preferable.

Furthermore, if necessary, a dispersant, a cross-linking agent, and
It is acceptable to mix usual additives such as anti-wrapping agents, thickening agents, preservatives and pigments. It may be added to the acrylic resin emulsion together with other compounding agents at the time of preparing the composition of the salt consisting of the organopolysiloxane compound, the alkanolamine and the acid, or may be added in advance to the acrylic resin emulsion at the time of polymerization or after the polymerization. You may stay.

The composition of the present invention can be applied to all textiles such as carpet, artificial grass, and moquette whose back surface is treated with an acrylic resin emulsion.

Next, the present invention will be specifically described with reference to examples. All the parts of the blended components in each example are parts by weight of the solid content.

Synthesis example (synthesis of acrylic resin emulsion) 100 parts of water and 1.0 part of Newcol 271A (sodium alkyldiphenyl ether sulfonate; Nippon Emulsifier Co., Ltd.) in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. throw into. Then ethyl acrylate 9
A mixture of 0 parts, 7 parts of acrylonitrile, 2 parts of N-methylolacrylamide, 1.0 part of acrylic acid, 0.5 parts of ammonium persulfate and 0.5 parts of sodium metabisulfite was added dropwise over 4 hours, and emulsion polymerization was carried out at a reaction temperature of 60 ° C. After 1 hour from the completion of the dropping, the mixture was cooled and 0.4 part of 28% ammonia water was added. The acrylic resin emulsion thus obtained had a solid content of 50%, a pH of 4.5 and a viscosity of 70 cps.

Comparative synthesis example (SBR latex synthesis) 120 parts water in a pressure resistant polymerization vessel with a stirrer, Newcol 271A
Charge 1.0 part, sodium ethylenediaminetetraacetate 0.05 part, potassium persulfate 0.2 part, and then charge 50 parts styrene, 47 parts butadiene, 3 parts acrylic acid, 0.5 parts tertiary decyl mercaptan, and after sufficient nitrogen replacement, 60-70 ° C.
And reacted for 10 hours. The pH of the obtained latex was adjusted to 8.0 with an aqueous potassium hydroxide solution, and then steam and nitrogen were blown to remove residual monomers, and finally the solid content and pH were adjusted to 50% solid content, viscosity 150 cps, and pH 8 .0 SBR
A latex was obtained.

[Example 1] 100 parts of the acrylic resin emulsion of the synthesis example, 300 parts of heavy calcium carbonate (SS30 Nitto Powder Co., Ltd.), organopolysiloxane compound (TPA4380: Toshiba Silicon Co., Ltd.)
0.6 parts, monoethanolamine hydrochloride 1.0 part were blended, and as a thickening agent, sodium polyacrylate (Aron A20L: Toagosei Co., Ltd.) 3.2 parts, dispersion pigment (Disperse Black SD-
9020) Add 1.0 parts and water to prepare solids
A composition having a viscosity of 0% and a viscosity of 15000 ± 1000 cps (measured value at 25 rpm, 12 rpm, BM type rotational viscometer No. 4 rotor) was obtained. Next, in order to measure the change with time of viscosity of the composition, the composition was placed in a glass sample bottle with a lid, and the viscosity was measured after the container was sealed and left at 25 ° C. for 10 days and at 40 ° C. for 10 days.
Next, this composition was uniformly applied to the back surface of the artificial machine of the artificial lawn where the base cloth was polypropylene and the pile was nylon so that the application amount was 1.0 kg / m ² (wet), and the temperature was 150 ° C immediately.
The state of occurrence of blisters was observed with the naked eye after being placed in a hot air dryer having a wind speed of 15 m / sec and dried for 7 minutes. Next, in the same manner, this composition was applied to an artificial lawn, and after drying, the applied surface was irradiated for 200 hrs in a fade meter, and then the presence or absence of cracks and the degree of hardening of the texture were observed. Table of these results
As shown in Fig. 1, it is understood that this composition of the present invention does not change with time of viscosity and has extremely excellent blister resistance and light resistance. The backing did not change at all even after immersing the backing in water for about 10 seconds, taking it out, leaving it at room temperature of 25 ° C for 1 hour, and then leaving it at 0 ° C for 1 hour. .

[Example 2] Solid content was exactly the same as in Example 1 except that 3.0 parts of 2-amino-2-methyl-1-propanol hydrochloride as a salt and 3.5 parts of sodium polyacrylate as a thickener were used.
A composition having 70% and a viscosity of 15000 cps was prepared.

Then, the viscosity aging stability, blister resistance, light resistance and appearance of the back surface were measured in the same manner as in Example 1. The results were extremely excellent as shown in Table 1.

Example 3 Completely the same as in Example 1 except that 1.2 parts of the organopolysiloxane compound, 3.5 parts of monoethanolamine hydrochloride, 2.8 parts of sodium polyacrylate as a thickening agent were used and no heavy calcium carbonate was used. A composition having a solid content of 70% and a viscosity of 15000 cps was prepared by the same method.

Then, the viscosity aging stability, blister resistance, light resistance and appearance of the back surface were measured in the same manner as in Example 1. The results were extremely excellent as shown in Table-1.

[Comparative Example 1] A solid content of 70% was obtained in the same manner as in Example 1 except that 3.0 parts of an organopolysiloxane compound and 2.7 sodium polyacrylate as a thickening agent were used and no monoethanolamine hydrochloride was added. A composition having a viscosity of 15000 cps was prepared.

Then, the viscosity aging stability, blister resistance, light resistance and appearance of the back surface were measured in the same manner as in Example 1. The results are
As shown in Table 1, this composition was inferior in viscosity-aging stability and was inferior in blister resistance to the composition of the present invention.

[Comparative Example 2] The solid content was 70% by the same method as in Example 1 except that 6.0 parts of monoethanolamine hydrochloride and 4.0 parts of sodium polyacrylate as a thickener were used and no organopolysiloxane was added. A composition having a viscosity of 15000 cps was prepared.

Then, the viscosity aging stability, blister resistance, light resistance and appearance of the back surface were measured in the same manner as in Example 1. The results are
As shown in 1, the composition containing no organopolysiloxane compound has very poor blister resistance.

Comparative Example 3 A composition having a solid content of 70% and a viscosity of 15000 cps was prepared in the same manner as in Example 1 except that 2.5 parts of ammonium sulfate was used instead of 2.5 parts of monoethanolamine hydrochloride as a salt.

Then, the viscosity aging stability, blister resistance, light resistance and appearance of the back surface were measured in the same manner as in Example 1. The results are
As shown in 1, the viscosity-aging stability, blister resistance, and light resistance were good, but the backing was immersed in water for about 10 seconds, left at room temperature of 25 ° C for 1 hour, and then at 0 ° C. After standing for 1 hour, the back surface was observed and ammonium sulfate immersed in water was precipitated by recrystallization and was whitened.

[Comparative Example 4] The same procedure as in Example 1 was performed except that 500 parts of heavy calcium carbonate and 4.0 parts of sodium polyacrylate as a thickening agent were used, and the organopolysiloxane compound and the ammonium salt of the acid were not added. A composition having a solid content of 70% and a viscosity of 15000 cps was prepared.

Then, the viscosity aging stability, blister resistance, light resistance and appearance of the back surface were measured in the same manner as in Example 1. The results are
As shown in No. 1, the composition containing neither organopolysiloxane compound nor salt was inferior in blister resistance to the composition of the present invention, although the amount of the filler was large.

[Comparative Example 5] The solid content was the same as in Example 1 except that 100 parts of SBR latex of Comparative Synthesis Example and 2.5 parts of sodium polyacrylate as a thickener were used and no monoethanolamine hydrochloride was added. A composition having 70% and a viscosity of 15000 cps was prepared.

Then, the viscosity aging stability, blister resistance, light resistance and appearance of the back surface were measured in the same manner as in Example 1. The results are
As shown in 1, the composition obtained by adding the organopolysiloxane compound to the SBR latex was inferior in viscosity-aging stability and light resistance.

Comparative Example 6 SBR latex 100 parts, nonionic activator (polyoxyethylene nonylphenyl ether, Neugen EA120 Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts, organopolysiloxane compound 0.
3 parts, 2.5 parts of sodium polyacrylate as a thickening agent were used, and in the same manner as in Example 1 except that monoethanolamine hydrochloride was not added, solid content 70%, viscosity 1500
A 0 cps composition was prepared.

Then, in the same manner as in Example 1, the viscosity-aging stability, blister resistance, backside appearance, and light resistance were measured. The results are
As shown in 1, the composition containing SBR latex had poor light resistance.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area C08L 33/04 LJE

Claims (3)

[Claims] 1. An acrylic resin emulsion 100 parts by weight (solid content), a filler 0 to 500 parts by weight, an organopolysiloxane compound 0.03 to 3 parts by weight, and an amorphous salt of an alkanolamine and an acid 0.5 to 10 parts. A composition for lining a textile product, which comprises parts by weight. 2. The composition for lining a textile product according to claim 1, wherein the filler is one or more inorganic fillers selected from heavy calcium carbonate, aluminum hydroxide, clay and talc. 3. The composition for lining a textile product according to claim 1, wherein the organopolysiloxane compound is a dimethylpolysiloxane adduct of polyalkylene oxide.