JPS62110987A - Composition for carpet packing - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a composition for carpet banking, and more particularly to a composition containing an aliphatic conjugated diene monomer, an ethylenically unsaturated carboxylic acid, and a composition thereof. The main component is a copolymer latex obtained by emulsion polymerization of other copolymerizable monomers, which has good drying efficiency; high Ml separation strength and thread removal strength, and a drying process after lamination. The present invention relates to a carpet backing composition having good blister resistance.

[Conventional technology]

Conventionally, carpet backing compositions are made by adding an inorganic filler and, if necessary, a dispersant, an aging stabilizer, an antifoaming agent, a foaming agent, a crosslinking agent, etc. to a copolymer latex, and then adding a thickener to an appropriate level. Manufactured by adjusting the viscosity.

Such carpet backing compositions are applicable to all carpets that are backed, such as tufted carpets, knitted carpets, or hooked carpets. In addition, as a backing method in this case, for example, in the case of a tufted carpet, the carpet is placed on the back side of a gray fabric obtained by tufting tufted yarn such as nylon crimped yarn or polyester crimped yarn onto a primary base fabric such as polypropylene. Apply the backing composition and dry it with hot air, or
After applying the composition, a secondary base fabric such as jute woven fabric or synthetic fiber nonwoven fabric is laminated together and dried with hot air.
Made with tufted carpet.

Therefore, the required properties of a carpet backing composition include high removal strength of tuft yarns in the manufacturing process or product and high peel strength between the primary base fabric and secondary base fabric;
In the drying process, the composition is required to have good drying efficiency and to have blister resistance (no blistering).

[Problem that the invention seeks to solve]

However, among conventional carpet banking compositions, unfortunately no composition has been found that satisfies all of the above-mentioned required properties.

In particular, in recent years, in the carpet processing manufacturing process,
Large dryer (modular type) to increase productivity
A drying method has been adopted in which the carpet runs at a faster speed in the dryer under conditions of high temperature and high air volume.
In this method, there have been problems such as a decrease in blister resistance, thread removal strength due to insufficient drying, or deterioration in peel strength between the primary base fabric and the secondary base fabric. To solve this problem, a carpet backing composition with good drying properties is desired, and a method has been proposed to increase the solids concentration in the composition. It has poor dispersibility and viscosity stability, and the above problems have not been satisfactorily solved. In addition, this method requires a high concentration of the copolymer latex, and there are also problems in the production of the copolymer latex. That is, in order to increase the concentration of the composition, for example, it is necessary to increase the particle size of the copolymer latex constituting the composition to cause a decrease in viscosity, but as a result, coagulation occurs and polymerization occurs. This is a big problem in the process.

The present invention was made against the background of the above-mentioned conventional technical problems, and an object of the present invention is to provide a carpet backing composition that has high thread extraction strength and peel strength, and has good drying efficiency and blister resistance in the drying process. do.

[Means for solving problems]

That is, the present invention provides (al aliphatic conjugated diene monomer 35
~65% by weight, (bl ethylenically unsaturated carboxylic acid monomer 5~8% by weight and (C) other monomers copolymerizable with these 25~64.5% by weight (however, (a) (bl
An aliphatic conjugated diene copolymer having an average particle diameter of 800 to 1,700 Å, a gel content of 90% by weight or more, and a glass transition temperature of 150 to +5°C. The present invention provides a carpet backing composition characterized by containing a latex (a) and an inorganic filler (b).

(a) used in the copolymer latex (a) of the present invention
As the aliphatic conjugated diene monomer, 1. Examples include 3-butadiene, isoprene, 2-chloro-1,3-butadiene, and 1°3-butadiene is preferred.

These (a) + aliphatic conjugated diene monomers can be used alone or in combination of two or more.

The aliphatic conjugated diene polymer (a) is an essential component for imparting appropriate flexibility and adhesive elasticity to the resulting copolymer latex (a), and its proportion is 35 to 65%. , commercial use is 40 to 60% by weight, and 35% by weight
If it is less than 6, the flexibility and adhesive strength will be poor as mentioned above.
If it exceeds 5% by weight, the resulting carpet will be too soft and have low peel strength.

Examples of the (b) ethylenically unsaturated carboxylic acid i-mer include itaconic acid, acrylic acid, methacrylic acid, fumaric acid, and maleic acid.

These (b) ethylenically unsaturated carboxylic acid monomers are:
Although one type can be used alone or two or more types can be used in combination, it is preferable to combine appropriate amounts of acrylic acid and methacrylic acid.

The amount of the (bl) ethylenically unsaturated carboxylic acid monomer used is 5 to 8% by weight, preferably 5.5 to 7.5%, and if it is less than 5%, the stability of the latex during polymerization may deteriorate. It is undesirable that coagulation is easily formed (and the mechanical and chemical stability of the obtained latex is poor, and furthermore, the obtained carpet backing composition shows changes over time, which is undesirable. On the other hand, if it exceeds 8% by weight, The viscosity of the latex is high, making it impractical.

Further, other monomers that can be copolymerized with fcl include aromatic vinyl compounds, alkyl (meth)acrylates, vinyl cyanide compounds, vinyl acetate, acrylamide, and the like.

Among these, examples of aromatic vinyl compounds include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and chlorostyrene, with styrene being particularly preferred.

In addition, as alkyl (meth)acrylates, (meth)methyl acrylate, (meth)ethyl acrylate,
(meth)butyl acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate,
Examples include (meth)propyl acrylate, (meth)octyl acrylate, (meth)benzyl acrylate, (meth)lauryl acrylate, (meth)stearyl acrylate, (meth)hydroxyethyl acrylate, and among these, methyl methacrylate is particularly preferred.

Historically, examples of the vinyl cyanide compound include acrylonitrile and methacrylaterile, with acrylonitrile being preferred.

These (c) other monomers may be used alone or in combination.
More than one species can be used together.

In particular, copolymerization using methyl methacrylate as the other it isomer (C) is preferred since it significantly improves polymerization stability.

The amount of these tel and other monomers used is 25 to 64.5
% by weight, preferably 30 to 59.5% by weight, and 25
A carpet backing composition using latex with a weight of less than 64.5% by weight will result in a carpet that is too soft in feel, while a carpet backing composition containing less than 64.5% by weight will result in a carpet that is too hard, resulting in problems in handling and construction. The main physical properties of this material, such as suture removal strength and peel strength from the secondary base fabric, are poor.

The copolymer latex (a) used in the present invention is obtained by emulsion polymerization of monomers fa) to fc) as described above.

Here, as the emulsifier, anionic emulsifiers such as sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium diphenyl ether disulfonate, sodium succinate dialkyl ester sulfonate, or polyoxyethylene alkyl ester, polyoxyethylene alkyl allyl ether, etc. One or more nonionic emulsifiers may be used.

In particular, sodium diphenyl ether disulfonate is an emulsifier that can significantly exhibit the effects of the present invention.

The amount of the emulsifier used is usually 0.2 to 4.0% by weight (based on the total amount of monomers (al to fcl), the same applies hereinafter), preferably 0.5 to 3.0% by weight. If it is less than 0.2% by weight, it is not preferable because it will cause coagulation, resulting in poor polymerization stability and hinder the production of copolymer latex.On the other hand, if it exceeds 4.0% by weight, the copolymer latex will be This is not preferable because the average particle diameter becomes small, the dispersibility of the filler (b) described later becomes poor during the production of the composition for carve/notvasoking, and the viscosity changes over time after being blended.

As the chain transfer agent, t-dodecylmercaptan, octylmercaptan, n-tetradecylmercaptan, octylmercaptan, t-hexylmercaptan, n-
Mercaptans such as hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide are usually
~0.5% by weight is used.

Historically, polymerization initiators include persulfate initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate; cumene hydroperoxide, isoprobyl-hensen hydroperoxide, para-menthane hydroperoxide, and hensyl bar. Examples include organic peroxides such as oxide; hydrogen peroxide, etc. In particular, when cumene hydroperoxide is used, the resulting copolymer latex can provide a composition with low drying efficiency, which is the object of the present invention. can.

The amount of such polymerization initiator used is preferably 0.03 to 2
．． 5% by weight, particularly preferably 0.05-2.0% by weight.

In addition, in order to promote emulsion polymerization, reducing agents such as sodium pyrobisulfite, sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, glucose, formaldehyde, sodium sulfoxylate, L-ascorbic acid, and sodium hydrogen sulfite; Chelating agents such as glycine, alanine, and sodium ethylenediaminetetraacetate can also be used in combination.

In the emulsion polymerization, in addition to the emulsifier, chain transfer agent, polymerization initiator, etc., various electrolytes, pH adjusters, etc. are used in combination as necessary, and the monomers (a) + to (c) 100
100 to 300 parts by weight of water and the emulsifier,
Using initiators, chain transfer agents, etc. in amounts within the above ranges,
Emulsion polymerization is carried out at a polymerization temperature of 5 to 80°C, preferably 30 to 50°C, and a polymerization time of 15 to 30 hours.

The method of adding each of the monomers (a)+ to (C) is not particularly limited, and any method such as a batch addition method, a continuous addition method, or a divided addition method may be employed.

In addition, it is preferable that the polymerization conversion rate of the obtained copolymer latex (a) is 99.5% or more.

The average particle diameter of the copolymer latex (a) emulsion polymerized in this way and used in the present invention is 800-1,7
00 Å, preferably 900 to 1.600 people. Here, the average particle size of the latex is determined by treating the latex with osmic acid and using an electron micrograph (30,000x magnification).
This value is calculated by measuring the particle size of 100 or more particles and taking the number average.

If the average particle diameter of the copolymer latex (a) is less than 800 particles, the stability during polymerization will be poor (and the dispersibility of the filler (b) will be poor when blended into the composition, resulting in changes in viscosity over time after blending). On the other hand, if the number exceeds 1,700, the drying efficiency of the resulting composition will be poor, and the adhesive strength will be weak (which will lead to fatal defects).

Here, the average particle diameter of the copolymer latex (a) can be easily adjusted by adjusting the oil used as an emulsifier and the polymerization temperature during emulsion polymerization.

Further, the gel content of the copolymer latex (a) is above the 90-heavy cylinder, preferably 95% by weight or more.

Here, the gel content refers to the toluene-insoluble content, that is, the latex prepared to have a pH of 8 or more is dried on a glass plate to form a film with a thickness of 0.3 g.
00m7! After leaving it at room temperature for 244 hours,
It is the weight percent obtained by filtering through a mesh wire mesh, drying and weighing what remains on the wire mesh, and dividing the value by the total latex solid content.

If the gel content is less than 90% by weight, the drying efficiency of the resulting carpet banking composition will be poor, the adhesive strength between the primary base fabric and the secondary base fabric will be weak, and the blister resistance will be poor.

Note that such adjustment of the gel content can be easily carried out by selecting the type and amount of the chain transfer agent, which is a molecular weight regulator. For example, when carbon tetrachloride or methyl bromide, which are halogenated compounds, are used as a chain transfer agent, the amount used is 0 to 3% by weight, and mercaptans such as t-dodecylmercaptan and n-dodecylmercaptan are used. If so, the amount used is O~0.5
Weight%. Other methods of adjusting gel content include:
There are factors such as the amount of initiator during polymerization and the temperature at which polymerization starts, and the desired latex can be obtained by combining these factors.

Historically, the glass transition temperature (Tg) of the copolymer constituting the aliphatic conjugated diene copolymer latex (a) is preferably -50°C to +5°C, more preferably -48°C to +2°C.
It is.

When the glass transition temperature of the copolymer constituting the copolymer latex (a) is within the above range, a carpet with good hand feel, ease of carpet application, peel strength, and thread removal strength can be obtained.

Here, the glass transition temperature (Tg) is a value calculated from the following formula.

Tg (a) T g fal T g
(b) T g (CIWa; heavy injection fraction Wb of monomer (a) + in copolymer (a); heavy oil fraction WC of monomer (b) in copolymer (a); Weight fraction of monomer (c) in copolymer (a) T g fal ; Value of Tg of the homopolymer of monomer fal expressed in absolute temperature T g (a) ; Weight fraction of monomer fat Value Tg of the homopolymer expressed in absolute temperature T g (bl ; Value Tg of the homopolymer of monomer (bl expressed in absolute temperature T g (c); Homo weight of monomer (c) The Tg of the copolymer (A) expressed as an absolute temperature Tg (a); The Tg of the copolymer (a) expressed as an absolute temperature.
Butadiene = 183”K, polystyrene = 373°K,
Polymethyl methacrylate-3786 to 1 polymethacrylic acid = 501''K.

In addition, the solid content concentration of copolymer latex (a) is usually adjusted to 45 to 57% by weight, preferably 50 to 55% by weight, and used. That is, copolymer latex (a)
If the solid content of the copolymer is less than 45% by weight, the latex concentration will be too low and the solid content of the composition of the present invention will tend to decrease, while if it exceeds 57% by weight, the copolymer latex The viscosity of the filler increases, making it difficult to disperse the filler.

Next, the filler (b) used in the present invention includes calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, barium sulfate, silicic acid, fluorite, titanium oxide, magnesium carbonate, calcium carbonate, etc. Examples include, but are not limited to, inorganic fillers.

These fillers (b) may be used alone or in combination of two or more.

The ratio of the copolymer latex (a) to the filler (b) is 250 to 750 parts by weight, preferably 3 parts by weight, based on 100 parts by weight of the latex (a).
The amount is about 00 to 700 parts by weight, and the filler (b) is about 250 parts by weight.
If the amount is less than 750 parts by weight, the proportion of the latte 7x (a) used will be large and uneconomical, and the blister resistance will deteriorate, while if it exceeds 750 parts by weight, the resulting carpet will have poor flexibility and low peel strength. becomes.

In addition, when the carpet banking composition of the present invention is subjected to puffing, the viscosity of the composition is usually adjusted to 20.00%.
0-40,000 cps, preferably 25,000-3
5. 000 cps, and the solid content concentration is usually 73 to 77% by weight, preferably 74 to 76% by weight using a thickener or water.

That is, if the viscosity of the composition is less than 20,000 cps, the permeability into the carpet will be large and the peel strength will be weak, while if it exceeds 40,000 cps, the coating properties will be poor (and unevenness will occur). The solid content concentration of the composition is 7
If it is less than 3% by weight, the moisture content is too high and the drying efficiency is poor, resulting in a decrease in suture removal strength and peel strength.
When it exceeds 7% by weight, the viscosity of the composition increases, resulting in poor coating efficiency and uneven coating, resulting in variations in quality such as peel strength and texture.

As described above, the carpet backing composition of the present invention mainly contains a copolymer latex (a) and a filler (b), but may also include a dispersant, an antifoaming agent, a crosslinking agent, etc. , thickeners, blowing agents, colorants, flame retardants, preservatives, anti-aging agents, stabilizers, vulcanization accelerators, antistatic agents, pF (adjusting agents, etc.) can be added.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, parts and percentages in the examples are based on weight unless otherwise specified.

Moreover, various test methods in the examples are as follows.

(1) Peel strength Measured according to JIS I, -1021 rug test method. That is, a backing composition with a solids content of 4% and 75% is applied to a gray fabric made by tufting nylon crimped yarn onto a primary fabric made of polypropylene, and then a 7 oz. After drying at 120°C for 20 minutes, the peel strength between the secondary base fabric and the gray fabric was measured.

(2) Initial peel strength A backing composition with a solids concentration of 75% is applied to a gray fabric made by tufting nylon crimped yarn onto a primary base fabric made of polypropylene, and then 7 oz juute is crimped as a secondary base fabric. The peel strength at the initial stage (3 minutes, 5 minutes, and 7 minutes after bonding) when bonded and dried at 120°C is determined by JIS.
Measured according to L-1021.

(3) Thread removal strength flS According to L-1021 (11), the pullout strength of one pile was measured under the same conditions.

(4) Initial suture removal strength The pullout strength of one pile was measured under the same conditions as in (2) according to JIS L-1021.

(5) Blister resistance The undried carpet was placed in a hot air dryer adjusted to a temperature of 150° C. and a wind speed of 8 m/sec, and the blisters that formed during drying were visually observed and judged. Judgment was made on a scale of 1 to 5. Grade 1 means that no blisters occur at all, and Grade 5 means that blisters occur all over the surface.

(6) Moisture Content Using a wood moisture meter (manufactured by Kerato Co., Ltd., model M-3A), a needle was pierced from the secondary base fabric side of the carpet to measure the moisture content. Poor drying properties indicate that the peel strength at the initial stage of drying is low, the moisture content after processing (drying at 120° C. for 20 minutes) is high, and therefore the tl peel strength of the product is low.

Examples 1 to 3 and Comparative Examples 1 to 9 11 Preparation of copolymer latex The charging composition shown in Table 1 was 100 parts of monomer, a molecular weight regulator, an emulsifier, an initiator, and 0.0 L-ascorbic acid.
7 parts, 0.005 parts of ferrous sulfate, 0.01 parts of sodium ethylenediaminetetraacetate, and 200 parts of water to an inner volume of 10 parts.
07! into a stainless steel reactor, and the polymerization temperature is 35~
Polymerization was continued by stirring at 60°C for 20 hours, resulting in copolymer latte 7.
Twelve types of latexes A-L were obtained.

The polymerization was carried out by batch charging, and the polymerization conversion rate of the obtained latex was all 99.5% or higher, the polymerization stability was good except for Late Nox E, and there was almost no coagulum. .

The properties of the obtained copolymer latex are also shown in Table 1.

In Table 1, the average particle diameter and gel content (toluene-insoluble content) of the copolymer latex are values measured according to the above.

The thus obtained copolymer Latte Nox A is used in the preparation of carpet banking compositions.
-H was used to obtain a composition for carve/notvasoking according to the following formulation, and various carpet tests were conducted using the composition. Table 2 shows the results.

(Left below) Formula (Part) Copolymer latex 100 Potassium pyrophosphate
0.8 styrenated phenol
1.0 heavy calcium carbonate 45
0 Thickener (sodium polyacrylate) 1.0 The composition for carpet banking is prepared by adding a dispersant such as potassium pyrophosphate to the copolymer latex, and then adding heavy calcium carbonate as a filler. After adding and thoroughly dispersing,
Solid content concentration is 75%, viscosity is approximately 30,000 cps
(measured using a Brookfield viscometer, BM type 11h4, at 6 rpm) using a thickener and water.

As is clear from Tables 1 and 2, Examples 1 to 3 are cases where the copolymer latex used in the present invention was used, and in all cases, the monomer composition was changed within the scope of the present invention. The average particle diameter and gel content of the resulting copolymer latex are also within the scope of the present invention. Thus, in Examples 1 to 3 in which the charging composition of the copolymer latex was changed within the scope of the present invention, the obtained carpet peel strength,
It has strong suture removal strength and good blister resistance.

On the other hand, Comparative Examples 1 to 9 are cases in which a copolymer latex outside the scope of the present invention was used and the solid content concentration of the composition was increased.

Of these, Comparative Example 1 uses a copolymer latex in which the conjugated diene monomer in the monomer composition is less than the range of the present invention, and the drying property of the carpet backing composition is good. However, the peel strength and suture removal strength are weak.
Blister resistance is also poor.

Comparative Example 2 is a case where a copolymer latex in which the ethylenically unsaturated carboxylic acid monomer in the monomer composition was less than the range of the present invention was used, and the drying properties of the carpet backing composition were poor. (Therefore, the initial peel strength and suture removal strength are weak, and the peel strength and suture removal strength after processing are also weak.

Comparative Example 3 is a case where a copolymer latex whose average particle diameter is outside the range of the present invention is used, and Comparative Example 4 is a case where a copolymer latex whose gel acid content is outside the range of the present invention is used. The carpet backing compositions obtained in either case have poor drying properties, and therefore have low initial peel strength and paddy removal strength, as well as poor peel strength and thread removal strength after processing.

Comparative Example 5 is an experimental example in which the gel content of the copolymer latex was outside the range of the present invention and the solid content concentration of the carpet backing composition was adjusted to 80%. The properties and components are similar to those of the backing composition used in the present invention, and although such a composition has good drying properties, it is not stable and its viscosity changes significantly over time. Therefore! OI separation strength and suture removal strength are weak.

Comparative Example 6 is a case in which a copolymer latex with a monomer composition of an aliphatic conjugated diene monomer exceeding the scope of the present invention was used, and the drying property was poor, resulting in poor peel strength and suture removal strength. It is weak and has poor blister resistance.

Comparative Example 7 is a case where a copolymer latex with a monomer composition in which the weight of ethylenically unsaturated carboxylic acid exceeds the scope of the present invention is used, and the viscosity of the compound changes over time and the drying properties are poor. . Therefore, the peel strength and suture removal strength are low, and the blister resistance is also poor.

Comparative Example 8 used a copolymer latex in which styrene was less than the range of the present invention as another monomer copolymerizable with an aliphatic conjugated diene monomer and an ethylenically unsaturated carboxylic acid monomer. In some cases, drying properties are poor, therefore peel strength and suture removal strength are weak, and blister resistance is poor.

Comparative Example 9 uses a copolymer latex whose average particle diameter is less than the range of the present invention, and although the drying property is somewhat good, the peel strength and suture removal strength are weak, and the blister resistance is poor. bad.

(The following is a blank space) [Effects of the Invention] The carpet banking composition of the present invention has better drying properties than conventional compositions, and the resulting carpet has a
1. Separation strength and suture removal strength are improved, and blister resistance is also improved. Therefore, to provide a composition for carpet banking that is suitable for a system in which it is possible to increase the running speed after car vent drying and to increase productivity, that is, a drying system using a large dryer with a high temperature and a large air volume. I can do it.

Claims (1)

[Claims] (1) (a) 35 to 65% by weight of aliphatic conjugated diene monomer, (b) 5 to 8% by weight of ethylenically unsaturated carboxylic acid monomer, and (c) other monomers copolymerizable with these. mass 25
~64.5% by weight (where (a) + (b) + (c) =
100% by weight) with an average particle diameter of 8.
00 to 1,700 Å, a gel content of 90% by weight or more, and a glass transition temperature of -50 to +5°C (a), and an inorganic filler (b). A carpet backing composition comprising: