JP2868922B2 - Resin cotton and polymer emulsion used for it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin wool obtained by subjecting a lump of fibers (web) formed into a sheet to a polymer treatment and a polymer emulsion used for the same.

[0002]

2. Description of the Related Art In recent years, resin cotton (sometimes referred to as fiber film) obtained by subjecting a web to polymer treatment has been on the market. The above-mentioned resin cotton belongs to the category of non-woven fabric. In the above-mentioned polymer treatment, usually, a polymer emulsion having a single structure having a glass transition point (hereinafter abbreviated as “Tg”) of −50 to + 60 ° C. alone is used alone. , Or arbitrarily blended.

[0003] By the treatment with the polymer emulsion, a polymer component is dispersed and attached to the fiber surface.
This polymer component serves as a binder between the fibers. That is, the adhesion of the polymer component to the fibers improves the durability, rebound resilience, bulkiness and the like of the product. Further, since the fibers are less likely to move, processing operations (cutting, sewing, etc.) of the final product using the resin cotton are facilitated. Further, the final product is less likely to lose its shape and has a certain elasticity, so that practical comfort is also improved.

[0004]

However, in the above-mentioned polymer treatment, the bonding force between the desired fibers,
That is, it has been empirically known that a polymer is required to have contradictory performances in terms of adhesion to fibers and hardness of a product.

[0005] That is, when a polymer having a low Tg is used, the adhesion between fibers can be practically satisfactory, but the hardness is insufficient. Further, if the Tg is too low, there is also a problem that tackiness occurs on the processed product surface and causes various troubles. Conversely, when a polymer having a high Tg is used, a phenomenon opposite to the above occurs.

For this reason, it has been proposed to use a blend of a polymer emulsion containing a polymer having a high Tg dispersed therein and a polymer emulsion containing a polymer having a low Tg dispersed therein. However, it was difficult to satisfy both the adhesive strength and the hardness.

[0007] In recent years, in the field of living environment, there has been a strong demand for more comfort and natural orientation has been increasing. In the bedding and clothing industry, the mainstream is shifting from synthetic fibers to natural fibers, and wool is rapidly increasing in place of polyester cotton as batting for bedding and clothing. Despite being excellent in water resistance and moisture absorption / desorption properties, defects are likely to occur due to felting due to repeated use or batting fibers blowing out from the surface cloth. Therefore, it has been considered effective to bond the fibers by treating the web with high-temperature steam or performing the above-described polymer treatment.

[0008] However, wool does not sufficiently exhibit polymer adhesiveness due to fats and oils essentially remaining in its fibers. Therefore, in the case of wool cotton, or resin cotton based on wool cotton and other cotton, for example, a cotton blend of polyester cotton, the polymer component is separated from the fiber due to long-term use, and the above-mentioned felting is caused. Not only does the prevention effect, blow-out prevention effect, etc. decrease, but also the separated polymer component becomes fine powder and scatters through the surface cloth of the final product (referred to as powder dropping phenomenon), or They may remain in the cloth and become clumpy, causing a serious damage to the image of the final product.

For this reason, for wool-based cotton, a polymer having a low Tg is used in order to enhance the adhesion between the polymer and the fiber, but the workability of the product (such as sewing workability) is improved.
In fact, important characteristics in use such as comfort and wearing comfort have been considerably sacrificed.

The present invention has been made in view of such circumstances, and an object of the present invention is to solve the above-mentioned disadvantages and to provide a practically satisfactory resin cotton.

[0011]

In order to achieve the above object, the present invention provides a resin cotton obtained by treating a web with a polymer emulsion, wherein the polymer component of the polymer emulsion has a core / shell heterophasic structure. The first aspect is a resin wool in which the core layer is formed of a polymer having a Tg of 50 to 0 ° C, and the shell layer is formed of a polymer having a Tg of 5 to 60 ° C. A second aspect is a polymer emulsion having a heterogeneous structure, wherein the core layer is formed of a polymer having a Tg of -50 to 0C, and the shell layer is formed of a polymer having a Tg of 5 to 60C.

[0012]

That is, the present inventors have conducted a series of studies on a method for simultaneously satisfying the conflicting properties of adhesive strength and hardness, which cannot be satisfied simultaneously by a single polymer. As a result, as a polymer emulsion,
The idea is that if the polymer component has a different core / shell structure, and if the difference in Tg between the constituent polymers of the core layer and the shell layer is provided, the above two properties can be satisfied simultaneously. And further research.
As a result, it was found that when the core layer was formed of a polymer having a Tg of 50 to 0 ° C. and the shell layer was formed of a polymer having a Tg of 5 to 60 ° C., the intended object was achieved.

Next, the present invention will be described in detail.

The resin cotton referred to in the present invention comprises fibers and a polymer serving as a binder. The composition ratio of the resin cotton is appropriately determined according to the required performance of the final product. Is preferably 10 to 100% by weight (hereinafter abbreviated as "%"). Also, with the polymer,
It is also possible to mix and use a low melting point fiber or powder called a binder fiber. However, in some cases, the International Wool Secretariat (IWS) regulates the amount of polymer in resin cotton to 10% or less as one of the wool mark certification conditions for final products. It is desirable to set the amount to be the amount.

The fibers used for the resin cotton of the present invention may be any fibers, whether natural or synthetic. However, the polymer of the present invention has a high adhesive effect, and therefore, wool alone or wool can be used. It is particularly useful to apply to hardly-adhered fibers which do not have a significant adhesive effect due to polymers, such as cotton mixed with other types of fibers, silicon-treated fibers alone or mixed with other types of fibers.

As a method of forming a web from the above-mentioned fibers, a method usually used in this industry can be applied as it is. Needle punching may be performed as needed. Also, there is no need to take special techniques for the polymer treatment method of the web.
Various methods such as an immersion method and a printing method can be used.

In the present invention, a special polymer emulsion is used in the above-mentioned polymer treatment method. That is,
In this polymer emulsion, the polymer component has a core / shell heterophasic structure, and the core layer has a Tg of -50 to 0 ° C.
And the shell layer has a Tg of 5 to 60 ° C.
Is formed of the above polymer.

The monomers used in the polymer emulsion are not particularly limited. For example, by forming an appropriate combination from the following monomers having an ethylenically unsaturated bond, It is necessary to set the polymer to have a Tg.

Examples of the above monomers include vinyl monomers such as ethylene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, styrene, and acrylonitrile; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
Examples include acrylic monomers such as ethylhexyl acrylate, methacrylic monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, and diene monomers such as butadiene and isoprene. These may be used alone or in combination of two or more. be able to.

Compounds having an ethylenically unsaturated bond called a functional monomer, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic anhydride, acrylamide, methacrylamide, and the like. N-methylolated acrylamide, N-methylolated methacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide,
Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. are used in combination. be able to.

Further, compounds having two or more ethylenically unsaturated compounds, for example, divinylbenzene, diaryl phthalate, diaryl malate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triaryl cyanurate, trimethylolpropane trimethacrylate These compounds can be copolymerized singly or in combination of two or more.

Various methods for producing a polymer emulsion having a heterophasic structure using the above monomers have been proposed and put into practical use, and an appropriate method can be adopted from these methods. However, the resulting polymer emulsion having a heterophasic structure has a Tg of the core layer of −50.
It is important that the Tg of the shell layer is in the range of 5 to 60C. Among them, Tg of the core layer is -20 to 0.
If the temperature and the shell layer Tg are set in the range of 10 to 40 ° C., more excellent effects can be obtained.

In the above-mentioned polymer emulsion, the composition ratio of the core layer and the shell layer can be appropriately changed according to the required performance of the final product, and is not limited. Composition ratio of 7 parts by weight
It is effective to set the range from 0:30 to 20:80.

When a web is treated with the above-mentioned polymer emulsion, the emulsion may be treated with a crosslinking agent such as a melamine, epoxy or urethane, an antistatic agent, a flame retardant, an antibacterial agent, a deodorant, A fungicide and the like can be added as necessary.

After the treatment with the above-mentioned polymer emulsion, the web is subjected to a dry heat treatment in the same manner as in the ordinary treatment. However, the ordinary equipment can be used as it is, and special equipment is required. And not

The resin cotton thus obtained is treated with the above-mentioned special polymer emulsion and has a Tg of-
Conventionally, a polymer component having a heterophasic structure comprising a core layer having a temperature of 50 to 0 ° C. and a shell layer having a Tg of 5 to 60 ° C. exhibits an excellent binder effect by dispersing and adhering to the fiber surface of the web. Silicone treated fibers and wool fibers, which were considered difficult to adhere to, can be sufficiently bonded, and the obtained resin cotton has excellent hardness and texture. Can be used.

Next, examples will be described together with comparative examples.

First, various polymer emulsions were obtained as follows. <Preparation of Polymer Emulsion having Heterophase Structure of the Present Invention> 800 parts by weight of water (hereinafter abbreviated as "parts") is placed in a two-liter polymerization flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet. ), Emulgen 935 (manufactured by Kao Corporation, polyoxyethylene nonyl phenyl ether) 20
Department, Neopellets No. 6 (manufactured by Kao Corporation, sodium dodecylbenzenesulfonate, 60% pure), and then heated to 70 ° C. with stirring while blowing in nitrogen gas. Next, an aqueous solution in which 1 part of sodium hydrogen sulfite and 1 part of potassium persulfate were respectively dissolved in 25 parts of water was added, and further, 180 parts of butyl acrylate, 90 parts of ethyl acrylate, 21 parts of acrylonitrile, and N-methylolated acrylamide 6 And a monomer mixture composed of 3 parts of acrylic acid were uniformly dropped over 1.5 hours. At the same time, an aqueous solution in which 1 part of potassium persulfate was dissolved in 50 parts of water was uniformly dropped by another dropping funnel over 1.5 hours. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 1 hour, and then an aqueous solution in which 1 part of sodium bisulfite and 1 part of tert-butyl hydroperoxide were dissolved in 25 parts of water was added. Furthermore, ethyl acrylate 3
01 parts, 315 parts of methyl methacrylate, 49 parts of acrylonitrile, N-methylolated acrylamide 21
Parts of a monomer mixture consisting of 14 parts of methacrylic acid.
The solution was dropped uniformly over 5 hours. After completion of the dropwise addition, an aqueous solution in which 0.5 part of sodium hydrogen sulfite and 0.5 part of tert-butyl hydroperoxide were dissolved in 25 parts of water was added. Thereafter, the mixture is reacted at 75 ° C. for 2 hours, so that the composition ratio of the core layer and the shell layer is 30:30 by weight.
A polymer emulsion having a heterogeneous structure of 70 and a solid content of 51% was obtained. The Tg of the core layer of the polymer component of this polymer emulsion is -20 ° C, and the Tg of the shell layer is 30 ° C.
It was. This polymer emulsion is referred to as Binder A.

The Tg was measured according to the following method (the same applies hereinafter). <Method of measuring Tg> The monomers constituting the core layer and shell layer of the polymer emulsion are separately emulsion-polymerized to obtain a polymer emulsion having a uniform structure. Then, each polymer emulsion is formed into a film by natural drying, and 10 mg of the film is precisely weighed to obtain a sample. The sample is subjected to a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation) to measure an endothermic peak, and a rising point of the endothermic peak is determined as a thermal glass transition point.

<Preparation of Polymer Emulsion Having Heterophase Structure Outside of the Present Invention> The monomer mixing ratio and the monomer dropping time were changed as follows. Otherwise in the same manner as in the above-mentioned preparation method, a polymer emulsion having a heterophase structure in which the composition ratio of the core layer and the shell layer was 85:15 by weight and the solid content was 51% was obtained. Core part monomer (first drop) 2-hexyl acrylate 8075 parts Acrylonitrile 255２５ N-methylolacrylamide 170 Acrylic acid 85〃 Shell part monomer (second drop) Ethyl acrylate 300 parts Methyl methacrylate 1020〃 Acrylonitrile 105〃 N- Methylol acrylamide 45〃 Methacrylic acid 30〃 Dropping time Core monomer (1st drop) 3 hours Shell part monomer (2nd drop) 1 hour

A core layer of the obtained polymer emulsion,
The Tg of the shell layer was -75 ° C and 75 ° C, respectively. This polymer emulsion is used as binder B.

<Preparation of Polymer Emulsion with Uniform Structure> In the same apparatus as above, 800 parts of water, 20 parts of Emulgen 935 (manufactured by Kao Corporation, supra), 20 parts of Neoperexus No.
6 (manufactured by Kao Corporation, supra), and then heated to 70 ° C. with stirring while blowing nitrogen gas. Then
2 parts sodium bisulfite, 2 sodium hydrogen persulfate
And 1 part of potassium persulfate in 50 parts of water. Further, butyl acrylate 600
Part, 300 parts of ethyl acrylate, acrylonitrile 7
A monomer mixture consisting of 0 parts, 20 parts of N-methylolacrylamide, and 10 parts of acrylic acid was uniformly dropped over 4 hours. At the same time, potassium persulfate 2
Aqueous solution in which 100 parts of water was dissolved in 100 parts of water.
It was dropped uniformly over time. After completion of the dropwise addition, the mixture was reacted at 75 ° C. for 2 hours to obtain a polymer emulsion having a solid content of 51% and a polymer component Tg of −20 ° C. This polymer emulsion is used as a binder C.

The monomer composition was changed as follows. Otherwise, polymerization was carried out in the same manner as above to obtain a polymer emulsion having a solid content of 51% and a polymer component having a Tg of 30 ° C. Ethyl acrylate 430 parts Methyl acrylate 450〃 Acrylonitrile 70〃 N-methylol acrylamide 30〃 Methacrylic acid 20〃 This polymer emulsion is used as a binder D.

<Preparation of a mixture of two types of polymer emulsions having different Tg> The above binder C and binder D
Was mixed at an apparent weight ratio of 30:70 to obtain a binder E.

[0035]

Example 1, Comparative Examples 1 to 4 A web having a basis weight of 250 g / m ² of wool alone was prepared by a usual card laminating method, and the binders A to E were respectively coated on both sides of the web with a solid content of 20 g / m ² ( 10 g / m ² per side) is uniformly applied by a spray method, dried and heat-treated at 130 ° C., and 5 kinds of wool resin cotton having a finished basis weight of 270 g / m ² (Example 1)
Products and Comparative Examples 1 to 4). 6 pieces of this resin cotton
The sheets were piled, and wool laying sheets A to E were sewn. Mattress A
Table 1 below shows the results of the performance evaluations of E.

[0036]

[Table 1]

[0037]

Example 2, Comparative Examples 5 to 8 Wool and polyester cotton (Kanebo, ester cotton H
38F6d × 51 mm) was mixed in a ratio of 50:50 on a weight basis to prepare a wool-blend web having a basis weight of 100 g / m ² . Then, each of the binders A to E was coated on both sides of the web with a solid content of 30 g / m ² (one side of 15 g / m ² ).
² ) was uniformly applied by a spray method, and dried and heat-treated at 150 ° C. to produce 5 kinds of wool resin cotton having a finished basis weight of 130 g / m ² . This resin cotton was quilted, and lightweight quilt hanging tons F to J were sewn. This Kaketon F ~ J
Are shown in Table 2 below.

[0038]

[Table 2] * 1: Rinsing with water, conforming to JIS L0217 104 method. Judgment was made based on the change in the appearance of the batting after three times of tests.

[0039]

Example 3, Comparative Examples 9-12 Polyester cotton Kanebo ester cotton H38Y (2d
× 51mm silicon processing type) and H38F (2d × 51
mm) in a ratio of 80:20 on a weight basis to give a basis weight of 7
A web of 0 g / m ² was produced. Then, the binders A to E were respectively applied to both surfaces of the web at a solid content of 15 g /
m ² (7.5 g / m ^{2 on} one side) is uniformly applied by a spray method, and dried and heat-treated at 160 ° C. to give a finished basis weight of 85 g.
/ M ² polyester resin cotton (5 products of Example 3 and Comparative Examples 9 to 12) were produced. This resin cotton was quilted, and down vests KO were sewn. This best KO
Table 3 shows the performance evaluation results.

[0040]

[Table 3] * 2: Dry cleaning, JIS L1018E-
Conforms to 2. Solvent was perchlorethylene. After the test was repeated three times, the appearance of the batting was judged by the change in appearance.

From the above results, it was found that the resin cotton of the example was satisfactory enough for practical use as a cotton wool for bedding and clothing. On the other hand, the resin cotton of the comparative example was unsatisfactory in some respects in performance.

[0042]

As described above, the resin cotton of the present invention uses a special polymer emulsion having a core / shell heterophasic structure in which the polymer component is set to a specific Tg as a binder. Had been contradictory,
It has both fiber adhesion and moderate hardness. Therefore, it is excellent in workability such as cutting and sewing, and when it is finished, it has appropriate hardness and elasticity without sagging. It can be widely used as a material for use. In particular,
By applying to wool-based cotton or silicon-treated fiber-based cotton, which is difficult to adhere with a polymer and has not been obtained in a sufficient quality, excellent quality can be provided.

Claims (2)

(57) [Claims] 1. A resin cotton obtained by treating a web with a polymer emulsion, wherein the polymer component of the polymer emulsion has a core / shell heterophasic structure, and the core layer has a glass transition point of -50 to 0 ° C. Resin cotton formed of a polymer, wherein the shell layer is formed of a polymer having a glass transition point of 5 to 60 ° C. 2. The polymer component has a core / shell heterophasic structure, wherein the core layer is formed of a polymer having a glass transition point of -50 to 0 ° C., and the shell layer has a glass transition point of 5 to 60 ° C.
A polymer emulsion characterized by being formed of a polymer at a temperature of ° C.