JPS6116701A - Elastic ski boots - 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 an elastic ski boot made of a nylon-based thermoplastic elastic resin.

(Prior Art) Conventionally, the upper outer skin and sole of ski boots have been made of polyurethane, ethylene-vinyl acetate copolymer resin (hereinafter referred to as E-vinyl acetate copolymer resin)
VA) type thermoplastic resins have been used, but they do not necessarily fully satisfy the properties required for this purpose. For example, it becomes brittle at low temperatures and may crack due to impact during use. EVA has extremely poor abrasion resistance and is said to be difficult to use over a long period of time.

Further, since the specific gravity of polyurethane is relatively high, the weight of the product becomes large, which is not preferable in terms of use. Furthermore, as a problem during molding, polyurethane and EVA require a long molding time, are susceptible to deterioration during molding, and are generally said to have poor yields when molding raw material resins into products.

(Problems to be Solved by the Invention) The present inventors have developed a ski shoe made of thermoplastic resin that has excellent low-temperature impact resistance, especially low-temperature impact resistance in the weld portion, abrasion resistance, low specific gravity, and good moldability. As a result of intensive research to develop polyamide resin, it has excellent abrasion resistance, is lightweight,
Moreover, it has been found that it is an extremely preferable material for ski shoes in terms of deterioration during molding and yield. However, ski shoes made of polyamide resin have poor low-temperature impact properties and cannot be used as ski boots.As a means to improve the low-temperature impact properties of polyamide resin, acid-modified olefin copolymers are blended. is known to do. However, when blending acid-modified olefin polymers, the fluidity during melt molding is poor, the low-temperature impact resistance of the weld part of the molded ski shoe is reduced, and flow marks and peeling of the gate part occur, resulting in molding. A problem arises in that the appearance of the product is deteriorated.

(Means for Solving the Problems) As a result of further research in order to obtain ski shoes made of polyamide resin without the above-mentioned drawbacks, the present inventors identified a polyamide resin, an acid-modified olefin copolymer, and a plasticizer. The present inventors have discovered that a polyamide resin composition formulated in a ratio of

That is, the present invention provides a ski shoe having an upper shell and/or sole made of a thermoplastic resin, wherein the resin is a polyamide resin (A) and an acid-modified olefin copolymer (B).
) and plasticizer (C), (Al/(Bl=4 a /6
0~9o/1o, (C)/((A)-+(B)
) to 1/100 to 20/100 in a weight ratio of polyamide resin compositions.

In the present invention, the polyamide resin used as one of the raw materials includes various well-known polyamide resins.

For example, dicarboxylic acids such as terephthalic acid, inphthalic acid, uric acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid and ethylenediamine, pentamethylenediamine, hexamethylenediamine, tecamethylenediamine, 1,4-cyclohexyl Polymerization and condensation of diamines such as diamine and m-xylylene diamine; Polymerization of cyclic lactams such as caprolactam and laurolactam; Polycondensation of aminocarboxylic acids such as aminoditenoic acid, aminononanoic acid and aminoundecanoic acid, or the above-mentioned cyclic lactams. It is obtained by copolymerization of dicarboxylic acid and diamine, etc., and includes 6 nylon, 66 nylon, 610 nylon, etc.
Examples include nylon, 612 nylon, 11 nylon, 12 nylon, 66/610 copolymer nylon, 6/66 copolymer nylon, and the like, and particularly preferred are 6 nylon, 66 nylon, 11 nylon, and 12 nylon.

Polyamide elastomers can also be mentioned as polyamide resins used in the present invention. Polyamide elastomer includes 6 nylon, 66 nylon, 11
It is a block copolymer having a hard segment made of a polyamide component such as nylon or 12-nylon, and a soft segment made of a polyester component and/or a polyether component.

As an example of polyamide elastomer, GRILAMID
FLY60 (manufactured by EMS CHEMIE, Switzerland),
Examples include PEBAX (manufactured by ATO, France).

In the present invention, regarding the acid-modified olefin copolymer added to improve the impact resistance of polyamide resin,
These include at least 50 mol%, preferably 80 mol% of 1-olefins, flHLt, ethylene, propylene,
Phthene-1, Isobutyne, Pentene-1, Hexene-1
1decene-1,4-methylbutene-1,4-methylpentene-1,4,4-dimethylpentene-1, vinylcyclohexane, styrene, α-methylstyrene, styrene substituted with lower alkyl substituents or similar It should be included. It is also possible to use mixtures of the abovementioned olefins. Copolymers obtained from ethylene and butene-1 or propylene are preferred, and commercially available products include, for example, Tafmer A4085 and Tafmer A4090.
, Tafmer A series such as Tafmer A20.090 [ethylene-butene-1 copolymer, manufactured by Mitsui Petrochemical Industries, Ltd.]
and TAFMER PO3 such as TAFMER PO280, TAFMER PO480, TAFMER P0680, TAFMER PO380, etc.
80 [ethylene-propylene copolymer, manufactured by Mitsui Petrochemical Industries, Ltd.].

The acid component can be obtained by direct copolymerization of an α,β-unsaturated carboxylic acid comonomer with the above-mentioned olefins, or by copolymerizing an α,β-unsaturated carboxylic acid or a functional derivative thereof, or a cis-type 2 It is introduced by a known method such as graft copolymerization of at least one compound selected from alicyclic carboxylic acids having a heavy bond in the ring or functional derivatives thereof.

Examples of α,β-unsaturated carboxylic acids or functional derivatives thereof include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid (anhydride), fumaric acid, and monoesters of the above carboxylic acids. . Suitable examples include acrylic acid, methacrylic acid and (anhydrous) maleic acid.

Examples of alicyclic carboxylic acids having a cis-type double bond in the ring include cis-4-cyclohexene-1,2-dicarboxylic acid, endo-bicyclo-C2,2,1]-5-hebutene-2 , 3-dicarboxylic acid, methyl-endo-cis-bicyclo-[: 2 , 2 , 1 ] -] 5-heptene-2,3-dicarboxylic acid, etc., and functional derivatives thereof include acid anhydrides, esters, Examples include acid amides.

Typical acid-modified olefin copolymers are illustrated below, but the invention is not limited thereto.

Ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-itaconic acid copolymer, ethylene-methyl maleate copolymer, ethylene-acrylic acid-
Methyl methacrylate copolymer, ethylene-methacrylic acid-ethyl acrylate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer, ethylene-acrylic acid-vinyl acetate copolymer, ethylene-acrylic acid-vinyl alcohol copolymer ethylene-methyl vinyl ether-acrylic acid copolymer, ethylene-propylene-acrylic acid copolymer, ethylene-styrene-acrylic acid copolymer, ethylene-methacrylic acid-acrylonitrile copolymer, ethylene-fumaric acid-methyl vinyl ether Copolymer, ethylene-vinyl chloride-acrylic acid copolymer, ethylene-vinylidene chloride-acrylic acid copolymer, ethylene-vinyl fluoride-methacrylic acid copolymer, ethylene-chlorotrifluoroethylene-methacrylic acid copolymer , chlorinated ethylene-methacrylic acid copolymer, ethylene-butene-1-
Methacrylic acid copolymer, ethylene-butene-1-(anhydrous) maleic acid copolymer, ethylene-propylene-(anhydrous) maleic acid copolymer, propylene-acrylic acid copolymer, butene-1-acrylic acid copolymer combination, ethylene-isobutylene-acrylic acid copolymer, 6-methylbutene-1
-acrylic acid copolymer, 4-methylpentene-1-methacrylic acid copolymer, 4,4'-dimethylpentene-1-
Acrylic acid copolymer, propylene-undecacrylic acid copolymer, propylene-α-methyl-styrene-(anhydride)maleic acid copolymer, propylene-butene-fumaric acid copolymer, ethylene-vinylcyclohexane-acrylic acid copolymer, chlorinated ethylene-acrylic acid copolymer, ethylene-butene-1-(anhydrous) endo-bicyclo-(2
,2,1) = 5-hebutene-2,6-dicarboxylic acid copolymer, ethylene-propylene-(anhydrous) endo-vinclaw [2,2゜1]-5-hebutene-2,3-dicarboxylic acid Copolymers and analogs, preferably ethylene-butene-1-(anhydride)maleic acid copolymers, ethylene-propylene-(anhydride)maleic acid copolymers, ethylene-butene-1-(anhydride)endo-bicyclo -[2,2,1]-5
-hebutene-2,3-dicarboxylic acid copolymer, ethylene-propylene-(anhydrous) endo-bicyclo-[2,2,
1:]-5-hebutene-2,3-dicarboxylic acid copolymer and the like.

It is important that such an acid-modified olefin copolymer contains a monomer having an acidic group in an amount of 0.01 to 20% by weight, preferably 0.05 to 10% by weight.

Note that the acid-modified olefin copolymer may also include a mixture of acid-modified polyethylene and unmodified olefin copolymer.

In the present invention, the plasticizers added to improve the fluidity of the polyamide resin include tricresyl phosphate, phosphoric acid (trisisopropylphenyl tributyl phosphate, triethyl phosphate, trioctyl phosphate, etc.)! Phosphate ester plasticizers such as Js (β-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tributoxyethyl phosphate, tris (β-chloropropyl) phosphate), )'J phenyl phosphate, octyldiphenyl phosphate, , polyester plasticizer, epoxy plasticizer, hydrophthalic anhydride plasticizer, butylbenzyl phthalate, dilauryl phthalate, diethyl phthalate,
Ester plasticizers such as dibutyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, diethyl phthalate, diisodecyl phthalate, dioctyl phthalate, dioctyl adipate, diindecyl adipate, di(butyl diglycol) adipate, di-2-ethylhexyl azelate, Stearic acid plasticizers, dioctyl sebacate, dibutyl sebacate, ester plasticizers such as acetyl tributyl citrate, acetyl triethyl citrate, di-2-ethylhexyl maleate, dibutyl maleate, tridilyte plasticizers, dibutyl fuma There are esters, plasticizers for rubber, chlorinated paraffin, etc.

Suitable plasticizers for nylon include aromatic sulfonamide compounds such as benzenesulfonic acid butylamide and benzoic acid ester plasticizers such as 2-ethylhexylbenzony Fs p-oxy 2-ethylhexylbenzoate. be able to.

In addition, when carrying out the present invention, other thermoplastic resins or elastomers, such as polyvinyl chloride, polyester, polyether polyester, urethanized polyester, ethylene-vinyl acetate copolymer, polyurethane, may be used without departing from the purpose of the present invention. , styrene elastomer, polybutadiene, vinyl chloride elastomer, acrylic poly(7-), ethylene-propylene copolymer, ethylene-butene-1 copolymer, etc. can also be used in combination. Also,
Addition of epoxy compounds is also possible.

In addition, in the present invention, inorganic and/or organic fillers, additives, and modifiers are not essential, but the physical properties can be improved by using the following fillers, additives, and modifiers as necessary. It can be measured. Suitable fillers include glass fibers, carbon fibers, metal fibers, aramid fibers, potassium titanate, asbestos, silicon carbide, ceramic fibers,
Fibrous reinforcement such as silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, nephelinsinite, Merck, atalpulgite, wollastonite, PMF .

Ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, zinc oxide,
Titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder,
Examples of reinforcing fillers include glass balloons, quartz, and quartz glass. In addition, a release agent, a coupling agent, a coloring agent, a lubricant, a heat-resistant stabilizer, a weather-resistant stabilizer, a foaming agent, a flame retardant, a flame retardant aid such as antimony trioxide, etc. may be added.

(Effects of the present invention) The essential components constituting the present invention are a polyamide resin, an acid-modified olefin copolymer, and a plasticizer.

In polyamide resin and acid-modified olefin copolymer,
If the acid-modified olefin copolymer is less than 10 parts, the low-temperature impact properties will be poor.If it exceeds 60 parts, the material itself will have good low-temperature impact properties, but the fluidity during melt molding will be poor. Second, the low-temperature impact resistance of the welt portion of the molded product deteriorates, and 70-marks and the like appear on the surface of the molded ski boot, which is unfavorable in terms of appearance.

In the present invention, 40 to 90 parts by weight of polyamide resin, preferably 50 to 80 parts by weight, and 60 parts by weight of acid-modified olefin copolymer are used.
~10 parts by weight, preferably 50-20 parts by weight, total 1
Since the plasticizer is present in 1 to 20 parts by weight, preferably 2 to 15 parts by weight, the material itself has good low-temperature impact resistance and fluidity, and the weld part of the molded product has good low-temperature impact resistance. A molded product with good quality and a good appearance can be obtained. Even if a plasticizer is added to a system containing more than 60 parts by weight of the acid-modified olefin copolymer, the fluidity will not be improved, and the low-temperature impact resistance and appearance of the weld portion will not be improved.

If the amount of plasticizer added is less than 1 part by weight, the effect of improving fluidity cannot be obtained, and if it exceeds 20 parts by weight, bleeding of the plasticizer will be significant and the surface will become dusty, which is not preferable.

(Examples) Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. All parts in the examples are parts by weight, and the test method used for evaluation was as follows.

(1) Flexural modulus Method according to ASTM D-790.

(2) Tensile strength, elongation A method based on JISK-6301.

(3) Izot impact strength Measured by notching a test piece in accordance with ASTM D-638.

(4) Fall impact test on the weld part of ski shoes - 20
The ski boots were left at ℃ for a day and night, and a 5-yen steel ball was dropped three times from a height of 1 m toward the weld area.

◎: No cracks in the weld part.

◎: Very good ○: Good ×: Poor (flow mark, gate part) Clear! 7
) (6) Plasticizer bleed After the molded product was left for one month under the conditions of 25"C and 65% R1, the state of plasticizer bleed was visually evaluated.

◎No nib reed ○: Slightly present ×: Severely present Example 1~? and Comparative Examples 1 to 7 GRILAMID L 20 as the polyamide resin
(12 nylon or GRIL manufactured by BMSCHEMIE)
ON A28 (same 6 nylon), GRILON T3
DDGM (66 Nylon Haril Sun BMNO (AT)
11 nylon manufactured by Company O), benzenesulfonic acid butylamide or 2-ethylhexyl benzoate as the plasticizer, and the following acid-modified copolymer [X] or [Y] as the acid-modified olefin copolymer. . The acid-modified copolymer (X) is an ethylene-propylene copolymer [Tafmer P-0280. Manufactured by Mitsui Petrochemical Industries ■ 1 in 100 parts
, 0.5 parts of 3-bis(tert-butylperoxypropyl)benzene and 1 part of maleic anhydride were uniformly mixed in a Henschel mixer, kneaded at 23D°C in an extruder, and pelletized. The acid-modified olefin copolymer [Y] was obtained in the same manner except that an ethylene-butene-1 copolymer [Tafmer A4090, manufactured by Mitsui Petrochemical Industries, Ltd.] was used as the raw material.

The above polymers and plasticizers were blended in the proportions shown in Table 1, mixed in a Henschel mixer, and kneaded at 180 to 260°C using a single screw extruder with a diameter of 50 to 260°C to form pellets.

Samples for physical property evaluation and ski shoes were made from the pellets using an injection molding machine. Table 1 shows the evaluation results.

Claims (1)

[Scope of Claims] 1. A ski shoe having an upper shell and/or sole made of a thermoplastic resin, the resin comprising a polyamide resin (A), an acid-modified olefin copolymer (B), and a plasticizer ( C
) and (A)/(B)=40/60 to 90/10, (
C)/{(A)+(B)}=1/100~20/100
An elastic ski shoe characterized by being made of a polyamide resin composition blended in a weight ratio of 2. Polyamide resin (A) is 6 nylon and/or 66
The elastic ski boot according to claim 1, characterized in that it is made of nylon. 3. Polyamide resin (A) is 12 nylon and/or 1
The elastic ski boot according to claim 1, characterized in that it is made of 1 nylon. 4. Polyamide resin (A) is 6 nylon and/or 66
1 to 99 parts by weight of nylon and 12 nylon and/or 11
The elastic ski boot according to claim 1, characterized in that it is made of 99 to 1 part by weight of nylon.