JP2009144102A - Shoes using thermoplastic elastomer composition - Google Patents

Abstract

[PROBLEMS] To provide a shoe excellent in moldability, oil resistance and slip resistance, and excellent in gloss and wear resistance.
(A) 100 parts by weight of a block copolymer having a crystalline ethylene block and an amorphous ethylene / α-olefin block;
(B) 5-60 parts by weight of a polypropylene resin having a melt flow rate (ASTM D-1238, 230 ° C., 2.16 kg load) of 700-1500 g / 10 min, and (c) a softener for non-aromatic rubber 50 to 180 parts by weight, and the component (a) is a mixture of a block copolymer (a1) having a cross-type molecular structure and a block copolymer (a2) having a linear-type molecular structure, A shoe having an upper portion made of a thermoplastic elastomer composition (A) having a weight ratio of a1) to (a2) of 95: 5 to 70:30.
[Selection] Figure 1

Description

  The present invention relates to a boot such as a boot made of a thermoplastic elastomer composition. In particular, the present invention relates to a shoe that has excellent moldability, oil resistance, and slip resistance, as well as excellent gloss and wear resistance.

  In recent years, synthetic rubber that requires a vulcanization process, or soft polyvinyl chloride (PVC) that does not require a vulcanization process, as a rubber-like material for footwear such as boots, injection molding processability, scratch resistance, It has been used extensively because of its excellent texture (comfort). However, the demand for thermoplastic elastomer (TPE) materials is increasing from the market in order to cope with recent environmental problems.

  The thermoplastic elastomers often requested by the market include styrene thermoplastic elastomer (SBC), olefin thermoplastic elastomer (TPO), urethane thermoplastic elastomer (TPU), polyester thermoplastic elastomer (TPEE), and polyamide. Examples thereof include thermoplastic elastomer (TPAE) and 1,2-polybutadiene-based thermoplastic elastomer.

  Among these, styrene-based thermoplastic elastomer (SBC) is particularly rich in flexibility and excellent in mechanical strength, etc., but has a double bond as a conjugated diene in its molecule. There are problems with heat resistance, weather resistance and oil resistance. In the styrenic thermoplastic elastomer, an elastomer obtained by hydrogenating an intramolecular double bond of a block copolymer of styrene and a conjugated diene is widely used as an elastomer having improved heat aging resistance (thermal stability) and weather resistance. Although it is used, since the Shore A hardness is 40 or more, it is softened by increasing the amount of the softening agent. In such a case, the surface of the molded product may become sticky or under heating stress In this case, the softening agent bleeds out, and the texture becomes harsh and unsuitable for boots.

  In addition, when a boot is formed by injection molding, when a thermoplastic elastomer is introduced into the mold from an injection runner at the sole (shoe bottom), generally, the resin in the mold is bent at the front to the trunk of the boot. The boots obtained at a low speed had a problem that the balance between hardness and flexibility was partially deteriorated.

  Then, the composition which mix | blended the high fluidity polypropylene resin, the softener for non-aromatic rubbers, and the hydrogenated petroleum resin with the styrene-type thermoplastic elastomer is known (for example, patent document 1). Boots molded from this composition have improved comfort and excellent wear resistance, but have insufficient gloss.

  Further, there is known a thermoplastic elastomer composition in which a polypropylene resin is blended with CEBC (block copolymer having a crystalline ethylene block and an amorphous ethylene / butene block) which is an olefinic thermoplastic elastomer (for example, Patent Document 2). Boots molded from this composition have improved gloss but are not sufficiently abrasion resistant.

Also, shoes made of thermoplastic elastomers, that is, rubber-like materials, need to have a good appearance in addition to requiring sufficient strength (for example, wear resistance) to withstand long-term use. What is excellent in gloss, in particular, in the part (upper part) above the shoe sole part (sole part), is excellent in gloss.
JP 2002-317096 A Japanese Patent Laying-Open No. 2005-248077

  An object of the present invention is to provide a shoe which improves the above-mentioned drawbacks and is excellent in moldability, oil resistance and slip resistance, and excellent in gloss and wear resistance.

  As a result of intensive studies to achieve the above object, the inventors of the present invention are excellent in gloss, moldability and durability of the upper part by constituting the upper part with a specific olefinic thermoplastic elastomer composition. I found that I could get shoes. Further, it has been found that a shoe having the above-described upper portion and a sole portion made of a specific styrene-based thermoplastic elastomer composition can further improve the abrasion resistance and slip resistance of the sole portion. .

That is, the present invention
(A) 100 parts by weight of a block copolymer having a crystalline ethylene block and an amorphous ethylene / α-olefin block,
(B) 5-60 parts by weight of a polypropylene resin having a melt flow rate (ASTM D-1238, 230 ° C., 2.16 kg load) of 700-1500 g / 10 min, and (c) a softener for non-aromatic rubber 50 to 180 parts by weight, and the component (a) is a mixture of a block copolymer (a1) having a cross-type molecular structure and a block copolymer (a2) having a linear-type molecular structure, Provided is a shoe having an upper part composed of a thermoplastic elastomer composition (A) in which the weight ratio of a1) and (a2) is 95: 5 to 70:30.

Further, the present invention provides a shoe having the above upper part,
(D) a block copolymer comprising at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound and / or hydrogenating the block copolymer. 100 parts by weight of a hydrogenated block copolymer obtained by
(E) 5 to 50 parts by weight of a polypropylene resin,
(C) Non-aromatic rubber softener 50 to 250 parts by weight, and (f) a hydrogenated petroleum resin 1 to 50 parts by weight A shoe having a sole part composed of a thermoplastic elastomer composition (B). provide.

  The present invention also provides a method for producing the above shoe, wherein the upper part is injection molded using the composition (A) and then the sole part is injection molded using the composition (B). .

  The shoe of the present invention is excellent in moldability, oil resistance, and slip resistance, and is excellent in gloss and wear resistance.

  The present invention is described in detail below. In the present specification, “shoe” includes boots and boots. The “sole part” means a shoe sole part, and the “upper part” means a part of the shoe above the shoe sole, that is, the upper part and the trunk part. FIG. 1 is a perspective view of a boot, wherein 1 indicates a sole portion and 2 indicates an upper portion.

1. Components of the thermoplastic elastomer composition (A) constituting the upper part
Ingredient (a)
Component (a) is a block copolymer having a crystalline ethylene block and an amorphous ethylene / α-olefin block. The crystalline ethylene block is obtained by hydrogenating a block copolymer of butadiene. Examples of the α-olefin include butene, octene, hexene and the like. Of these, butene is preferred. As the block copolymer, CEBC (a block copolymer having a crystalline ethylene block and an amorphous ethylene / butene block) is preferable. Using CEBC results in a more glossy product.

  The block copolymer includes a cross-type molecular structure and a linear type. In the present invention, the component (a) is a mixture of a cloth type (a1) and a linear type (a2). By being a mixture, both tensile strength and moldability (fluidity) can be achieved. In the cross type and the linear type, the α-olefins may be the same or different. Further, each of the cross type and the linear type may be two or more. The mixing ratio (weight ratio) of the cloth type (a1) and the linear type (a2) is 95: 5 to 70:30, preferably 95: 5 to 77:23. If the proportion of the cross mold (a1) is less than the above blending ratio, the moldability (fluidity) is poor. On the other hand, if the blending ratio is higher than the above, the tensile strength and tear strength are inferior, and due to insufficient strength, cracks are generated and the durability is adversely affected.

  The cloth type (a1) preferably contains 50 to 60% by weight of α-olefin and 50 to 40% by weight of ethylene. Moreover, it is preferable that a weight average molecular weight is 320,000-350,000. The linear type (a2) preferably contains 30 to 50% by weight of α-olefin and 70 to 50% by weight of ethylene. The weight average molecular weight is preferably 280,000 to 300,000. As an example of the product of the cross type (a1), Dynalon 6201B (CEBC) manufactured by JSR Corporation may be mentioned. As an example of a product of the linear type (a2), Dynalon 6100B (CEBC) manufactured by JSR Corporation may be mentioned.

Ingredient (b)
Component (b) is a polypropylene resin having a melt flow rate (MFR, ASTM D-1238, L condition, 230 ° C., 2.16 kg load) of 700 to 1500 g / 10 min. This improves the fluidity of the resulting composition, improves the moldability, and has an effect of adjusting the hardness. Such components include, for example, random and block copolymers of isotactic polypropylene and propylene with other α-olefins such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. A polymer can be mentioned.

  Component (b) has an MFR of 700 to 1500 g / 10 min, preferably 750 to 1300 g / 10 min. If the MFR is less than 700 g / 10 minutes, it is difficult to mold shoes with the resulting composition, and if it exceeds 1500 g / 10 minutes, it is difficult to produce composition pellets.

  The compounding quantity of a component (b) is 5-60 weight part with respect to 100 weight part of component (a), Preferably it is 10-40 weight part. Below the above lower limit, the upper part is inferior in gloss and inferior in durability (deforms and wears). When the above upper limit is exceeded, the moldability is inferior (deformation occurs at the time of mold release), and the oil resistance, texture and comfort of the resulting shoe are also inferior.

Ingredient (c)
Component (c) is a non-aromatic rubber softener and contributes to controlling the flexibility of the resulting upper part and improving the comfort.
Examples of component (c) include non-aromatic mineral oils or liquid or low molecular weight synthetic softeners. The mineral oil softener used for rubber is a mixture of the aromatic ring, naphthene ring, and paraffin chain, and the paraffin chain carbon number accounts for 50% or more of the total carbon number. A naphthene ring having 30 to 40% carbon atoms is called naphthene, and a naphthene ring having 30% or more aromatic carbon is called aromatic.

  The mineral oil-based rubber softeners used as the component (c) of the present invention are those of the above paraffinic and naphthenic types. Aromatic softeners are not preferred because the component (a) becomes soluble due to their use, and the physical properties of the resulting composition cannot be improved. The component (c) of the present invention is preferably a paraffin-based one, and a paraffin-based one having a small aromatic ring component is particularly suitable. Examples of the liquid or low molecular weight synthetic softener include polybutene, hydrogenated polybutene, and low molecular weight polyisobutylene.

  These non-aromatic rubber softeners have a dynamic viscosity of 20 to 50000 cSt at 37.8 ° C, a dynamic viscosity of 5 to 1500 cSt at 100 ° C, a pour point of -10 to -15 ° C, and a flash point. It is preferable that (COC) shows 170-300 degreeC. Furthermore, a thing with a weight average molecular weight of 100-2,000 is preferable.

  The compounding quantity of a component (c) is 50-180 weight part with respect to 100 weight part of component (a), Preferably it is 80-130 weight part. If it is less than the above lower limit, it is difficult to control the flexibility, the moldability is deteriorated and the oil resistance is also inferior. If the above upper limit is exceeded, blocking is likely to occur during the production of the composition pellets, and the softening agent tends to bleed out from the obtained upper part, resulting in a decrease in texture, a decrease in strength, a decrease in durability (cracks), and stickiness. Arise. Stickiness causes undesired adhesion of dirt.

  In addition to the components (a) to (c), the composition (A) constituting the upper part may further include various anti-blocking agents, sealability improvers, heat stabilizers, and antioxidants as necessary. , Light stabilizers, ultraviolet absorbers, lubricants, crystal nucleating agents, antibacterial agents, colorants and the like.

2. Component of thermoplastic elastomer composition (B) constituting sole part
Ingredient (d)
Component (d) is a block copolymer comprising at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound and / or Hydrogenated block copolymer component, for example, an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as ABA, BABA, ABBABA, etc. Examples thereof include polymers and / or hydrogenated products thereof.

  The above (hydrogenated) block copolymer (hereinafter, (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer) is an aromatic vinyl. The compound is contained in an amount of 5 to 60% by weight, preferably 20 to 50% by weight.

  The polymer block A mainly composed of an aromatic vinyl compound is preferably composed of only an aromatic vinyl compound, or 50% by weight or more, preferably 70% by weight or more (hydrogenated) conjugated diene compound. (Hereinafter, the (hydrogenated) conjugated diene compound means a conjugated diene compound and / or a hydrogenated conjugated diene compound) and a copolymer block.

  The polymer block B mainly composed of (hydrogenated) conjugated diene compound is preferably composed of only (hydrogenated) conjugated diene compound or (hydrogenated) conjugated diene compound of 50% by weight or more, preferably 70% by weight. This is a copolymer block of the above and an aromatic vinyl compound.

  The number average molecular weight of the block copolymer is preferably in the range of 5,000 to 1,500,000, more preferably 10,000 to 550,000, still more preferably 50,000 to 400,000. Distribution is 10 or less. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

  Further, in the polymer block A mainly composed of these aromatic vinyl compounds and the polymer block B mainly composed of conjugated diene compounds, the distribution of units derived from the conjugated diene compound or aromatic vinyl compound in the molecular chain is random, It may be tapered (in which the monomer component increases or decreases along the molecular chain), partially in a block form, or any combination thereof. When there are two or more polymer blocks A mainly composed of aromatic vinyl compounds or polymer blocks B mainly composed of conjugated diene compounds, each polymer block has a different structure even if each has the same structure. There may be.

  As the aromatic vinyl compound constituting the block copolymer, for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. preferable. In addition, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and These combinations are preferred.

  Specific examples of the block copolymer include styrene-butadiene-styrene copolymer (SBS) and styrene-isoprene-styrene copolymer (SIS).

  The hydrogenated block copolymer is a hydrogenated product of the above block copolymer, and includes at least two polymer blocks A mainly composed of an aromatic vinyl compound and a polymer block B mainly composed of a conjugated diene compound. It is a hydrogenated block copolymer comprising at least one block copolymer.

  In the block copolymer hydrogenated polymer block B mainly composed of a conjugated diene compound, the microstructure is arbitrary and the hydrogenation rate is arbitrary, but preferably 50% or more, more Preferably it is 55% or more, More preferably, it is 60% or more. For example, in the polybutadiene block, the 1,2-microstructure is preferably 20 to 50% by weight, particularly preferably 25 to 45% by weight. Moreover, the thing which hydrogenated the 1, 2- bond selectively may be sufficient. In the polyisoprene block, preferably 70 to 100% by weight of isoprene has a 1,4-microstructure, and at least 90% of the aliphatic double bonds derived from isoprene are hydrogenated.

  When using a hydrogenated block copolymer depending on the purpose, the above hydrogenated product can be suitably used according to the intended use.

  Specific examples of the hydrogenated block copolymer include styrene-ethylene / butene / styrene copolymer (SEBS), styrene / ethylene / propylene / styrene copolymer (SEPS), and styrene / ethylene / ethylene / propylene / styrene copolymer. Examples thereof include a polymer (SEEPS) and a styrene-butadiene-butylene-styrene copolymer (partially hydrogenated styrene-butadiene-styrene copolymer, SBBS).

  Many methods have been proposed as a method for producing these block copolymers or hydrogenated block copolymers. Typical methods include, for example, the method described in Japanese Patent Publication No. 40-23798, It can be obtained by block polymerization in an inert medium using a lithium catalyst or Ziegler type catalyst, and the hydrogenated block copolymer can be obtained by hydrogenating the block copolymer by a known method.

Ingredient (e)
The component (e) is a polypropylene resin. This improves the fluidity of the resulting composition, improves the moldability, and has an effect of adjusting the hardness. Such components include, for example, random and block copolymers of isotactic polypropylene and propylene with other α-olefins such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. A polymer can be mentioned.

  In addition, the component (e) is not particularly limited in melt flow rate (MFR, ASTM D-1238, L condition, 230 ° C., 2.16 kg load), preferably 40 to 1500 g / 10 minutes, more preferably 45 to 45%. 1300 g / 10 min.

  The amount of component (e) is 5 to 50 parts by weight, preferably 10 to 45 parts by weight, per 100 parts by weight of component (d). If it is less than the above lower limit, the fluidity is inferior and the moldability is poor, and the compatibility with the component (d) becomes insufficient, so the tensile strength, wear resistance, and durability are also deteriorated. When the above upper limit is exceeded, the wear resistance deteriorates due to the poor wear resistance of the component (e) itself, and the comfort of the obtained shoes deteriorates, and deformation at the time of mold release remains during molding.

Ingredient (c)
Component (c) is a non-aromatic rubber softener and contributes to controlling the flexibility of the obtained sole portion and improving the comfort. As this component, the same component (c) described above with respect to the upper part is used.

  The compounding quantity of a component (c) is 50-250 weight part with respect to 100 weight part of component (d), Preferably it is 100-200 weight part. If it is less than the above lower limit, the flexibility becomes insufficient and the comfort becomes worse. In addition, lack of flexibility deteriorates moldability and also deteriorates oil resistance, slip resistance, wear resistance and durability. When the above upper limit is exceeded, blocking is likely to occur during the production of the composition pellets, and the softening agent tends to bleed out from the obtained sole portion, resulting in a decrease in strength and wear resistance, and stickiness. Note that the stickiness at the sole portion is effective in preventing slipping and is a preferable phenomenon.

Ingredient (f)
Component (f) is a hydrogenated petroleum resin. This improves the balance between the flexibility of the sole portion and the slip resistance, and also improves the moldability. Component (f) includes hydrogenated petroleum resins such as hydrogenated aliphatic petroleum resins, hydrogenated aromatic petroleum resins, hydrogenated copolymerized petroleum resins and hydrogenated alicyclic petroleum resins, and hydrogenated terpenes. Based resins and the like.

  Here, the petroleum resin is a copolymer obtained using a resinous material obtained in various processes in the petroleum refining industry and the petrochemical industry, or unsaturated hydrocarbons obtained in those processes, particularly in the naphtha decomposition process. This refers to the resin obtained. For example, aliphatic petroleum resins made mainly from C5 fraction, aromatic petroleum resins made mainly from C9 fraction, alicyclic petroleum resins made mainly from cyclopentadiene compounds, and their copolymerization Based petroleum resin. The hydrogenated petroleum resin can be obtained by hydrogenating these petroleum resins by a known method.

  Among these, a hydrogenated petroleum resin obtained by copolymerizing a cyclopentadiene compound and an aromatic vinyl compound such as styrene is preferable.

  The compounding quantity of a component (f) is 1-50 weight part with respect to 100 weight part of component (d), Preferably it is 5-30 weight part. If the amount is less than 1 part by weight, the slip resistance deteriorates. If it exceeds 50 parts by weight, blocking occurs during pellet production.

In addition to the components (c) to (f), the composition (B) constituting the sole part may further include various anti-blocking agents, sealability improvers, heat stabilizers, and antioxidants as necessary. , Light stabilizers, ultraviolet absorbers, lubricants, crystal nucleating agents, antibacterial agents, coloring agents, and the like can also be contained.
Here, examples of the antioxidant include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4 , 4-dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like, phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and the like. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred. The antioxidant is preferably 0 to 3.0 parts by weight, particularly preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight of the total of the components (c) to (f).

3. Production of thermoplastic elastomer composition The composition (A) constituting the upper part and the composition (B) constituting the sole part are each produced by melt-kneading the above components simultaneously or in any order. obtain.

  The method of melt kneading is not particularly limited, and generally known methods can be used. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders can be used. For example, the above operation can be performed continuously by using an appropriate L / D twin screw extruder, Banbury mixer, pressure kneader, or the like. Here, the temperature of melt kneading is preferably 160 to 220 ° C.

4). Manufacturing of shoes The manufacturing method of shoes is not specifically limited, A well-known method can be used. For example, after suspending a sock-like lining material in a last mold, fitting the last mold, bottom mold and side mold, and injecting the upper composition into the shoe forming gap to form the trunk and upper Similarly, the sole composition can be similarly injected into the shoe forming gap to form a shoe sole to produce a shoe. As the sock-like lining material, woven fabric, knitted fabric, artificial leather, synthetic leather, or the like can be used.

  The present invention will be specifically described by the following examples and comparative examples, but the present invention is not limited to the examples.

Examples 1-15 and Comparative Examples 1-13
With respect to the thermoplastic elastomer composition (A) constituting the upper portion, the components (parts by weight) shown in Table 1 are used, and for the thermoplastic elastomer composition (B) constituting the sole portion, Table 2 is shown. Using each amount (part by weight) of each component, each component was put into a twin screw extruder having an L / D of 47, melt kneaded at a kneading temperature of 180 ° C. and a screw rotation speed of 350 rpm, and then pelletized. The obtained pellets were injection molded to prepare test pieces, which were subjected to the following tests (1) to (9). The evaluation results are shown in Tables 1 and 2. The upper compositions A1 to A6 in Table 1 and the sole compositions B1 to B9 in Table 2 are compositions according to the present invention.

Furthermore, using the pellets obtained above, boots were injection molded by the following procedure, and the following tests (10) to (17) were performed. The evaluation results are shown in Tables 3 and 4.
The sock-like lining material is suspended in the last mold, the last mold, the bottom mold and the side mold are fitted together, and the upper composition (A) is injected into the boot forming gap to form the trunk and upper part. Thereafter, the sole composition (B) was injected into the boot shoe forming gap to mold the shoe sole, thereby producing boots.
Table 3 shows the evaluation of the upper part when each of the upper compositions A1 to A13 in Table 1 is combined with the sole composition B1 to produce boots, and Table 4 shows the sole composition in Table 2. It is evaluation of a sole part when manufacturing boots combining each of thing B1-B15 with composition A1 for uppers.
The test methods and materials used are as follows.

1. Test method (1) Melt flow rate (MFR) of upper composition: Measured at 160 ° C. under a load of 2.16 kg according to ASTM D-1288.
(2) Melt flow rate (MFR) of the composition for sole: Measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D-1238.
(3) Hardness (HDA): In accordance with JIS K 6252, a 6.3 mm thick press sheet was used as a test piece.
(4) Tensile strength: Based on JIS K 6251, the test piece was a 2 mm thick injection sheet punched into a No. 3 dumbbell-type test piece. The tensile speed was 500 mm / min.
(5) 100% elongation stress: In accordance with JIS K 6251, the test piece was a 2 mm thick injection sheet punched into a No. 3 dumbbell-type test piece. The tensile speed was 500 mm / min.
(6) Elongation at break: In accordance with JIS K 6251, the test piece was a 2 mm-thick injection sheet punched into a No. 3 dumbbell-type test piece. The tensile speed was 500 mm / min.

(7) Oil resistance: As the test piece, a 2 mm-thick injection sheet was used by punching it into a circle having a diameter of 22 mm. The test piece was immersed in isooctane at 23 ° C. for 24 hours, and the volume change rate (%) obtained from the weight and specific gravity was measured.
(8) Abrasion resistance (only the composition for the sole is evaluated): The test piece is a 2 mm-thick injection sheet that is punched into a 100 mm diameter circle and used in accordance with JIS K 7204, with a wear wheel H-22, a load of 1 kg, The weight loss (mm ² ) at 1000 revolutions was measured.
(9) Blocking resistance: Evaluated by the presence or absence of blocking during pellet production.
○: No blocking.
Δ: Blocking can be prevented (by using an additive or the like).
X: There is blocking.

(10) Gloss (Evaluation of upper part only): The surface condition of the upper part of boots formed by injection molding was determined according to the following criteria.
○: Glossy.
Δ: Semi-glossy (half glossy).
X: No gloss.

(11) Moldability (fluidity): The situation at the time of molding of boots by injection molding was determined according to the following criteria.
◯: There were no sink marks and burrs, and the molding was good.
Δ: Molding was possible but flow marks and weld lines were observed.
X: Resin did not flow to the flow end of the mold, and molding was impossible.

(12) Formability (deformation at the time of mold release): The situation at the time of mold release in the injection molding of boots was determined according to the following criteria.
○: There is no distortion and mold release is possible.
(Triangle | delta): Some distortion arises at the time of mold release.
X: Distortion occurs at the time of mold release, and deformation is severe.

(13) Stickiness (Evaluation of upper part only): The upper part of an injection-molded boot was touched by hand and judged according to the following criteria.
○: There is no stickiness on the surface of the boots.
Δ: Slightly sticky on the boot surface.
X: There is stickiness on the surface of the boots and it is also dirty.

(14) Texture (comfort): Five female workers in the landscaping industry wear the injection-molded boots for 2 months (actual movement 8 hours / day), conduct a monitor test, and judge according to the following criteria did.
○: Four or more people can wear without feeling uncomfortable.
Δ: Three people can wear without feeling uncomfortable.
X: Two or fewer people can wear without feeling uncomfortable.

(15) Slip resistance (only the sole part is evaluated): Five female workers in the landscaping industry wear the injection-molded boots for 2 months (actual operation 8 hours / day) and conduct a monitor test. Judged by the criteria of.
○: Four or more people were able to work without slipping.
Δ: Three people were able to work without slipping.
X: Two or less people were able to work without slipping.

(16) Durability (deformation wear): Five women workers in the landscaping industry wear the injection-molded boots for two months (actual movement 8 hours / day) and conduct a monitor test to determine the appearance of the boots. Evaluation was made according to the following criteria.
○: It was determined that all five people had practically no deformation wear.
Δ: One or two people recognized slight deformation wear.
X: Three or more people judged to have deformation wear and lack practicality.

(17) Durability (crack) (Evaluation of the upper part only): Five women workers in the landscaping industry wear the injection-molded boots for 2 months (actual operation 8 hours / day) and conduct a monitor test. The appearance of the upper part of the boots was evaluated according to the following criteria.
○: All five boots did not crack for 2 months.
Δ: No crack occurred within one week, but one or more shoes were cracked after 2 months.
X: Cracks occurred in one or more shoes within one week.

2. material
Ingredient (a1)
Dynalon 6201B: Block copolymer (CEBC) having a crystalline ethylene block and an amorphous ethylene / butene block, manufactured by JSR Corporation, cross type, number average molecular weight (Mn): 280,000, weight average molecular weight (Mw) : 340,000, MFR: 0.5 g / 10 min (ASTM D-1238, 230 ° C., 2.16 kg), density: 0.88 (unit g / cm ³ ), glass transition temperature: −50 ° C. (ASTM D -3418)

Ingredient (a2)
Dynalon 6100B: block copolymer having crystalline ethylene block and amorphous ethylene / butene block: (CEBC), manufactured by JSR Corporation, linear type, weight average molecular weight (Mw): 290,000, MFR: 0.6 g / 10 min (ASTM D-1238, 230 ° C., 2.16 kg), density: 0.88 (unit: g / cm ³ ), glass transition temperature: −55 ° C. (ASTM D-3418)

Ingredient (b)
(B) HF461X: Daelim Industrial Co. , Ltd., Ltd. Homopolypropylene, MFR: 800 g / 10 min (ASTM D-1238, 230 ° C., 2.16 kg)

Ingredient (b) (for comparison)
J229E: Prime polymer, random polypropylene, MFR: 50 g / 10 min (ASTM D-1238, 230 ° C., 2.16 kg)

Ingredient (c)
Diana process oil PW-90: Idemitsu Kosan Co., Ltd., paraffinic oil

Ingredient (d)
(1) Septon 4055: manufactured by Kuraray Co., Ltd., SEEPS, styrene content: 30% by weight, isoprene content: 70% by weight, number average molecular weight (Mn): 260,000, weight average molecular weight (Mw): 320,000 Hydrogenation rate: 90% or more (2) Kraton G1651H: manufactured by Kraton Polymer, SEBS, styrene content: 30% by weight, number average molecular weight (Mn): 300,000, weight average molecular weight (Mw): 370,000

Ingredient (e)
(1) J229E: Prime Polymer Co., Ltd., random polypropylene, MFR: 50 g / 10 min (ASTM D-1238, 230 ° C., 2.16 kg)
(2) HF461X: Daelim Industrial Co. , Ltd., Ltd. Homopolypropylene, MFR: 800 g / 10 min (ASTM D-1238, 230 ° C., 2.16 kg)

Ingredient (f)
P-140: Idemitsu Petrochemical Co., Ltd., hydrogenated C5 petroleum resin

Optional component BM-102MT: manufactured by Fuji Chemical Co., Ltd., antibacterial agent

  As is clear from Tables 3 and 4, the shoes of Examples 1 to 15 according to the present invention all showed good characteristics.

  On the other hand, as shown in Table 3, in Comparative Example 1, since only the component (a1) is used as the component (a), the tensile strength of the composition (A) is inferior, and the resulting shoe is durable. Inferior to this, cracks occurred. In Comparative Example 2, the ratio of the component (a1) in the component (a) is less than the lower limit of the present invention, and the moldability (fluidity) is inferior. In Comparative Example 3, the amount of component (b) was less than the lower limit of the present invention, the gloss was slightly inferior and the durability (deformation wear) was also poor. In Comparative Example 4, the amount of component (b) exceeded the upper limit of the present invention, the oil resistance was poor, the deformation at the time of mold release remained, and the texture was inferior. In Comparative Example 5 in which a polypropylene resin having an MFR outside the scope of the present invention was used as the component (b), the moldability (fluidity) was inferior. In Comparative Example 6, the amount of component (c) is less than the lower limit of the present invention, and is inferior in oil resistance and moldability (fluidity). In Comparative Example 7, the amount of the component (c) exceeds the upper limit of the present invention, blocking occurs during pellet production, and the component (c) bleeds out to reduce the texture, strength, and durability (crack). And stickiness occurred.

  Moreover, as shown in Table 4, in Comparative Example 8, the amount of the component (e) is less than the lower limit of the present invention, the moldability (fluidity) is poor, and a test piece and shoes cannot be produced. It was. In Comparative Example 9, the amount of the component (e) exceeds the upper limit of the present invention, which is inferior in wear resistance and inferior in shoe formability (release property) and texture (comfort). In Comparative Example 10, since the amount of the component (c) is less than the lower limit of the present invention and the flexibility is insufficient, the comfort is deteriorated. In addition, moldability (fluidity, deformation at the time of mold release), oil resistance, slip resistance, wear resistance, and durability (deformation wear) are also poor. In Comparative Example 11, the amount of component (c) exceeds the upper limit of the present invention, there are many bleeds, blocking occurs during pellet production, and strength reduction and wear resistance deterioration occur. In Comparative Example 12 in which component (f) was not added, the slip resistance was poor, and in Comparative Example 13 in which component (f) was added in excess of the upper limit of the present invention, blocking occurred during pellet production.

It is a perspective view which shows an example of the shoes of this invention.

Explanation of symbols

1 Sole part 2 Upper part

Claims (3)

(A) 100 parts by weight of a block copolymer having a crystalline ethylene block and an amorphous ethylene / α-olefin block,
(B) 5-60 parts by weight of a polypropylene resin having a melt flow rate (ASTM D-1238, 230 ° C., 2.16 kg load) of 700-1500 g / 10 min, and (c) a softener for non-aromatic rubber 50 to 180 parts by weight, and the component (a) is a mixture of a block copolymer (a1) having a cross-type molecular structure and a block copolymer (a2) having a linear-type molecular structure, A shoe having an upper portion made of a thermoplastic elastomer composition (A) having a weight ratio of a1) to (a2) of 95: 5 to 70:30. (D) a block copolymer comprising at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound and / or hydrogenating the block copolymer. 100 parts by weight of a hydrogenated block copolymer obtained by
(E) 5 to 50 parts by weight of a polypropylene resin,
(C) A non-aromatic rubber softening agent 50 to 250 parts by weight, and (f) a hydrogenated petroleum resin 1 to 50 parts by weight, and a sole part composed of a thermoplastic elastomer composition (B). Item 1. A shoe according to item 1. The method for producing a shoe according to claim 2, wherein after molding the upper part using the composition (A), the sole part is injection molded using the composition (B).

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