JPH08217933A - Resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin compsn. excellent in moisture-absorbing and -releasing properties at the surface, water-absorbing properties, prevention of dewing, and dyeability and suitable esp. for fibers by compounding a modified polyolefin with a natural org. powder. CONSTITUTION: This compsn. comprises 97-1wt.% modified polyolefin, 0-96wt.% thermoplastic resin, and 3-50wt.% natural org. powder. Examples of the modified polyolefin are a graft polymer and a copolymer. The graft polymer is obtd. by grafting a carboxylic acid, a metal carboxylate, a carboxylic ester, an acid anhydride, etc., onto a polyolefin. The copolymer is obtd. by copolymerizing ethylene with a free-radical-polymerizable acid anhydride, if necessary together with another free-radical-polymerizable monomer. Pref., the org. powder, esp. pref. a collagen powder, contains at least 85wt.% particles having particle sizes of 40μm or lower.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for producing a molded article which is excellent in surface absorption / desorption, water absorption, dew condensation prevention and dyeability.

[0002]

2. Description of the Related Art In recent years, polyvinyl chloride used for sheets such as vinyl chloride and artificial leather, non-woven fabrics, furniture, parts such as handles for automobiles, etc., and polyolefin-based flexible resins replacing them have been used for high-class products in recent years. Therefore, it has been demanded to impart unprecedented properties such as improved dyeability and moisture absorption / desorption to give a good touch. In particular, in recent years, development of a flexible material that can replace polyvinyl chloride has been required due to environmental hygiene problems, and at the same time, flexibility, dyeability, and high-quality hand feeling are also required.

As a method for satisfying such requirements, a method of improving the resin surface by kneading a leather powder with a polyvinyl chloride or polyolefin type thermoplastic resin (see, for example, JP-A-1-197599, Kaisho 62-24
No. 0400), a method for improving moisture absorption and desorption by kneading synthetic resin such as synthetic rubber or ethylene-vinyl acetate copolymer with gelatin or collagen (JP-A-62-252459). . However, since a resin composition of only a natural organic powder such as leather powder or collagen powder and a thermoplastic resin does not have sufficient moisture absorption / release properties, it is necessary to add a large amount of the natural organic powder. Therefore, a molded product of stable quality could not be obtained, and it was particularly difficult to mold into a fibrous material.

[0004]

DISCLOSURE OF THE INVENTION The present invention improves the moisture absorption and desorption by uniformly dispersing a natural product organic powder in a thermoplastic resin, and has a good property with a dry and warm feeling, and An object of the present invention is to provide a resin composition which is excellent in dyeability and is particularly suitable for fibrous materials.

[0005]

Means for Solving the Problems As a result of various studies for solving the above problems, the present inventors have found that a resin composition comprising a modified polyolefin and an organic powder of a natural product has a surface absorbing / releasing property, a water absorbing property and a dew condensation property. The inventors have found that they are excellent in prevention properties and dyeability and are particularly suitable for fibers, and have completed the present invention.

That is, the above-mentioned problem is caused by a resin composition comprising (A) 97 to 1% by weight of modified polyolefin, (B) 0 to 96% by weight of thermoplastic resin, and (C) 3 to 50% by weight of natural product organic powder. Can be resolved. Hereinafter, the present invention will be described in detail.

The modified polyolefin (A) includes a graft polymer and a copolymer. The graft polymer is a polymer obtained by graft-polymerizing a carboxylic acid group, a metal carboxylate group, a carboxylic acid ester group, an acid anhydride group and the like onto a polyolefin. As the carboxylic acid group, an acetic acid group, an acrylic acid group, a methacrylic acid group, a fumaric acid group, an itaconic acid group, and the like, and as a carboxylic acid metal base, a sodium salt, a calcium salt, a magnesium salt, a zinc salt, and the like, as a carboxylic acid ester group. Is a methyl ester group, an ethyl ester group,
Examples of the acid anhydride group such as a propyl ester group, a butyl ester group, and a vinyl ester group may include a maleic anhydride group. Here, the polyolefin is a homopolymer or copolymer of ethylene or an α-olefin having 1 to 20 carbon atoms, such as polyethylene, polypropylene,
Poly 4-methyl pentene-1 etc. can be illustrated.

The copolymer is a copolymer of ethylene and a radical-polymerizable acid anhydride or a copolymer of a radical-polymerizable comonomer.

Here, the radical-polymerizable acid anhydride has at least one radical-polymerizable unsaturated bond and one acid anhydride group in the molecule, and the acid anhydride group is introduced into the polymer chain by polymerization. Refers to such compounds. Examples of such compounds include maleic anhydride, itaconic anhydride, endic anhydride, citraconic anhydride, 1-butene-3,4-
Dicarboxylic acid anhydride, succinic anhydride having 18 or less carbon atoms and substituted with an alkenyl group having a terminal double bond, anhydrous carboxylic acid having 18 or less carbon atoms and substituted with an alkenedienyl group having a terminal double bond Examples thereof include succinic acid, and maleic anhydride and itaconic anhydride are particularly preferable. Two or more radically polymerizable acid anhydrides may be used at the same time.

The radical-polymerizable comonomer is an ethylenically unsaturated compound, and examples thereof include ethylenically unsaturated ester, ethylenically unsaturated amide, ethylenically unsaturated carboxylic acid, and ethylenically unsaturated ether compound. it can.

Ethylenically unsaturated ester compounds include vinyl acetate, methyl (meth) acrylate, (meth)
Examples thereof include propyl acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, and benzyl (meth) acrylate. Examples of the ethylenically unsaturated amide compound include (meth) acrylamide and N-
Methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide,
N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N,
N-diethyl (meth) acrylamide etc. can be illustrated. Examples of the ethylenically unsaturated compound include (meth) acrylic acid, fumaric acid, maleic acid, crotonic acid, itaconic acid and the like. Examples of the ethylenically unsaturated ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether and the like. Further, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, acrolein, trimethoxyvinylsilane, triethoxyvinylsilane, vinyl chloride, vinylidene chloride and the like are also included.

Of these, (meth) acrylic acid esters and vinyl acetate are preferable, and (meth) acrylic acid ester is particularly preferable. Two or more radically polymerizable comonomers may be used at the same time.

The thermoplastic resin (B) generally has a melting point of 2
30 ° C or lower, preferably 200 ° C or lower, 60 to 1
60 ° C. is particularly preferred. As the thermoplastic resin satisfying this condition, polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, ethylene / hexene copolymer, a copolymer containing a small amount of diene therein, and 1,4-butanediol / Examples thereof include polyesters such as succinic acid copolymer, 1,4-butanediol / adipic acid copolymer, ethylene glycol / succinic acid copolymer, and 1,4-cyclohexanedimethanol / adipic acid copolymer. Two or more types of thermoplastic resins may be used.

(C) As the natural product organic powder, leather powder (waste) generally obtained by crushing animal tissue containing a large amount of collagen such as the skin of pigs, cows, etc., and further purified collagen powder Examples thereof include silk powder obtained by crushing silk thread, chitin obtained by purifying and crushing shells of crustaceans such as chaff, crab, and shrimp, and chitosan powder, and collagen powder is particularly preferable.

In order to make the surface of the fiber smooth, to give a texture, and to obtain a dyeing property without spots, the particle diameter of the natural product organic powder is 4
The content of particles having a size of 0 μm or less is preferably 85% by weight or more. If it is less than 85% by weight, the spinnability and stretchability of the resulting resin composition when molded into a fibrous material may be deteriorated, and the uniformity of dyeing may be lost.

The water absorption is preferably as high as possible in order to improve the water absorption and release properties, but if it exceeds 300% by weight, the volume of the powder increases unnecessarily due to water absorption and the strength of the fiber decreases, which is not practical.

The apparent bulk density is preferably as small as possible in order to increase the moisture absorption / desorption rate, but 0.03 to 0.3 g / cc is preferable. If it is less than 0.03 g / cc, dust is likely to reach and it is difficult to uniformly disperse it in the resin. Further, if it exceeds 0.3 g / cc, the moisture absorption / desorption rate is remarkably reduced, which is not preferable.

The component (A) in the resin composition is 97-1% by weight, preferably 70-5% by weight, particularly preferably 50-10% by weight. If it is less than 1% by weight, the particles of the natural product organic powder are not sufficiently dispersed, and a resin composition having good spinnability cannot be obtained.

The thermoplastic resin in the resin composition is 0 to 96% by weight. That is, the thermoplastic resin may be omitted,
It has a function of diluting the modified polyolefin and the natural product organic powder. The content of the natural product organic powder in the resin composition is 3 to 50% by weight, preferably 7 to 30% by weight, and more preferably 10 to 20% by weight. When the content of the natural product organic powder is less than 3% by weight, the resulting fiber does not have sufficient moisture absorption / release properties and dyeability, and when it exceeds 50% by weight, it is not uniformly dispersed in the resin composition, and thus the spinnability is deteriorated. Not only that, the strength of the obtained fiber is not sufficient.

The resin composition of the present invention comprises the above (A),
Although the main components are the three components (B) and (C), other additives may be added if necessary so long as the characteristics of the above components are not impaired. As additives, dyes, pigments, fillers, nucleating agents, fibrous materials, plasticizers, lubricants, release agents,
Coupling agent, foaming agent, heat resistance agent, heat resistance agent, flame retardant,
Examples include antistatic agents.

The resin composition of the present invention is prepared by mixing the respective components and then kneading them. As a method therefor, a conventionally known melt kneading method can be used. The mixing is performed using a ribbon mixer, a Henschel mixer, or the like, and as a kneader, a single-screw or twin-screw extruder or a Banbury mixer is generally used. If the kneading capacity of a molding machine such as a fiber molding machine is sufficient, dry blending may be used. The order of compounding is not particularly limited, and the components may be compounded sequentially or simultaneously.

The temperature at the time of melt-kneading may be selected at a temperature at which the components (A) and (B) are sufficiently melted and the components are not decomposed, depending on the components, blending, etc.
0 to 250 ° C, preferably 150 to 200 ° C, 1
60-190 degreeC is especially preferable. If the temperature is lower than 120 ° C., the natural product organic powder is not sufficiently dispersed, and when used for fibers, the spinnability is significantly reduced. If the temperature exceeds 250 ° C., the natural product organic powder is thermally deteriorated, and not only the obtained resin composition for fibers is colored but also the moisture absorbing / releasing property and the dyeability are significantly deteriorated.

The resin composition of the present invention can be manufactured into various molded articles by injection molding, extrusion molding, blow molding and the like. Among them, it can be suitably used for extrusion molding of multifilaments, monofilaments and the like. Multifilament or monofilament is a bag base fabric, belt,
It can be processed into clothing and used as staples for spun yarn. INDUSTRIAL APPLICABILITY The resin composition of the present invention is used as a material that does not exist in conventional polyolefins, such as interior materials for houses, automobiles, vehicles, etc., as well as fiber materials that are required to have fashionability and high moisture absorption and desorption properties such as sports goods. To be done.

In the case of multifilament molding, the resin composition is discharged from a multifilament nozzle by an extruder, cooled and solidified in a cooling duct, a sizing agent is applied by an oiling roller, and the resin composition is wound on a roll. The extrusion temperature is preferably as high as possible within the range where the resin composition does not deteriorate and the aggregate of filaments can be molded and processed. For example, when polypropylene is used as the component (C), it is preferably 200 to 230 ° C. The undrawn yarn that has been wound up is drawn and strengthened. At this time, once wound on a bobbin and then stretched in another step,
There is a method of drawing directly after being wound up.

In the case of monofilament molding, the resin composition is extruded from a monofilament nozzle by an extruder and cooled and solidified in a cooling water tank. The extrusion temperature is preferably as high as possible within the range where the resin composition is not deteriorated and the filament assembly can be molded. For example (C)
When high density polyethylene is used as a component,
230 ° C is preferred. The cooled unstretched monofilament is stretched and strengthened. For the stretching, methods such as wet stretching, steam stretching, hot plate stretching, and heating rolls are used, and multistage stretching can also be performed by any combination of these.

[0026]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, each physical-property value of an Example and a comparative example was measured by the following method.

(1) Dispersion Degree of Collagen and Resin Melting and kneading with an extruder at a predetermined temperature, and the extruded strand was visually evaluated for its dispersion state in the following four stages. A: Very evenly dispersed. B: Evenly dispersed. C: Some dispersion. D: It is separated without being mixed at all.

(2) Spinnability during melt-spinning Melt-spinning was carried out at a predetermined temperature, and the maximum speed at which stable winding could be performed for a long time was determined. Then, the spinnability was evaluated by the "maximum draft ratio", which is the ratio of the linear velocity of the melt extruded from the nozzle to the winding speed at that time.

[Equation 1]

(3) Moisture Absorption / Desorption Property A sample (knitted into about 10 cm × 15 cm) was previously dried at 80 ° C. overnight, and then transferred to a 35 ° C. 90% RH environment for 2 hours to increase the amount of weight increase. Was measured (hygroscopicity test). Then, it was immediately transferred to an environment of 35 ° C. and 35% RH, and the amount of weight loss with time was measured for up to 1 hour (moisture release test). Then, the moisture absorption rate after 2 hours and the moisture release rate after 1 hour were calculated and evaluated by the formulas shown below.

[Equation 2]

(Equation 3)

(4) Dyeability test As a dye, KNH Red RS12 manufactured by Nippon Kayaku Co., Ltd.
Sample No. 5 was diluted with water to a dye concentration of 1%, the sample was immersed in a boiled dye solution for 2 hours and then pulled up, and the dyeing level was visually evaluated in four levels. A: It is dyed very well. B: It is dyed well. C: It is dyed. D: Not dyed at all.

Example 1 As the component (A), the melt flow rate (measured by JIS K6760) was 10 g /
10 minutes ethylene and ethylene-ethyl acrylate-maleic anhydride terpolymer (ethylene copolymer)
4.5 kg, the melt flow rate (measured according to JIS K6758) as the component (B) is 28 g / 10 minutes,
85.5 kg of ethylene copolymerized polypropylene having an ethylene content of 6.8% by weight, and the content of particles having an average particle diameter of 8 μm and 40 μm or less as component (C) of 9
10 kg of 0% or more collagen powder (trade name: Triazet CX260-1 manufactured by Showa Denko KK) was placed in a tumbler, mixed for 10 minutes, and then melt-kneaded at 170 ° C. by a 30 mmφ bidirectional extruder to pelletize. To obtain a resin composition.

This resin composition was extruded at 170 ° C. by a 40 mmφ multifilament production apparatus equipped with 68 nozzles of 0.6 mmφ and the strand discharged from the nozzle was cooled by cold air of 10 ° C. and then wound up. The roll was wound up. Then, in a separate step, it was guided to a hot roll of 80 ° C. and stretched 5 times with the next hot roll. As a result, the spinnability was excellent, and the fibers obtained were as shown in Table 1.
As shown in, the dispersibility of the organic powder and the resin is very good,
It was excellent in hygroscopicity, moisture release and dyeability, and had a high-quality feel with a leather-like texture.

Example 2 (A) Modified polyolefin,
A resin composition was produced in the same manner as in Example 1 except that the weights of the (B) thermoplastic resin and (C) collagen, which was a natural organic powder, were changed to obtain fibers. The results are shown in Table 1.

(Example 3) As the component (C), collagen particles (trade name: Triazet CX280-1 manufactured by Showa Denko KK) having a content of particles having an average particle size of 20 μm and 40 μm or less of 85% or more are used. A resin composition was produced in the same manner as in Example 1 except that the weights of the thermoplastic resin (B) and the collagen (C) natural organic powder were changed, and fibers were obtained. The results are shown in Table 1.

Example 4 As the component (B), the melt flow rate (measured by JIS K6760) was 20 g /
A resin composition was produced in the same manner as in Example 1 except that high density polyethylene having a density of 0.96 g / cm ³ for 10 minutes was used to obtain fibers. The results are shown in Table 1.

(Example 5) As the component (B), the melt flow rate (measured by JIS K6758) is 800 g.
Except that low viscosity polypropylene, which is / 10 minutes, was used.
A resin composition was produced in the same manner as in Example 1 to obtain fibers. The results are shown in Table 1.

(Example 6) As the component (B), the melt flow rate (measured by JIS K7210) was 10 g.
A resin composition was produced in the same manner as in Example 1 except that a 1-4-butanediol / succinic acid copolymer aliphatic polyester of / 10 minutes was used to obtain fibers. The results are shown in Table 1.

(Example 7) A resin composition was prepared in the same manner as in Example 1 except that a modified polyethylene (ethylene graft copolymer) added with 0.30% by weight of maleic anhydride was used as the component (A). The thing was manufactured and the fiber was obtained. The results are shown in Table 1.

Comparative Example 1 A resin composition was produced in the same manner as in Example 1 except that the weights of the components (A), (B) and (C) were changed, and an attempt was made to form fibers. However, the dispersibility of collagen and resin was poor and spinning was impossible.

Comparative Example 2 As the component (B), the melt flow rate (measured according to JIS K6758) was 14 g.
Except that a propylene homopolymer of / 10 minutes was used.
In Example 1, a resin composition was produced by a method not using the component (A), and an attempt was made to form a fiber, but the dispersibility of collagen and resin was poor and spinning was impossible.

(Comparative Example 3) A resin composition was prepared in the same manner as in Example 1 except that collagen powder was not added as the component (C), and fibers were obtained.
The dyeability was poor.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

As described above, the resin composition of the present invention is
Since the natural product organic powder is well dispersed, the fibers obtained after spinning can be provided with the functions of excellent surface absorption / desorption, water absorption, dew condensation prevention and dyeability. As a material not found in conventional polyolefins, it is used for interior materials such as houses, automobiles, and vehicles, as well as for textile materials such as sports equipment, which are required to have fashionability and high moisture absorption and desorption.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Ken Uekura, 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Sho, Kawasaki Plastics Research Laboratory (72) Mina Saito 5 Ogimachi, Kawasaki-ku, Kawasaki-shi, Kanagawa No. 1 Showa Denko Chemicals Laboratory

Claims (4)

[Claims] 1. A resin composition comprising (A) 97 to 1% by weight of a modified polyolefin, (B) 0 to 96% by weight of a thermoplastic resin, and (C) 3 to 50% by weight of a natural product organic powder. 2. The resin composition according to claim 1, wherein the content of the particles of the natural product organic powder having a particle diameter of 40 μm or less is 85% by weight or more. 3. The natural product organic powder is collagen powder or leather powder, as claimed in claim 1 or claim 2.
The resin composition according to. 4. The resin composition according to claim 1, which is for fiber molding.