JPH0510224B2 - - Google Patents
Info
- Publication number
- JPH0510224B2 JPH0510224B2 JP59088894A JP8889484A JPH0510224B2 JP H0510224 B2 JPH0510224 B2 JP H0510224B2 JP 59088894 A JP59088894 A JP 59088894A JP 8889484 A JP8889484 A JP 8889484A JP H0510224 B2 JPH0510224 B2 JP H0510224B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- salt
- laminate
- polyurethane
- 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.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 claims description 61
- 239000011347 resin Substances 0.000 claims description 61
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 59
- -1 amine compound Chemical class 0.000 claims description 39
- 229920002635 polyurethane Polymers 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 23
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 19
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 16
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000004970 Chain extender Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 4
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 claims description 3
- JSCFNQDWXBNVBP-UHFFFAOYSA-N 1,2-diphenylguanidine;phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.C=1C=CC=CC=1N=C(N)NC1=CC=CC=C1 JSCFNQDWXBNVBP-UHFFFAOYSA-N 0.000 claims description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002845 discoloration Methods 0.000 description 14
- 239000010985 leather Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GENYBPRYOMJDAG-UHFFFAOYSA-N 3,4-dioctylphthalic acid Chemical compound CCCCCCCCC1=CC=C(C(O)=O)C(C(O)=O)=C1CCCCCCCC GENYBPRYOMJDAG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N benzothiazolyl mercaptan Natural products C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LIGIARLVFBHRJF-UHFFFAOYSA-N n'-[2-(diethylamino)ethyl]-n,n,n'-triethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CCN(CC)CC LIGIARLVFBHRJF-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Description
本発明は、有機アミン系化合物を鎖延長剤とし
て用いて得られたポリウレタン、例えば、発泡シ
ートに塩化ビニル系樹脂からなるシート（所謂レ
ザーを含む。）を積層させてなる積層体、及びそ
のような積層体の製造方法に関する。
詳しくは、本発明は、アミン系化合物を鎖延長
剤として用いて得られたポリウレタン、例えば、
発泡シートに塩化ビニル系樹脂からなるシートを
積層させてなり、上記アミン系化合物による塩化
ビニル系樹脂からなるシートにおける変色劣化を
防止した積層体、及びそのような積層体の製造方
法に関する。
塩化ビニル系樹脂は、熱や紫外線等により脱塩
酸して着色することが知られている。このため
に、従来より塩化ビニル系樹脂の加工に際しては
種々の安定剤を添加し、かかる着色による品質劣
化の防止が図られている。
しかし、塩化ビニル系樹脂の着色或いは変色
は、上記のような熱や紫外線のみならず、塩化ビ
ニル系樹脂がポリウレタンと接触する場合にも生
じる。例えば、塩化ビニル系樹脂シートとポリウ
レタンとの接着材料を密閉状態に長期間おいた場
合等に、塩化ビニル系樹脂が変色劣化する。特
に、この傾向は、環境温度が高いほど著しい。
より具体的には、例えば、塩化ビニル系樹脂か
らなる所謂レザーの裏面にポリウレタンからなる
発泡シートを熱接着してなる製靴用胛被や、塩化
ビニル系樹脂レザーからなる胛被にポリウレタン
からなる注型靴底を接着させてなる靴を、比較的
高温で長期間密閉した場合に、塩化ビニル系樹脂
レザーが黄色乃至黄色味を帯びた紫色に変色す
る。
このような塩化ビニル系樹脂の変色は、ポリウ
レタンが鎖延長剤としてアミン系化合物を含む場
合に起こることから、そのようなアミン系化合物
が原因であるとみられている。
そこで、上記のように、アミン系化合物を鎖延
長剤として用いて得られたポリウレタン、例え
ば、発泡シートに塩化ビニル系樹脂シートを接着
積層させた場合に、そのようなアミン系化合物に
よる塩化ビニル系樹脂シートの変色劣化を防止す
るために、従来、塩化ビニル系樹脂に二酸化チタ
ンやステアリン酸亜鉛のような脂肪酸亜鉛塩を多
量に添加する方法が知られている。
しかし、前者の方法によれば、塩化ビニル系樹
脂からなるシートの変色は多少とも軽減される
が、塩化ビニル系樹脂からなるシートの有する好
ましい物理的性質の劣化が生じると共に、製造費
用も高価となる。また、後者の方法によれば、多
量の脂肪酸亜鉛塩の添加によつて、塩化ビニル系
樹脂からなるシートの変色は相当改善されるもの
の、耐熱性が著しく劣化し、その製造工程におけ
る圧延加工時に、熱のために樹脂が急激に分解す
ることがある。
本発明者らは、上記したような塩化ビニル系樹
脂からなるシートをアミン系化合物を鎖延長剤と
して用いて得られたポリウレタン、例えば、発泡
シートに積層させる場合に生じる塩化ビニル系樹
脂からなるシートの変色を防止するために鋭意研
究した結果、塩化ビニル系樹脂からなるシートに
グアニジン系化合物又はその塩を少量含有させる
ことにより、上記変色を有効に防止し得ることを
見出して、本発明に至つたものである。
即ち、本発明は、塩化ビニル系樹脂シートとア
ミン系化合物を鎖延長剤として用いて得られたポ
リウレタン、例えば、発泡シートに積層体におい
て、上記ジアミン系化合物による塩化ビニル系樹
脂シートの変色劣化を防止した積層体、及びその
ような積層体の製造方法を提供することを目的と
する。
本発明は、塩化ビニル系樹脂からなるシートと
アミン系化合物を鎖延長剤として用いて得られた
ポリウレタンとの積層体において、塩化ビニル系
樹脂からなるシートにグアニジン系化合物又はそ
の塩を含有させることを特徴とする。
また、本発明によるかかるアミン系化合物を鎖
延長剤として用いて得られたポリウレタンに塩化
ビニル系樹脂からなるシートを積層させて積層体
を製造する方法は、塩化ビニル系樹脂からなるシ
ートにグアニジン系化合物又はその塩を含有させ
ることを特徴とする。
本発明において、塩化ビニル系樹脂からなるシ
ートを構成する塩化ビニル系樹脂は、塩化ビニル
の単独重合体のほか、塩化ビニルの共重合体を含
み、かかる共重合体としては、例えば、塩化ビニ
ルとエチレン、酢酸ビニル、ビニルエーテル、マ
レイン酸エステル、塩化ビニリデン、アクリル酸
エステル等の１種又はそれ以上の単量体との共重
合体を挙げることができる。また、これら塩化ビ
ニル系樹脂と他の樹脂との混合物であつてもよ
い。
また、本発明において用いる塩化ビニル系樹脂
は、メルカプトベンゾチアゾール系化合物又はそ
の塩と、塩化ビニル系樹脂と共に、塩化ビニル系
樹脂が通常含有する各種の添加剤、例えば、可塑
剤、安定剤、顔料、充填剤、紫外線吸収剤、酸化
防止剤、帯電防止剤等を含有してもよい。また、
塩化ビニル系樹脂シートの好ましい性質を損なわ
ない範囲であれば、脂肪酸金属塩、例えば、亜鉛
や、酸化チタンを含有してもよい。
本発明において、塩化ビニル系樹脂は、所謂軟
質、硬質のいずれかであつてもよいが、軟質の場
合、塩化ビニル系樹脂は、通常、ポリ塩化ビニル
又は塩化ビニル共重合体100重量部について、可
塑剤20〜200重量部及び安定剤0.3〜５重量部含
む。
本発明において用いるグアニジン系化合物又は
その塩としては、グアニジン骨格を有する種々の
ものを使用し得るが、好ましくは、ジアリールグ
アニジン、特に、ジフエニルグアニジン、ジ−ｏ
−トリルグアニジン、これらの有機酸塩、例え
ば、ジフエニルグアニジンフタル酸塩等を挙げる
ことができる。これらは塩化ビニル系樹脂に単独
で配合されてもよく、或いは２種以上の混合物と
して配合されてもよい。
上記グアニジン系化合物又はその塩の塩化ビニ
ル系樹脂への添加量は、使用する樹脂やその組
成、例えば、可塑剤や充填剤が含有されるとき
は、その種類や配合量等にもよるが、通常、塩化
ビニル系樹脂100重量部に対して0.1〜２重量部の
範囲が好適であり、特に、0.5〜1.5重量部の範囲
が好適である。
このようにグアニジン系化合物又はその塩を含
有する塩化ビニル系樹脂は、アミン系化合物によ
る変色が有効に防止される。その添加量が塩化ビ
ニル系樹脂100重量部に対して、0.1重量部よりも
少ないときは、変色に対する抑制効果は小さく、
一方、２重量部を越える多量を添加しても、着色
抑制効果の飽和がみられると共に、ブルーム等の
障害が起こることがある。
本発明による塩化ビニル系樹脂からなるシート
とアミン系化合物を鎖延長剤として用いて得られ
たポリウレタン、例えば、発泡シートとの積層体
は、以上のように、塩化ビニル系樹脂からなるシ
ートにグアニジン系化合物又はその塩を含有させ
ているので、塩化ビニル系樹脂からなるシートに
おけるアミン系化合物による変色が有効に防止さ
れる。
従つて、本発明による上述したような積層体
は、ポリウレタンからなる発泡シートを塩化ビニ
ル系樹脂レザーに接着してなる胛被、ポリウレタ
ンからなる靴底と塩化ビニル系樹脂レザー胛被と
からなる靴、塩化ビニル系樹脂とポリウレタンと
の複合材料からなるシートや各種成形品等に好適
に使用することができる。
以下に実施例により本発明を詳細に説明する
が、本発明はこれら実施例により限定されるもの
ではない。
実施例 １
第１表に示すように、ポリ塩化ビニル可塑剤、
安定剤等を配合し、10インチ試験用ロールにて温
度160℃で５分間混練して、0.2mm厚みのシートに
加工し、発明品１〜４及び比較品１〜３を得た。
各発明品及び比較品のそれぞれを５cm角に裁断
して、試験片とした。ペンタエチルジエチレント
リアミンをジオクチルフタル酸に溶解した20％溶
液に、上記各試験片を常温で３時間浸漬後、表面
を拭き、120℃のギヤー・オーブン中で所定時間
曝露させ、変色の程度を調べた。結果を第２表に
示す。ここに、評価は次によつた。即ち、１はか
すかに黄色又は紫色を呈したもの、５は著しく黄
色または紫色に着色したことを示し、変色度を１
〜５の５段階で評価した。
以上から明らかなように、塩化ビニル系樹脂
100重量部に対し、グアニジン系化合物又はその
塩の添加によつて、塩化ビニル系樹脂における変
色が有効に抑制される。
The present invention relates to a laminate made by laminating a polyurethane obtained using an organic amine compound as a chain extender, such as a foam sheet, and a sheet made of vinyl chloride resin (including so-called leather), and such a polyurethane. The present invention relates to a method for manufacturing a laminate. Specifically, the present invention relates to polyurethane obtained using an amine compound as a chain extender, for example,
The present invention relates to a laminate in which a sheet made of vinyl chloride resin is laminated to a foamed sheet, and which prevents discoloration and deterioration of the sheet made of vinyl chloride resin caused by the above-mentioned amine compound, and a method for producing such a laminate. It is known that vinyl chloride resins are colored by dehydrochlorination by heat, ultraviolet rays, etc. For this reason, various stabilizers have been conventionally added during processing of vinyl chloride resins to prevent quality deterioration due to such coloring. However, the vinyl chloride resin is colored or discolored not only by heat and ultraviolet rays as described above, but also when the vinyl chloride resin comes into contact with polyurethane. For example, when an adhesive material between a vinyl chloride resin sheet and polyurethane is kept in a sealed state for a long period of time, the vinyl chloride resin will discolor and deteriorate. In particular, this tendency becomes more pronounced as the environmental temperature increases. More specifically, for example, a shoe cover made by thermally bonding a foam sheet made of polyurethane to the back side of so-called leather made of vinyl chloride resin, or a shoe cover made of polyurethane to a cover made of vinyl chloride resin leather. When shoes with molded soles are sealed at relatively high temperatures for a long period of time, the vinyl chloride resin leather changes color to yellow or yellowish purple. Such discoloration of vinyl chloride resin occurs when polyurethane contains an amine compound as a chain extender, and therefore, such amine compound is thought to be the cause. Therefore, as mentioned above, when a polyurethane obtained using an amine compound as a chain extender is used, for example, when a vinyl chloride resin sheet is adhesively laminated on a foam sheet, the polyurethane obtained by using an amine compound as a chain extender is In order to prevent discoloration and deterioration of resin sheets, a method is conventionally known in which a large amount of a fatty acid zinc salt such as titanium dioxide or zinc stearate is added to a vinyl chloride resin. However, according to the former method, although the discoloration of the sheet made of vinyl chloride resin is reduced to some extent, the favorable physical properties of the sheet made of vinyl chloride resin deteriorate, and the manufacturing cost is also high. Become. In addition, according to the latter method, although the discoloration of the sheet made of vinyl chloride resin is considerably improved by adding a large amount of fatty acid zinc salt, the heat resistance is significantly deteriorated, and during rolling processing in the manufacturing process. , the resin may rapidly decompose due to heat. The present inventors discovered a sheet made of a vinyl chloride resin that is produced when laminating a sheet made of a vinyl chloride resin as described above onto a polyurethane, such as a foamed sheet, obtained by using an amine compound as a chain extender. As a result of intensive research in order to prevent discoloration, it was discovered that the above discoloration can be effectively prevented by incorporating a small amount of a guanidine compound or its salt into a sheet made of vinyl chloride resin, and the present invention has been achieved based on this research. It is ivy. That is, the present invention provides a polyurethane obtained by using a vinyl chloride resin sheet and an amine compound as a chain extender, for example, a foamed sheet laminated with the polyurethane, to prevent discoloration and deterioration of the vinyl chloride resin sheet caused by the diamine compound. It is an object of the present invention to provide a laminate and a method for manufacturing such a laminate. The present invention provides a laminate of a sheet made of a vinyl chloride resin and a polyurethane obtained using an amine compound as a chain extender, in which the sheet made of a vinyl chloride resin contains a guanidine compound or a salt thereof. It is characterized by In addition, the method of manufacturing a laminate by laminating a sheet made of a vinyl chloride resin on a polyurethane obtained using such an amine compound as a chain extender according to the present invention is such that a sheet made of a vinyl chloride resin is laminated with a guanidine It is characterized by containing a compound or a salt thereof. In the present invention, the vinyl chloride resin constituting the sheet made of vinyl chloride resin includes not only a homopolymer of vinyl chloride but also a copolymer of vinyl chloride. Copolymers with one or more monomers such as ethylene, vinyl acetate, vinyl ether, maleic ester, vinylidene chloride, and acrylic ester can be mentioned. Further, it may be a mixture of these vinyl chloride resins and other resins. In addition, the vinyl chloride resin used in the present invention includes a mercaptobenzothiazole compound or a salt thereof, the vinyl chloride resin, and various additives normally contained in the vinyl chloride resin, such as plasticizers, stabilizers, and pigments. , fillers, ultraviolet absorbers, antioxidants, antistatic agents, etc. may be contained. Also,
Fatty acid metal salts such as zinc and titanium oxide may be contained within a range that does not impair the desirable properties of the vinyl chloride resin sheet. In the present invention, the vinyl chloride resin may be either so-called soft or hard, but in the case of soft vinyl chloride resin, the amount of polyvinyl chloride or vinyl chloride copolymer is usually 100 parts by weight. Contains 20-200 parts by weight of plasticizer and 0.3-5 parts by weight of stabilizer. As the guanidine compound or its salt used in the present invention, various compounds having a guanidine skeleton can be used, but diarylguanidine, particularly diphenylguanidine, di-o
-Tolylguanidine, organic acid salts thereof, such as diphenylguanidine phthalate, and the like. These may be blended singly in the vinyl chloride resin, or may be blended as a mixture of two or more. The amount of the above-mentioned guanidine compound or its salt added to the vinyl chloride resin depends on the resin used and its composition, for example, if a plasticizer or filler is contained, the type and amount of the compound, etc. Usually, the range of 0.1 to 2 parts by weight is suitable for 100 parts of vinyl chloride resin, and the range of 0.5 to 1.5 parts by weight is particularly suitable. In this way, the vinyl chloride resin containing the guanidine compound or its salt is effectively prevented from discoloring due to the amine compound. When the amount added is less than 0.1 part by weight per 100 parts by weight of vinyl chloride resin, the effect of suppressing discoloration is small;
On the other hand, even if a large amount exceeding 2 parts by weight is added, the effect of suppressing coloration may become saturated and problems such as bloom may occur. As described above, a laminate of a sheet made of a vinyl chloride resin according to the present invention and a polyurethane, such as a foamed sheet, obtained using an amine compound as a chain extender is produced by adding guanidine to a sheet made of a vinyl chloride resin. Since the resin composition contains a vinyl chloride resin or a salt thereof, discoloration caused by an amine compound in a sheet made of a vinyl chloride resin is effectively prevented. Therefore, the above-mentioned laminate according to the present invention is suitable for use in a shoe cover made of a polyurethane foam sheet adhered to vinyl chloride resin leather, and a shoe cover made of a polyurethane sole and a vinyl chloride resin leather cover. It can be suitably used for sheets and various molded products made of composite materials of vinyl chloride resin and polyurethane. EXAMPLES The present invention will be explained in detail below with reference to Examples, but the present invention is not limited to these Examples. Example 1 As shown in Table 1, polyvinyl chloride plasticizer,
Stabilizers and the like were blended and kneaded for 5 minutes at 160° C. using a 10-inch test roll to form sheets with a thickness of 0.2 mm to obtain Invention Products 1 to 4 and Comparative Products 1 to 3. Each of the invention products and the comparison product was cut into 5 cm square pieces to prepare test pieces. After immersing each of the above test pieces in a 20% solution of pentaethyldiethylenetriamine dissolved in dioctyl phthalic acid at room temperature for 3 hours, the surface was wiped and exposed for a predetermined time in a gear oven at 120°C to examine the degree of discoloration. . The results are shown in Table 2. Here, the evaluation was as follows. That is, 1 indicates a faint yellow or purple coloration, 5 indicates a marked yellow or purple coloration, and the degree of discoloration is rated as 1.
Evaluation was made on a scale of 5 to 5. As is clear from the above, vinyl chloride resin
By adding the guanidine compound or its salt to 100 parts by weight, discoloration in the vinyl chloride resin can be effectively suppressed.
【表】【table】
【表】【table】
【表】
実施例 ２
実施例１にて得た発明品２及び比較品１のそれ
ぞれに基布をラミネートして靴用胛被を作製し
た。エチレンジアミンを鎖延長剤として使用した
ポリオールを架橋剤とするポリウレタン注型靴底
を上記胛被に接着して靴を製作し、これをポリエ
チレン袋内に密封し、70℃で48時間加熱した。こ
の結果、比較品１を用いて作製された靴は塩化ビ
ニル系樹脂部分が黄紫色を呈したが、発明品２を
用いて作製した靴においては何ら変色がみられな
かつた。[Table] Example 2 Inventive product 2 and comparative product 1 obtained in Example 1 were each laminated with a base fabric to produce shoe covers. Shoes were manufactured by adhering a polyurethane cast sole made of polyol as a crosslinking agent using ethylenediamine as a chain extender to the above-mentioned shoe jacket, which was then sealed in a polyethylene bag and heated at 70°C for 48 hours. As a result, the vinyl chloride resin portion of the shoes produced using Comparative Product 1 exhibited a yellow-purple color, but no discoloration was observed in the shoes produced using Invention Product 2.
Claims (1)
化合物を鎖延長剤として用いて得られたポリウレ
タンとの積層体において、塩化ビニル系樹脂から
なるシートにグアニジン系化合物又はその塩を含
有させることを特徴とする積層体。 ２ グアニジン系化合物がジアリールグアニジン
又はその有機酸塩であることを特徴とする特許請
求の範囲第１項記載の積層体。 ３ グアニジン系化合物又はその塩が、ジフエニ
ルグアニジン、ジ−ｏ−トリルグアニジン及びジ
フエニルグアニジンフタル酸塩から選ばれる少な
くとも１種であることを特徴とする特許請求の範
囲第２項記載の積層体。 ４ グアニジン系化合物又はその塩を塩化ビニル
系樹脂100重量部について0.1〜２重量部含有させ
ることを特徴とする特許請求の範囲第１項乃至第
３項いずれかに記載の積層体。 ５ ポリウレタンが発泡シートであることを特徴
とする特許請求の範囲第１項記載の積層体。 ６ アミン系化合物を鎖延長剤として用いて得ら
れたポリウレタンに塩化ビニル系樹脂からなるシ
ートを積層させて積層体を製造する方法におい
て、塩化ビニル系樹脂からなるシートにグアニジ
ン系化合物又はその塩を含有させることを特徴と
する積層体の製造方法。 ７ グアニジン系化合物がジアリールグアニジン
又はその有機酸塩であることを特徴とする特許請
求の範囲第６項記載の方法。 ８ グアニジン系化合物又はその塩が、ジフエニ
ルグアニジン、ジ−ｏ−トリルグアニジン及びジ
フエニルグアニジンフタル酸塩から選ばれる少な
くとも１種であることを特徴とする特許請求の範
囲第６項記載の方法。 ９ グアニジン系化合物又はその塩を塩化ビニル
系樹脂100重量部について0.1〜２重量部含有させ
ることを特徴とする特許請求の範囲第６項乃至第
８項いずれかに記載の方法。 １０ ポリウレタンが発泡シートであることを特
徴とする特許請求の範囲第６項記載の方法。[Claims] 1. In a laminate of a sheet made of a vinyl chloride resin and a polyurethane obtained using an amine compound as a chain extender, a guanidine compound or its salt is added to the sheet made of a vinyl chloride resin. A laminate characterized by containing: 2. The laminate according to claim 1, wherein the guanidine compound is diarylguanidine or an organic acid salt thereof. 3. The laminate according to claim 2, wherein the guanidine compound or its salt is at least one selected from diphenylguanidine, di-o-tolylguanidine, and diphenylguanidine phthalate. . 4. The laminate according to any one of claims 1 to 3, characterized in that the guanidine compound or its salt is contained in an amount of 0.1 to 2 parts by weight per 100 parts by weight of the vinyl chloride resin. 5. The laminate according to claim 1, wherein the polyurethane is a foam sheet. 6 In a method of manufacturing a laminate by laminating a sheet made of vinyl chloride resin on polyurethane obtained using an amine compound as a chain extender, a guanidine compound or its salt is added to the sheet made of vinyl chloride resin. 1. A method for manufacturing a laminate, comprising: 7. The method according to claim 6, wherein the guanidine compound is diarylguanidine or an organic acid salt thereof. 8. The method according to claim 6, wherein the guanidine compound or its salt is at least one selected from diphenylguanidine, di-o-tolylguanidine, and diphenylguanidine phthalate. 9. The method according to any one of claims 6 to 8, characterized in that the guanidine compound or its salt is contained in an amount of 0.1 to 2 parts by weight per 100 parts by weight of the vinyl chloride resin. 10. The method according to claim 6, wherein the polyurethane is a foam sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8889484A JPS60231752A (en) | 1984-05-02 | 1984-05-02 | Vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8889484A JPS60231752A (en) | 1984-05-02 | 1984-05-02 | Vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60231752A JPS60231752A (en) | 1985-11-18 |
| JPH0510224B2 true JPH0510224B2 (en) | 1993-02-09 |
Family
ID=13955673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8889484A Granted JPS60231752A (en) | 1984-05-02 | 1984-05-02 | Vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60231752A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0742409B2 (en) * | 1987-11-27 | 1995-05-10 | 株式会社東芝 | Mold cleaning body and mold cleaning method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5048048A (en) * | 1973-08-31 | 1975-04-28 | ||
| JPS5067857A (en) * | 1973-10-19 | 1975-06-06 | ||
| JPS54145753A (en) * | 1978-05-03 | 1979-11-14 | Firestone Tire & Rubber Co | Heattstabilized polyvinyl chloride dispersion resin |
| JPS5763346A (en) * | 1980-10-03 | 1982-04-16 | Daihachi Kagaku Kogyosho:Kk | Crosslinkable vinyl chloride pasty resin composition |
-
1984
- 1984-05-02 JP JP8889484A patent/JPS60231752A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5048048A (en) * | 1973-08-31 | 1975-04-28 | ||
| JPS5067857A (en) * | 1973-10-19 | 1975-06-06 | ||
| JPS54145753A (en) * | 1978-05-03 | 1979-11-14 | Firestone Tire & Rubber Co | Heattstabilized polyvinyl chloride dispersion resin |
| JPS5763346A (en) * | 1980-10-03 | 1982-04-16 | Daihachi Kagaku Kogyosho:Kk | Crosslinkable vinyl chloride pasty resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60231752A (en) | 1985-11-18 |
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