JP2003147181A - Resin composition and its production method and use - Google Patents
Resin composition and its production method and useInfo
- Publication number
- JP2003147181A JP2003147181A JP2001346742A JP2001346742A JP2003147181A JP 2003147181 A JP2003147181 A JP 2003147181A JP 2001346742 A JP2001346742 A JP 2001346742A JP 2001346742 A JP2001346742 A JP 2001346742A JP 2003147181 A JP2003147181 A JP 2003147181A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- polycaprolactone
- polyvinyl alcohol
- core material
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、特定樹脂からなる
樹脂組成物に関する。より詳しくは、ポリカプロラクト
ンとポリビニルアルコールからなる樹脂組成物で、とり
わけ紳士靴、婦人靴、子供靴、ブーツ、スポーツ靴、カ
ジュアル靴、サンダル、スリッパ等、各種の履物の製造
に使用する先芯、月形芯等の履物芯材用に適する樹脂組
成物に関するものである。TECHNICAL FIELD The present invention relates to a resin composition comprising a specific resin. More specifically, a resin composition composed of polycaprolactone and polyvinyl alcohol, especially men's shoes, women's shoes, children's shoes, boots, sports shoes, casual shoes, sandals, slippers, etc. The present invention relates to a resin composition suitable for a footwear core material such as a lunar core.
【０００２】[0002]
【従来の技術】従来、靴用の芯材は、靴の先およびかか
と部分等に保形性を与えるために使用されるもので、熱
可塑性樹脂を含浸させた織布や不織布を、靴先およびか
かと部分の内側に接着させて用いられている。従来の靴
の芯材は、靴に対する接着方法から、いくつかのタイプ
に分類することができる。第一のタイプは、芯材を溶剤
で再活性して靴の所定部位に接着するものであり、例え
ばポリスチレンエマルジョン、スチレン・アクリル共重
合エマルジョンなどの熱可塑性樹脂エマルジョンを織布
や不織布へ含浸させ、乾燥固化してシート状にしたもの
が挙げられる。第二のタイプは、接着剤によって芯材を
靴に接着する方法であり、例えば第一のタイプで用いら
れる組成のシートを、天然ゴムラテックス形の接着剤で
接着させるものが挙げられる。第三のタイプは、熱再活
性により芯材を靴に接着する方法であり、例えば、上記
の組成及び方法で製造したシート上に、エチレン・酢酸
ビニル共重合系ホットメルト性接着剤やポリカプロラク
トンを主体とする熱可塑性樹脂組成物と織布や不織布か
らなるシートを熱再活性によって靴に接着させるものが
挙げられる。例えば、特開平５６−１４８３０１号公報
には、重量平均分子量が１０，０００から２００，００
０のポリカプロラクトンを主体とする靴用熱可塑性芯材
が記載されている。2. Description of the Related Art Conventionally, a core material for shoes has been used for imparting shape-retaining properties to the tip and heel of a shoe. A woven or non-woven fabric impregnated with a thermoplastic resin is used as a shoe tip. It is used by adhering it to the inside of the heel part. Conventional shoe cores can be classified into several types according to the method of adhering to the shoe. The first type is to reactivate the core material with a solvent and bond it to a predetermined part of the shoe.For example, a thermoplastic resin emulsion such as polystyrene emulsion or styrene-acrylic copolymer emulsion is impregnated into the woven or non-woven fabric. , A sheet formed by drying and solidifying. The second type is a method of adhering the core material to the shoe with an adhesive, and for example, a sheet of the composition used in the first type is adhered with a natural rubber latex type adhesive. The third type is a method of adhering a core material to shoes by heat reactivation. For example, an ethylene / vinyl acetate copolymer hot-melt adhesive or polycaprolactone is placed on a sheet produced by the above composition and method. Examples thereof include those in which a sheet made of a woven fabric or a non-woven fabric and a thermoplastic resin composition mainly composed of are bonded to shoes by thermal reactivation. For example, in JP-A-56-148301, the weight average molecular weight is 10,000 to 200,000.
No. 0 polycaprolactone-based thermoplastic core material for shoes is described.
【０００３】前記の各タイプの靴の芯材には、いずれも
解決すべき課題が残されている。まず、第一のタイプの
芯材及びその接着方法は、低コストであって接着時の作
業性が良好であるが、接着時に有機溶剤を使用すること
から、製靴工程での作業環境の問題や火災などの危険が
あり、時代の要請にマッチしない。第二のタイプの接着
方法は、接着剤を使用して靴に芯材を接着するため、作
業工数が増えることから作業性が悪いということが最大
の難点である。第三のタイプの芯材及び接着方法は、熱
再活性により芯材を靴に接着できることから、有機溶剤
を使用しなくてよく作業性に優れるなどの利点を有して
いる。しかし、このタイプに用いられる芯材の製造は、
織布等に対してスチレンエマルジョンなどの熱可塑性樹
脂を含浸して乾燥固化させる工程と、エチレン・酢酸ビ
ニル樹脂を主成分にする接着剤をコーティングする工程
が必要であり、製造コストが高くなってしまうという欠
点がある。更には、織布や不織布上に、ホットメルト性
接着剤を塗布した構造であるため、切断面をスキ加工し
た時に、ホットメルト性接着剤を塗布されていない面が
接着面として現われてしまうという欠点がある。また、
ポリカプロラクトンを主体とする熱可塑性樹脂組成物と
織布や不織布からなる芯材は、熱可塑性樹脂組成物中の
増量材又は補強剤としてポリ塩化ビニル樹脂が使用され
ているため、不要な靴を焼却する際に発生するダイオキ
シン問題を抱えることとなる。The core material of each of the above types of shoes still has problems to be solved. First, the core material of the first type and its bonding method are low in cost and have good workability at the time of bonding, but since an organic solvent is used at the time of bonding, there is a problem in the working environment in the shoe manufacturing process. There is a risk of fire, and it does not match the demands of the times. The second type of adhesion method is that the core material is adhered to the shoe by using an adhesive, so that the number of work steps is increased, and the workability is poor, which is the greatest difficulty. The third type of core material and the bonding method have the advantage that the core material can be bonded to the shoe by heat reactivation and therefore workability is excellent without using an organic solvent. However, the manufacture of the core material used in this type is
It requires the steps of impregnating woven cloth with a thermoplastic resin such as styrene emulsion to dry and solidify it, and the step of coating an adhesive containing ethylene / vinyl acetate resin as the main component, which increases the manufacturing cost. There is a drawback that Furthermore, since it has a structure in which a hot-melt adhesive is applied onto a woven fabric or a non-woven fabric, the surface to which the hot-melt adhesive has not been applied appears as an adhesive surface when the cut surface is processed. There are drawbacks. Also,
The core material composed of a thermoplastic resin composition mainly composed of polycaprolactone and a woven fabric or a non-woven fabric uses a polyvinyl chloride resin as an extender or a reinforcing agent in the thermoplastic resin composition, so that unnecessary shoes You will have the dioxin problem that occurs when you incinerate.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、接着
時に有機溶剤が不要であって、熱再活性により接着が可
能となる履物芯材を与え、かつ、一つの工程で製造可能
な樹脂組成物を提供する。また、スキ加工がなされても
新たにその面に接着剤を塗布することなく、芯材の接着
面全体が熱再活性による接着が可能な履物芯材となり、
更に使用が済んだ段階で焼却する際、成形体構成組成に
よるダイオキシンの発生が無い履物芯材を与える樹脂組
成物を提供する。SUMMARY OF THE INVENTION An object of the present invention is to provide a footwear core material which does not require an organic solvent at the time of bonding and can be bonded by heat reactivation, and which can be manufactured in one step. A composition is provided. In addition, even if it is skived, the entire bonding surface of the core material becomes a footwear core material that can be bonded by heat reactivation without newly applying an adhesive agent on the surface,
Further, the present invention provides a resin composition that gives a footwear core material that does not generate dioxin due to the composition of a molded body when incinerated at the stage of use.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、ポリカプ
ロラクトンのマトリックス中に、特定粒径を有するポリ
ビニルアルコールが粉粒状で分散した樹脂組成物、およ
びそれから成形されてなる履物芯材がかかる問題点を解
決し得ることを見い出し、本発明を完成するに至った。DISCLOSURE OF THE INVENTION The inventors of the present invention apply to a resin composition in which polyvinyl alcohol having a specific particle diameter is dispersed in a granular form in a matrix of polycaprolactone, and a footwear core material formed from the resin composition. The inventors have found that the problems can be solved and completed the present invention.
【０００６】すなわち本発明の第１は、ポリカプロラク
トン（Ａ）２５〜９５重量％とポリビニルアルコール
（Ｂ）５〜７５重量％（（Ａ）と（Ｂ）の合計は１００
重量％）からなり、該ポリビニルアルコール（Ｂ）がポ
リカプロラクトン（Ａ）のマトリックス中に粒径２ｍｍ
以下の粉粒状で分散していることを特徴とする樹脂組成
物を提供する。本発明の第２は、ポリカプロラクトン
（Ａ）の数平均分子量が１０，０００〜１５０，０００
である本発明の第１の樹脂組成物を提供する。本発明の
第３は、履物芯材用である本発明の第１又は２の樹脂組
成物を提供する。本発明の第４は、ポリカプロラクトン
（Ａ）２５〜９５重量％と粒径２ｍｍ以下の粉粒状のポ
リビニルアルコール（Ｂ）５〜７５重量％（（Ａ）と
（Ｂ）の合計は１００重量％）の混合物を、該ポリカプ
ロラクトン（Ａ）の融点以上、該ポリビニルアルコール
（Ｂ）の融点未満の温度で混練することを特徴とする本
発明の第１〜３のいずれかの樹脂組成物の製造方法を提
供する。本発明の第５は、混練温度が８０〜２００℃で
ある本発明の第４の樹脂組成物の製造方法を提供する。
本発明の第６は、本発明の第１又は２の樹脂組成物を成
形してなる履物芯材を提供する。That is, the first aspect of the present invention is that the total of 25 to 95% by weight of polycaprolactone (A) and 5 to 75% by weight of polyvinyl alcohol (B) ((A) and (B) is 100).
%), And the polyvinyl alcohol (B) has a particle size of 2 mm in the matrix of polycaprolactone (A).
Provided is a resin composition characterized by being dispersed in the form of powder as described below. A second aspect of the present invention is that the polycaprolactone (A) has a number average molecular weight of 10,000 to 150,000.
A first resin composition of the present invention is provided. A third aspect of the present invention provides the first or second resin composition of the present invention for a footwear core material. The fourth aspect of the present invention is that 25 to 95% by weight of polycaprolactone (A) and 5 to 75% by weight of powdery polyvinyl alcohol (B) having a particle size of 2 mm or less (the total of (A) and (B) is 100% by weight). ) Is mixed at a temperature not lower than the melting point of the polycaprolactone (A) and lower than the melting point of the polyvinyl alcohol (B) to produce the resin composition according to any one of the first to third aspects of the present invention. Provide a way. A fifth aspect of the present invention provides a method for producing the fourth resin composition of the present invention, which has a kneading temperature of 80 to 200 ° C.
A sixth aspect of the present invention provides a footwear core formed by molding the first or second resin composition of the present invention.
【０００７】[0007]
【発明の実施の形態】以下、本発明について詳しく説明
する。本発明で用いるポリカプロラクトン（Ａ）は、本
発明の樹脂組成物において、後記ポリビニルアルコール
（Ｂ）との合計１００重量％になる基準のもと、２５〜
９５重量％、好ましくは、３０〜７０重量％の範囲で含
有される。ポリカプロラクトン（Ａ）の割合が２５重量
％未満の場合に履物芯材用の成形体として用いると、熱
再活性による接着性が十分得られない。また、ポリカプ
ロラクトン（Ａ）の割合が９５重量％より大きいとき
は、履物芯材用としての保形性が満足されず、更に原料
コストの面からも好ましくない。本発明の樹脂組成物に
用いられるポリカプロラクトン（Ａ）の数平均分子量
は、本発明の樹脂組成物を履物芯材とした際の耐屈曲性
等の点から、好ましくは１０，０００〜１５０，００
０、更に好ましくは３０，０００〜１３０，０００の範
囲である。なお、ポリカプロラクトン（Ａ）の数平均分
子量が１５０，０００より大きい場合、履物芯材用の成
形体を製造する際の取扱作業性等が悪くなる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the resin composition of the present invention, the polycaprolactone (A) used in the present invention is 25 to 25% based on the total amount of 100% by weight with the polyvinyl alcohol (B) described below.
It is contained in an amount of 95% by weight, preferably 30 to 70% by weight. When the proportion of polycaprolactone (A) is less than 25% by weight, when it is used as a molded article for a footwear core material, sufficient adhesiveness due to heat reactivation cannot be obtained. Further, when the proportion of polycaprolactone (A) is more than 95% by weight, the shape retaining property as a footwear core material is not satisfied, and further it is not preferable in terms of raw material cost. The number average molecular weight of the polycaprolactone (A) used in the resin composition of the present invention is preferably 10,000 to 150, from the viewpoint of bending resistance when the resin composition of the present invention is used as a footwear core material. 00
0, and more preferably 30,000 to 130,000. When the number average molecular weight of polycaprolactone (A) is larger than 150,000, handling workability and the like at the time of producing a molded body for a footwear core material are deteriorated.
【０００８】本発明の樹脂組成物を構成するポリビニル
アルコール（Ｂ）（ＰＶＡと省略することもある。）
は、通常合成繊維用に用いられるＰＶＡ、フィルム用に
用いられる粉粒状のＰＶＡ（いずれも、ポリ酢酸ビニル
完全ケン化物）、部分ケン化物、特殊変性部分ケン化
物、又はそれらの混合物であってもよい。本発明の樹脂
組成物において、ポリビニルアルコール（Ｂ）は、ポリ
カプロラクトン（Ａ）マトリックス中に粒径２ｍｍ以下
の粉粒状で分散し、樹脂組成物中に前記ポリカプロラク
トン（Ａ）との合計１００重量％のもと、５〜７５重量
％の範囲で含有されなければならない。ＰＶＡの粒子
は、他の高分子の粒子、例えばポリ塩化ビニルやポリプ
ロピレン粒子などと比較して、ＰＶＡ自身の分子構造か
らマトリックスのポリカプロラクトンと適度の親和性を
有するため安定して分散し、またこの樹脂組成物から得
られる履物芯材の表面に存在する粒子の脱落が殆ど無
い。更に混練により容易にポリカプロラクトンのマトリ
ックス中に分散し、一旦分散した後は、粒子の再凝集は
認められない。ここで、粉粒状とは、粉粒状で製造され
たそのままの状態、またはその後の粉砕、破砕、造粒、
乾燥、篩い分け等の操作により生じた粉状又は粒子状で
あり、形状は問わない。もちろん粒子表面の少なくとも
一部が溶融して円味を帯びたもの、球状またはその近似
形態であってもよい。又、「ポリカプロラクトンマトリ
ックス中に分散している」とは、得られた樹脂組成物を
薄くシートに成形し、透過光で目視観察した際に、実質
的に粒子の偏在が認められないことを意味する。ポリビ
ニルアルコール（Ｂ）が粒径２ｍｍ以下でかつ粉粒状の
形状が保持されない場合、本発明の効果を発現しない。
即ちポリカプロラクトン（Ａ）と粉粒状のポリビニルア
ルコール（Ｂ）とを加熱混合する際、ポリビニルアルコ
ールの融点以上で混合すると、ポリビニルアルコール
（Ｂ）が溶融し、ポリカプロラクトン（Ａ）とメルトブ
レンドされ、均一な溶融体を形成する。この場合には、
冷却しても組成物に粉粒状のポリビニルアルコールが目
視でも観測されない。このような樹脂組成物を成形して
得られる履物芯材は、熱再活性により靴の所定部位に接
着させる際に接着強度が低下する。また、粉粒状のポリ
ビニルアルコール（Ｂ）がその形状を保持しながらもポ
リカプロラクトン中に偏在する場合は、多くの場合、履
物芯材としての保形性や機械強度が満足されないし、仮
にそれらが満足されたとしてもそれらのバラツキが大き
い。更に熱再活性により靴の所定部位に接着させる際の
接着強度が低下する。樹脂組成物に含有されるポリビニ
ルアルコール（Ｂ）の割合が５重量％未満の場合、履物
芯材用成形体としての保形性や機械強度が満足されな
い。また、ポリビニルアルコール（Ｂ）の割合が７５重
量％より大きいときは、樹脂組成物を成形して得られる
履物芯材を熱再活性により靴の所定部位に接着させる際
の接着強度が満足されない。Polyvinyl alcohol (B) constituting the resin composition of the present invention (may be abbreviated as PVA).
Is a PVA usually used for synthetic fibers, a granular PVA used for a film (all are completely saponified with polyvinyl acetate), a partially saponified product, a specially modified partially saponified product, or a mixture thereof. Good. In the resin composition of the present invention, polyvinyl alcohol (B) is dispersed in the polycaprolactone (A) matrix in the form of powder particles having a particle size of 2 mm or less, and the total weight of the polycaprolactone (A) and the polycaprolactone (A) is 100% by weight. %, Must be contained in the range of 5 to 75% by weight. Compared with other polymer particles such as polyvinyl chloride and polypropylene particles, PVA particles have a moderate affinity with the polycaprolactone of the matrix due to the molecular structure of PVA itself, and thus are stably dispersed. Particles existing on the surface of the footwear core material obtained from this resin composition are hardly detached. Further, it is easily dispersed in the polycaprolactone matrix by kneading, and once dispersed, no reaggregation of particles is observed. Here, the term "granularity" means the state in which it is produced in a granular form, or the subsequent pulverization, crushing, granulation,
It is in the form of powder or particles produced by operations such as drying and sieving, and the shape is not limited. Of course, at least a part of the particle surface may be melted to give a rounded shape, a spherical shape, or a similar shape. Further, “dispersed in a polycaprolactone matrix” means that when the obtained resin composition is thinly formed into a sheet and visually observed by transmitted light, uneven distribution of particles is not substantially recognized. means. When the polyvinyl alcohol (B) has a particle size of 2 mm or less and the powdery or granular shape is not retained, the effect of the present invention is not exhibited.
That is, when the polycaprolactone (A) and the powdery polyvinyl alcohol (B) are mixed by heating at a melting point of polyvinyl alcohol or higher, the polyvinyl alcohol (B) is melted and melt-blended with the polycaprolactone (A), Form a uniform melt. In this case,
Even when cooled, no particulate polyvinyl alcohol was visually observed in the composition. The footwear core material obtained by molding such a resin composition has a reduced adhesive strength when it is adhered to a predetermined portion of a shoe due to heat reactivation. Further, when the polyvinyl alcohol (B) in the form of powder is unevenly distributed in the polycaprolactone while maintaining its shape, in many cases, the shape retention and mechanical strength of the footwear core material are not satisfied. Even if they are satisfied, their variations are large. Furthermore, the heat reactivation reduces the adhesive strength when it is adhered to a predetermined part of the shoe. When the proportion of polyvinyl alcohol (B) contained in the resin composition is less than 5% by weight, the shape retention and mechanical strength of the molded article for footwear core material are not satisfied. When the proportion of polyvinyl alcohol (B) is more than 75% by weight, the adhesive strength at the time of adhering the footwear core material obtained by molding the resin composition to a predetermined part of the shoe by thermal reactivation is not satisfied.
【０００９】分散しているポリビニルアルコール（Ｂ）
粒子の粒径は２ｍｍ以下、好ましくは１．５〜０．１ｍ
ｍである。ポリビニルアルコール（Ｂ）の粒径が２ｍｍ
より大きいときは、履物芯材の接着表面にポリビニルア
ルコール粒子が突き出すようになるため、あるいはポリ
ビニルアルコールの粒子が履物芯材表面から外れ易くな
るため、得られた芯材を熱再活性により靴の所定部位に
接着させる際の接着強度を低下させてしまう。Dispersed polyvinyl alcohol (B)
The particle size of the particles is 2 mm or less, preferably 1.5 to 0.1 m
m. Particle size of polyvinyl alcohol (B) is 2 mm
When the value is larger, polyvinyl alcohol particles come to stick out on the adhesive surface of the footwear core material, or the particles of polyvinyl alcohol easily come off the surface of the footwear core material. The adhesive strength at the time of adhering to a predetermined part will be reduced.
【００１０】本発明の樹脂組成物には、必要に応じて各
種添加物を添加してもよい。これらの添加物は特に限定
されるものではないが、例えば、履物芯材としての成形
体を熱再活性により靴の所定部位に接着させる際のオー
プンタイムを調節するためにロジン及びその誘導体、テ
ルペン化合物、炭化水素系化合物、パラフィンワック
ス、低分子量ポリエチレンワックスを少量添加しても構
わない。また、抗酸化剤（酸化防止剤）を、樹脂組成物
の熱溶融混合時や成形して得られる履物芯材の熱溶融に
よる加工時、あるいは履物芯材を熱により再活性させる
際の熱安定性を向上させるために少量添加することも構
わない。その他として、履物芯材の耐寒性、柔軟性、耐
衝撃性、表面高度などの改良を目的にオレフィン系樹
脂、スチレン系樹脂、ウレタン系樹脂及びエステル系の
共重合体や、ガラス繊維、ガラスビーズ、炭酸カルシウ
ム、硫酸バリウム、酸化チタン、クレー、クルクなどの
フイラーを本発明の効果を阻害しない範囲で任意に添加
しても構わない。If desired, various additives may be added to the resin composition of the present invention. Although these additives are not particularly limited, for example, rosin and its derivative, terpene in order to adjust the open time when the molded article as a footwear core material is adhered to a predetermined part of the shoe by heat reactivation. A small amount of a compound, a hydrocarbon compound, paraffin wax or low molecular weight polyethylene wax may be added. Also, heat stability when an antioxidant (antioxidant) is melt-mixed with the resin composition, when the footwear core obtained by molding is heat-melted, or when the footwear core is reactivated by heat. A small amount may be added to improve the properties. In addition, olefin resins, styrene resins, urethane resins and ester copolymers, glass fibers, glass beads for the purpose of improving the cold resistance, flexibility, impact resistance, surface height, etc. of footwear core materials. Fillers such as calcium carbonate, barium sulfate, titanium oxide, clay and krk may be optionally added within a range that does not impair the effects of the present invention.
【００１１】本発明の樹脂組成物の製造には、特に限定
した方法及び装置を用いる必要はない。一般的にはポリ
カプロラクトンのペレット、粉粒状のＰＶＡ、更には任
意に添加する添加剤を加熱混練し、コンパウンドとす
る。例えば一軸あるいは二軸押出機によってコンパウン
ドすることができるが、その際、ポリビニルアルコール
（Ｂ）を溶融させないように、用いるポリビニルアルコ
ール（Ｂ）の融点（軟化点）未満、ポリカプロラクトン
の融点以上に加熱混練温度を設定する必要があり、好ま
しくは８０〜２００℃の範囲である。加熱混練に先立
ち、本発明の樹脂組成物の構成原料を予めドライブレン
ドしておいてもよい。本発明の樹脂組成物を一旦ペレッ
ト等として取り出し、あるいは樹脂組成物の製造に引き
続き、履物芯材成形用のシート成形機や射出成形機に投
入し、ポリビニルアルコール（Ｂ）の融点よりも低い温
度で履物芯材としての成形体を得ることができる。It is not necessary to use a particularly limited method and apparatus for producing the resin composition of the present invention. Generally, pellets of polycaprolactone, powdered and granular PVA, and further optionally added additives are kneaded by heating to form a compound. For example, it can be compounded by a single-screw or twin-screw extruder, in which case the polyvinyl alcohol (B) is heated to a temperature below the melting point (softening point) of the polyvinyl alcohol (B) and above the melting point of the polycaprolactone so as not to melt the polyvinyl alcohol (B). It is necessary to set the kneading temperature, and it is preferably in the range of 80 to 200 ° C. Prior to the heat kneading, the constituent raw materials of the resin composition of the present invention may be previously dry blended. The resin composition of the present invention is once taken out as pellets or the like, or subsequently to the production of the resin composition, is put into a sheet molding machine or an injection molding machine for molding a footwear core material, and the temperature is lower than the melting point of polyvinyl alcohol (B). A molded body as a footwear core can be obtained.
【００１２】[0012]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらに限定されるものではない。EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.
【００１３】（実施例１〜１０、比較例１〜４）表１に
示す組成（混練温度以外は配合した重量部を示す。）の
樹脂組成物を製造した。これらの樹脂組成物は、予め各
構成成分原料を所定の割合でドライブレンドした後、東
洋精機製ラボプラストミル（ミキサー部Ｒ−６０）に一
括投入し、表１に示した混練温度、混練回転数５０ｒ．
ｐ．ｍ．、混練時間３分の混練条件にて混練し、組成物
を得た。混練温度は、比較例１を除き、使用ポリビニル
アルコールの融点より低い温度（１００℃）に設定し
た。(Examples 1 to 10 and Comparative Examples 1 to 4) Resin compositions having the compositions shown in Table 1 (parts by weight were shown except for the kneading temperature) were produced. These resin compositions were previously dry-blended with respective constituent raw materials at a predetermined ratio and then put into a Labo Plastomill (mixer section R-60) manufactured by Toyo Seiki at once, and the kneading temperature and kneading rotation shown in Table 1 were used. Number 50 r.
p. m. Then, kneading was carried out under a kneading condition of 3 minutes to obtain a composition. The kneading temperature was set to a temperature (100 ° C.) lower than the melting point of the polyvinyl alcohol used except for Comparative Example 1.
【００１４】調製した各組成物（実施例１〜１０、比較
例１〜４）を１１０℃に加熱したプレス成形機におい
て、一次圧力１０ｋｇ／ｃｍ2で３分間、二次圧力の圧
力１００ｋｇ／ｃｍ2で２分間、加圧することにより厚
さ１．２ｍｍのシートを作成した。これらのシートにつ
いて、履物芯材用成形体としての特性を確認する為の評
価を行い、その結果を表２に示した。尚、比較例２の成
形体は、シートに成形した際、脆性が高いため屈曲を与
えるとシートが割れる為、履物芯材用成形体として要求
される耐屈曲性や靱性がないと判断し、各評価は行わな
かった。また、比較例１の組成物においては、組成物を
製造する際の混練温度がポリビニルアルコールの融点
（２１７℃）より高い温度で混練をしたので、ポリビニ
ルアルコールが溶融し、かつポリカプロラクトンに溶け
込みＰＶＡの粒子形状が保持されなかったが、それ以外
の実施例、比較例は、ポリビニルアルコールの粒子形状
は保持されていた。また、ポリビニルアルコールの粒子
形状が保持されていた組成物においては、上記シートの
透過光による目視観察の結果、粒子の偏在や塊はなく、
均一に分散されていることが分かった。Each of the prepared compositions (Examples 1 to 10 and Comparative Examples 1 to 4) was heated to 110 ° C. in a press molding machine at a primary pressure of 10 kg / cm 2 for 3 minutes and a secondary pressure of 100 kg / cm. A sheet having a thickness of 1.2 mm was prepared by pressurizing at 2 for 2 minutes. These sheets were evaluated to confirm the characteristics as a molded article for a footwear core material, and the results are shown in Table 2. The molded product of Comparative Example 2 was found to have no bending resistance or toughness required as a molded product for a footwear core material, because the molded product of Comparative Example 2 had a high brittleness when molded into a sheet, and the sheet would crack when bent. Each evaluation was not performed. Further, in the composition of Comparative Example 1, since the kneading temperature at the time of producing the composition was higher than the melting point of polyvinyl alcohol (217 ° C.), the polyvinyl alcohol was melted and dissolved in polycaprolactone. However, the particle shape of polyvinyl alcohol was maintained in the other Examples and Comparative Examples. Further, in the composition in which the particle shape of polyvinyl alcohol was retained, as a result of visual observation by the transmitted light of the sheet, there was no uneven distribution or agglomeration of particles,
It was found to be evenly dispersed.
【００１５】以下、物性などの測定方法を記す。
ポリカプロラクトンの数平均分子量：ＧＰＣ測定によ
り、ポリスチレン換算から求めた分子量である。ＧＰＣ
は、カラムに昭和電工（株）製Ｓｈｏｄｅｘ ＧＰＣ
ＫＦ−６、ＫＦ−８０４、ＫＦ−８０２５、ＫＦ−８０
１を用い、検出器は（株）島津製作所製ＲＩＤ−６Ａを
用い、溶離液はテトラヒドロフランを使用し、カラム温
度５０℃、流速１．０ｍｌ／ｍｉｎにて測定を行った。
接着性：実施例１〜１０及び比較例１、３〜４で製造し
たシートを縦７ｃｍ×横２．５ｃｍ×厚み１．２ｍｍの
サイズに調製した。これらの短冊シートを１５０℃の乾
燥器中に水平設置されたステンレス板上に４０秒間乗せ
た後、直ちに乾燥器中より取り出して３０秒間自然放置
させ、その後直ちに、予めプレス板内にセットしておい
たポリエステル製の織布にこれら短冊シートを載せ、３
０℃に温調されたプレスで、圧力１ｋｇ／ｃｍ2、１０
秒間コールドプレスを行い、これらの短冊シートとポリ
エステル製の織布を接着させた。その際、短冊シートの
縦２ｃｍ分をＴ形剥離試験の為のつかみしろとしてアル
ミ箔を挟み織布と接着しないように施した。接着性は、
ＯＲＩＥＮＴＥＣ社製テンシロンで剥離スピード１００
ｍｍ／ｍｉｎでＴ形剥離試験を行い、平均剥離強度で評
価した。
耐屈曲性：実施例１〜１０及び比較例１、３〜４のシー
トを縦１４ｃｍ×横３．０ｃｍ×厚み１．２ｍｍのサイ
ズに調製した。これらの短冊シートの縦方向が屈曲する
様に耐屈曲試験機にセットし、縦幅１０．５ｃｍに対し
てストローク４．７ｃｍの繰り返し屈曲をこれらの短冊
シートに与えた。このときの繰り返し屈曲スピードは、
３００回（１往復：１回）／分に設定した。評価は、短
冊シートが折れたときの屈曲回数により行った。The methods for measuring physical properties will be described below. Number average molecular weight of polycaprolactone: It is a molecular weight obtained by polystyrene conversion by GPC measurement. GPC
Is a Shodex GPC manufactured by Showa Denko KK
KF-6, KF-804, KF-8025, KF-80
1 was used, the detector was RID-6A manufactured by Shimadzu Corporation, and the eluent was tetrahydrofuran. The column temperature was 50 ° C. and the flow rate was 1.0 ml / min. Adhesiveness: The sheets produced in Examples 1 to 10 and Comparative Examples 1 and 3 to 4 were prepared in a size of 7 cm in length × 2.5 cm in width × 1.2 mm in thickness. These strip sheets were placed on a stainless steel plate horizontally installed in a dryer at 150 ° C. for 40 seconds, immediately taken out of the dryer and naturally left for 30 seconds, and immediately thereafter, set in a press plate in advance. Place these strip sheets on the woven polyester cloth, and
Press at a temperature of 0 ° C, pressure 1kg / cm 2 , 10
Cold pressing was performed for 2 seconds to bond these strip sheets to the polyester woven fabric. At that time, a length of 2 cm of the strip sheet was used as a grip for the T-shaped peel test so that the aluminum foil was sandwiched between the strips so as not to adhere to the woven fabric. Adhesiveness is
ORIENTEC's Tensilon peeling speed 100
A T-type peel test was performed at mm / min, and the average peel strength was evaluated. Flex resistance: The sheets of Examples 1 to 10 and Comparative Examples 1 and 3 to 4 were prepared to have a size of 14 cm in length × 3.0 cm in width × 1.2 mm in thickness. These strip sheets were set in a bending resistance tester so that they bend in the longitudinal direction, and these strip sheets were repeatedly bent with a stroke of 4.7 cm for a vertical width of 10.5 cm. The repeated bending speed at this time is
It was set to 300 times (1 round trip: 1 time) / minute. The evaluation was performed by the number of times of bending when the strip sheet was folded.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【表２】 [Table 2]
【００１８】[0018]
【発明の効果】本発明によれば、熱再活性による接着が
良好で、且つ、履物芯材用として必要な物性、例えば、
耐屈曲性が良好で、ハロゲン系化合物を使用しないこと
から、燃焼時ダイオキシンの発生の問題もない成形体、
及びそれを与える樹脂組成物を提供することができる。EFFECTS OF THE INVENTION According to the present invention, the adhesion by heat reactivation is good and the physical properties required for a footwear core material, for example,
A molded product that has good flex resistance and does not use halogen compounds, so there is no problem of dioxin generation during combustion,
And the resin composition which gives it can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 29/04 Ｃ０８Ｌ 29/04 Ｄ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C08L 29/04 C08L 29/04 D
Claims (6)
量％とポリビニルアルコール（Ｂ）５〜７５重量％
（（Ａ）と（Ｂ）の合計は１００重量％）からなり、該
ポリビニルアルコール（Ｂ）がポリカプロラクトン
（Ａ）のマトリックス中に粒径２ｍｍ以下の粉粒状で分
散していることを特徴とする樹脂組成物。1. Polycaprolactone (A) 25 to 95% by weight and polyvinyl alcohol (B) 5 to 75% by weight
(The total of (A) and (B) is 100% by weight), and the polyvinyl alcohol (B) is dispersed in the matrix of polycaprolactone (A) in the form of powder particles having a particle diameter of 2 mm or less. Resin composition.
量が１０，０００〜１５０，０００である請求項１に記
載の樹脂組成物。2. The resin composition according to claim 1, wherein the polycaprolactone (A) has a number average molecular weight of 10,000 to 150,000.
の樹脂組成物。3. The resin composition according to claim 1, which is used for a footwear core material.
量％と粒径２ｍｍ以下の粉粒状のポリビニルアルコール
（Ｂ）５〜７５重量％（（Ａ）と（Ｂ）の合計は１００
重量％）の混合物を、該ポリカプロラクトン（Ａ）の融
点以上、該ポリビニルアルコール（Ｂ）の融点未満の温
度で混練することを特徴とする請求項１〜３のいずれか
に記載の樹脂組成物の製造方法。4. The total amount of polycaprolactone (A) 25 to 95% by weight and powdery or granular polyvinyl alcohol (B) 5 to 75% by weight ((A) and (B) having a particle diameter of 2 mm or less is 100).
%) Of the polycaprolactone (A) above the melting point of the polyvinyl alcohol (B) and below the melting point of the polyvinyl alcohol (B), the resin composition according to claim 1. Manufacturing method.
４に記載の樹脂組成物の製造方法。5. The method for producing a resin composition according to claim 4, wherein the kneading temperature is 80 to 200 ° C.
形してなる履物芯材。6. A footwear core formed by molding the resin composition according to claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001346742A JP2003147181A (en) | 2001-11-12 | 2001-11-12 | Resin composition and its production method and use |
| TW91124625A TW593536B (en) | 2001-11-12 | 2002-10-24 | Resin composition, method for the preparation thereof |
| BR0206430-8A BR0206430A (en) | 2001-11-12 | 2002-10-31 | Resin composition, method to produce it, and shoe reinforcer |
| PCT/JP2002/011379 WO2003042301A1 (en) | 2001-11-12 | 2002-10-31 | Resin composition, process for its production and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001346742A JP2003147181A (en) | 2001-11-12 | 2001-11-12 | Resin composition and its production method and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003147181A true JP2003147181A (en) | 2003-05-21 |
Family
ID=19159853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001346742A Pending JP2003147181A (en) | 2001-11-12 | 2001-11-12 | Resin composition and its production method and use |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2003147181A (en) |
| BR (1) | BR0206430A (en) |
| TW (1) | TW593536B (en) |
| WO (1) | WO2003042301A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185823A (en) * | 2021-05-27 | 2021-07-30 | 中国科学院长春应用化学研究所 | Polycaprolactone composite material and preparation method thereof |
| CN115989147A (en) * | 2020-08-31 | 2023-04-18 | 三菱化学株式会社 | Support material for laminated molding, and method for producing laminated molded article and three-dimensional structure using same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4492767B2 (en) * | 2000-02-25 | 2010-06-30 | 三菱瓦斯化学株式会社 | Resin composition |
-
2001
- 2001-11-12 JP JP2001346742A patent/JP2003147181A/en active Pending
-
2002
- 2002-10-24 TW TW91124625A patent/TW593536B/en not_active IP Right Cessation
- 2002-10-31 BR BR0206430-8A patent/BR0206430A/en not_active Application Discontinuation
- 2002-10-31 WO PCT/JP2002/011379 patent/WO2003042301A1/en active Application Filing
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115989147A (en) * | 2020-08-31 | 2023-04-18 | 三菱化学株式会社 | Support material for laminated molding, and method for producing laminated molded article and three-dimensional structure using same |
| EP4205979A4 (en) * | 2020-08-31 | 2024-02-14 | Mitsubishi Chem Corp | Support material for laminated molding, and methods for manufacturing laminated molded object and three-dimensional structure using same |
| CN113185823A (en) * | 2021-05-27 | 2021-07-30 | 中国科学院长春应用化学研究所 | Polycaprolactone composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW593536B (en) | 2004-06-21 |
| BR0206430A (en) | 2003-12-23 |
| WO2003042301A1 (en) | 2003-05-22 |
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