JPS609900B2 - Laminate for interior materials - Google Patents
Laminate for interior materialsInfo
- Publication number
- JPS609900B2 JPS609900B2 JP52068299A JP6829977A JPS609900B2 JP S609900 B2 JPS609900 B2 JP S609900B2 JP 52068299 A JP52068299 A JP 52068299A JP 6829977 A JP6829977 A JP 6829977A JP S609900 B2 JPS609900 B2 JP S609900B2
- Authority
- JP
- Japan
- Prior art keywords
- group concentration
- polyamide resin
- interior materials
- present
- laminate
- 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
Links
Landscapes
- Finishing Walls (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】
本発明は、内装材用積層物、即ち自動車の天井、ドアー
、窓枠、トランク等の内側に又は建造物の室内の壁等に
装着する積層物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminate for interior decoration, that is, a laminate that is attached to the inside of the ceiling, door, window frame, trunk, etc. of an automobile, or to the interior wall of a building.
従来、例えば、実動車用天井材の場合、骨材と表皮材と
を塗布型の接着剤で接合していたが、近年溶剤に起因す
る公害問題、即ち環境汚染、人体の健康に及ぼす悪影響
、あるいは工程が煩雑なために工数が長く生産性が悪い
等の問題により、溶剤を使用しないホットメルト接着剤
による研究が行なわれており、フィルム状のホットメル
ト接着剤を使用する方法が最も簡便であるので、各種の
フィルム状ホットメルト接着剤が検討された。そして、
エチレン−酢酸ビニル共重合樹脂（以下ＥＶＡと略）に
代表されるビニル系フィルム、あるいはポリエチレン（
以下ＰＥと略）等に代表されるポリオレフィン系フィル
ムなどが検討されてきたが、いずれも内装材用としては
不適当なものであった。即ち自動車用及びィンテリャ用
内装材に要求される品質のうち８０ｏｏ以上の耐熱テス
トに合格することが必要であるが、前述のＥＶＡはこの
ような温度下における接着強度が低いため８０ｑｏ以上
の条件下では、表皮材が骨材よりはがれ、例えば天井材
などの場合、表皮材が垂れ下がるなどの欠点があった。In the past, for example, in the case of ceiling materials for production vehicles, aggregate and skin materials were bonded using a coated adhesive, but in recent years pollution problems caused by solvents, such as environmental pollution and adverse effects on human health, have been emerging. Alternatively, due to problems such as complicated processes that require long man-hours and poor productivity, research is being conducted on hot melt adhesives that do not use solvents, and the simplest method is to use hot melt adhesives in the form of a film. Therefore, various film-like hot melt adhesives were investigated. and,
Vinyl films such as ethylene-vinyl acetate copolymer resin (hereinafter abbreviated as EVA) or polyethylene (
Polyolefin films represented by PE (hereinafter abbreviated as PE) have been studied, but none of them were suitable for use as interior materials. In other words, among the qualities required for interior materials for automobiles and interiors, it is necessary to pass a heat resistance test of 80 oo or higher, but the aforementioned EVA has low adhesive strength at such temperatures, so it cannot be used under conditions of 80 qo or higher. However, the skin material peels off from the aggregate, resulting in the skin material sagging in the case of ceiling materials, for example.
一方、内装材に使用される表皮材には、主に発泡ポリゥ
‐レタン又は発泡ポリエチレン等の緩衝材と塩化ビニル
系のシートとの積層物が用いられるため、１００℃以上
の温度で熱接着させると、表皮材が熱により汚損される
等の問題点があるが、前述のポリエチレン等で代表され
るポリオレフィンフィルムでは、ＥＶＡに比べ接着温度
を高くしないと充分な接着強度が得られず、そのために
表皮材が熱により汚損されるばかりでなく、接着時間も
長く（通常３０〜５の砂）、加工適性及び生産性の両面
において満足できるものではなかった。On the other hand, the skin material used for interior materials is mainly a laminate of a cushioning material such as foamed polyurethane or foamed polyethylene and a vinyl chloride sheet, so it is thermally bonded at a temperature of 100°C or higher. However, with polyolefin films such as the aforementioned polyethylene, sufficient adhesive strength cannot be obtained unless the bonding temperature is higher than with EVA. Not only was the skin material stained by the heat, but the adhesion time was also long (usually 30 to 5 sand), and both processing suitability and productivity were unsatisfactory.
以上述べた如く、内装材に使用されるホットメルト接着
剤に関しては、性能及び加工両面においてともに満足す
るものは未だ見出されていないのが現状である。一方、
最近ラゥリルラクタムを必須成分とした低融点のポリア
ミド共重合体（ナイロン６／６６／１２）からなるホッ
トメルト接着剤が開発された（例えば特公昭４５−２２
２４び号公報参照）。As mentioned above, the current situation is that no hot melt adhesive used for interior materials has been found that satisfies both performance and processability. on the other hand,
Recently, a hot melt adhesive made of a low melting point polyamide copolymer (nylon 6/66/12) containing lauryl lactam as an essential component has been developed (for example,
(See Publication No. 24).
又、更に低融点の四元系ポリアミド共重合体も開発され
た（例えば特開昭５０−３５２９０、持関昭５０−３５
２９１、特開昭５０−２２０３４号公報参照）。本発明
者らは、先にこれらのポリアミド共重合体の内ある特定
の性状のものが自動車用内装材の骨材と表皮材との接着
に好適であることを見出し特許出願した（特糠昭５１−
紙７７号）。In addition, quaternary polyamide copolymers with even lower melting points were developed (for example, JP-A No. 50-35290, Mochiseki No. 50-35).
291, see Japanese Unexamined Patent Publication No. 50-22034). The present inventors have previously discovered that polyamide copolymers with certain specific properties are suitable for adhesion between the aggregate and skin material of automobile interior materials and filed a patent application (Tokunoka Akira). 51-
Paper No. 77).
一方、自動車産業界においては、自動車のコントダゥレ
の追求がきびしく、それを構成する材料のコントダゥレ
あるいは作業工程の合理化に鋭意努力が払われている。On the other hand, in the automobile industry, there is a strict pursuit of contours for automobiles, and earnest efforts are being made to contour the materials that make up the automobiles or to rationalize the work process.
その中にあって、骨材についても種々検討され最近ガラ
ス繊維からなる骨材についても使用されるようになった
。しかしながらガラス繊維からなる骨材を用いて従来の
ポリアミド樹脂からなるホットメルト接着フィルムで表
皮材と接着させて自動車用内装材を製造しても充分なる
接着力が得られずｔガラス繊維とポリアミド樹脂ホット
メルト接着フィルムとの間が剥離することが判明した。Among these, various types of aggregates have been studied, and recently aggregates made of glass fibers have also come to be used. However, even when manufacturing automobile interior materials by using aggregate made of glass fibers and bonding them to skin materials using conventional hot-melt adhesive films made of polyamide resin, sufficient adhesion strength cannot be obtained.T Glass fibers and polyamide resin It was found that the film peeled off from the hot melt adhesive film.
本発明者らは、この原因について鋭意検討した所、ポリ
アミド樹脂末端アミノ基濃度を高くすることによりガラ
ス繊維との接着力が高くなることを見出し本発明を完成
した。The present inventors conducted extensive research into the cause of this problem, and found that increasing the concentration of amino groups at the end of the polyamide resin increased the adhesive strength with glass fibers, and completed the present invention.
すなわち本発明は、融点が約９０〜約１３０ｑ０末端ア
ミノ基濃度が２．０×１０‐５ｍｏｌ／ｇ以上で末端ア
ミノ基濃度／末端カルボキシル基濃度の値が０．３以上
であるポリアミド樹脂を用いて、表皮材とガラス繊維か
らなる骨材とを熱接着せしめて成る内装材用積層物に関
する。That is, the present invention uses a polyamide resin having a melting point of about 90 to about 130q, a terminal amino group concentration of 2.0 x 10-5 mol/g or more, and a value of terminal amino group concentration/terminal carboxyl group concentration of 0.3 or more. The present invention relates to a laminate for interior materials made by thermally bonding a skin material and an aggregate made of glass fibers.
本発明に使用するポリアミド樹脂としては特公昭４５一
２２２４ぴ号公報、特開昭４７−１６５９叫号公報等に
記載された例えばナイロン６／６６／１２、ナイロン６
／６１０／１２、ナイロン６／６１２ノ１２、などの三
花共重合体或は特関昭５０−３５２９び号、同５０−３
５２９１、同５０−２２０３４号公報等に記載された例
えばナイロン６／６６／６１０／１２、ナイロン６ノ６
６／６１２／１２などの４元共重合体などが好ましい。Examples of the polyamide resins used in the present invention include nylon 6/66/12, nylon 6, etc., which are described in Japanese Patent Publication No. 45-2224, Japanese Patent Application Laid-open No. 1659/1986, etc.
/610/12, Sanhana copolymer such as nylon 6/612-12, or special Seki No. 50-3529, No. 50-3
For example, nylon 6/66/610/12, nylon 6-6, etc. described in 5291, 50-22034, etc.
Quaternary copolymers such as 6/612/12 are preferred.
又これらの多元共重合体の内、例えばナイロン６／６６
／１２の内６６の塩をへキサメチレンジアミンとダィマ
ー酸とを用いた塩とその１部又は全部を置き換えたもの
でも良い。又、特開昭４９−５００３２、同５０−１８
５３４、同５０−１８５３ふ同５０−１８５９２、同５
０−１８５９３号公報に記載のボリアミド樹脂なども例
示される。Among these multi-component copolymers, for example, nylon 6/66
A part or all of the salt 66 of /12 may be replaced with a salt using hexamethylene diamine and dimer acid. Also, JP-A-49-50032, JP-A-50-18
534, 50-1853, 50-18592, 5
Examples include polyamide resins described in Japanese Patent No. 0-18593.
又本発明の実施に当っては更にＥＶＡ（好ましくは酢酸
ビニル含有量５〜２０％）をポリアミド共重合体１０の
重量部に対して３〜１５重量部加えることによりブロッ
キング性が改良されるため、雛型紙を必要とすることが
なく、その結果作業性が改善される。又ステアリン酸カ
ルシウムなどの有機酸金属塩を少量添加しても同様の効
果が得られる。本発明で使用されるポリアミド樹脂の融
点は約９０〜約１３０ｑｏであることを要する。Furthermore, in carrying out the present invention, the blocking property is improved by further adding 3 to 15 parts by weight of EVA (preferably vinyl acetate content 5 to 20%) to 10 parts by weight of the polyamide copolymer. , no template paper is required, and as a result, workability is improved. A similar effect can also be obtained by adding a small amount of an organic acid metal salt such as calcium stearate. The polyamide resin used in the present invention must have a melting point of about 90 to about 130 qo.
約９０ｏｏ以下であると前述した如く、自動車用内装材
に要求される酸熱テストに合格しないことになり好まし
くない。If it is less than about 90 oo, as mentioned above, it will not pass the acid heat test required for automobile interior materials, which is not preferable.
一方、約１３０ｑＣ以上であると接着温度が高くなり、
その結果表皮材が熱で汚損されることになる。On the other hand, if the temperature is about 130qC or higher, the bonding temperature will be high;
As a result, the skin material becomes contaminated by heat.
本発明において重要なことは、ポリアミド樹脂の末端ア
ミノ基濃度が２．０×１０‐５ｍｏｌ／ｇで以上で〜末
端アミノ基濃度／末端カルボキシル基濃度の値が０．３
以上であることである。What is important in the present invention is that the terminal amino group concentration of the polyamide resin is 2.0 x 10-5 mol/g or more and the value of terminal amino group concentration/terminal carboxyl group concentration is 0.3.
That is all.
ポリアミド樹脂の末端アミノ基濃度の値がこれらの値以
下の値であると、ガラス繊維との間で充分なる接着力が
得られず、自動車用内装材として商品価値のないものと
なる。If the terminal amino group concentration of the polyamide resin is below these values, sufficient adhesive strength with glass fibers will not be obtained and the resin will have no commercial value as an interior material for automobiles.
又末端アミノ基濃度は１５．０×１０‐５ｍｏｌ／ｇ以
下、末端アミノ基濃度ノ末端カルポキシル基濃度の値は
５．０以下で充分である。Further, it is sufficient that the terminal amino group concentration is 15.0 x 10-5 mol/g or less, and the value of the terminal amino group concentration to the terminal carpoxyl group concentration is 5.0 or less.
数平均分子量（末端基濃度から計算したもの）は７００
０〜３００００が好ましい。Number average molecular weight (calculated from end group concentration) is 700
0 to 30,000 is preferable.
この数平均分子量が７００正未満ではポリアミド樹脂自
体の機械的強度が小さく充分な薮着強度が得られず、３
００００を越えると溶融粘度が大きくなり作業性に難点
が生じ好ましくない。これらポリアミド樹脂をつくる方
法としては公知の重合法が適用できるがし分子量調整剤
として添加する酢酸、アジピン酸等の有機酸やへキサメ
チレンジアミン等のアミンの添加量と重合反応率をコン
トロールして、末端アミノ基濃度「末端ァミノ基濃度／
末端カルボキシル基濃度の値が本発明の範囲内に入るよ
うに調整することが必要である。又数平均分子量も同様
に上記した範囲内に入るように調整することが好ましい
。また、２種以上のポリアミド樹脂をブレンドする場合
は、原料ポリァミド樹脂の末端ァミノ基濃度、末端アミ
ノ基濃度／末端カルポキシル基濃度の値は本発明の範囲
外であっても問題はないが、ブレンドして得られたポリ
アミド樹脂のそれらの値は本発明の範囲内に入るように
しなければならない。又数平均分子量も上記した範囲内
に入るようにすることが好ましい。なおポリアミド樹脂
の末端アミノ基濃度と末端カルボキシル基濃度は、公知
の滴定法により定量した。If this number average molecular weight is less than 700 positive, the mechanical strength of the polyamide resin itself is low and sufficient bushing strength cannot be obtained, and 3
If it exceeds 0,000, the melt viscosity becomes too large, resulting in difficulties in workability, which is not preferable. Known polymerization methods can be used to produce these polyamide resins, but the addition amount and polymerization reaction rate of organic acids such as acetic acid and adipic acid and amines such as hexamethylene diamine added as molecular weight regulators are controlled. , terminal amino group concentration “terminal amino group concentration/
It is necessary to adjust the value of the terminal carboxyl group concentration so that it falls within the range of the present invention. It is also preferable that the number average molecular weight is similarly adjusted to fall within the above range. In addition, when blending two or more types of polyamide resins, there is no problem even if the terminal amino group concentration, terminal amino group concentration/terminal carpoxy group concentration of the raw material polyamide resin is outside the range of the present invention, but blending These values for the polyamide resins obtained must be within the scope of the present invention. It is also preferable that the number average molecular weight falls within the above range. Note that the terminal amino group concentration and terminal carboxyl group concentration of the polyamide resin were determined by a known titration method.
本発明に使用するポリアミド樹脂としてはフィルム状の
ものが使い易く、作業工程も合理化でき好適であるが、
勿論粉末状、ネット状のものでも使用できる。The polyamide resin used in the present invention is preferably in the form of a film because it is easy to use and the work process can be streamlined.
Of course, powder or net forms can also be used.
フィルムの場合、その厚みは２０〜６０山が好ましく、
又必要に応じてフィルムに適当に穴を開けても良い。In the case of a film, the thickness is preferably 20 to 60 ridges,
Further, holes may be appropriately punched in the film if necessary.
本発明に使用する表皮材としては、一般に自動車用内装
材として市販されている塩ビレザーが好適であり、これ
はポリ塩化ビニールシートと発泡ポリウレタンとをはり
合わせたものである。As the skin material used in the present invention, vinyl chloride leather, which is generally commercially available as an interior material for automobiles, is suitable, and this is made by laminating a polyvinyl chloride sheet and polyurethane foam.
尚、融点とは例えばＰｅｒｋｉｎ、Ｅｌｍｅｒ社製差動
式熱量計ＤＳＣ−ＩＢで昇塩側度１０００／分で測定し
た場合の融解最大ピーク温度を示すものである。熱援着
の方法としては、真空成型法やホットプレス＊成型法な
ど従来公知の方法を用いることができる。本発明の自動
車用内装材は、好ましくは先ず、ポリ塩化ビニルシート
及び発泡ポリウレタン等より成る表皮材に本発明のポリ
アミド樹脂フィルムを発泡ポリウレタン側に貼り合せ、
これを成形した骨材に熱接着せしめるものである。Incidentally, the melting point refers to the maximum melting peak temperature when measured, for example, with a differential calorimeter DSC-IB manufactured by Perkin and Elmer at a rate of salt rise of 1000/min. As a method for thermally assisted bonding, conventionally known methods such as a vacuum forming method and a hot press *molding method can be used. The automotive interior material of the present invention preferably first includes laminating the polyamide resin film of the present invention to a skin material made of a polyvinyl chloride sheet, foamed polyurethane, etc. on the foamed polyurethane side,
This is then thermally bonded to the molded aggregate.
もちろん、表皮材と骨材との間に本発明のポリアミド樹
脂フィルムを設置し熱接着せしめても良い。Of course, the polyamide resin film of the present invention may be placed between the skin material and the aggregate and thermally bonded thereto.
本発明になる内装材用積層物は、低温度で熱接着されて
いるため、表皮材の熱による汚損がないこと、８０午０
における耐熱テストに合格することなどの利点がある。Since the laminate for interior materials of the present invention is thermally bonded at a low temperature, there is no staining of the skin material due to heat.
It has the advantage of passing the heat resistance test.
又短時間（例えば５〜１晩教間）で熱接着できるため、
作業性が合理化され、生産性が大中に向上する。更に自
動車用内装材のうち、異形成型物（例えば凸凹の大きい
もの）でも充分なる熱接着が得られるという利点もある
。本発明の内装材用積層物は第１図に例示される。図中
１は骨材、２は表皮材、３は１と２とを熱接着せしめる
ポリアミド樹脂層を示す。実施例
ホットメルト接着フィルム３としては、次のようなもの
を用いた。Also, because it can be thermally bonded in a short time (for example, 5 to 1 night),
Work efficiency is streamlined and productivity is greatly improved. Furthermore, among automobile interior materials, there is an advantage that sufficient thermal adhesion can be obtained even with irregularly shaped articles (for example, those with large irregularities). The laminate for interior materials of the present invention is illustrated in FIG. In the figure, 1 is an aggregate, 2 is a skin material, and 3 is a polyamide resin layer for thermally bonding 1 and 2 together. As the example hot melt adhesive film 3, the following was used.
以上のポリアミド樹脂を用いて厚み５０仏のフィルムを
成形し、これを用いて第２図に示すような構成で骨材と
表皮材を接着せしめた。A film having a thickness of 50 mm was formed using the above polyamide resin, and the aggregate and skin material were bonded together using the film as shown in FIG.
即ち、９０００の上熱板８と２００ｏｏの下熱板９の間
に上よりポリ塩化ビニルシート７及び発泡ポリウレタン
６より成る表皮材１０、接着フィルム５、骨材４の順で
挿入し、圧力を０．３ｋ９／めで２筋砂間で各々接着せ
しめた。接着した各試料をＪＩＳＫ６７４４一７１に従
って１８０ｏピーリングの接着強度試験及び接着耐熱試
験に供した。後者の試験は第３図に示されているように
、接着ラップ面積が２５肌×２５肌で、２５雌の荷重を
課し、８０ｏｏのオープン中に５分間放置し、接着剥れ
（脱落）を観察するものである。測定の結果を次の表に
示す。耐熱試験の欄において○印は脱落しない、×印は
脱落したを示す。測定結果That is, a skin material 10 made of a polyvinyl chloride sheet 7 and foamed polyurethane 6, an adhesive film 5, and an aggregate 4 were inserted from above between an upper hot plate 8 of 9000 mm and a lower hot plate 9 of 200 mm, and pressure was applied. Each was adhered between two strips of sand at 0.3k9/me. Each bonded sample was subjected to a 180° peeling adhesive strength test and an adhesive heat resistance test in accordance with JIS K6744-71. In the latter test, as shown in Figure 3, the adhesive wrap area was 25 skins x 25 skins, a load of 25 women was applied, and the adhesive was left open for 5 minutes at 80mm, and the adhesive peeled (falled off). It is something to observe. The results of the measurements are shown in the table below. In the column of heat resistance test, the mark ○ indicates that the sample did not fall off, and the mark x indicates that it did fall off. Measurement result
第１図は本発明に係る自動車用内装材の断面図である。
第２図及び第３図は接着方法及び耐熱試験を各々示すも
のである。１，４・・・・・・骨材、３，５・・・・・
・ポリアミド樹脂フィルム、２．１０・・・・・・表皮
材。
第１図
第２図
第３図FIG. 1 is a sectional view of an automobile interior material according to the present invention. Figures 2 and 3 show the adhesion method and heat resistance test, respectively. 1, 4... aggregate, 3, 5...
- Polyamide resin film, 2.10...Skin material. Figure 1 Figure 2 Figure 3
Claims (1)
．０×１０＾−＾５ｍｏｌ／ｇ以上で、末端アミノ基濃
度／末端カルボキシル基濃度の値が０．３以上であるポ
リアミド樹脂を用いて、表皮材とガラス繊維からなる骨
材とを熱接着せしめて成る内装材用積層物。1 Melting point is about 90 to about 130°C, terminal amino group concentration is 2
．． The skin material and the aggregate made of glass fiber are thermally bonded using a polyamide resin having a content of 0x10^-^5 mol/g or more and a value of terminal amino group concentration/terminal carboxyl group concentration of 0.3 or more. A laminate for interior materials made of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52068299A JPS609900B2 (en) | 1977-06-09 | 1977-06-09 | Laminate for interior materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52068299A JPS609900B2 (en) | 1977-06-09 | 1977-06-09 | Laminate for interior materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS543181A JPS543181A (en) | 1979-01-11 |
| JPS609900B2 true JPS609900B2 (en) | 1985-03-13 |
Family
ID=13369754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52068299A Expired JPS609900B2 (en) | 1977-06-09 | 1977-06-09 | Laminate for interior materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS609900B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005146269A (en) * | 2003-10-22 | 2005-06-09 | Daicel Degussa Ltd | Resin composition for jointing |
| JPWO2004050363A1 (en) * | 2002-12-02 | 2006-03-30 | ダイセル・デグサ株式会社 | Composite molded body and method for producing the same |
| US8173262B2 (en) | 2003-10-03 | 2012-05-08 | Daicel-Evonik Ltd. | Molded composite article, process for producing the same, and a joinable resin |
-
1977
- 1977-06-09 JP JP52068299A patent/JPS609900B2/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2004050363A1 (en) * | 2002-12-02 | 2006-03-30 | ダイセル・デグサ株式会社 | Composite molded body and method for producing the same |
| JP2010173325A (en) * | 2002-12-02 | 2010-08-12 | Daicel-Evonik Ltd | Composite molded object and manufacturing method for the same |
| US8173262B2 (en) | 2003-10-03 | 2012-05-08 | Daicel-Evonik Ltd. | Molded composite article, process for producing the same, and a joinable resin |
| JP2005146269A (en) * | 2003-10-22 | 2005-06-09 | Daicel Degussa Ltd | Resin composition for jointing |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS543181A (en) | 1979-01-11 |
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