JPH06128437A - Resin composition for carpet coating use - Google Patents

Abstract

PURPOSE:To provide a resin composition for carpet coating use capable of imparting a carpet with high rigidity and heat-resistant shape-retainability. CONSTITUTION:The resin composition for carpet coating use is produced by mixing (A) an aqueous dispersion of a copolymer resin having a glass transition temperature of 10-60 deg.C and produced by the emulsion polymerization of a monomer mixture consisting of at least (a) an aromatic vinyl monomer and (b) a (meth)acrylic acid ester monomer with (B) 1-20 pts.wt. (in terms of solid component based on 100 pts.wt. of the solid component of the resin A) of a resin solubilized by the addition of an alkali to a solubilization ratio of >=10wt.% and having a glass transition temperature of >=80 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for coating a carpet, which is particularly useful as a backing coating agent for a fibrous interior material for vehicles such as automobiles, and has high rigidity and heat-resistant shape retention. The present invention relates to a resin composition for applying a carpet.

[0002]

2. Description of the Related Art Conventionally, as a fiber interior material for a vehicle, a construction in which a film of polyethylene or the like is backed after a resin aqueous emulsion is applied to a needle punched carpet or a tufted carpet is widely used. Further, in recent years, as the interior material, a material having a hard texture has been required for the purpose of improving workability during assembly to a vehicle body, and a styrene-acryl-based and ethylene-acetic acid-based coating which has excellent rigidity-imparting properties as a coating agent. A vinyl-based resin aqueous emulsion is used.

[0003]

However, due to the recent trend of reducing the weight and cost of carpets, when the coating amount of resin emulsion is reduced and the film such as polyethylene is thinned, the hard texture is impaired and the heat resistance is reduced. There is a problem that the shape retention is lowered. An object of the present invention is to provide a resin composition for carpet coating which solves the above conventional problems and can provide high rigidity-imparting property and heat-resistant shape-retaining property even with a small coating amount.

[0004]

As a result of intensive investigations, the present inventors were able to achieve the above object by adopting the following constitution. That is, the resin composition for carpet coating of the present invention has (A) a glass transition temperature of 10 to 60 ° C.
An aqueous dispersion of a copolymer resin obtained by emulsion polymerization of a monomer mixture comprising at least (a) an aromatic vinyl monomer and (b) a (meth) acrylic acid ester monomer. In addition, (B) a resin having a glass transition temperature of 80 ° C. or higher is mixed with 1 to 20 parts by weight of the resin solid content based on 100 parts by weight of the resin solid content of (A), and the (B) resin is alkali-added. The solubilization treatment of the resin (B) is performed so that the solubilization rate of the resin (B) is 10% by weight or more.

Among the raw material monomers for producing the resin aqueous dispersion (A) used for preparing the resin composition for coating a carpet of the present invention, (a) as an aromatic vinyl monomer. Is, for example, styrene (Tg 100 ° C.), α
Methylstyrene (Tg 160 ° C) etc. is used,
Examples of the (b) (meth) acrylic acid ester include methyl acrylate (Tg 8 ° C.) and ethyl acrylate (Tg −
22 ° C.), butyl acrylate (Tg −55 ° C.), 2-ethylhexyl acrylate (Tg −80 ° C.), methyl methacrylate (Tg 105 ° C.), ethyl methacrylate (Tg 65 ° C.), n-butyl methacrylate (Tg) Two
0 ° C.), n-hexyl methacrylate (Tg −5 ° C.) and the like are used. Further, other monomers may be used within a range capable of keeping the glass transition temperature of the copolymer resin within a target range, and as (c) the other monomer, acrylonitrile (Tg 130 ° C.) vinyl acetate ( Tg 30
C), unsaturated carboxylic acid monomers (eg acrylic acid,
Methacrylic acid, itaconic acid), (meth) acrylic acid, hydroxy group-containing monomer (eg hydroxyethyl (meth) acrylate, hydroxypropyl (meth))
Acrylate) and the like.

The numerical value shown in parentheses is the glass transition temperature of the homopolymer. The same applies hereinafter. Using the above-mentioned (a) aromatic vinyl monomer and (b) (meth) acrylic acid ester monomer, the glass transition temperature is 10 to 60.
An aqueous dispersion of a copolymer resin having a temperature of 0 ° C. is produced.

The glass transition temperature of the resin may be in the range of 10 to 60 ° C., but the above-mentioned (a) aromatic vinyl monomer 30 is used.
To 80% by weight, (b) (meth) acrylic acid ester monomer 20 to 70% by weight, and (c) other monomer 0 to 2
It is preferably composed of 0% by weight. If (a) the aromatic vinyl monomer is less than 30% by weight or (b) the (meth) acrylic acid ester monomer is less than 20% by weight, it is difficult to obtain sufficient rigidity when applied to the carpet. .

The glass transition temperature of the copolymer resin is 10 ° C.
If it is less than 60 ° C, sufficient rigidity cannot be obtained when it is applied to a carpet, and if it exceeds 60 ° C, the toughness of the carpet is lost and sufficient rigidity cannot be obtained. The resin aqueous dispersion (A) of the present invention is produced by appropriately combining the monomers (a) to (c) one by one, or a plurality of each, or only (a) and (b).

The aqueous resin dispersion (A) is produced by usual emulsion polymerization. In the emulsion polymerization method using an emulsifier to carry out the polymerization with a water-soluble polymerization initiator,
A method of performing polymerization by soap-free polymerization or the like is used. Examples of the emulsifier include various anionic, cationic and nonionic emulsifiers, and further polymeric emulsifiers.

The polymerization initiator used in emulsion polymerization is preferably an inorganic peroxide such as potassium persulfate, ammonium persulfate or hydrogen peroxide. These inorganic peroxides include
You may use it together with a reducing agent as a redox initiator. Various methods can be used as a method for supplying the monomer in the emulsion polymerization. For example, various methods such as a batch charging method, a monomer addition method and an emulsion addition method can be used. Further, a seed polymerization method or a power feed polymerization method in which the composition of the added monomer is sequentially changed can be used.

Next, the resin (B) used in the present invention is
The glass transition temperature is 80 ° C. or higher, and 10% by weight of the glass is solubilized by the addition of alkali. Examples thereof include a saponified product of maleic anhydride-styrene copolymer and a copolymer of unsaturated carboxylic acid. However, since the glass transition temperature, the degree of alkali solubilization, and the molecular weight can be freely designed, unsaturated carboxylic acid is used. More preferred are acid copolymers.

This unsaturated carboxylic acid copolymer is prepared from an unsaturated carboxylic acid monomer such as acrylic acid (Tg 1
00 ° C.), methacrylic acid (Tg 130 ° C.), itaconic acid (Tg 150 ° C.), and those obtained by copolymerization with other monomers copolymerizable therewith. As other monomers, since it is necessary to raise the glass transition temperature of the resin, methacrylic acid ester, lower ester of acrylic acid, styrene, and (c) of the (A) resin aqueous dispersion
Those listed as other monomers are used.

The glass transition temperature of the resin (B) is required to be 80 ° C. or higher, preferably 85 to 130.
If the temperature is below 80 ° C, not only the heat-resistant shape-retaining property cannot be imparted, but also the target high rigidity cannot be imparted.
Polymerization for producing the resin (B) is carried out by solution polymerization or emulsion polymerization.

The solvent used for the solution polymerization is not particularly limited, but a water-soluble or hydrophilic solvent is preferable from the viewpoint of the compatibility with the produced polymer resin and water. Specific examples thereof include monoalcohols having 1 to 4 carbon atoms,
For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and t-butyl alcohol; ethylene glycol and its derivatives, such as ethylene glycol monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether; diethylene glycol. And derivatives thereof such as diethylene glycol monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether; other 1,4-
Examples include dioxane and water. These solvents are 1
One kind may be used, or two or more kinds may be appropriately used in combination. As the solvent, those having a boiling point of 200 ° C. or less are generally preferable from the viewpoint of distilling after the polymerization or drying speed.

The polymerization initiator for solution polymerization is preferably oil-soluble. Specific examples thereof include azo initiators such as azobisisobutyronitrile and azobisvaleronitrile; organic peroxide initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxide; and other peroxides. Inorganic peroxide type initiators such as hydrogen and ammonium persulfate can also be used. These initiators may be used alone or in appropriate combination of two or more. Further, a reducing agent such as Rongalit, L-ascorbic acid, or an organic amine may be used in combination with these initiators and used as a redox initiator.

Regarding the emulsion polymerization method, the same method as the method for producing the (A) resin aqueous dispersion described above can be adopted, but since a polymer resin obtained by emulsion polymerization generally has a high molecular weight, addition of an alkali is carried out. When it is solubilized by water, it is difficult to sufficiently solubilize it, and therefore it is preferable to polymerize using a chain transfer agent. As the chain transfer agent,
For example, various mercaptans, α-methylstyrene,
Examples thereof include alkyl halides and alcohols.
The amount used is 0.03 to 5% by weight based on all the monomers. Further, if the molecular weight is too large, the viscosity increases, which is not preferable for practical use. Therefore, the weight average molecular weight is preferably 100,000 or less.

The resin (B) prepared by the solution polymerization or emulsion polymerization described in detail above is prepared by adding an alkali.
The resin is solubilized so that the resin has a solubilization rate of 10% by weight or more, preferably 20% by weight. The solubilization treatment (that is, addition of alkali) is a polymerization for producing the resin (B). It may be before starting, at the time of polymerization thereof, before mixing (A) resin aqueous dispersion with (B) resin, or during mixing thereof. However, it may be after the mixing. In any case, the "solubilization rate" described in the present specification means the solubilization rate measured by the following method.

That is, in any of the above cases, the resin (A) is not mixed with the resin aqueous dispersion at all, and the solubilization treatment is performed under the same conditions as the solubilization treatment actually carried out otherwise. The composition was prepared, and the obtained resin composition was diluted with water so that the nonvolatile content was 15% by weight, and the diluted solution was centrifuged at a centrifugal acceleration of 1.8 × 10 ⁵ g for 60 minutes to obtain a composition. Solubilization represented by the following formula when the nonvolatile content in the obtained supernatant was measured to be w parts by weight, and the nonvolatile content in the above-mentioned diluent used for centrifugation was measured to be W parts by weight. Say the rate. Solubilization rate = w / W x 100 (% by weight)

The alkali used for the solubilization treatment is an inorganic water-soluble alkali, such as sodium hydroxide or potassium hydroxide; or an inorganic salt which shows alkalinity when dissolved in water, such as sodium hydrogen carbonate or pyrophosphate. Sodium and the like; ammonia water, organic amines and the like can be mentioned, but ammore water is preferable because of its volatility. As mentioned above, the addition of alkali does not necessarily have to occur after the formation of the polymer, and in some cases (B)
The unsaturated carboxylic acid before polymerization for forming the polymer resin may be neutralized by adding an alkali, and then the polymerization may be carried out. Further, the addition of alkali in the case of solution polymerization, may be in the presence of the solvent used for the polymerization,
After the solvent is distilled off, an alkali may be added to the polymer resin as an aqueous solution to partially or completely solubilize it with water. The amount of alkali used may be an amount that completely neutralizes the carboxyl groups in the polymer resin or an amount that partially neutralizes it.

In the present invention, the mixing ratio of the (A) resin aqueous dispersion and the (B) resin is 1 to 20 parts by weight of (B) with respect to 100 parts by weight of the resin solid component, respectively, and preferably Is 1.5 to 15 parts by weight. When the mixing ratio of (B) is less than 1 part by weight, the effect of improving the rigidity-imparting property and the effect of improving the heat-resistant shape-retaining property are hardly recognized, and 2
If it exceeds 0 parts by weight, the heat-resistant shape retention property is good,
The toughness is reduced and the rigidity is reduced.

The carpet coating resin composition of the present invention may contain various additives, if necessary, to the extent that the effects are not impaired.
For example, antifoaming agents, thickeners, lower alcohols, pigments, Portland cement, sand, water repellents, and other emulsions such as SBR latex and ethylene-vinyl acetate emulsion can be blended.

[0022]

[Examples] Hereinafter, a detailed description will be given of preparation examples of aqueous resin dispersions, preparation examples of polymer resins, examples and comparative examples. The "parts" and "%" described in these examples are on a weight basis. Preparation example of resin aqueous dispersion A1 Temperature adjuster, anchor type stirrer, reflux condenser, supply container,
The following mixture was charged into a reaction vessel equipped with a thermometer and a nitrogen gas introduction tube.

Water 120 parts 35% aqueous solution of sodium salt of sulfuric acid half ester of p-nonylphenol (hereinafter referred to as “p-NPhNa”) reacted with 20 mol ethylene oxide 2 parts 2 parts p reacted with 25 mol ethylene oxide 20% aqueous solution of nonylphenol (hereinafter referred to as "p-NPh") 4 parts Next, after replacing the inside of the reaction vessel with nitrogen gas, 10% of the following feed I was added and heated to 90 ° C.

Feed I Water 200 parts 35% aqueous solution of P-NPhNa 5 parts Styrene 260 parts Butyl acrylate 138 parts Acrylic acid 2 parts Then, dissolved in 2.5 parts potassium persulfate in 80 parts water ( 10% of "Feed II") is charged into the reaction vessel, and then all the rest of Feed I and Feed II
Is charged into the container over 3.5 hours and, after the supply is completed, is maintained at 90 ° C for 2 hours for polymerization to give an aqueous resin dispersion (glass transition temperature 27 ° C, solid content 50%). Obtained.

Production Examples A2 to A7 of Resinous Aqueous Dispersion Liquid The types and amounts of the unsaturated monomers were changed as shown in Table 1, and other conditions were the same as in Preparation Example A1.

[0026]

[Table 1]

Preparation Example B1 of Polymer Resin Temperature controller, anchor type stirrer, reflux condenser, supply container,
After the inside of a reaction vessel equipped with a thermometer and a nitrogen introducing tube was replaced with nitrogen gas, 200 parts of butyl cellosolve was charged therein. Separately, the following compositions were prepared as the feed I and the feed II. Feed I Methyl methacrylate 120 parts Acrylic acid 15 parts Methacrylic acid 15 parts Feed II Butylcellosolve 100 parts Azobisisobutyronitrile 6 parts

Next, while heating the inside of the reaction vessel to 80 ° C. with stirring, the feed I and the feed II were uniformly and continuously added thereto over a period of 3 hours to cause a reaction, and after the addition was completed, a further reaction was conducted. The polymerization reaction was terminated by maintaining the temperature at 80 ° C. for a time. The polymerization product was cooled to room temperature to obtain a butyl cellosolve solution of the carboxyl group-containing copolymer. From the solution of the carboxyl group-containing copolymer (glass transition temperature 107 ° C.), butyl cellosolve was almost completely distilled off by a rotary evaporator, and then water and ammonia water were added to polymer resin B1.
(Solid content 20%, pH 8) was obtained. The solubilization rate of this B1 resin was 30%.

Preparation Example B2 of Polymer Resin Temperature controller, anchor type stirrer, reflux condenser, supply container,
The following mixture was placed in a reaction vessel equipped with a thermometer and a nitrogen gas introduction tube. Water 100 parts Lauryl sulphate 4 parts Next, after replacing the inside of the reaction vessel with nitrogen gas, 10% of the following feed I was added and heated to 90 ° C. Feed I Water 150 parts Lauryl sulphate 2 parts Styrene 50 parts Methyl methacrylate 80 parts Ethyl acrylate 20 parts Methacrylic acid 50 parts t-Dodecyl mercaptan 0.4 parts Then 1 part sodium persulfate was dissolved in 50 parts water. 10% of the product (referred to as "Feed II") was charged into the reaction vessel, and then the rest of the feed I and the rest of the feed II were fed into the vessel over 3 hours. Polymerization was carried out for 2 hours at 90 ° C. after completion of the supply to obtain a polymer resin B2.

Preparation Examples B3 to B5 of Polymer Resin Preparation was carried out according to Preparation Example B2 except that the type and amount of unsaturated monomer were changed as shown in Table 2.

[0031]

[Table 2]

Example 1 With respect to 100 parts by weight of the resin solid content of the resin aqueous dispersion A1,
Polymer resin B1 was mixed in a resin solid content of 10 parts by weight. The obtained resin composition for carpet coating has a basis weight of 350 g / m.
Impregnated coated so as to 200 g / m ² on a dry coating amount in the ^second polyester needle punched carpet, 13
Bending strength, toughness, mold fidelity, and heat-resistant shape retention were tested and evaluated by the following test methods for those dried at 0 ° C. for 30 minutes. The results are shown in Table 3.

Bending strength: A test piece having a width of 50 mm and a length of 150 mm and a span of 100 mm was subjected to a three-point bending test at a speed of 250 mm / min using an Instron type tester. ○: Deformation under a load of 1.5 kg or more △: Deformation under a load of 1.0 to 1.5 kg ×: Deformation under a load of 1.0 kg or less

Toughness: The bending angle at which the maximum load in the bending strength test was exhibited was measured. ○ …… 120 ° or less △ …… 120 ° to 140 ° × …… 140 ° or more

Mold fidelity: width 100 mm, length 200 mm
The surface temperature of the test piece of 190
After being heated to ℃, it was pressed and molded with a concave-convex mold.
The mold fidelity of the molded test piece after being taken out from the mold was evaluated. ○ …… The shape of the mold is kept as it is △ …… Slightly deformed × …… The molding has a restitution

Heat-Resistant Shape Retention: The test piece after the evaluation of mold fidelity was put in an oven at 80 ° C., left for 24 hours, and then the degree of deformation when taken out was evaluated. ◎ …… The shape of the mold is maintained as it is ○ …… Slightly deformed △ …… The shape has a return × …… The shape is not retained

Examples 2 to 4 and Comparative Examples 1 to 8 The kind and amount of the resin aqueous dispersion and polymer resin were changed as shown in Table 3, and otherwise the same as in Example 1 except that the resin composition for carpet coating was used. The products were prepared and the physical properties of the carpets produced using them were tested in the same manner. Table 3 and Table 4 show the test results of the blending ratio and the physical properties of the carpet in each of these Examples and Comparative Examples.

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

INDUSTRIAL APPLICABILITY The resin composition for coating a carpet of the present invention imparts a high rigidity-imparting property and a heat-resistant shape-retaining property to a carpet, and is therefore particularly useful when applied to a fibrous carpet for vehicles.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C09D 133/00 PGE 7921-4J // A47G 27/02 Z 7137-3K D06M 15/263 (C08L 25 / 14 33:02) 7921-4J

Claims (2)

[Claims] 1. A monomer having (A) a glass transition temperature of 10 to 60 ° C. and comprising at least (a) an aromatic vinyl monomer and (b) a (meth) acrylic acid ester monomer. In an aqueous dispersion of a copolymer resin obtained by emulsion polymerization of a mixture, (B) a resin having a glass transition temperature of 80 ° C. or higher is added to 1 to 20 parts by weight of resin solids based on 100 parts by weight of resin solids of (A). Partial mixture, and the resin for carpet coating is characterized in that the resin (B) is solubilized by addition of an alkali so that the solubilization rate of the resin (B) becomes 10% by weight or more. Composition. 2. The resin composition for carpet coating according to claim 1, wherein the resin (B) is a copolymer containing an unsaturated carboxylic acid and has a weight average molecular weight of 100,000 or less.