JPH0957914A - Laminate - Google Patents
LaminateInfo
- Publication number
- JPH0957914A JPH0957914A JP23606595A JP23606595A JPH0957914A JP H0957914 A JPH0957914 A JP H0957914A JP 23606595 A JP23606595 A JP 23606595A JP 23606595 A JP23606595 A JP 23606595A JP H0957914 A JPH0957914 A JP H0957914A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- polyvinyl chloride
- plasticizer
- laminate
- filler
- 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.)
- Granted
Links
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は汚染除去性に優れた
ポリ塩化ビニル系積層体に関し、より詳しくは充填剤及
び可塑剤を含有するポリ塩化ビニル層/接着剤層/エチ
レン含有量20〜50モル%酢酸ビニル成分のケン化度
95モル%以上のエチレン−ビニルアルコール共重合体
層からなる積層体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvinyl chloride laminate excellent in stain removability, and more specifically, a polyvinyl chloride layer containing a filler and a plasticizer / adhesive layer / ethylene content of 20 to 50. The present invention relates to a laminate comprising an ethylene-vinyl alcohol copolymer layer having a saponification degree of 95 mol% or more of a mol% vinyl acetate component.
【0002】[0002]
【従来の技術】従来よりポリ塩化ビニルシートはその柔
軟性、透明性、経済性、加工性等の点から、壁紙や自動
車の内装用資材、農業用資材、事務用什器等においてい
わゆる塩ビレザーとして多用されてきた。しかしなが
ら、一方では、含有中の可塑剤による汚染(移行、滲出
等)が最大の欠点であることも事実である。この防止策
として可塑剤の減量が考えられるが、可塑剤の含有量が
減ると軟質ポリ塩化ビニルシートの特徴である柔軟性が
低下してしまい本来の特性が失われてしまう。2. Description of the Related Art Conventionally, polyvinyl chloride sheets have been used as so-called vinyl chloride leather in wallpaper, automobile interior materials, agricultural materials, office furniture, etc. because of their flexibility, transparency, economy, and processability. It has been used a lot. However, on the other hand, it is also a fact that contamination (migration, leaching, etc.) due to the contained plasticizer is the greatest drawback. As a measure to prevent this, it is conceivable to reduce the amount of the plasticizer, but if the content of the plasticizer is reduced, the flexibility, which is a characteristic of the soft polyvinyl chloride sheet, is reduced and the original properties are lost.
【0003】この欠点を鑑み、軟質ポリ塩化ビニルシー
トに防汚用のエチレン−ビニルアルコール共重合体(以
下EVOHと略記する)層を積層する方法(実開昭59
−172797号公報)や軟質ポリ塩化ビニルシートと
特定のEVOHを積層する方法(特開昭60−2245
42号公報)が提案されている。In view of this drawback, a method of laminating an antifouling ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH) layer on a soft polyvinyl chloride sheet (Actual Development 59).
No. 172797) or a method for laminating a soft polyvinyl chloride sheet and a specific EVOH (Japanese Patent Laid-Open No. 60-2245).
No. 42) has been proposed.
【0004】[0004]
【発明が解決しようとする課題】しかしながら実開昭5
9−172797号公報開示技術では、ポリ塩化ビニル
中の可塑剤の移行により、ポリ塩化ビニルとEVOHの
接着性が乏しく、接着剤層の厚みを厚くする必要がある
ためコスト高となるという問題があった。又特開昭60
−224542号公報開示技術では、接着剤層の厚みは
薄くできるものの、そのため可塑剤の移行により接着力
が低下し、更に得られた積層体は壁紙等の内装用資材に
供した場合、可塑剤の滲出により、コーヒー等が付着す
ると表面が汚染してしまうという問題があり、更に表面
硬度、耐候性の点でも不十分であった。[Problems to be solved by the invention]
In the disclosed technology of 9-172797, there is a problem that the adhesiveness between polyvinyl chloride and EVOH is poor due to the migration of the plasticizer in polyvinyl chloride, and the cost of the adhesive layer increases because the adhesive layer needs to be thickened. there were. In addition, JP-A-60
In the disclosed technology, although the thickness of the adhesive layer can be reduced, the adhesive force is reduced due to the migration of the plasticizer, and when the obtained laminate is used as an interior material such as wallpaper, the plasticizer is used. However, there is a problem that the surface is contaminated when coffee or the like adheres due to the leaching out of the product, and the surface hardness and the weather resistance are insufficient.
【0005】[0005]
【課題を解決するための手段】本発明者らは、かかる課
題を解決するため鋭意研究を重ねた結果、充填剤及び可
塑剤を含有するポリ塩化ビニル層/接着剤層/エチレン
含有量20〜50モル%酢酸ビニル成分のケン化度95
モル%以上のEVOH層からなり、ポリ塩化ビニル層に
含有される充填剤量(x)及び可塑剤量(y)、接着剤
層の厚み(α)が下式を満足する積層体が壁紙等の内装
用資材に供した時にコーヒー等の付着に対する汚染除去
性に優れ、更には可塑剤の移行防止性、耐薬品性、表面
硬度、耐候性等にも優れているという事実を見出し、本
発明を完成した。 2.5<(100+x+y)/y<20 30≦α・x≦100 但しx、yはポリ塩化ビニル100重量部に対するそれ
ぞれの含有量(重量部)を表し、αは接着剤層の厚み
(μ)を表す。Means for Solving the Problems As a result of intensive studies to solve such problems, the present inventors have found that a polyvinyl chloride layer containing a filler and a plasticizer / adhesive layer / ethylene content of 20- Saponification degree of 50 mol% vinyl acetate component 95
A laminate comprising a mol% or more EVOH layer and having the amount of filler (x) and the amount of plasticizer (y) and the thickness (α) of the adhesive layer contained in the polyvinyl chloride layer satisfying the following formula is wallpaper, etc. According to the present invention, it has been found that when it is used as an interior material, it is excellent in decontaminating properties against adhesion of coffee and the like, and is also excellent in plasticizer migration prevention property, chemical resistance, surface hardness, weather resistance, etc. Was completed. 2.5 <(100 + x + y) / y <20 30 ≦ α · x ≦ 100 where x and y represent the respective contents (parts by weight) relative to 100 parts by weight of polyvinyl chloride, and α is the thickness of the adhesive layer (μ ) Represents.
【0006】[0006]
【発明の実施の形態】以下本発明を詳細に説明する。本
発明で用いるポリ塩化ビニル層には、ポリ塩化ビニルに
充填剤、可塑剤、安定剤、難燃剤、着色剤、発泡剤、防
かび剤、防臭剤、帯電防止剤等を含有して、シートやフ
ィルム状に成形されたもので、該充填剤としてはステア
リン酸バリウム、ステアリン酸亜鉛、ソルビタンステア
レート、炭酸カルシウム、水酸化アルミニウム、クレ
ー、コロイダルシリカ、酸化チタン、雲母、石綿などが
ある。該充填剤の含有量、即ち充填剤量(x)はポリ塩
化ビニルを100重量部とした時、20〜100重量部
が好ましい。該充填剤量(x)が20重量部未満の場
合、寸法安定性が低下し、又施工性も低下するため好ま
しくなく、100重量部を越えると柔軟性が低下し、更
に強度や耐薬品性等が低下するため好ましくない。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The polyvinyl chloride layer used in the present invention contains polyvinyl chloride as a filler, a plasticizer, a stabilizer, a flame retardant, a colorant, a foaming agent, a fungicide, a deodorant, an antistatic agent, etc. Or a film-shaped material, and examples of the filler include barium stearate, zinc stearate, sorbitan stearate, calcium carbonate, aluminum hydroxide, clay, colloidal silica, titanium oxide, mica, and asbestos. The content of the filler, that is, the filler amount (x) is preferably 20 to 100 parts by weight when polyvinyl chloride is 100 parts by weight. When the amount (x) of the filler is less than 20 parts by weight, the dimensional stability and the workability are deteriorated, which is not preferable, and when it exceeds 100 parts by weight, the flexibility is deteriorated and the strength and the chemical resistance are further reduced. And so on are not preferable.
【0007】又ポリ塩化ビニル層に含まれる可塑剤とし
ては、例えばジブチルフタレート、ジ−2−エチルヘキ
シルフタレート、ジイソオクチルフタレート、ジイソデ
シルフタレート、ジノニルフタレート、ジデシルフタレ
ート、ジラウリルフタレート、ブチルラウリルフタレー
ト、ブチルベンジルフタレート、ジシクロヘキシルフタ
レート、アルコールの炭素数13以上のフタル酸ジエス
テルなどのフタレート系可塑剤、トリクレジルホスフェ
ート、トリブチルホスフェート、トリ−2−エチルヘキ
シルホスフェートなどのホスフェート系、塩素化パラフ
ィンなどの含塩素系可塑剤、ジ−ペンタエリスリトール
脂肪酸エステルなどの多価アルコール系可塑剤、トリオ
クチルトリメリテートなどのトリメリット酸系可塑剤な
どがあり、好ましくはジブチルフタレート、ジー2−エ
チルヘキシルフタレート、ジイソオクチルフタレート、
ブチルベンジルフタレートが用いられる。Examples of the plasticizer contained in the polyvinyl chloride layer include dibutyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butyl lauryl phthalate. , Butylbenzyl phthalate, dicyclohexyl phthalate, phthalate plasticizers such as alcohol phthalic acid diesters having 13 or more carbon atoms, phosphates such as tricresyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, chlorinated paraffins and the like. Chlorine-based plasticizers, polyhydric alcohol-based plasticizers such as di-pentaerythritol fatty acid ester, and trimellitic acid-based plasticizers such as trioctyl trimellitate are preferred. Dibutyl phthalate, di 2-ethylhexyl phthalate, diisooctyl phthalate,
Butyl benzyl phthalate is used.
【0008】該可塑剤の含有量、即ち可塑剤量(y)は
ポリ塩化ビニルを100重量部とした時、10〜70重
量部が好ましく、更に好ましくは20〜60重量部であ
る。該可塑剤量が10重量部未満の場合、ポリ塩化ビニ
ルの柔軟性が不十分となるなど、いわゆる軟質ポリ塩化
ビニルとしての特性の十分な発現が期待できず、70重
量部を越えると強度等の物理的特性の低下等をきたし好
ましくない。ポリ塩化ビニル層の厚みとしては、50〜
2000μが好ましく、更に好ましくは、70〜200
μである。厚みが50μ未満の場合、こし,ボリューム
感が低下し、2000μを越えると施工性不良となり好
ましくない。The content of the plasticizer, that is, the amount (y) of the plasticizer is preferably 10 to 70 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of polyvinyl chloride. When the amount of the plasticizer is less than 10 parts by weight, the flexibility of the polyvinyl chloride becomes insufficient, and the so-called soft polyvinyl chloride cannot sufficiently exhibit its characteristics. Is unfavorable because it causes deterioration of physical properties of The thickness of the polyvinyl chloride layer is 50 to
2000μ is preferable, and more preferably 70 to 200.
μ. When the thickness is less than 50 μ, the feeling of strain and volume deteriorates, and when it exceeds 2000 μ, the workability becomes poor, which is not preferable.
【0009】本発明の接着剤層に用いる接着剤は、EV
OHとポリ塩化ビニルの両者に接着性を示すものであれ
ば特に限定されないが、例えばエチレングリコール、プ
ロピレングリコールとアジピン酸等の二塩基酸とを重縮
合して得られるポリエステル系接着剤、酢酸ビニルと塩
化ビニルの共重合体の部分ケン化物等を分子中に2個以
上のイソシアネート基を有する化合物、例えば1モルの
1,6−ヘキサメチレングリコールと2モルの2,4−
トリレンジイソシアネートとの反応物とか、1モルのト
リメチロールプロパンと3モルのトリレンジイソシアネ
ートとの反応物とを混合して得られる接着剤等の反応型
ポリウレタン系接着剤、ポリ塩化ビニル−酢酸ビニル系
接着剤又は該系に、例えば無水マレイン酸などの第3成
分を含む接着剤、ポリアクリル酸ないしアクリル酸を主
体とする共重合物を一成分とし、他の成分が塩化ビニル
系樹脂であるグラフトポリマー等を接着剤として用いる
ことができ、好ましくは反応型ポリウレタン系接着剤を
用いる。The adhesive used in the adhesive layer of the present invention is EV
The adhesive is not particularly limited as long as it exhibits adhesiveness to both OH and polyvinyl chloride. For example, a polyester-based adhesive obtained by polycondensing ethylene glycol, propylene glycol and a dibasic acid such as adipic acid, vinyl acetate A compound having two or more isocyanate groups in the molecule, such as a partially saponified product of a copolymer of vinyl chloride and vinyl chloride, for example, 1 mol of 1,6-hexamethylene glycol and 2 mol of 2,4-
Reactive polyurethane adhesives such as adhesives obtained by mixing a reaction product with tolylene diisocyanate or a reaction product with 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate, polyvinyl chloride-vinyl acetate A system adhesive or an adhesive containing a third component such as maleic anhydride, a polyacrylic acid or a copolymer mainly composed of acrylic acid as one component, and another component as a vinyl chloride resin. A graft polymer or the like can be used as an adhesive, and a reactive polyurethane adhesive is preferably used.
【0010】接着剤層の厚み(α)は特に限定されない
が、0.3μ≦α≦5.0μが好ましく、更に好ましく
は0.5μ≦α≦3.0μである。αが0.3μ未満で
は接着強度不足となり好ましくなく、5.0μを越える
と柔軟性が低下するため好ましくない。尚上記の厚み
(α)は、接着剤が溶剤系等の場合は塗布乾燥後の厚み
を表わす。The thickness (α) of the adhesive layer is not particularly limited, but is preferably 0.3 μ ≦ α ≦ 5.0 μ, more preferably 0.5 μ ≦ α ≦ 3.0 μ. If α is less than 0.3 μ, adhesive strength becomes insufficient, which is not preferable, and if it exceeds 5.0 μ, flexibility is deteriorated, which is not preferable. The above thickness (α) represents the thickness after coating and drying when the adhesive is solvent-based or the like.
【0011】本発明のEVOH層に用いるEVOHは、
エチレン含有量が20〜50モル%であり、好ましくは
25〜45モル%である。エチレン含有量が20モル%
未満では耐水性不良、汚染除去性が不充分となり好まし
くなく、50モル%を越えると可塑剤移行防止能が不充
分となり、耐油、耐溶剤性が不良となり好ましくない。The EVOH used in the EVOH layer of the present invention is
The ethylene content is 20 to 50 mol%, preferably 25 to 45 mol%. 20 mol% ethylene content
If it is less than 50 mol%, the water resistance is poor and the stain removability is insufficient, and if it exceeds 50 mol%, the plasticizer migration preventing ability is insufficient, and the oil resistance and solvent resistance are poor, which is not preferable.
【0012】又酢酸ビニル成分のケン化度としては、9
5モル%以上が好ましく、95モル%未満の場合、可塑
剤移行防止能が不充分となり、耐油、耐溶剤性が不良と
なり好ましくない。The saponification degree of the vinyl acetate component is 9
5 mol% or more is preferable, and if it is less than 95 mol%, the plasticizer migration preventing ability becomes insufficient, and oil resistance and solvent resistance are poor, which is not preferable.
【0013】EVOH層の厚みは特に限定されないが、
0.5〜20μ程度が好ましく、0.5μ未満では、十
分な可塑剤の移行防止性が発揮し難く、一方20μ以上
の厚みではそのコントロールに困難を生じる。The thickness of the EVOH layer is not particularly limited,
The thickness is preferably about 0.5 to 20 μ, and when it is less than 0.5 μ, it is difficult to exhibit sufficient plasticizer migration-preventing property, while when it is 20 μ or more, the control thereof becomes difficult.
【0014】本発明においては上記のポリ塩化ビニル、
接着剤及びEVOHからなるポリ塩化ビニル層/接着剤
層/EVOH層からなる積層体において、充填剤量
(x)、可塑剤量(y)及び接着層の厚み(α)を下式
を満足するようにコントロールすることが最大の特徴で
ある。 2.5<(100+x+y)/y<20 30≦α・x≦100 但しx、yはポリ塩化ビニル樹脂100重量部に対する
それぞれの含有量(重量部)を表し、αは接着剤層の厚
み(μ)を表す。In the present invention, the above polyvinyl chloride,
In a laminate composed of a polyvinyl chloride layer / adhesive layer / EVOH layer composed of an adhesive and EVOH, the amount of filler (x), the amount of plasticizer (y) and the thickness (α) of the adhesive layer satisfy the following formula: It is the greatest feature to control it. 2.5 <(100 + x + y) / y <20 30 ≦ α · x ≦ 100 where x and y represent the respective contents (parts by weight) relative to 100 parts by weight of the polyvinyl chloride resin, and α is the thickness of the adhesive layer ( μ).
【0015】即ちポリ塩化ビニル層中の充填剤量(x)
及び可塑剤量(y)から算出される(100+x+y)
/yの範囲としては2.5<(100+x+y)/y<
20であることが必要であり、好ましくは3.0<(1
00+x+y)/y<10、更に好ましくは3.5<
(100+x+y)/y<8.0である。(100+x
+y)/yが2.5以下の時には可塑剤のポリ塩化ビニ
ル層表面への移行が顕著となり好ましくなく、又20以
上の時には、柔軟性の低下及び二次加工性の低下が認め
られ好ましくない。That is, the amount of filler (x) in the polyvinyl chloride layer
And calculated from the amount of plasticizer (y) (100 + x + y)
The range of / y is 2.5 <(100 + x + y) / y <
It must be 20 and preferably 3.0 <(1
00 + x + y) / y <10, more preferably 3.5 <
(100 + x + y) / y <8.0. (100 + x
When + y) / y is 2.5 or less, the transfer of the plasticizer to the surface of the polyvinyl chloride layer is remarkable, which is not preferable, and when it is 20 or more, flexibility and secondary processability are deteriorated, which is not preferable. .
【0016】また接着剤層の厚み(α)とポリ塩化ビニ
ル層中の充填剤量(x)との積α・xの範囲は30≦α
・x≦100であることが必要であり、好ましくは30
≦α・x≦100であり、更に好ましくは25≦α・x
≦75である。α・xが30未満の時には汚染除去性が
低下し、基材と剥離性が顕著となり好ましくなく、又1
00を越えると、柔軟性、基材との接着力が低下し好ま
しくない。The product of the thickness (α) of the adhesive layer and the amount of filler (x) in the polyvinyl chloride layer, α · x, is in the range of 30 ≦ α.
X is required to be 100 or less, preferably 30
≦ α · x ≦ 100, more preferably 25 ≦ α · x
≦ 75. When α · x is less than 30, the stain removability deteriorates and the releasability from the substrate becomes remarkable, which is not preferable.
If it exceeds 00, the flexibility and the adhesive force with the substrate are lowered, which is not preferable.
【0017】本発明ではポリ塩化ビニル層/接着剤層/
EVOH層からなる積層体が上記の条件を満足していれ
ばよく、その各層の形成法、積層方法については特に限
定されないが、通常はポリ塩化ビニルフィルム又はシー
トの片面に接着剤を介してEVOH層を溶液コーティン
グ法、押出コーティング法、ドライラミネーション法等
の公知の方法により形成させる方法が用いられる。かか
る方法について以下に説明する。In the present invention, polyvinyl chloride layer / adhesive layer /
It suffices that the laminate comprising the EVOH layer satisfies the above conditions, and the method for forming each layer and the method for laminating each layer are not particularly limited, but the EVOH layer is usually provided on one side of the polyvinyl chloride film or sheet with an EVOH via an adhesive. A method of forming a layer by a known method such as a solution coating method, an extrusion coating method, and a dry lamination method is used. This method will be described below.
【0018】溶液コーティング法で本発明の積層体を作
製するには、マイヤーバー、コンマ、グラビア及びリバ
ースロール方式等のローラーコーティング法、スプレー
コーティング法、ディップコーティング法等の公知の方
法で、予めポリウレタン系あるいはポリエステル系の接
着剤をコートして接着剤層を設けたポリ塩化ビニル層上
に水−アルコール含有EVOH溶液をコーティングして
積層体を作製する。この場合、ウレタン系接着剤が好適
に用いられ、該接着剤の塗布量としては、乾燥後の接着
剤層の厚み(α)が上記条件を満足する塗布量であれば
良く、具体的には0.3〜5g/m2、好ましくは0.5
〜3g/m2程度である。In order to prepare the laminate of the present invention by the solution coating method, it may be prepared in advance by a known method such as a roller coating method such as a Meyer bar, a comma, a gravure and a reverse roll method, a spray coating method or a dip coating method. A polyvinyl chloride layer coated with a system or polyester adhesive to form an adhesive layer is coated with a water-alcohol-containing EVOH solution to prepare a laminate. In this case, a urethane-based adhesive is preferably used, and the amount of the adhesive applied may be such that the thickness (α) of the adhesive layer after drying satisfies the above condition, and specifically, 0.3-5 g / m 2 , preferably 0.5
It is about 3 g / m 2 .
【0019】その後、公知の方法で乾燥が行われる。具
体的には、乾燥温度が30〜150℃、好ましくは70
〜120℃程度で3秒〜5分程度加熱すればよい。かか
る乾燥において塗膜中の揮発分(水、アルコール)が除
去されるのであるが、通常揮発分が2重量%以下となる
まで行えば良い。Thereafter, drying is performed by a known method. Specifically, the drying temperature is 30 to 150 ° C., preferably 70.
It may be heated at about 120 ° C for about 3 seconds to 5 minutes. Although the volatile components (water, alcohol) in the coating film are removed by such drying, it is usually carried out until the volatile components become 2% by weight or less.
【0020】押出コーティング法で本発明の積層体を作
製するには、予めポリエステル系接着剤あるいは反応型
ポリウレタン系接着剤をポリ塩化ビニル層上のコートし
て接着剤層を設ける。接着剤については上記溶液コーテ
ィング法と同様に塗布すればよく、該接着剤の塗布量と
しては、上記と同様に接着剤層の厚み(α)を満足する
塗布量であれば良く、具体的には0.3〜5g/m2、好
ましくは0.5〜3g/m2程度である。その後公知のエ
クストルージョンコーター等の溶融押出機によりEVO
Hを120〜220℃程度の温度でポリ塩化ビニル層上
にダイより押出してコーティングして積層体を作製す
る。To prepare the laminate of the present invention by the extrusion coating method, a polyester-based adhesive or a reactive polyurethane-based adhesive is coated on the polyvinyl chloride layer in advance to form an adhesive layer. The adhesive may be applied in the same manner as in the solution coating method, and the application amount of the adhesive may be the same as the above, as long as it satisfies the thickness (α) of the adhesive layer. Is about 0.3 to 5 g / m 2 , preferably about 0.5 to 3 g / m 2 . Then, using a known melt extruder such as an extrusion coater, EVO
H is extruded and coated on the polyvinyl chloride layer from a die at a temperature of about 120 to 220 ° C. to prepare a laminate.
【0021】ドライラミネーション法で本発明の積層体
を作製するには、EVOHフィルム(未延伸、一軸延
伸、二軸延伸)を作製して、有機チタン接着剤、反応型
ポリウレタン系接着剤、ポリエステル系接着剤等の公知
の接着剤を用いてポリ塩化ビニルフィルムとドライラミ
ネートして積層体を作製する。又この場合反応型ポリウ
レタン系接着剤が好適に用いられ該接着剤のEVOHフ
ィルム又はポリ塩化ビニルフィルムへの塗布量として
は、上記と同様接着剤層の厚み(α)を満足する塗布量
であれば良く、具体的には1〜10g/m2、好ましくは
2〜5g/m2程度である。該接着剤の塗布はグラビアコ
ート、ロールコート、ドクターロールコート、ドクター
ナイフコート、バーコート、カーテンフローコートなど
の任意の手段で行われる。In order to produce the laminate of the present invention by the dry lamination method, an EVOH film (unstretched, uniaxially stretched, biaxially stretched) is prepared, and an organic titanium adhesive, a reactive polyurethane-based adhesive, a polyester-based adhesive is used. A publicly known adhesive such as an adhesive is used to dry laminate with the polyvinyl chloride film to produce a laminate. In this case, a reactive polyurethane adhesive is preferably used, and the coating amount of the adhesive on the EVOH film or polyvinyl chloride film should be the coating amount satisfying the thickness (α) of the adhesive layer as described above. It is sufficient, specifically, it is about 1 to 10 g / m 2 , preferably about 2 to 5 g / m 2 . The adhesive is applied by any means such as gravure coating, roll coating, doctor roll coating, doctor knife coating, bar coating and curtain flow coating.
【0022】本発明ではポリ塩化ビニル層に充填剤、可
塑剤を含むが、これとは別に接着剤層又はEVOH層中
の少なくとも1つの層に可塑剤、安定剤、界面活性剤、
架橋性物質(エポキシ化合物、多価金属、無機又は有機
の多塩基酸又はその塩等)、充填剤、着色剤、補強材と
しての繊維(ガラス繊維、炭素繊維等)、艶消剤(タル
ク、シリカ系粉末、ポリエチレン、ポリウレタン等の樹
脂微粒子粉末)等を本発明の効果を阻害しない範囲にお
いて配合することもできる。In the present invention, the polyvinyl chloride layer contains a filler and a plasticizer. Separately from this, at least one layer in the adhesive layer or EVOH layer contains a plasticizer, a stabilizer, a surfactant,
Crosslinkable substances (epoxy compounds, polyvalent metals, inorganic or organic polybasic acids or salts thereof, etc.), fillers, colorants, fibers as reinforcing materials (glass fibers, carbon fibers, etc.), matting agents (talc, Silica-based powder, resin fine particle powder such as polyethylene, polyurethane, etc.) may be blended within a range that does not impair the effects of the present invention.
【0023】本発明においてはかかるEVOH層の赤外
線吸収スペクトルにおける1090cm-1に対する114
0cm-1の吸光度比を0.65以上とすることが好まし
く、更に0.70〜1.30となる様にコントロールす
ることが好ましい。1090cm-1に対する1140cm-1
の吸光度比が0.65未満のときは可塑剤移行防止能が
低下し、更に耐薬品性、表面強度が不足し好ましくな
い。In the present invention, 114 at 1090 cm -1 in the infrared absorption spectrum of such an EVOH layer.
The absorbance ratio at 0 cm -1 is preferably 0.65 or more, and more preferably controlled to be 0.70 to 1.30. 1,140 cm -1 for 1,090 cm -1
When the absorbance ratio is less than 0.65, the ability to prevent migration of the plasticizer is lowered, and further chemical resistance and surface strength are insufficient, which is not preferable.
【0024】かかる赤外線吸収スペクトルにおける11
40cm-1はEVOHの結晶性バンドが現れる点であ
り、一方1090cm-1はC−0の伸縮運動に基づく吸
収が現れる点である。本発明では吸光度比を上記の如く
特定することが好ましく、換言すれば本発明では結晶性
が向上したEVOH層を用いることが好ましく、かかる
EVOH層は気体ないし液体の遮断性が著しく向上する
ため、添加物移行防止等の用途に大変適している。11 in the infrared absorption spectrum
40 cm -1 is the point where the crystalline band of EVOH appears, while 1090 cm -1 is the point where absorption based on the stretching motion of C-0 appears. In the present invention, it is preferable to specify the absorbance ratio as described above. In other words, in the present invention, it is preferable to use an EVOH layer having improved crystallinity, and since such an EVOH layer has a significantly improved gas or liquid barrier property, Very suitable for applications such as preventing additive migration.
【0025】該コントロールの方法として通常は熱処理
する方法が採用され、該処理は乾燥を実施した温度より
20℃以上高い温度、通常は100℃以上から、170
℃程度の温度で1〜60秒程度行われる。上記の溶液コ
ーティング法や押出コーティング法でEVOH層を形成
する場合には、積層後熱処理をすれば良く、ドライラミ
ネーション法においては積層前のEVOHフィルム単体
あるいは積層後に熱処理をすればよい。A heat treatment method is usually employed as the control method, and the treatment is carried out at a temperature higher than the temperature at which the drying is carried out by 20 ° C. or higher, usually from 100 ° C. or higher to 170.
The temperature is about 1 ° C. for about 1 to 60 seconds. When the EVOH layer is formed by the solution coating method or the extrusion coating method, heat treatment after lamination may be performed, and in the dry lamination method, the EVOH film before lamination or heat treatment after lamination may be performed.
【0026】又上記で述べた積層法により得られた積層
体は、意匠性等の付加価値を高めるために該積層体の少
なくとも一方の表面にエンボス加工を施して凹凸模様を
形成することも有用であり、凹凸模様としては木目導管
模様、塗装板の表面を模したもの、抽象模様、石目模
様、布目模様、万線模様、木肌模様及びそれらを組み合
わせたもの等を用いることができる。又エンボス加工に
より形成する凹凸模様の深さは模様により異なるが、壁
紙用途の場合、通常20〜100μ程度に形成するの
が、良好な立体感を付与することとなり好ましい。Further, in the laminate obtained by the above-mentioned lamination method, it is also useful to form an uneven pattern by embossing at least one surface of the laminate in order to enhance added value such as designability. As the concavo-convex pattern, a wood grain conduit pattern, a pattern imitating the surface of a coated plate, an abstract pattern, a stone pattern, a cloth pattern, a line pattern, a bark pattern, and combinations thereof can be used. Further, the depth of the uneven pattern formed by embossing varies depending on the pattern, but in the case of wallpaper use, it is preferable to form it to about 20 to 100 μ, because it gives a good three-dimensional effect.
【0027】エンボス加工により凹凸模様を形成する方
法としては、EVOH層を形成した後に所望の凹凸模様
を形成した通常の熱エンボス機を用いてエンボス加工を
施す方法や、エクストルージョンコート装置の冷却ロー
ル等に所望の凹凸模様を付与したエンボスロールを用
い、EVOH層を形成するのと同時にエンボス加工を行
う所謂ダブリングエンボス法等いわゆるメカニカルエン
ボス法あるいは発泡抑制剤や発泡促進剤を含むインクを
印刷し、発泡工程で凹凸模様をつけるケミカルエンボス
法等が用いられる。As a method for forming an uneven pattern by embossing, a method of embossing using a normal hot embossing machine in which an EVOH layer is formed and then a desired uneven pattern is formed, or a cooling roll of an extrusion coater Using an embossing roll imparted with a desired concavo-convex pattern, etc., printing an ink containing a so-called mechanical embossing method or a so-called foaming inhibitor or a foaming accelerator, which is a so-called doubling embossing method for forming an EVOH layer and at the same time embossing, A chemical embossing method or the like that gives an uneven pattern in the foaming process is used.
【0028】かくして得られた積層体は、建築用や自動
車用の内装用資材、農業用資材、事務用什器等の広い用
途を有しているが、特に壁紙等の内装用資材や農業用ビ
ニルシート等の農業用資材、塩ビレザーを用いた手帳等
の表紙、事務用品保護シート等に大変有用である。The laminate thus obtained has a wide range of uses such as interior materials for construction and automobiles, agricultural materials, office furniture, etc., but especially interior materials such as wallpaper and agricultural vinyl. It is very useful for agricultural materials such as sheets, covers such as notebooks using PVC leather, office supplies protection sheets, etc.
【0029】本発明の積層体を用いて壁紙を製作する場
合は、本発明の積層体に洋紙、和紙、不織布、アスベス
ト、紙、ガラス、繊維、布等の基材を粘(接)着を塗布
し、カレンダー法、ラミネート法等の方法で張り合わせ
る。かかる壁紙を壁に貼着する場合には、一般に用いら
れる公知の接着剤を基材に塗布し、壁面に圧着させれば
よい。When a wallpaper is produced using the laminate of the present invention, the laminate of the present invention is adhered (adhered) with a base material such as foreign paper, Japanese paper, non-woven fabric, asbestos, paper, glass, fiber or cloth. Apply and adhere by a method such as calendering or laminating. When such a wallpaper is attached to a wall, a well-known and commonly used adhesive may be applied to the base material and pressure-bonded to the wall surface.
【0030】本発明の積層体を農業用ビニルシートに用
いる場合も壁紙等の内装用資材と同様の方法で得られた
ポリ塩化ビニル層/接着剤層/EVOH層からなる積層
体をそのまま利用することができる。Also when the laminate of the present invention is used for an agricultural vinyl sheet, the laminate comprising a polyvinyl chloride layer / adhesive layer / EVOH layer obtained by the same method as the interior material such as wallpaper is used as it is. be able to.
【0031】[0031]
【実施例】以下、実施例を挙げて本発明を具体的に説明
する。尚、実施例中、「部」、「%」とあるのは、特に
断りのない限り重量基準である。 実施例1 厚さ12μエチレン含有30モル%、酢酸ビニルのケン
化度99.8モル%のEVOHフィルム(一軸延伸フィ
ルム)にグラビアコーターで接着剤として固形分濃度2
0重量%の反応型ポリウレタン系接着剤と硬化剤cat
−10(東洋モートン社製)を塗布量2g/m2となるよ
うにコートし(乾燥後の厚さ0.5μ)、温度110
℃、3分間乾燥後、軟質ポリ塩化ビニル100部に対し
て可塑剤として、ジ−2−エチルヘキシルフタレート5
0部、充填剤としてステアリン酸バリウム50部を含有
する厚さ1mmのシートにドライラミネーション法で1
10℃の温度条件下、EVOHフィルムを積層した。そ
の後に木目導管模様を形成した通常の熱エンボス機を用
いてエンボス加工を施した。なお積層体を作製する際に
用いたEVOHフィルムは120〜150℃で1分間熱
処理を施したもので、該フィルムの赤外線吸収スペクト
ルの吸光度比(D1140/D1090)をJISK−0117
に基づいて測定したところ0.82であった。更に該積
層体について下記の接着力、汚染除去性、可塑剤移行防
止能、耐薬品性、表面強度、耐候性の評価を行った。EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, “part” and “%” are based on weight unless otherwise specified. Example 1 An EVOH film (uniaxially stretched film) having a thickness of 12 μm, containing 30 mol% of ethylene, and a saponification degree of vinyl acetate of 99.8 mol% was used as an adhesive with a gravure coater to have a solid content concentration of 2
0% by weight reactive polyurethane adhesive and curing agent cat
-10 (manufactured by Toyo Morton Co., Ltd.) was coated at a coating amount of 2 g / m 2 (thickness after drying 0.5 μ), and the temperature was 110.
After drying at 3 ° C for 3 minutes, di-2-ethylhexyl phthalate 5 was added as a plasticizer to 100 parts of soft polyvinyl chloride.
1 part by dry lamination method to a 1 mm thick sheet containing 0 part and 50 parts barium stearate as a filler.
EVOH films were laminated under a temperature condition of 10 ° C. After that, embossing was performed using an ordinary hot embossing machine having a wood grain pattern. The EVOH film used for producing the laminate was heat-treated at 120 to 150 ° C. for 1 minute, and the absorbance ratio (D 1140 / D 1090 ) of the infrared absorption spectrum of the film was JISK-0117.
It was 0.82 when measured based on. Further, the following adhesive strength, stain removability, plasticizer migration preventing ability, chemical resistance, surface strength, and weather resistance of the laminate were evaluated.
【0032】また該積層体を用いて積層体/反応型ウレ
タン系粘着剤/基材(洋紙)の構成からなる壁紙を作製
し壁に貼着したが、従来の壁紙と何ら遜色のない作業性
及び仕上がりであった。A wallpaper comprising a laminate / reactive urethane-based pressure-sensitive adhesive / base material (paper) was prepared using the laminate and attached to a wall, but the workability was no different from that of the conventional wallpaper. And it was finished.
【0033】接着力 EVOH層とポリ塩化ビニル層の接着力を積層体完成直
後と10日後にT−ピール法で接着力を測定し、経時的
な接着力の低下を下記の基準で評価した。 ○・・・1%未満 △・・・1〜5%未満 ×・・・5%以上Adhesive strength The adhesive strength between the EVOH layer and the polyvinyl chloride layer was measured by the T-peel method immediately after the completion of the laminate and 10 days later, and the decrease in adhesive strength over time was evaluated according to the following criteria. ○: less than 1% △: 1 to less than 5% ×: 5% or more
【0034】汚染除去性 積層体のEVOH表面に70℃のホットコーヒーを直径
2cm程度の大きさに塗布あるいは滴下し、室温で24時
間放置後に水を含ませたさらし木綿でふき取った後の積
層体の汚染除去性を以下の様に評価した。なおポリ塩化
ビニルシート単独層についても同様に行った。 ○・・・完全にふき取れて汚染の痕跡が残らない。 △・・・ポリ塩化ビニルシート単独のよりも汚染除去性
は良いが、汚染の痕跡が残る。 ×・・・ポリ塩化ビニルシート単独と同じ程度の汚染除
去性で汚染の痕跡が残る。Decontamination property A laminate after hot coffee at 70 ° C. having a diameter of about 2 cm is applied or dropped on the EVOH surface of the laminate and left standing at room temperature for 24 hours and wiped off with bleached cotton soaked with water The stain removability of was evaluated as follows. The same procedure was performed for the polyvinyl chloride sheet single layer. ○: Completely wiped off and no trace of contamination remains. Δ: The stain removability is better than that of the polyvinyl chloride sheet alone, but traces of stain remain. X: Traces of contamination remain with the same level of stain removability as the polyvinyl chloride sheet alone.
【0035】可塑剤移行防止能 70℃、90%RHの雰囲気下、100mm×100m
mの積層体のEVOH表面に直径50mm、厚み3mm
のポリスチレン円板を接触させ、その上から10kg/
m2の荷重をかけ、10日間の可塑剤の移行量をポリスチ
レン円板の単位面積当たりの重量変化で測定した。 ○・・・1mg/cm2未満 △・・・1〜1.5mg/cm2未満 ×・・・1.5mg/cm2以上Prevention of migration of plasticizer 100 mm × 100 m in an atmosphere of 70 ° C. and 90% RH
50 mm in diameter and 3 mm in thickness on the EVOH surface of the laminated body of m
Contact the polystyrene disc of 10 kg /
The load of m 2 was applied, and the transfer amount of the plasticizer for 10 days was measured by the weight change per unit area of the polystyrene disc. ○ ··· 1mg / cm 2 less than △ ··· 1~1.5mg / cm 2 less than × ··· 1.5mg / cm 2 or more
【0036】耐薬品性 20℃、7日間100mm×100mmの積層体のEV
OH表面に酢酸エチル、メチルエチルケトン、トルエン
を含ませた各スポンジ(100mmφ円形×10mm厚
み)を直接接触させた後、該積層体を取り出し、重量変
化を測定して以下の様に評価した。 ○・・・3種の溶剤すべてにおいて、0.01重量%未
満の重量増 ×・・・3種の溶剤の内少なくとも1種において0.0
1重量%以上の重量増Chemical resistance EV of 100 mm × 100 mm laminated body at 20 ° C. for 7 days
Each sponge (100 mmφ circle × 10 mm thickness) containing ethyl acetate, methyl ethyl ketone, and toluene was directly contacted with the OH surface, and then the laminate was taken out and the weight change was measured and evaluated as follows. ◯: Weight increase of less than 0.01% by weight in all three solvents x: 0.0 in at least one of the three solvents
Weight increase of 1% or more
【0037】表面強度 JIS L 0823による表面摩耗堅ロウ度テストを
行い、以下の様に評価した。 ○・・・表面が試験前と変化なし。 △・・・表面がやや摩耗された状態である。 ×・・・表面が完全に摩耗された状態である。Surface Strength A surface abrasion / hardness test according to JIS L 0823 was conducted and evaluated as follows. ○: The surface is the same as before the test. Δ: The surface is slightly worn. X: The surface is completely worn.
【0038】耐候性 100mm×100mmの積層体のEVOH表面に25
4nmのUV照射(15W)を光源から30cm離し、
60日間放置した時の黄変を、YI値で以下の様に評価
した。 ○・・・2未満 △・・・2〜5未満 ×・・・5以上Weather resistance 25 on the EVOH surface of a 100 mm × 100 mm laminate
UV irradiation of 4 nm (15 W) is separated from the light source by 30 cm,
Yellowing after standing for 60 days was evaluated by the following YI value. ○ ・ ・ ・ less than 2 △ ・ ・ ・ less than 2-5 × ・ ・ ・ 5 or more
【0039】実施例2〜4 充填剤、可塑剤の量、接着層の厚みを表1に示す様に適
宜変化させて、実施例1と同様に積層体を作製し、同様
に評価した。Examples 2 to 4 A laminate was prepared in the same manner as in Example 1 except that the amounts of the filler, the plasticizer and the thickness of the adhesive layer were changed as shown in Table 1, and the same evaluation was performed.
【0040】実施例5 エンボスロールの替わりに、通常のロールを用いた以外
は、実施例1と同様に積層体を作製し同様に評価した。Example 5 A laminate was prepared and evaluated in the same manner as in Example 1 except that a normal roll was used instead of the embossing roll.
【0041】実施例6 エチレン含有30%、酢酸ビニルのケン化度99.8モ
ル%のEVOH16部、水42部、メタノール42部か
らなる溶液を、グラビア方式のローラーコーティング法
で、予め反応型ポリウレタン系接着剤をアンカーコート
して接着剤層を設けたポリ塩化ビニル層上に塗布量とし
ては15〜20g/m2(wet時)でコーティングして
積層体を作製する。その後、乾燥温度が100℃、で1
80秒加熱する。又続いて170℃程度の温度で熱処理
をした。その後実施例1と同様にエンボス加工を行って
得られた積層体について同様に評価した。Example 6 A solution of 16 parts of EVOH having an ethylene content of 30% and a saponification degree of vinyl acetate of 99.8 mol%, 42 parts of water, and 42 parts of methanol was prepared in advance by a gravure roller coating method to prepare a reactive polyurethane. A polyvinyl chloride layer provided with an adhesive layer by anchor coating with a system adhesive is coated at a coating amount of 15 to 20 g / m 2 (when wet) to prepare a laminate. Then, the drying temperature is 100 ℃, 1
Heat for 80 seconds. Further, subsequently, heat treatment was performed at a temperature of about 170 ° C. After that, the laminate obtained by performing embossing in the same manner as in Example 1 was evaluated in the same manner.
【0042】比較例1〜5 充填剤量、可塑剤量、接着剤層の厚みを表1に示す様に
適宜変化させて実施例1と同様に積層体を作製し、同様
に評価した。実施例及び比較例の評価結果を表3に示
す。Comparative Examples 1 to 5 Laminates were prepared in the same manner as in Example 1 except that the amount of filler, the amount of plasticizer, and the thickness of the adhesive layer were changed as shown in Table 1, and the same evaluation was performed. Table 3 shows the evaluation results of the examples and comparative examples.
【0043】[0043]
【表1】 ポリ塩化ビニル層 接着剤層 EVOH層中のEVOH 充填剤 可塑剤 の厚み エチレン含量 ケン化度 x(部) y(部) α(μ) (モル%) (モル%) 実施例1 50 50 1.0 30 99.8 実施例2 30 45 1.0 30 99.8 実施例3 70 30 1.0 35 99.8 実施例4 50 50 1.5 35 99.8 実施例5 50 50 1.0 45 99.8実施例6 50 50 1.0 45 99.8 比較例1 50 50 0.2 30 99.8 比較例2 50 150 1.0 30 99.8 比較例3 120 10 0.5 30 99.8 比較例4 50 50 3.0 30 99.8比較例5 10 90 2.5 30 99.8 Table 1 Polyvinyl chloride layer Adhesive layer EVOH filler in EVOH layer Thickness of plasticizer Ethylene content Saponification degree x (part) y (part) α (μ) (mol%) (mol%) Example 1 50 50 1.0 30 99.8 Example 2 30 45 1.0 30 99.8 Example 3 70 30 1.0 1.0 35 99.8 Example 4 50 50 1.5 35 35 99.8 Example 5 50 50 1.0 45 99.8 Example 6 50 50 1.0 45 99.8 Comparative Example 1 50 50 0.2 30 99.8 Comparative Example 2 50 150 1.0 30 99.8 Comparative Example 3 120 10 0. 5 30 99.8 Comparative Example 4 50 50 3.0 3.0 30 99.8 Comparative Example 5 10 90 2.5 30 30 99.8
【0044】[0044]
【表2】 [Table 2]
【0045】[0045]
【表3】 接着力 汚染除 可塑剤移 耐薬品性 表面強度 耐候性 去性 行防止能 実施例1 ○ ○ ○ ○ ○ ○ 実施例2 ○ ○ ○ ○ ○ ○ 実施例3 ○ ○ ○ ○ ○ ○ 実施例4 ○ ○ ○ ○ ○ ○ 実施例5 ○ ○ ○ ○ △ ○実施例6 ○ ○ ○ ○ 〇 ○ 比較例1 × △ △ ○ △ × 比較例2 × × × × × × 比較例3 × ○ ○ ○ ○ △ 比較例4 × ○ △ △ ○ ○ 比較例5 × × × × × × [Table 3] Adhesion force Contamination removal Plasticizer transfer Chemical resistance Surface strength Weather resistance Abrasion resistance Ability example 1 ○ ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ ○ Example 5 ○ ○ ○ ○ △ ○ Example 6 ○ ○ ○ ○ ○ ○ Comparative Example 1 × △ △ ○ △ × Comparative Example 2 × × × × × × Comparative Example 3 × ○ ○ ○ ○ △ Comparative Example 4 × ○ △ △ ○ ○ Comparative Example 5 × × × × × ×
【0046】[0046]
【発明の効果】本発明のポリ塩化ビニル層/接着剤層/
EVOH層からなる積層体はポリ塩化ビニル層の可塑剤
量、充填剤量及び接着剤層の厚みが特定の関係を満足す
るため、汚染除去性に優れ、更には可塑剤移行防止能、
耐薬品性、表面強度、耐候性等にも優れ、特に壁紙等の
内装用資材に大変有用である。The polyvinyl chloride layer / adhesive layer / of the present invention
Since the laminate comprising the EVOH layer satisfies the specific relationships of the plasticizer amount of the polyvinyl chloride layer, the filler amount, and the thickness of the adhesive layer, it is excellent in stain removability and further has a plasticizer migration preventing ability,
It has excellent chemical resistance, surface strength, weather resistance, etc. and is very useful especially for interior materials such as wallpaper.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 B32B 27/22 B32B 27/22 27/30 101 27/30 101 33/00 33/00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location B32B 27/22 B32B 27/22 27/30 101 27/30 101 33/00 33/00
Claims (4)
ニル層/接着剤層/エチレン含有量20〜50モル%酢
酸ビニル成分のケン化度95モル%以上のエチレン−ビ
ニルアルコール共重合体層からなり、該ポリ塩化ビニル
層に含有される充填剤量(x)、可塑剤量(y)及び接
着剤層の厚み(α)が下式を満足することを特徴とする
積層体。 2.5<(100+x+y)/y<20 30≦α・x≦100 但しx、yはポリ塩化ビニル100重量部に対するそれ
ぞれの含有量(重量部)を表し、αは接着剤層の厚み
(μ)を表す。1. A polyvinyl chloride layer containing a filler and a plasticizer / adhesive layer / ethylene content of 20 to 50 mol% and an ethylene-vinyl alcohol copolymer layer having a saponification degree of 95 mol% or more of a vinyl acetate component. And a filler amount (x), a plasticizer amount (y), and an adhesive layer thickness (α) contained in the polyvinyl chloride layer satisfying the following formulas. 2.5 <(100 + x + y) / y <20 30 ≦ α · x ≦ 100 where x and y represent the respective contents (parts by weight) relative to 100 parts by weight of polyvinyl chloride, and α is the thickness of the adhesive layer (μ ) Represents.
の赤外線吸収スペクトルの1090cm-1に対する114
0cm-1の吸光度比が0.65以上であることを特徴とす
る請求項1記載の積層体。2. 114 to 1090 cm -1 of infrared absorption spectrum of ethylene-vinyl alcohol copolymer layer
The laminated body according to claim 1, wherein the absorbance ratio at 0 cm -1 is 0.65 or more.
施したことを特徴とする請求項1あるいは2記載の積層
体。3. The laminate according to claim 1, wherein at least one surface is embossed.
する請求項1〜3いずれか記載の積層体。4. The laminated body according to claim 1, wherein the laminated body is an interior material.
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JP23606595A JP4191804B2 (en) | 1995-08-21 | 1995-08-21 | Laminated body |
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JP4191804B2 JP4191804B2 (en) | 2008-12-03 |
Family
ID=16995210
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001058379A (en) * | 1999-08-23 | 2001-03-06 | Yamade Techno Kk | Outdoor waterproof sheet and execution thereof |
EP2647660A1 (en) * | 2012-04-02 | 2013-10-09 | Sika Technology AG | PVC-membrane with reduced plasticizer migration |
US9873228B2 (en) | 2015-03-18 | 2018-01-23 | Ricoh Company, Ltd. | Powder material for three dimensional modeling, kit for three dimensional modeling, green body for three dimensional modeling, method of manufacturing three dimensional object, method of manufacturing three-dimensional green body, device for manufacturing three-dimensional object, and device for manufacturing three-dimensional green body |
-
1995
- 1995-08-21 JP JP23606595A patent/JP4191804B2/en not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001058379A (en) * | 1999-08-23 | 2001-03-06 | Yamade Techno Kk | Outdoor waterproof sheet and execution thereof |
EP2647660A1 (en) * | 2012-04-02 | 2013-10-09 | Sika Technology AG | PVC-membrane with reduced plasticizer migration |
WO2013150009A1 (en) * | 2012-04-02 | 2013-10-10 | Sika Technology Ag | Pvc membrane with reduced plasticizer migration |
CN104220498A (en) * | 2012-04-02 | 2014-12-17 | Sika技术股份公司 | Pvc membrane with reduced plasticizer migration |
US20150118404A1 (en) * | 2012-04-02 | 2015-04-30 | Sika Technology Ag | Pvc membrane with reduced plasticizer migration |
US9428912B2 (en) | 2012-04-02 | 2016-08-30 | Sika Technology Ag | PVC membrane with reduced plasticizer migration |
US9873228B2 (en) | 2015-03-18 | 2018-01-23 | Ricoh Company, Ltd. | Powder material for three dimensional modeling, kit for three dimensional modeling, green body for three dimensional modeling, method of manufacturing three dimensional object, method of manufacturing three-dimensional green body, device for manufacturing three-dimensional object, and device for manufacturing three-dimensional green body |
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