JP3090707B2 - Carpet with yellowing prevention - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carpet in which a raw carpet is hardly yellowed. More specifically, the present invention relates to a carpet improved so that the raw carpet material is not yellowed even by nitric oxide (NOX) gas in the air.

[0002]

2. Description of the Related Art A tile carpet, a sound-insulating carpet, and the like have recently suffered from a problem that the outer surface of a carpet, that is, a raw carpet, is discolored to yellow and its appearance is impaired over time. It is not clear why these problems have occurred recently, but conventional carpets are generally darker in color, so yellowing is noticeable despite yellowing. However, it was not considered a problem.On the other hand, white carpets have come to be preferred for recent sound insulation carpets for automobiles and the like,
It is considered that yellowing became noticeable because it became noticeable. However, its cause and its prevention method are not yet known. Conventionally, carpet backing materials
Thermoplastic compositions containing thermoplastic resins such as soft polyolefins have been used. These thermoplastic compositions are liable to be deteriorated, embrittled or softened (hereinafter collectively referred to as thermal deterioration) by the action of heat, oxygen, or the like during processing or use of carpet. The melting backing step of the backing material tends to have a particularly high temperature in order to lower the viscosity. Therefore, as a countermeasure, a method has been adopted in which various sulfur-based, phosphorus-based or phenol-based antioxidants are used alone or in combination and added at the time of production and processing of a thermoplastic material. As described above, the addition of additives is essential, but at the same time, it is considered that these additives promote yellowing.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a carpet in which even a white carpet does not lose its appearance due to yellowing of the carpet material with time.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the surface of carpet, that is, the prevention of yellowing of the raw material. As a result, the yellowing portion is the surface of the carpet, He found that the main cause was not only in the outer material but also in the backing material. That is, it was confirmed that the carpet backing material lined with the raw material discolored the carpet surface material due to some interaction with the raw material. Although the mechanism and route of action of discoloration are not yet clear,
Carpets with a backing material are promoted yellowing, and yellowing is not seen only on carpets or outer materials that do not use a backing material, and it is found that the causal relationship between the backing material and yellowing is clear. By using a specific compound as an additive for the backing material, it was confirmed that the raw material of carpet, that is, that the yellowing of the surface material could be prevented, and that the problem of conventional thermal deterioration could be prevented at the same time, and the present invention was completed. .

The invention of claim 1 of the present invention relates to a method for producing pentaerythritol represented by the general formula 1 per 100 parts by weight of a functional group-containing soft polyolefin (hereinafter sometimes referred to as a thermoplastic resin). Diphosphite,

Embedded image (Wherein R 1 and R 2 are the same or different aryl groups) (2) 3,9-bis (1,1-dimethyl-2- (β- (3-t-butyl-4-hydroxy) represented by the formula 2 −
5-methylphenyl) propionyloxy) ethyl)-
2,4,8,10-tetraoxaspiro (5,5) undecane,

Embedded image (3) Tetrakis (2,4-di-t-) represented by Formula 3
Butyl phenyl) -4,4 biphenylene diphosphonite,

Embedded image One or more additives selected from the group consisting of 0.005
A carpet fabric in a nitrogen oxide (NOx) atmosphere, characterized by backing a functional group-containing soft polyolefin composition containing 0.15 parts by weight and a plasticizer (hereinafter sometimes referred to as a thermoplastic resin composition). It is a carpet in which yellowing is prevented.

According to a second aspect of the present invention, there is provided a carpet in which yellowing is prevented according to the first aspect, wherein the carpet is a tile carpet or a sound insulating carpet.

According to a third aspect of the present invention, there is provided a flexible polyolefin composition having a functional group, wherein the carboxylic acid group, carboxylic ester group, acid anhydride group, epoxy group, hydroxyl group,
A polyolefin having at least one functional group in a molecule selected from the group consisting of an amino group, an alkenyl cyclic imino ether group, a polyfunctional group, a reactive silane group and a vinyl ester group. 2. A carpet according to item 1, wherein yellowing is prevented. According to a fourth aspect of the present invention, there is provided a carpet raw material comprising: (1) pentaerythritol diphosphite represented by the general formula 1 per 100 parts by weight of a functional group-containing soft polyolefin;

Embedded image (Wherein R 1 and R 2 are the same or different aryl groups) (2) 3,9-bis (1,1-dimethyl-2- (β- (3-t-butyl-4-hydroxy) represented by the formula 2 −
5-methylphenyl) propionyloxy) ethyl)-
2,4,8,10-tetraoxaspiro (5,5) undecane,

Embedded image (3) Tetrakis (2,4-di-t-) represented by Formula 3
Butyl phenyl) -4,4 biphenylene diphosphonite,

Embedded image One or more additives selected from the group consisting of 0.005
A method for preventing yellowing of a raw carpet under a nitrogen oxide (NOx) atmosphere, characterized by backing a soft polyolefin composition containing a functional group containing 0.15 parts by weight and a plasticizer.

The aryl group represented by the general formula 1 is a residue obtained by removing one hydrogen atom from the benzene ring of an aromatic compound. Specific examples of pentaerythritol diphosphite having these aryl groups include, for example, di ( 2,4-
Di-tert-butylphenyl) pentaerythritol diphosphite or di (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite can be used.

These additives (1), (2) and (3)
Is the amount of the thermoplastic resin 1 contained in the thermoplastic composition.
0.0 parts by weight, alone or as a total amount of 0.0
05 to 0.15 parts by weight, preferably 0.01 to 0.1 parts by weight.
The range is 5 parts by weight. If the amount is less than 0.005 part by weight, the effect of preventing the backing material itself, which has been conventionally regarded as a problem, is not sufficient. It is also not preferable. These additives may be used alone or in combination of two or more. However, besides these additives, other antioxidants, especially 3,5-di-tert-
It is not preferable to include a phenol-based additive such as butyl-4-hydroxytoluene (hereinafter referred to as BHT) or a phosphite-based additive because it may cause yellowing. That is, in the present invention, the additive (1),
It is important to use (2) and (3) alone or to mix and use two or more of them.

The backing material used in the present invention prevents the raw carpet material, that is, the yellowing of the surface material, and does not cause thermal deterioration of the backing material itself. Therefore, there is no problem of deterioration when molding with a processing machine such as an extruder. Does not occur. Therefore, the physical properties of the backed carpet are excellent. The material of the carpet raw material backing such a thermoplastic composition is not particularly limited, and natural fibers such as wool, cotton, and hemp, and polyolefins such as polypropylene, polyamides such as nylon, and polyesters such as polyethylene terephthalate. Synthetic fibers such as polyacrylate, polyvinylidene chloride, and the like, or a fiber material having a non-uniformity can be used. In particular, in the case of materials such as polyamide and polyester, the yellowing prevention effect of the present invention is remarkable. Generally, carpets
Weaving carpet, net carpet,
It is classified into a tufted carpet, a needle punched carpet and the like, and in the present invention, a tufted carpet and a needle punched carpet can be preferably used.
In addition, as a classification method for carpets, there are tile carpets and sound insulation carpets in which the type of backing material and thickness are carefully selected according to the purpose of use, along with ordinary indoor carpets. And a particularly improved sound-insulating carpet.

[0011] The thermoplastic composition of the present invention may be prepared by adding asphalts such as straight asphalt and blown asphalt, dimethyl phthalate, diisopropyl phthalate, dibutyl phthalate and phthalic acid to thermoplastic resin or natural or synthetic rubber, if necessary. Plasticizers such as phthalate or polyester such as dioctyl, calcium carbonate, magnesium carbonate, calcium sulfate, calcium silicate, clay, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, An inorganic filler such as silicon nitride, silica, carbon black and fly ash is blended.

The thermoplastic resin and synthetic rubber used in the present invention include EPR resins, polyvinyl chloride resins, polyvinylidene chloride resins, polycarbonate resins, polyester resins, polyamide resins, ABS resins and the like. , EPDM, SBS, SEBS, etc., but are not limited thereto. Among these, a thermoplastic composition containing a polyolefin-based resin is preferable, and further, a carboxylic acid group, a carboxylic ester group, an acid anhydride group, an epoxy group, a hydroxyl group,
A thermoplastic composition containing a polyolefin having a functional group such as an amino group, an alkenyl cyclic imino ether group, a polyfunctional group, a reactive silane group or a vinyl ester group can be preferably used. Examples of polyolefins having these functional groups include ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-ethyl methacrylate (E
And soft polyolefins such as EMA).

In the case of the tile carpet or the sound insulating carpet described above, which is a preferred embodiment of the carpet of the present invention, a plasticizer is often added because a large amount of an inorganic filler may be blended. For example, usually the amount of mineral filler is between polyolefin and asphalt 10
The amount is 50 to 200 parts by weight, and the amount of the plasticizer is 5 to 50 parts by weight based on 0 parts by weight.

As in this example, the plasticizer is present in the backing layer of the tile carpet or the sound insulating carpet,
When the carpet is left, evaporation of the plasticizer is observed, and the evaporation of the plasticizer promotes the yellowing of the raw material of the carpet. As a result, when the thermoplastic composition of the present invention is not used, the backing layer itself is substantially yellow. Even if the composition does not change, a phenomenon in which the raw carpet fabric turns yellow is observed. In other words, a satisfactorily carpet with less yellowing of the raw carpet fabric is not obtained simply by selecting a composition having less yellowing as the backing material. Further, when the above functional group-containing soft polyolefin is used, the functional group-containing soft polyolefin is used because it is easily decomposed at the time of high-temperature melting backing of the backing material, so that it is easily thermally degraded, and particularly, the carpet surface is easily yellowed. Thus, it can be understood that the yellowing prevention effect of the present invention can be particularly remarkably obtained by using the thermoplastic composition of the present invention.

The method for producing the yellowing-preventing carpet of the present invention is not particularly limited, and a normal carpet production method can be used. For example, soft polyolefin, additives and other compounds are charged and kneaded in an extruder, etc.
A method of extruding into a sheet shape, and pressing and laminating on a raw carpet at the time of heat melting can be used. The amount of the backing material, can be selected appropriately according to the purpose, is 0.8~1.5kg / m ² in 2.5~3.5kg / m ^2, sound insulation carpet in normally carpet tiles .

[0016]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples without departing from the gist of the present invention. (Carpet evaluation method) (1) Thermal degradation test: As a measure of thermal degradation when the thermoplastic composition as a backing material is melt-kneaded, the composition is subjected to Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) At 200 ° C, 4
Kneading was performed for 15 minutes under the condition of 0 rpm, and the degree of thermal deterioration was evaluated from the torque reduction rate (%). (2) NOx yellowing test: NOx 600 ppm in carpet
Was allowed to stand at room temperature for 24 hours in an air atmosphere containing, and the degree of yellowing of the white carpet surface was visually evaluated as follows. ◎ No yellowing is observed ○ Some yellowing is observed, but there is no practical problem x Clear yellowing

Example 1 A tufted carpet raw material comprising a polyester nonwoven fabric having a basis weight of 100 g / cm ² and a yarn material made of nylon yarn was added to an ethylene-vinyl acetate copolymer (vinyl acetate 2
8%, MFR value 10, hereinafter referred to as EVA) 40 parts by weight, octyl phthalate (hereinafter referred to as DOP) 10
Parts by weight, 50 parts by weight of calcium carbonate, and di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name: PEP-
36, manufactured by Asahi Denka Kogyo Co., Ltd.), kneaded in an extruder, and extruded to a thickness of 1.2 kg / m ² to obtain a thermoplastic composition sheet. Crimping with
Backed to make a carpet. The carpet thus obtained was subjected to thermal degradation and NOx of 600 pp.
The color stability under an air atmosphere containing m was measured.
It was shown to. The degree of thermal deterioration is small, and of course under normal atmosphere,
No yellowing is observed even under NOx atmosphere.

Example 2 Example 1 was repeated with the amount of the additive being 0.004 parts by weight, and the results are shown in Table 1. As in the case of Example 1, the degree of thermal deterioration is small, and yellowing is not observed under a normal atmosphere as well as a NOx atmosphere.

Example 3 The additive was 3,9-bis (1,1-dimethyl-2- (β-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl) -2,4,8,1
Example 1 was repeated, except that 0.02 part by weight of 0-tetraoxaspiro (5,5) undecane (trade name: AO-80, manufactured by Asahi Denka Kogyo KK) was used. The results are shown in Table 1. As in the case of Example 1, the degree of thermal deterioration is small, and yellowing is not observed under a normal atmosphere as well as a NOx atmosphere.

Example 4 Example 3 was repeated with the amount of the additive being 0.004 parts by weight, and the results are shown in Table 1. As in the case of Example 3, the degree of thermal deterioration is small, and yellowing is not observed under a normal atmosphere as well as a NOx atmosphere.

Example 5 The additive was 0.02 parts by weight of tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene diphosphonite (trade name: P-EPQ, manufactured by Asahi Denka Kogyo KK). Example 1 was repeated, and the results are shown in Table 1. As in the case of Example 1, the degree of thermal deterioration is small, and yellowing is not observed under a normal atmosphere as well as a NOx atmosphere.

Example 6 Example 5 was repeated with the amount of the additive being 0.004 parts by weight, and the results are shown in Table 1. As in the case of Example 5, the degree of thermal deterioration is small, and yellowing is not observed under a normal atmosphere as well as a NOx atmosphere.

Example 7 In addition to 0.02 parts by weight of PEP-36 (trade name, manufactured by Asahi Denka Kogyo KK) of Example 1 as an additive, AO-80 was added.
Example 1 was repeated by adding 0.02 parts by weight (trade name, manufactured by Asahi Denka Kogyo KK), and the results are shown in Table 1. As in the case of Example 1, the degree of thermal deterioration is small, and yellowing is not observed under a normal atmosphere as well as a NOx atmosphere.

Example 8 In addition to 0.02 parts by weight of PEP-36 (trade name, manufactured by Asahi Denka Kogyo KK) of Example 1 as an additive, P-EPQ was added.
Example 1 was repeated by adding 0.02 parts by weight (trade name, manufactured by Asahi Denka Kogyo KK), and the results are shown in Table 1. As in the case of Example 1, the degree of thermal deterioration is small, and yellowing is not observed under a normal atmosphere as well as a NOx atmosphere.

Comparative Example 1 Example 1 was repeated, except that the additive was changed to 0.02 parts by weight of the conventionally used BHT, and the stability was measured.
It was shown to. Although the degree of thermal deterioration was small, yellowing was observed under the NOx atmosphere.

Examples 9 to 16 Instead of EVA, an ethylene-ethyl acrylate copolymer (ethyl acrylate 20%, MFR value 14;
Examples 1 to 8 were repeated using EA), and the stability measurement results are shown in Table 2. Even in the case of EEA, the degree of thermal deterioration is small, and yellowing is not observed under a normal atmosphere as well as a NOx atmosphere.

Comparative Example 2 Example 9 was repeated, except that the additive was changed to 0.02 parts by weight of the conventionally used BHT, and the stability was measured.
It was shown to. Although the degree of thermal deterioration was small, yellowing was observed under the NOx atmosphere.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

According to the present invention, it is possible to obtain a carpet which has little heat deterioration and has excellent physical properties, and which does not cause yellowing of the raw carpet fabric even in a NOx atmosphere.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ identification code FI C09K 15/32 C08K 5/15 (58) Investigated field (Int.Cl. ⁷ , DB name) C09K 15/08 A47G 27/02 B60N 3/04 C08K 5/151 C08L 23/02 C09K 15/32 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] (1) A pentaerythritol diphosphite represented by the general formula (1) per 100 parts by weight of a functional group-containing soft polyolefin: (Wherein R 1 and R 2 are the same or different aryl groups) (2) 3,9-bis (1,1-dimethyl-2- (β- (3-t-butyl-4-hydroxy) represented by the formula 2 −
5-methylphenyl) propionyloxy) ethyl)-
2,4,8,10-tetraoxaspiro (5,5) undecane, (3) Tetrakis (2,4-di-t-) represented by Formula 3
Butyl phenyl) -4,4 biphenylene diphosphonite, One or more additives selected from the group consisting of 0.005
A carpet in which a carpet raw material is prevented from yellowing in a nitrogen oxide (NOx) atmosphere, characterized by backing a functional group-containing soft polyolefin composition containing 0.15 parts by weight and a plasticizer. 2. The carpet according to claim 1, wherein the carpet is a tile carpet or a sound insulating carpet. 3. The functional group-containing soft polyolefin composition comprises a carboxylic acid group, a carboxylic ester group, an acid anhydride group,
Including a polyolefin having at least one functional group in the molecule selected from the group consisting of an epoxy group, a hydroxyl group, an amino group, an alkenyl cyclic imino ether group, a polyfunctional group, a reactive silane group and a vinyl ester group. The carpet according to claim 1, wherein yellowing is prevented. 4. A carpet raw material containing, per 100 parts by weight of a functional group-containing soft polyolefin, (1) pentaerythritol diphosphite represented by the general formula (1): (Wherein R 1 and R 2 are the same or different aryl groups) (2) 3,9-bis (1,1-dimethyl-2- (β- (3-t-butyl-4-hydroxy) represented by the formula 2 −
5-methylphenyl) propionyloxy) ethyl)-
2,4,8,10-tetraoxaspiro (5,5) undecane, (3) Tetrakis (2,4-di-t-) represented by Formula 3
Butyl phenyl) -4,4 biphenylene diphosphonite, One or more additives selected from the group consisting of 0.005
A method for preventing yellowing of a raw carpet under a nitrogen oxide (NOx) atmosphere, characterized by backing a functional group-containing soft polyolefin composition containing 0.15 parts by weight and a plasticizer.