JP2003238921A - Binder - Google Patents
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- JP2003238921A JP2003238921A JP2002038131A JP2002038131A JP2003238921A JP 2003238921 A JP2003238921 A JP 2003238921A JP 2002038131 A JP2002038131 A JP 2002038131A JP 2002038131 A JP2002038131 A JP 2002038131A JP 2003238921 A JP2003238921 A JP 2003238921A
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- weight
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリビニルアルコ
ール系樹脂を主成分とするバインダー（接着剤）に関
し、更に詳しくは、耐着色（変色）性に優れ、かつ湿潤
状態での接着性にも優れたバインダーに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder (adhesive) containing a polyvinyl alcohol-based resin as a main component, and more specifically, it has excellent resistance to discoloration (discoloration) and adhesiveness in a wet state. Regarding the binder.
【０００２】[0002]
【従来の技術】従来より、ポリビニルアルコール系樹脂
（以下、ＰＶＡと略記することがある）は、バインダー
（接着剤）として各種用途に用いられており、セラッミ
クやガラス繊維等の無機物用のバインダーから、顔料、
染料、塗料等のバインダー、合成繊維からなる不織布等
のバインダーまで幅広く利用されている。2. Description of the Related Art Conventionally, polyvinyl alcohol-based resins (hereinafter sometimes abbreviated as PVA) have been used as binders (adhesives) for various purposes, and are used as binders for inorganic substances such as ceramics and glass fibers. , Pigments,
It is widely used in binders such as dyes and paints, and in binders such as nonwoven fabrics made of synthetic fibers.
【０００３】そして、これらの用途の多くが、接着後高
温で養生されたり、あるいは養生後も高温状態で使用さ
れることがあり、これらの熱履歴により該バインダーが
変色（着色）を起こして、最終的にその商品価値を損な
う恐れがあり、また、一方で、ガラス繊維不織布用バイ
ンダーやボード用バインダー等の用途においては、接着
後の製品が建材用途に用いられることも多く、この場
合、屋内での適用時には結露水等により、又屋外での適
用時には雨等により湿潤状態に晒されることも多く、湿
潤状態での接着性も要求されるところである。Many of these applications are sometimes cured at a high temperature after bonding or used at a high temperature even after curing. The heat history of these causes the binder to change color (color), In the end, the commercial value may be impaired, and on the other hand, in applications such as binders for glass fiber non-woven fabrics and binders for boards, products after bonding are often used for building materials, in which case they are used indoors. It is often exposed to a wet state by dew condensation water or the like when applied in the above, or by rain or the like when applied outdoors, and adhesiveness in the wet state is also required.
【０００４】かかる熱による変色の対策として、本出願
人は、特公昭５２−２３３８２号公報で、ラクトン環を
有する変性ＰＶＡに特定の条件でヒドラジンを反応させ
ることを提案した。As a countermeasure against such discoloration due to heat, the present applicant has proposed in Japanese Patent Publication No. 52-23382 to react modified PVA having a lactone ring with hydrazine under specific conditions.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
特公昭５２−２３３８２号公報開示技術では、耐着色性
の改善効果は見られるものの、ＰＶＡの接着性について
は十分に考慮しておらず、湿潤状態での接着力について
は改善の余地があることが判明した。However, in the technique disclosed in Japanese Patent Publication No. 52-23382, although the effect of improving the coloring resistance can be seen, the adhesiveness of PVA is not sufficiently taken into consideration and the wetness is not considered. It was found that there is room for improvement in the adhesive strength in the state.
【０００６】[0006]
【問題を解決するための手段】そこで、本発明者はかか
る事情を鑑みて、熱履歴による着色の影響を受けにく
く、かつ湿潤状態での接着性が良好なバインダーを得る
べく鋭意研究を重ねた結果、ＰＶＡ（Ａ）、ｐＫａが
３．５以下の有機酸（Ｂ）及びヒドラジド化合物（Ｃ）
を含有してなるバインダーが、上記の課題を解決できる
ことを見出して本発明を完成するに至った。In view of the above circumstances, the present inventor has conducted diligent research in order to obtain a binder which is not easily affected by coloring due to heat history and has good adhesiveness in a wet state. As a result, PVA (A), an organic acid having a pKa of 3.5 or less (B) and a hydrazide compound (C)
The present invention has been completed by finding that a binder containing the above can solve the above problems.
【０００７】[0007]
【発明の実施の形態】以下に本発明を詳しく説明する。
本発明に用いられるＰＶＡ（Ａ）は特に限定されるもの
ではなく、一般的にはポリ酢酸ビニルの低級アルコール
溶液をアルカリや酸などのケン化触媒によってケン化し
たケン化物又はその誘導体が用いられ、更には酢酸ビニ
ルと共重合性を有する単量体と酢酸ビニルとの共重合体
のケン化物等を用いることもできる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The PVA (A) used in the present invention is not particularly limited, and generally a saponified product obtained by saponifying a lower alcohol solution of polyvinyl acetate with a saponification catalyst such as an alkali or an acid or a derivative thereof is used. Further, it is also possible to use a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability with vinyl acetate.
【０００８】該単量体としては、例えばエチレン、プロ
ピレン、イソブチレン、α−オクテン、α−ドデセン、
α−オクタデセン等のオレフィン類、アクリル酸、メタ
クリル酸、クロトン酸、マレイン酸、無水マレイン酸、
イタコン酸等の不飽和酸類あるいはその塩あるいはモノ
又はジアルキルエステル等、アクリロニトリル、メタア
クリロニトリル等のニトリル類、アクリルアミド、メタ
クリルアミド等のアミド類、エチレンスルホン酸、アリ
ルスルホン酸、メタアリルスルホン酸等のオレフィンス
ルホン酸あるいはその塩、アルキルビニルエーテル類、
Ｎ−アクリルアミドメチルトリメチルアンモニウムクロ
ライド、アリルトリメチルアンモニウムクロライド、ジ
メチルジアリルアンモニウムクロリド、ジメチルアリル
ビニルケトン、Ｎ−ビニルピロリドン、塩化ビニル、塩
化ビニリデン、ポリオキシエチレン（メタ）アリルエー
テル、ポリオキシプロピレン（メタ）アリルエーテルな
どのポリオキシアルキレン（メタ）アリルエーテル、ポ
リオキシエチレン（メタ）アクリレート、ポリオキシプ
ロピレン（メタ）アクリレート等のポリオキシアルキレ
ン（メタ）アクリレート、ポリオキシエチレン（メタ）
アクリルアミド、ポリオキシプロピレン（メタ）アクリ
ルアミド等のポリオキシアルキレン（メタ）アクリルア
ミド、ポリオキシエチレン（１−（メタ）アクリルアミ
ド−１，１−ジメチルプロピル）エステル、ポリオキシ
エチレンビニルエーテル、ポリオキシプロピレンビニル
エーテル、ポリオキシエチレンアリルアミン、ポリオキ
シプロピレンアリルアミン、ポリオキシエチレンビニル
アミン、ポリオキシプロピレンビニルアミン等が挙げら
れる。Examples of the monomer include ethylene, propylene, isobutylene, α-octene, α-dodecene,
Olefins such as α-octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride,
Unsaturated acids such as itaconic acid or salts thereof or mono- or dialkyl esters thereof, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, olefins such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid Sulfonic acid or its salt, alkyl vinyl ethers,
N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethyldiallylammonium chloride, dimethylallyl vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl Polyoxyalkylene (meth) allyl ether such as ether, polyoxyethylene (meth) acrylate, polyoxyalkylene (meth) acrylate such as polyoxypropylene (meth) acrylate, polyoxyethylene (meth)
Acrylamide, polyoxyalkylene (meth) acrylamide such as polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, poly Examples thereof include oxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine and the like.
【０００９】かかるＰＶＡ（Ａ）のケン化度は特に限定
されないが、水溶液として使用することを考慮すれば、
５０モル％以上とすることが好ましく、かかるケン化度
のより好ましい下限は６０モル％で、更には７０モル
％、特には８０モル％である。かかるケン化度の上限は
特に制限はないが、水溶液としたときの安定性を考慮す
れば、上限は９９．９モル％が好ましく、更には９９．
７モル％、特には９９．５モル％である。The degree of saponification of such PVA (A) is not particularly limited, but considering that it is used as an aqueous solution,
The amount is preferably 50 mol% or more, and the more preferable lower limit of the saponification degree is 60 mol%, further 70 mol%, and particularly 80 mol%. The upper limit of the degree of saponification is not particularly limited, but considering the stability in an aqueous solution, the upper limit is preferably 99.9 mol%, and further 99.
It is 7 mol%, especially 99.5 mol%.
【００１０】また、平均重合度（ＪＩＳ Ｋ６７２６に
準拠）についても特に限定されないが、２００〜４００
０が好ましく、かかる平均重合度が２００未満では、接
着性が低下する傾向にあり、逆に４０００を越えると水
溶液とした場合の粘度が高くなりすぎて好ましくない。
かかる平均重合度のより好ましい下限は３００で、さら
には４００、特には５００で、逆により好ましい上限は
３８００で、さらには３５００、特には３２００であ
る。The average degree of polymerization (according to JIS K6726) is also not particularly limited, but it is 200 to 400.
0 is preferable, and when the average degree of polymerization is less than 200, the adhesiveness tends to decrease, and conversely, when it exceeds 4000, the viscosity in an aqueous solution becomes too high, which is not preferable.
A more preferable lower limit of the average degree of polymerization is 300, further 400, particularly 500, and a more preferable upper limit thereof is 3800, further 3500, particularly 3200.
【００１１】さらに、本発明においては、ＰＶＡ中の酢
酸ナトリウム量を２重量％以下にすることが着色防止効
果向上の点で好ましく、より好ましい上限は１．５重量
％で、さらには１．０重量％である。ＰＶＡ中の酢酸ナ
トリウム量の調整にあたっては、ＰＶＡをメタノールや
メタノール／酢酸メチル混合溶液等で洗浄することによ
り調整することができるが、これに限定されるものでは
ない。Further, in the present invention, it is preferable that the amount of sodium acetate in PVA is 2% by weight or less from the viewpoint of improving the coloring prevention effect, and the more preferable upper limit is 1.5% by weight, and further 1.0%. % By weight. The amount of sodium acetate in PVA can be adjusted by washing PVA with methanol, a mixed solution of methanol / methyl acetate, or the like, but is not limited thereto.
【００１２】本発明に用いられるｐＫａが３．５以下の
有機酸（Ｂ）としては、アスパラギン酸（ｐＫａ＝１．
９３）、クエン酸（ｐＫａ＝２．９０）、サリチル酸
（ｐＫａ＝２．８１）、シュウ酸（ｐＫａ＝１．０
４）、ｄ−酒石酸（ｐＫａ＝２．８２）、ピクリン酸
（ｐＫａ＝０．３３）、フマル酸（ｐＫａ＝２．８
５）、マレイン酸（ｐＫａ＝１．７５）、マロン酸（ｐ
Ｋａ＝２．６５）、リンゴ酸（ｐＫａ＝３．２４）、ニ
トロ酢酸（ｐＫａ＝１．４６）、フルオロ酢酸（ｐＫａ
＝２．５９）、クロロ酢酸（ｐＫａ＝２．６８）、ジク
ロロ酢酸（ｐＫａ＝１．３０）、トリクロロ酢酸（ｐＫ
ａ＝０．６６）、ヨード酢酸（ｐＫａ＝２．９８）、２
−クロロプロピオン酸（ｐＫａ＝２．７１）、ｏ−アミ
ノ安息香酸（ｐＫａ＝２．００）、ｍ−アミノ安息香酸
（ｐＫａ＝３．１２）、ｐ−アミノ安息香酸（ｐＫａ＝
２．４１）、ｏ−ニトロ安息香酸（ｐＫａ＝２．７
１）、ｍ−ニトロ安息香酸（ｐＫａ＝３．４５）、ｐ−
ニトロ安息香酸（ｐＫａ＝３．４４）、ｏ−ブロモ安息
香酸（ｐＫａ＝２．８５）、ｏ−クロロ安息香酸（ｐＫ
ａ＝２．９２）等を挙げることができ、中でも、ｐＫａ
が１．０〜３．４の有機酸が好ましく、さらには１．５
〜３．３で、本発明ではｐＫａが３．５を越える有機酸
を用いても目的を達成することは困難である。As the organic acid (B) having a pKa of 3.5 or less used in the present invention, aspartic acid (pKa = 1.
93), citric acid (pKa = 2.90), salicylic acid (pKa = 2.81), oxalic acid (pKa = 1.0).
4), d-tartaric acid (pKa = 2.82), picric acid (pKa = 0.33), fumaric acid (pKa = 2.8).
5), maleic acid (pKa = 1.75), malonic acid (p
Ka = 2.65), malic acid (pKa = 3.24), nitroacetic acid (pKa = 1.46), fluoroacetic acid (pKa
= 2.59), chloroacetic acid (pKa = 2.68), dichloroacetic acid (pKa = 1.30), trichloroacetic acid (pK
a = 0.66), iodoacetic acid (pKa = 2.98), 2
-Chloropropionic acid (pKa = 2.71), o-aminobenzoic acid (pKa = 2.00), m-aminobenzoic acid (pKa = 3.12), p-aminobenzoic acid (pKa =
2.41), o-nitrobenzoic acid (pKa = 2.7).
1), m-nitrobenzoic acid (pKa = 3.45), p-
Nitrobenzoic acid (pKa = 3.44), o-bromobenzoic acid (pKa = 2.85), o-chlorobenzoic acid (pK
a = 2.92) and the like, among which pKa
Is preferably 1.0 to 3.4, more preferably 1.5
In the present invention, it is difficult to achieve the object even when an organic acid having a pKa of more than 3.5 is used.
【００１３】なお、本発明におけるｐＫａとは酸解離定
数であり、多塩基酸の場合は、第１段目の値をＫａとし
た時に、ｐＫａ＝−ｌｏｇＫａで定義される値である。In the present invention, pKa is an acid dissociation constant, and in the case of polybasic acid, it is a value defined by pKa = -logKa when the value of the first step is Ka.
【００１４】また、本発明に用いられるヒドラジド化合
物（Ｃ）としては、ホルムヒドラジド、アセトヒドラジ
ド、メチルカルバゼード、ラウリン酸ヒドラジド、サリ
チル酸ヒドラジド等のモノヒドラジドや、シュウ酸ジヒ
ドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジ
ド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジ
ド、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジ
ド、ドデカンジヒドラジド、カルボヒドラジド等のジヒ
ドラジド、更にはポリアクリル酸ヒドラジド等を挙げる
ことができ、これらの中でも、ジヒドラジド化合物が好
ましく、更にはアジピン酸ジヒドラジド、カルボヒドラ
ジドが好適に用いられる。Examples of the hydrazide compound (C) used in the present invention include monohydrazides such as form hydrazide, acetohydrazide, methylcarbazide, lauric acid hydrazide and salicylic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide and amber. Dihydrazides such as acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, dodecane dihydrazide, carbohydrazide, and further polyacrylic acid hydrazide can be mentioned. Among these, dihydrazide compounds are preferable, Further, adipic acid dihydrazide and carbohydrazide are preferably used.
【００１５】本発明のバインダーは、上記の如き（Ａ）
〜（Ｃ）を含有するもので、その含有（配合）割合は特
に限定されないが、（Ａ）に対する（Ｂ）の含有量は、
０．１〜５重量％であることが好ましく、かかる含有量
が０．１重量％未満では、着色防止効果が小さく、逆に
５重量％を越えると湿潤時の接着力が低下する傾向にあ
り好ましくない。かかる（Ｂ）の含有量のより好ましい
下限は０．２重量％で、更には０．３重量％、特には
０．４重量％で、逆により好ましい上限は４重量％で、
更には３重量％、特には２重量％である。The binder of the present invention has the above-mentioned (A).
To (C), the content (blending) ratio thereof is not particularly limited, but the content of (B) relative to (A) is
The content is preferably 0.1 to 5% by weight, and when the content is less than 0.1% by weight, the anti-coloring effect is small, and conversely, when the content exceeds 5% by weight, the adhesive strength when wet tends to decrease. Not preferable. The more preferable lower limit of the content of (B) is 0.2% by weight, further 0.3% by weight, particularly 0.4% by weight, and the more preferable upper limit is 4% by weight.
Furthermore, it is 3% by weight, especially 2% by weight.
【００１６】また、（Ａ）に対する（Ｃ）の含有量も、
０．１〜５重量％であることが好ましく、かかる含有量
が０．１重量％未満では、着色防止効果が小さく、逆に
５重量％を越えると湿潤時の接着力が低下する傾向にあ
り好ましくない。かかる（Ｂ）の含有量のより好ましい
下限は０．２重量％で、更には０．３重量％、特には
０．４重量％で、逆により好ましい上限は４重量％で、
更には３重量％、特には２重量％である。The content of (C) relative to (A) is also
The content is preferably 0.1 to 5% by weight, and when the content is less than 0.1% by weight, the anti-coloring effect is small, and conversely, when the content exceeds 5% by weight, the adhesive strength when wet tends to decrease. Not preferable. The more preferable lower limit of the content of (B) is 0.2% by weight, further 0.3% by weight, particularly 0.4% by weight, and the more preferable upper limit is 4% by weight.
Furthermore, it is 3% by weight, especially 2% by weight.
【００１７】本発明のバインダーは、上記の如き（Ａ）
〜（Ｃ）を含有してなるもので、その混合方法について
は特に制限はないが、通常は水溶液として用いられるこ
とが多いため、（Ａ）〜（Ｃ）を一括混合した後に水に
溶解させる方法、（Ａ）を水に溶解させた後、（Ｂ）及
び（Ｃ）或いはこれらの水溶液を添加する方法等を挙げ
ることができる。The binder of the present invention has the above-mentioned (A).
~ (C) is contained, and the mixing method is not particularly limited, but since it is usually used as an aqueous solution, (A) to (C) are collectively mixed and then dissolved in water. Examples of the method include a method of dissolving (A) in water and then adding (B) and (C) or an aqueous solution thereof.
【００１８】かかるバインダーの水溶液の濃度は、被着
体の種類や使用方法により一概に言えないが、通常は１
〜３０重量％（さらには３〜２０重量％、特には５〜１
５重量％）とすることが好ましく、かかる濃度が１重量
％未満では十分な接着力が発揮できないことがあり、逆
に３０重量％を越えると水溶液の粘度が高くなりすぎて
作業性が低下して好ましくない。The concentration of the aqueous solution of such a binder cannot be generally determined depending on the type of adherend and the method of use, but is usually 1
-30% by weight (further 3-20% by weight, especially 5-1)
5% by weight), and if the concentration is less than 1% by weight, sufficient adhesive force may not be exerted. On the contrary, if it exceeds 30% by weight, the viscosity of the aqueous solution becomes too high and the workability deteriorates. Is not preferable.
【００１９】本発明のバインダーには、上記の（Ａ）〜
（Ｃ）以外に必要に応じて、消泡剤、離型剤、界面活性
剤（シリコン系、フッ素系、ポリエチレングリコール系
等）、防腐剤、防虫剤、防錆剤、増粘剤、無機充填材
（クレイ、シリカ、炭酸カルシウム、タルク等）などの
公知の添加剤を添加することもできる。また、上記
（Ｂ）のナトリウム塩、カリウム塩、アンモニウム塩等
の有機酸塩を含有させることもできる。The binder of the present invention includes the above (A) to
In addition to (C), if necessary, defoaming agent, mold release agent, surfactant (silicon type, fluorine type, polyethylene glycol type, etc.), preservative, insect repellent, rust preventive, thickener, inorganic filler Known additives such as materials (clay, silica, calcium carbonate, talc, etc.) can be added. Further, an organic acid salt such as the sodium salt, potassium salt, or ammonium salt of the above (B) can be contained.
【００２０】かくして、本発明のバインダーが得られる
わけであるが、かかるバインダーは、ガラス繊維不織布
用バインダー、ボード（石膏、セメント、炭酸カルシウ
ム、珪酸カルシウム等）用バインダー、セラミック用バ
インダー、紙用バインダー（サイズ剤）、顔料用バイン
ダー、染料用バインダー、塗料用バインダー、合成繊維
不織布用バインダー、合板用接着剤、段ボール用接着
剤、その他一般の接着剤・粘着剤等に用いることがで
き、これらの中でも、ガラス繊維不織布用バインダーや
ボード（石膏、セメント、炭酸カルシウム、珪酸カルシ
ウム等）用バインダーとして特に有用で、これらについ
て具体的に説明する。なお、本発明のバインダーは、こ
れらの用途に限定されるものではない。Thus, the binder of the present invention can be obtained. Such binders include binders for glass fiber nonwoven fabrics, binders for boards (gypsum, cement, calcium carbonate, calcium silicate, etc.), binders for ceramics, binders for paper. (Sizes), binders for pigments, binders for dyes, binders for paints, binders for synthetic fiber nonwoven fabrics, adhesives for plywood, adhesives for corrugated boards, and other general adhesives / adhesives, etc. Among them, it is particularly useful as a binder for glass fiber non-woven fabric and a binder for boards (gypsum, cement, calcium carbonate, calcium silicate, etc.), and these will be specifically described. The binder of the present invention is not limited to these uses.
【００２１】まず、ガラス繊維不織布用バインダー用途
について説明する。対象となるガラス繊維は、ロービン
グ、ストランドなどをカットした単繊維状のもので、例
えば直径が９〜１３μｍ、長さが数ｍｍから数十ｍｍ程
度の円形断面を有するものを用いることができ、これ以
外にも断面が楕円形状のものを用いることも可能であ
る。また、ガラスの材質には制限がなく、Ｅガラス、Ｃ
ガラス、Ｓガラス、Ｄガラス、クォーツガラスなどを使
用することができる。First, the use of the binder for glass fiber nonwoven fabric will be described. The target glass fiber is a monofilament-shaped one obtained by cutting roving, strands, etc., and for example, a glass fiber having a circular cross section with a diameter of 9 to 13 μm and a length of several mm to several tens mm can be used. Other than this, it is also possible to use one having an elliptical cross section. Also, there is no limitation on the material of glass, and E glass, C
Glass, S glass, D glass, quartz glass, etc. can be used.
【００２２】本発明のバインダーの水溶液をガラス繊維
不織布に付着させるには、予め抄紙機で形成されたガラ
ス繊維集合体に付着させればよく、付着させる方法とし
ては、該水溶液をスプレーなどを用いて散布する方法、
該水溶液中に直接含浸させる方法、ロールなどで付着さ
せる方法などを挙げることができるが、これらに限定さ
れるものではない。In order to adhere the aqueous solution of the binder of the present invention to the glass fiber non-woven fabric, it may be adhered to the glass fiber aggregate preliminarily formed by a paper machine. As a method for adhering the solution, a spray or the like is used. How to spread,
Examples of the method include, but are not limited to, a method of directly impregnating the aqueous solution and a method of attaching the solution with a roll or the like.
【００２３】該水溶液を付着させた後、乾燥して、バイ
ンダーを硬化させ不織布を得る。バインダーの付着量
は、バインダー水溶液として不織布の３〜２５重量％程
度が好ましく、３重量％より少ないとガラス繊維不織布
の強度が低く実用的でなく、また２５重量％より多いと
乾燥、硬化に多くの時間と熱が必要となって好ましくな
い。After adhering the aqueous solution, it is dried to cure the binder to obtain a nonwoven fabric. The amount of the binder attached is preferably about 3 to 25% by weight of the nonwoven fabric as an aqueous binder solution, and if it is less than 3% by weight, the strength of the glass fiber nonwoven fabric is low and not practical, and if it is more than 25% by weight, it tends to be dried and hardened. It is not preferable because it requires time and heat.
【００２４】得られたガラス繊維不織布は、必要に応じ
て、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂、
不飽和ポリエステル樹脂、ビニルエステル樹脂のような
熱硬化性樹脂を含浸し加熱する事により更に補強するこ
ともでき、これらの樹脂の付着量は４０〜９５重量％程
度の範囲で、含浸する樹脂には無機充填剤（水酸化アル
ミニウム、水酸化マグネシウム、クレー、ワラストナイ
ト、タルク、炭酸カルシウム、ガラスパウダーなど）や
難燃（助）剤（臭素系、リン系、アンチモン系、窒素系
など）を添加してもよい。The obtained glass fiber non-woven fabric may contain epoxy resin, phenol resin, polyimide resin,
It can be further reinforced by impregnating a thermosetting resin such as an unsaturated polyester resin or a vinyl ester resin and heating it. The amount of these resins deposited is in the range of 40 to 95% by weight. Is an inorganic filler (aluminum hydroxide, magnesium hydroxide, clay, wollastonite, talc, calcium carbonate, glass powder, etc.) and flame retardant (auxiliary) agent (bromine, phosphorus, antimony, nitrogen, etc.) You may add.
【００２５】次に、ボード用バインダー用途について説
明する。かかるボードに用いられる原料としては、クレ
ー、シリカ、カオリン、水酸化アルミニウム、炭酸カル
シウム、珪酸カルシウム、ガラスパウダー、シラス、ス
ラグ、セメントなどの無機粉体を挙げることができ、こ
れらの無機粉体に、本発明のバインダーの水溶液を混合
し、乾燥、あるいは無機粉体と該水溶液の混合物を金網
などの多孔質体上に流し込み、脱水、乾燥の後、プレス
成形して所望の形状を得ることができる。Next, the use of the board binder will be described. Examples of raw materials used for such boards include clay, silica, kaolin, aluminum hydroxide, calcium carbonate, calcium silicate, glass powder, shirasu, slag, and inorganic powder such as cement. The aqueous solution of the binder of the present invention may be mixed and dried, or a mixture of the inorganic powder and the aqueous solution may be poured onto a porous body such as a wire net, dehydrated, dried, and then press-molded to obtain a desired shape. it can.
【００２６】このときに用いる本発明のバインダーの使
用量は、無機粉末に対して固形分量で０．５〜３０重量
％が好ましく、かかる使用量が０．５重量％未満では、
得られる成形物の強度が低下する傾向にあり、逆に３０
重量％を越えると乾燥時にバインダーが膜状になって乾
燥を妨げたり、過剰な水分が成形物中に残ったりするこ
とがあり好ましくない。また、ボードを製造する際に
は、補強繊維（ガラス繊維、炭素繊維、ＰＶＡ繊維、パ
ルプ等）、難燃剤（臭素系、リン系、アンチモン系、窒
素系等）、着色剤、離型剤などを添加しても良い。The amount of the binder of the present invention used at this time is preferably 0.5 to 30% by weight in terms of solid content with respect to the inorganic powder, and when the amount is less than 0.5% by weight,
The strength of the obtained molded product tends to decrease, and conversely 30
If the content exceeds 5% by weight, the binder may become a film during drying to hinder the drying, or excess water may remain in the molded product, which is not preferable. When manufacturing a board, reinforcing fibers (glass fiber, carbon fiber, PVA fiber, pulp, etc.), flame retardants (bromine-based, phosphorus-based, antimony-based, nitrogen-based, etc.), colorants, release agents, etc. May be added.
【００２７】上記のガラス繊維不織布やボードは、製造
時の加熱乾燥段階においてバインダーが着色する恐れが
あり、またその後においても熱履歴を受ける（例えば、
ガラス繊維不織布用途においては、断熱材として使用さ
れる場合に発熱体からの高温に晒され、また、ボードに
おいても建築外装等に使用される場合に夏場の高温に晒
される等）ことも多く、耐着色（変色）性に優れた本発
明のバインダーが有用となる。In the above-mentioned glass fiber nonwoven fabric or board, the binder may be colored during the heating and drying stage during the production, and after that, it is subjected to a heat history (for example,
In glass fiber non-woven fabric applications, when it is used as a heat insulating material, it is often exposed to the high temperature from the heating element, and when it is also used as a building exterior for boards, it is often exposed to the high temperatures in summer, etc., The binder of the present invention having excellent resistance to discoloration (discoloration) is useful.
【００２８】また、上記のガラス繊維不織布やボードは
建材用途に使用された場合、屋内での結露や屋外での雨
水により湿潤状態に晒されるおそれがあり、その際にも
接着力の保持性に優れた本発明のバインダーが有用とな
る。Further, when the above-mentioned glass fiber nonwoven fabric or board is used for building materials, it may be exposed to a wet condition due to dew condensation indoors or rainwater outdoors, and in that case also the adhesive strength is not maintained. The excellent binder of the present invention becomes useful.
【００２９】[0029]
【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
ことわりのない限り重量基準を示す。EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "parts" and "%" are based on weight unless otherwise specified.
【００３０】実施例１
ＰＶＡ［平均重合度１２００、ケン化度９９．０モル
％、酢酸ナトリウム量０．５％］（Ａ）１００部、ｄ−
酒石酸（ｐＫａ＝２．８２）（Ｂ）０．５部及びアジピ
ン酸ジヒドラジド（Ｃ）１．０部を水に溶解させて、固
形分１０％の水溶液（バインダー水溶液）を調整した。Example 1 PVA [Average degree of polymerization: 1200, degree of saponification: 99.0 mol%, amount of sodium acetate: 0.5%] (A) 100 parts, d-
0.5 parts of tartaric acid (pKa = 2.82) (B) and 1.0 part of adipic dihydrazide (C) were dissolved in water to prepare an aqueous solution (binder aqueous solution) having a solid content of 10%.
【００３１】得られたバインダー水溶液を用いて、下記
の要領で、耐着色性、接着力および湿潤接着性の評価を
行った。
（耐着色性）上記のバインダー水溶液を型枠に流し込ん
で、２３℃、５０％ＲＨの雰囲気下で３日間風乾させ
て、厚さ１００μｍのフィルムを得た。得られたフィル
ムを２００℃雰囲気中に４０分間放置し、その時のＹＩ
値を測定した。Using the obtained aqueous binder solution, the coloring resistance, adhesive strength and wet adhesiveness were evaluated in the following manner. (Coloring resistance) The above binder aqueous solution was poured into a mold and air-dried for 3 days in an atmosphere of 23 ° C. and 50% RH to obtain a film having a thickness of 100 μm. The obtained film was left in an atmosphere of 200 ° C. for 40 minutes, and the YI
The value was measured.
【００３２】（接着力）上記のバインダー水溶液を水に
て希釈し、固形分６％とした後、紙（坪量６５ｇ／
ｍ2）に２ｇ／ｍ2塗布し、同紙を重ねて転圧して、１０
５℃で１５分間養生後に、引張試験機（島津製作所社製
『オートグラフ』）を用いて、２３℃雰囲気中で引張速
度３００ｍｍ／ｍｉｎで剥離強度（ｇ／ｉｎｃｈ）を測
定した。(Adhesive strength) The above binder aqueous solution was diluted with water to a solid content of 6%, and then paper (basis weight 65 g /
m 2 ), 2 g / m 2 is applied, and the same paper is piled up and rolled to obtain 10
After curing at 5 ° C. for 15 minutes, the peel strength (g / inch) was measured at a tensile speed of 300 mm / min in a 23 ° C. atmosphere using a tensile tester (“Autograph” manufactured by Shimadzu Corporation).
【００３３】（湿潤接着性）上記のバインダー水溶液２
００部にガラスチョップドストランド（直径約９μｍ、
長さ約６ｍｍの円形断面）１部を混合・分散させ、角型
シートマシンにて、抄造した後、１１０℃で１５分間乾
燥させて、坪量５０ｇ／ｍ2、バインダー付着量５ｇ／
ｍ2のガラス繊維不織布を得た。これを２０℃の水に１
時間浸漬させてガラス繊維不織布の状況を目視観察し
て、以下のように評価した。
○・・・全くガラス繊維の解れが見られない
△・・・僅かにガラス繊維の解れが見られる
×・・・ほとんどガラス繊維が解れている(Wet Adhesiveness) The above aqueous binder solution 2
Glass chopped strands (diameter about 9 μm,
1 part (circular cross section having a length of about 6 mm) is mixed and dispersed, and after being made into paper by a square sheet machine, it is dried at 110 ° C. for 15 minutes to have a basis weight of 50 g / m 2 and a binder adhesion amount of 5 g /
A glass fiber nonwoven fabric of m 2 was obtained. Add 1 to 20 ℃ water
The condition of the glass fiber nonwoven fabric was visually observed by immersing it for a period of time and evaluated as follows. ○: No unraveling of the glass fiber was observed △: Slight unraveling of the glass fiber was observed ×: Almost all of the glass fiber was unraveled
【００３４】実施例２
実施例１において、アジピン酸ジヒドラジド（Ｃ）に変
えて、カルボヒドラジド（Ｃ）を用いてバインダー水溶
液を調整して、同様に評価を行った。Example 2 The same evaluation as in Example 1 was carried out by using carbohydrazide (C) instead of adipic acid dihydrazide (C) to prepare an aqueous binder solution.
【００３５】実施例３
実施例１において、ｄ−酒石酸（Ｂ）に変えて、クエン
酸（ｐＫａ＝２．９０）（Ｂ）を用いてバインダー水溶
液を調整して、同様に評価を行った。Example 3 The same evaluation as in Example 1 was carried out by using d-tartaric acid (B) instead of citric acid (pKa = 2.90) (B) to prepare an aqueous binder solution.
【００３６】実施例４
実施例１において、アジピン酸ジヒドラジド（Ｃ）の配
合量を０．５部に変えてバインダー水溶液を調整して、
同様に評価を行った。Example 4 In Example 1, the amount of adipic dihydrazide (C) was changed to 0.5 part to prepare an aqueous binder solution,
It evaluated similarly.
【００３７】実施例５
実施例１において、ｄ−酒石酸（Ｂ）の配合量を１．０
部に変えてバインダー水溶液を調整して、同様に評価を
行った。Example 5 In Example 1, the blending amount of d-tartaric acid (B) was 1.0.
In the same manner, the binder aqueous solution was prepared in place of parts.
【００３８】実施例６
実施例１において、ＰＶＡとして酢酸ナトリウム量が
０．８％のものを用いた以外は同様にバインダー水溶液
を調整して、同様に評価を行った。Example 6 A binder aqueous solution was prepared in the same manner as in Example 1 except that PVA having a sodium acetate content of 0.8% was used, and the same evaluation was performed.
【００３９】比較例１
実施例１において、アジピン酸ジヒドラジド（Ｃ）を配
合せずにバインダー水溶液を調整して、同様に評価を行
った。Comparative Example 1 The same evaluation as in Example 1 was carried out by preparing an aqueous binder solution without adding adipic acid dihydrazide (C).
【００４０】比較例２
実施例１において、ｄ−酒石酸（Ｂ）を配合せずにバイ
ンダー水溶液を調整して、同様に評価を行った。Comparative Example 2 In Example 1, the binder aqueous solution was prepared without blending d-tartaric acid (B), and the same evaluation was performed.
【００４１】比較例３
実施例１において、ｄ−酒石酸（Ｂ）に変えてプロピオ
ン酸（ｐＫａ＝４．６７）を用いた以外は同様にバイン
ダー水溶液を調整して、同様に評価を行った。実施例及
び比較例の評価結果を表１に示す。Comparative Example 3 A binder aqueous solution was prepared in the same manner as in Example 1 except that d-tartaric acid (B) was replaced with propionic acid (pKa = 4.67), and the same evaluation was performed. Table 1 shows the evaluation results of the examples and comparative examples.
【００４２】 〔表１〕 耐着色性（ＹＩ値） 接着力（g/inch） 湿潤接着性 実施例１ １４．５ ３８０ ○ 〃 ２ １３．１ ３６０ ○ 〃 ３ １２．８ ３７０ ○ 〃 ４ ２１．７ ４００ ○ 〃 ５ １１．０ ３４０ ○ 〃 ６ ２３．２ ３９０ ○ 比較例１ ５５．０ ２２０ × 〃 ２ ８６．１ ２４０ × 〃 ３ ７９．５ ２００ × [Table 1] Coloring resistance (YI value) Adhesive strength (g / inch) Wet adhesiveness Example 1 14.5 380 ○ 〃 2 13.1 360 ○ 〃 3 12.8 370 ○ 〃 4 21. 7 400 ○ 〃 5 11.0 340 ○ 〃 6 23.2 390 ○ Comparative Example 1 55.0 220 × 〃 2 86.1 240 × 〃 3 79.5 200 ×
【００４３】[0043]
【発明の効果】本発明のバインダーは、ＰＶＡ（Ａ）、
ｐＫａが３．５以下の有機酸（Ｂ）及びヒドラジド化合
物（Ｃ）を含有しているため、耐着色（変色）性及び湿
潤時の接着性に優れ、さらには接着力にも優れ、ガラス
繊維不織布用バインダー、ボード（石膏、セメント、炭
酸カルシウム、珪酸カルシウム等）用バインダー、セラ
ミック用バインダー、紙用バインダー（サイズ剤）、顔
料用バインダー、染料用バインダー、塗料用バインダ
ー、合成繊維不織布用バインダー、合板用接着剤、段ボ
ール用接着剤、その他一般の接着剤・粘着剤等に用いる
ことができ、これらの中でも、ガラス繊維不織布用バイ
ンダーやボード（石膏、セメント、炭酸カルシウム、珪
酸カルシウム等）用バインダーとして特に有用である。The binder of the present invention is PVA (A),
Since it contains an organic acid (B) having a pKa of 3.5 or less and a hydrazide compound (C), it has excellent resistance to discoloration (discoloration) and adhesiveness when wet, and also has excellent adhesiveness, and glass fiber. Non-woven fabric binder, board (gypsum, cement, calcium carbonate, calcium silicate, etc.) binder, ceramic binder, paper binder (size), pigment binder, dye binder, paint binder, synthetic fiber non-woven fabric binder, It can be used as an adhesive for plywood, an adhesive for corrugated board, and other general adhesives / adhesives. Among these, binders for glass fiber non-woven fabrics and boards (plaster, cement, calcium carbonate, calcium silicate, etc.) Is particularly useful as
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J002 BE021 EF016 EF026 EF036 EF056 EF076 EF096 EQ027 FD206 FD207 GJ02 4J040 DD021 HB26 HB28 HC03 HC15 HC17 LA06 LA07 NA10 NA11 4L047 AA05 BA15 BA21 BC05 ─────────────────────────────────────────────────── ─── Continued front page F term (reference) 4J002 BE021 EF016 EF026 EF036 EF056 EF076 EF096 EQ027 FD206 FD207 GJ02 4J040 DD021 HB26 HB28 HC03 HC15 HC17 LA06 LA07 NA10 NA11 4L047 AA05 BA15 BA21 BC05
Claims (4)
Ｋａが３．５以下の有機酸（Ｂ）及びヒドラジド化合物
（Ｃ）を含有してなることを特徴とするバインダー。1. A polyvinyl alcohol resin (A), p
A binder comprising an organic acid (B) having a Ka of 3.5 or less and a hydrazide compound (C).
するｐＫａが３．５以下の有機酸（Ｂ）の含有量が０．
１〜１０重量％で、かつヒドラジド化合物（Ｃ）の含有
量が０．１〜１０重量％であることを特徴とする請求項
１記載のバインダー。2. The content of the organic acid (B) having a pKa of 3.5 or less with respect to the polyvinyl alcohol resin (A) is 0.
The binder according to claim 1, which is 1 to 10% by weight and the content of the hydrazide compound (C) is 0.1 to 10% by weight.
を特徴とする請求項１または２記載のバインダー。3. The binder according to claim 1, which is used as a binder for glass nonwoven fabric.
とする請求項１または２記載のバインダー。4. The binder according to claim 1, which is used as a board binder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002038131A JP4464596B2 (en) | 2002-02-15 | 2002-02-15 | binder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002038131A JP4464596B2 (en) | 2002-02-15 | 2002-02-15 | binder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003238921A true JP2003238921A (en) | 2003-08-27 |
| JP4464596B2 JP4464596B2 (en) | 2010-05-19 |
Family
ID=27779523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002038131A Expired - Fee Related JP4464596B2 (en) | 2002-02-15 | 2002-02-15 | binder |
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