JPS5836297A - Paper size agent - Google Patents
Paper size agentInfo
- Publication number
- JPS5836297A JPS5836297A JP13174581A JP13174581A JPS5836297A JP S5836297 A JPS5836297 A JP S5836297A JP 13174581 A JP13174581 A JP 13174581A JP 13174581 A JP13174581 A JP 13174581A JP S5836297 A JPS5836297 A JP S5836297A
- Authority
- JP
- Japan
- Prior art keywords
- sizing agent
- olefin
- reaction
- anhydride
- maleic anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
- D21H17/16—Addition products thereof with hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/567—Preparation of carboxylic acid anhydrides by reactions not involving carboxylic acid anhydride groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Paper (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 本発明ム紙の内部サイズ剤に関するものである。[Detailed description of the invention] The present invention relates to an internal sizing agent for mu paper.
更に詳しくは、サイズ効果が良好で、かつ硬水分散性に
優れた合成サイズ剤に関するものである。More specifically, the present invention relates to a synthetic sizing agent that has good sizing effects and excellent hard water dispersibility.
当業界においては、天然ロジンまたは変性ロジンから製
造されるサイズ剤、特にロジンのマレイン酸付加物をけ
ん化して得られる強化ロジンサイズ剤が最も優れたもの
として使用されている。しかるに、天産品であるロジン
は供給が不安定であると共に、近年価格の上昇が激しい
ため、これに代替し得る所謂合成サイズ剤が研究されて
いる。In the industry, sizing agents manufactured from natural rosin or modified rosin, particularly reinforced rosin sizing agents obtained by saponifying maleic acid adducts of rosin, are most used. However, the supply of rosin, which is a natural product, is unstable and the price has increased sharply in recent years, so so-called synthetic sizing agents that can replace it are being researched.
19にアルキルまたはアルケニルコハク酸の水溶性塩(
4!公昭40−565号)、あるいはアルキルまたはア
ルケニルコノ・り酸およびその酸無水物を分散剤により
水中に分散してサイズ剤として用いる方法(特公昭39
−2305号、特開昭49−94907号)が提唱され
ている。しかし、前者はサイズ効果、硬水・分散性など
の点で多少不満足である。また、後者はサイズ剤の貯蔵
安定性に欠陥がある。本発明者らは、これらのアルキル
またはアルケニルコハク酸型サイズ剤の欠点を改善すべ
く鋭意研究全行なったところ、これらのコハク酸タイプ
化合物のうち、ある特殊な水溶性塩がサイズ効果のみな
らず硬水分散性に特に優れた特性を持つ事を見い出し、
本発明を完成するに到った。19, a water-soluble salt of alkyl or alkenyl succinic acid (
4! Publication No. 40-565), or a method of dispersing alkyl or alkenylcono-phosphoric acid and its acid anhydride in water with a dispersant and using it as a sizing agent (Japanese Patent Publication No. 39 of 1971)
-2305 and Japanese Patent Application Laid-Open No. 49-94907). However, the former is somewhat unsatisfactory in terms of size effect, hard water, dispersibility, etc. Moreover, the latter has a defect in the storage stability of the sizing agent. The present inventors conducted extensive research to improve the drawbacks of these alkyl or alkenyl succinic acid type sizing agents, and found that among these succinic acid type compounds, a certain special water-soluble salt has not only a size effect but also a size effect. Discovered that it has particularly excellent hard water dispersibility,
The present invention has now been completed.
すなわち、本発明は、下記の一般式(1)で示される直
鎖型内部オレフィンに無水マレイン酸を付加することに
よって得られる生成物の水溶性塩および/または該生成
物の水素添加物の水溶性塩からなる紙サイズ剤に関する
ものである。That is, the present invention provides a water-soluble salt of a product obtained by adding maleic anhydride to a linear internal olefin represented by the following general formula (1) and/or a water-soluble hydrogenated product of the product. The present invention relates to a paper sizing agent made of a synthetic salt.
R1−CH= CH−R2・・・・・(1)上式(1)
中、RoおよびR2はそれぞれ炭素数1から11の直鎖
アルキル基であり、がっR1とR2の炭素数の合計は6
から12である。R1-CH= CH-R2...(1) Above formula (1)
In the formula, Ro and R2 are each a straight-chain alkyl group having 1 to 11 carbon atoms, and the total number of carbon atoms in R1 and R2 is 6.
12.
本発明のサイズ剤の出発原料として使用される直鎖型内
部オレフィンは、式(I)に示したように8から14の
炭素原子を持つ化合物である。オレフィンの炭素数が7
以下の場合には硬水分散性は良好であるが、サイズ効果
が劣り、炭素数が15以上に゛なるとサイズ効果および
硬水分散性が共に劣るので好ましくない。また、オレフ
ィンの炭素数は前記範囲の内lOから12がさらに好ま
しい。捷た式(1)から明らかなように、二重結合の位
置は、末端すなわちα−位でなければ、どの位置であっ
てもさしつかえない。これらのオレフィンは単独でまた
は二種以上の混合物として用いられる。経済的見地から
は、種々の位置に二重結合をもつ混合直鎖型内部オレフ
ィンを使用することが好ましい。The linear internal olefin used as a starting material for the sizing agent of the present invention is a compound having 8 to 14 carbon atoms as shown in formula (I). The number of carbon atoms in the olefin is 7
In the following cases, the hard water dispersibility is good, but the size effect is poor, and when the carbon number is 15 or more, both the size effect and the hard water dispersibility are poor, which is not preferable. Further, the number of carbon atoms in the olefin is more preferably 10 to 12 within the above range. As is clear from the shortened formula (1), the position of the double bond may be any position as long as it is not at the terminal, that is, at the α-position. These olefins may be used alone or as a mixture of two or more. From an economic point of view, it is preferred to use mixed linear internal olefins with double bonds in various positions.
直鎖型内部オレフィンは単独で本発明のサイズ剤の原料
として用いられる他如、前記オレフィンと同炭素数のα
−オレフィンを25wt%以下、好ましくは5wt%以
下含有するものも好ましく使用できる。このようなα−
オレフィンを少量含む直鎖型内部オレフィン混合物は、
直鎖型内部オレフィンを製造する際に副生ずるα−オン
フィンを含むもの、あるいは直鎖型内部オレフィンにα
−オレフィンを混合したものであってもよい。The linear internal olefin can be used alone as a raw material for the sizing agent of the present invention.
- Those containing an olefin of 25 wt% or less, preferably 5 wt% or less can also be preferably used. Such α−
Linear internal olefin mixtures containing small amounts of olefins are
Those containing α-onfin, which is produced as a by-product during the production of linear internal olefins, or those containing α-onfins in linear internal olefins
- It may be a mixture of olefins.
本発明に用いられるオレフィンは、(イ)炭素数8から
14のα−オレフィンをンリカアルミナ、アルミナ、塩
化アルミニウム等の酸性触媒によって異性化する方法、
(ロ)炭素数8から14のn〜i?ラフインk c r
203HAl103、MoO3’AI203、Fe2O
3・Al2O3、P t−L 120 ・Al2O3等
の酸化物触媒によって脱水素する方法。The olefin used in the present invention is produced by (a) a method of isomerizing an α-olefin having 8 to 14 carbon atoms using an acidic catalyst such as phosphoric alumina, alumina, or aluminum chloride;
(b) n~i with 8 to 14 carbon atoms? Rough-in k cr
203HAl103, MoO3'AI203, Fe2O
3. A method of dehydrogenation using an oxide catalyst such as Al2O3, P t-L 120 .Al2O3.
(・・)低分子量のα−オレフィン2分子からR・e2
0□、WO3・5i02. MoO3・Al2O3、C
o□MoO3Al2O3等の触媒を用いた不均化反応に
よる方法等によって得ることができる。(...) R・e2 from 2 molecules of low molecular weight α-olefin
0□, WO3・5i02. MoO3・Al2O3,C
It can be obtained by a disproportionation reaction using a catalyst such as o□MoO3Al2O3.
本発明における直鎖型内部オレフィンと無水マレイン酸
との付加反応は次のようにして行なわれる。すなわち、
直鎖型内部オンフィンと無水マレイン酸を、触媒の存在
T1たは無触媒で、好ましくは窒素など不活性雰囲気中
で、常圧または加圧のもとに、180から250°C1
好ましくは190から220°Cに加熱し、1から50
時間、好ましくは10から36時間反応させる。オレフ
ィンと無水マレイン酸のモル比は特に限定する必要はな
いが、オンフィン1モルに対して無水マレイン酸0.4
から2モルを用いることが好ましい。反応終了後未反応
オレフィンと無水マレイン酸を蒸留により除くことによ
って本発明における反応生成物が得られる。The addition reaction between a linear internal olefin and maleic anhydride in the present invention is carried out as follows. That is,
The linear internal fins and maleic anhydride are heated at 180 to 250° C. in the presence of a catalyst or in the absence of a catalyst, preferably in an inert atmosphere such as nitrogen, under normal or elevated pressure.
Preferably heated to 190 to 220°C and heated to 1 to 50°C.
The reaction time is preferably 10 to 36 hours. The molar ratio of olefin and maleic anhydride does not need to be particularly limited, but 0.4 maleic anhydride to 1 mole of olefin
It is preferable to use 2 mol from . After the reaction is completed, the reaction product of the present invention is obtained by removing unreacted olefin and maleic anhydride by distillation.
これらの付加反応においては、反応生成物の大部分は、
次の一般式(II)に示すような1:1付加物すなわち
アルケニルコハク酸無水物である。In these addition reactions, most of the reaction products are
It is a 1:1 adduct, ie, an alkenylsuccinic anhydride, as shown in the following general formula (II).
1
上記式(11)中、R′は炭素数1から11の直鎖アル
キル基で、R″は水素または炭素数1から10の直鎖ア
ルキル基であり、かつR′およびR″の炭素数の合計は
5から11である。しかしこれ以外の1:2付加物、オ
レフィン/無水マレイン酸共重合体、無水マレイン酸重
合体等が少量副生ずる。これらの副生物は除去せずに、
1:1付加物であるアルケニルコハク酸無水物と共にそ
のまま用いてもよい。また副生物を除去してアルケニル
コハク酸無水物のみを用−いてもよい。経済性の見地か
らは、これらの副生物を分離せずに、反応粗生成物をそ
のままアルカリけん化してサイズ剤とすることが好まし
い。1 In the above formula (11), R' is a straight chain alkyl group having 1 to 11 carbon atoms, R'' is hydrogen or a straight chain alkyl group having 1 to 10 carbon atoms, and R' and R'' have a carbon number of The sum is from 5 to 11. However, small amounts of other 1:2 adducts, olefin/maleic anhydride copolymers, maleic anhydride polymers, etc. are produced as by-products. Without removing these by-products,
It may be used as is with the 1:1 adduct alkenylsuccinic anhydride. Alternatively, by-products may be removed and only alkenylsuccinic anhydride may be used. From the standpoint of economy, it is preferable to directly saponify the reaction crude product to form a sizing agent without separating these by-products.
アルキルコハク酸無水物は上記のアルケニルコハク酸無
水物を水添することによって容易に得られ、これも本発
明の範囲に属するものである。Alkyl succinic anhydrides can be easily obtained by hydrogenating the above alkenyl succinic anhydrides and are also within the scope of the present invention.
このようにして得られたアルケニルコハク酸無水物また
はアルキルコハク酸無水物は、苛性ソーダ、苛性カリ、
炭酸ソーダ、炭酸カリおよび/またはアンモニア水溶液
でけん化溶解して透明なサイズ剤とする。The alkenyl succinic anhydride or alkyl succinic anhydride obtained in this way can be used for caustic soda, caustic potash,
A transparent sizing agent is obtained by saponifying and dissolving in an aqueous solution of soda carbonate, potassium carbonate and/or ammonia.
本発明によって得られるサイズ剤は、公知のロノン系サ
イズ剤と全く同様に取扱うことができる。The sizing agent obtained by the present invention can be handled in exactly the same manner as known ronone-based sizing agents.
例えば叩解工程中もしくは叩解工程を経た・やルゾスラ
リーに本発明の内部添加サイズ剤を加えた後、硫酸バン
ドを添加して、pT(を約4.0〜5.5、好ましくは
4.2〜5.0に調整することによって/4’ルゾを定
着させる。その場合、本発明のサイズ剤の使用量は、紙
の種類およびその用途によって異なるが、一般には・ぐ
ルプに対して0.1〜3wt%程度とするのが好ましい
。For example, during the refining process or after adding the internally added sizing agent of the present invention to the Ruzo slurry that has undergone the refining process, sulfuric acid bandate is added to obtain a pT of about 4.0 to 5.5, preferably 4.2 to /4' Luso is fixed by adjusting it to 5.0. In that case, the amount of the sizing agent of the present invention to be used varies depending on the type of paper and its use, but generally it is 0.1 to 4' Luso. It is preferable to set it to about 3 wt%.
本発明のサイズ剤はサイズ効果に優れ、硬水分散性に優
れた特性を持つ工業的に有用なサイズ剤である。なお本
発明によって得られるサイズ剤は単独で使用できること
はもちろん、必要あれば、従来使用のロジン系サイズ剤
、石油樹脂系サイズ剤、α−オレフィン系のアルケニル
コハク酸の水溶性塩、分岐オレフィン系のアルケニルコ
ハク酸の水溶性塩、あるいは紙力増強剤などと任意の割
合で併用することもできる。また、併用によって、従来
品の欠点、たとえば硬水分散性を改良することができる
。The sizing agent of the present invention is an industrially useful sizing agent that has excellent sizing effects and excellent hard water dispersibility. Note that the sizing agent obtained by the present invention can of course be used alone, and if necessary, it can be used in combination with conventionally used rosin-based sizing agents, petroleum resin-based sizing agents, water-soluble salts of α-olefin-based alkenylsuccinic acids, and branched olefin-based sizing agents. It can also be used in combination with a water-soluble salt of alkenylsuccinic acid or a paper strength enhancer in any proportion. In addition, by using them in combination, the drawbacks of conventional products, such as hard water dispersibility, can be improved.
次に実施例により本発明のサイズ剤の製造および使用に
ついて更に詳細に説明するが、本発明はその要旨をこえ
ない限り、これらの例に限定されるものではない。Next, the production and use of the sizing agent of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.
実施例1
シリカアルミナ(水沢化学社製)180m/i流通式ス
テンレス製反応器に充填し、反応器内の温度を150°
Cとし、n−デセン−1f 3m//minの流速でフ
ィードした。流出してきた反応液を回収し、赤外吸収ス
被りトルを測定したところ、ビニル基の吸収帯(910
cm 1)が減少し、新たにビニレン基の吸収帯(96
5cm ’)が出現した。得られた生成物はα−オレフ
ィンを4.6wt%含む内部オレフィンである。ここで
得られたn−デセ728Of (2モル)、無水マレイ
ン酸196f(2モル)’il/、のオートクレーブに
仕込み、系内を窒素で充分に置換後、190°Cで別時
間反応させた。反応混合物を減圧蒸留装置に移し、未反
応n−デセン、無水マレイン酸を除去した。このように
して回収した反応生成物をガスクロマトグラフィー(G
C)およびデルノセーミエーンヨンクロマトグラフィー
(GPC)により分析したところ、アルケニルコノ・り
酸無水物96チおよび1:2付加物4チであった。これ
を苛性カリ水溶液でけん化して固形分40チのサイズ剤
とした。Example 1 Silica alumina (manufactured by Mizusawa Chemical Co., Ltd.) was filled into a 180 m/i flow-through stainless steel reactor, and the temperature inside the reactor was adjusted to 150°.
C, and n-decene-1f was fed at a flow rate of 3 m//min. When the reaction solution that flowed out was collected and the infrared absorption spectrum was measured, it was found that the vinyl group absorption band (910
cm 1) decreases, and a new vinylene group absorption band (96
5 cm') appeared. The resulting product is an internal olefin containing 4.6 wt% of α-olefin. The n-decene 728Of (2 mol) obtained here and maleic anhydride 196f (2 mol)'il/ were charged into an autoclave, and after the system was sufficiently purged with nitrogen, the reaction was carried out at 190°C for another hour. Ta. The reaction mixture was transferred to a vacuum distillation apparatus to remove unreacted n-decene and maleic anhydride. The reaction product thus recovered was subjected to gas chromatography (G
C) and analysis by GPC, it was found to be 96 units of alkenylconophosphate anhydride and 4 units of 1:2 adduct. This was saponified with a caustic potassium aqueous solution to obtain a sizing agent with a solid content of 40 inches.
実施例2
30m1のRe2O7・Al2O3を流通式ステンレス
製反応器に充填し、室温でn−ヘキセン−1f 5 m
/m i nの流速でフィードした。流出した反応液の
GC分析よりn−ヘキセン−1からn−デセン−5への
転化率は52%であった。蒸留によって反応液からn−
デセン−5を回収した。ここで得られたn−デセン−5
280f(2モル)、無水マレイン酸196 P (2
モル)を1tオートクレーブに仕込み、系内を窒素で充
分に置換した後、220°Cで24時間反応させた。反
応混合物を減圧蒸留装置に移し、未反応のn−デセン−
5および無水マレイン酸を除去した。回収した反応生成
物は、GC分析およびGPC分析によりアルケニルコハ
ク酸無水物98%および1:2付加物2チであった。こ
れを苛性カリ水溶液でけん化して固形分40f)のサイ
ズ剤とした。Example 2 30 ml of Re2O7.Al2O3 was charged into a flow-through stainless steel reactor, and n-hexene-1f 5 m was charged at room temperature.
It was fed at a flow rate of /min/min. GC analysis of the reaction solution that flowed out showed that the conversion rate of n-hexene-1 to n-decene-5 was 52%. n- is removed from the reaction solution by distillation.
Decene-5 was recovered. n-decene-5 obtained here
280f (2 mol), maleic anhydride 196 P (2
1 mol) was charged into a 1 t autoclave, the system was sufficiently purged with nitrogen, and then reacted at 220°C for 24 hours. The reaction mixture was transferred to a vacuum distillation apparatus to remove unreacted n-decene-
5 and maleic anhydride were removed. The reaction product recovered was 98% alkenylsuccinic anhydride and 2 1:2 adducts by GC and GPC analysis. This was saponified with a caustic potassium aqueous solution to obtain a sizing agent with a solid content of 40 f).
比較例1
n−デセン−1を実施例2と同様にしてマレイン化して
アルケニルコノ・り酸無水物を得た。これを苛性カリ水
溶液でけん化して固形分40%のサイズ剤を得た。Comparative Example 1 n-decene-1 was maleated in the same manner as in Example 2 to obtain an alkenylcono-phosphate anhydride. This was saponified with a caustic potassium aqueous solution to obtain a sizing agent with a solid content of 40%.
比較例2
塩化アルミニウムを触媒として、常法によりイソゾチレ
ンのオリゴメリゼーションをおこなった。Comparative Example 2 Isozotylene was oligomerized by a conventional method using aluminum chloride as a catalyst.
得られた生成物より沸点165°C〜184°Cの留分
を蒸留により回収した。質量分析およびGC分析により
、この留分は炭素数10.11 、12の成分がそれぞ
れ20%、 60% 、 20%の分岐型混合オレフィ
ンであることを確認した。このオレフィ゛ンを実施例2
と同様にしてマレイン化しアルケニルコハク酸無水物を
得た。これを苛性カリ水溶液でけん化して固形分40%
のサイズ剤を得た。A fraction with a boiling point of 165°C to 184°C was recovered from the obtained product by distillation. Mass spectrometry and GC analysis confirmed that this fraction was a branched mixed olefin containing 20%, 60%, and 20% of components with 10.11 and 12 carbon atoms, respectively. This olefin was prepared in Example 2.
Maleation was carried out in the same manner as above to obtain alkenylsuccinic anhydride. This was saponified with a caustic potassium aqueous solution and the solid content was 40%.
A sizing agent was obtained.
実施例3
n−i9ラフイン混合物(C18%、C1125%%
CI228 %、C1328チ、C1411%)を水素
ガスと共にPt−Li2.0・Al2O3触媒30rt
lf充填した反応器に、 15m1!/minの流速
およびH2/n−ノやラフイン=S、O(モル比)でフ
ィードして脱水素反応を行なわせた。反応器内の温度は
470°Cに保った。流出油中のオレフィンの転化率は
約12チであった。またこのオレフィンの炭素分布はG
C分析の結果C1o 11 %、c■28%、Cr22
5%、C1326%、C1410チであった。またこの
オレフィン留分は赤外吸収スペクトルによりα−オレフ
ィンを4 wt%含む内部オレフィンであることが確認
された。Example 3 n-i9 rough-in mixture (C18%, C1125%%
CI228%, C1328CH, C1411%) with hydrogen gas at 30rt Pt-Li2.0・Al2O3 catalyst
15ml in the reactor filled with lf! The dehydrogenation reaction was carried out by feeding at a flow rate of /min and H2/n-no, rough-in = S, O (molar ratio). The temperature inside the reactor was maintained at 470°C. The conversion of olefins in the oil spill was about 12 inches. Also, the carbon distribution of this olefin is G
Results of C analysis C1o 11%, c28%, Cr22
5%, C1326%, C1410chi. Further, this olefin fraction was confirmed by infrared absorption spectrum to be an internal olefin containing 4 wt% of α-olefin.
このようにして得られたn−パラディンとn−オレフィ
ンとの混合物を実施例1と同一条件でマレイン化しく但
しn−オレフィン/無水マレイン酸=署そル)、 n
−ノ45フィンおよび未反応n−オレフィン、無水マレ
イン酸を除去して、アルケニルコハク酸無水物を蒸留に
よって回収した。分析の結果、これには1:2付加物が
含まれないことが確認された。次に苛性カリ水溶液でけ
ん化して固形分40%のサイズ剤を得た。The mixture of n-paladin and n-olefin thus obtained was maleated under the same conditions as in Example 1, except that n-olefin/maleic anhydride=signal), n
-No45 fins, unreacted n-olefins, and maleic anhydride were removed, and alkenylsuccinic anhydride was recovered by distillation. As a result of analysis, it was confirmed that this did not contain a 1:2 adduct. Next, it was saponified with a caustic potassium aqueous solution to obtain a sizing agent with a solid content of 40%.
実施例4
実施例3によって得られたアルケニルコハク酸無水物2
60tおよびPd−活性炭(pdl、0wt%)触媒4
、Of 1に500dのオートクレーブに仕込み、水素
圧を69Kr/iに保ち、120°Cで8時間水素添加
することにより、アルキルコハク酸無水物2552を得
た。これを苛性カリ水溶液でけん、化して、固形分40
−のサイズ剤を得た。Example 4 Alkenylsuccinic anhydride 2 obtained according to Example 3
60t and Pd-activated carbon (PDL, 0wt%) catalyst 4
, Of 1, the mixture was charged into a 500 d autoclave, the hydrogen pressure was maintained at 69 Kr/i, and hydrogenation was carried out at 120°C for 8 hours to obtain alkyl succinic anhydride 2552. This was saponified with a caustic potassium aqueous solution, and the solid content was 40%.
A sizing agent of - was obtained.
実施例5
n−ドデセン−1t−実施例1と同様にして異性化し次
後マレイン化した。反応混合物から未反応のn−ドデセ
ン、無水マレイン酸を除去して、アルケニルコハク酸無
水物を留出することによって得た。分析の結果、アルケ
ニルコ・・り酸無水物は100%であった。これを苛性
カリ水溶液でけん化して固形分40チのサイズ剤を得た
。Example 5 n-dodecene-1t-Isomerized and then maleated in the same manner as in Example 1. Unreacted n-dodecene and maleic anhydride were removed from the reaction mixture, and alkenylsuccinic anhydride was obtained by distillation. As a result of analysis, the content of alkenylco-phosphate anhydride was 100%. This was saponified with a caustic potassium aqueous solution to obtain a sizing agent with a solid content of 40 inches.
実施例6
n−へゾテン−1を原料として実施例2と同様にして不
均化反応を行ない、n−ドデセン−6を得た。転化率は
40チであった。蒸留によって回収したn−ドデセン−
6168r(1モル)、無水マレイン酸59f(0,6
モル)を500肩lのオートクレーブに仕込み、系内金
窒素で充分に置換した後、190°Cで36時間反応さ
せた。反応混合物から未反応のn−ドデセン−6および
無水マレイン酸を除去した。Example 6 A disproportionation reaction was carried out in the same manner as in Example 2 using n-hezotene-1 as a raw material to obtain n-dodecene-6. The conversion rate was 40%. n-dodecene recovered by distillation
6168r (1 mol), maleic anhydride 59f (0,6
mol) was charged into a 500 liter autoclave, the system was sufficiently purged with gold nitrogen, and then reacted at 190°C for 36 hours. Unreacted n-dodecene-6 and maleic anhydride were removed from the reaction mixture.
回収した反応生成物は145fであった。苛性カリ水溶
液でけん化して固形分40tIIのサイズ剤を得た。The reaction product recovered was 145f. It was saponified with a caustic potassium aqueous solution to obtain a sizing agent with a solid content of 40tII.
比較例3
n−ドデセン−1を比較例1と同様にしてマレイン化し
て得られたアルケニルコノ・り酸無水物を、苛性カリ水
溶液でけん化して固形分40チのサイズ剤を得た。Comparative Example 3 An alkenylcono-phosphate anhydride obtained by maleating n-dodecene-1 in the same manner as in Comparative Example 1 was saponified with an aqueous caustic potassium solution to obtain a sizing agent with a solid content of 40 cm.
比較例4
n−ペンタデカンを原料として実施例3と同様にして脱
水素反応を行なった。流出油中のn−ぜンタデセンは1
0%であった。n−ペンタデカンとれ−(/タデセンと
の混合液を実施例3と同様にしてマレイン化し、蒸留に
よりアルケニルコハク酸無水物を得た後、固形分41の
サイズ剤を得た。Comparative Example 4 A dehydrogenation reaction was carried out in the same manner as in Example 3 using n-pentadecane as a raw material. n-Zentadecene in spilled oil is 1
It was 0%. A mixture of n-pentadecane and tadecene was maleated in the same manner as in Example 3, and alkenylsuccinic anhydride was obtained by distillation, followed by a sizing agent with a solid content of 41.
比較例5
n−へブタンを原料として、比較例4と同様にして、脱
水素反応およびマレイン化反応を行ない、得られたアル
ケニルコハク酸無水物から固形分40チのサイズ剤を得
た。Comparative Example 5 Using n-hebutane as a raw material, a dehydrogenation reaction and a maleation reaction were carried out in the same manner as in Comparative Example 4, and a sizing agent with a solid content of 40% was obtained from the obtained alkenylsuccinic anhydride.
実施例7
実施例5で得られたサイズ剤と比較例3で得られたサイ
ズ剤を80/20の割合で混合した。Example 7 The sizing agent obtained in Example 5 and the sizing agent obtained in Comparative Example 3 were mixed in a ratio of 80/20.
実施例8
Cg 11.1 ’14% ’C912−396、C1
o 17.1 %、C1,14,7%、C1゜15.4
96%CI314.3チおよびCl415.1%の組成
からなるn−α−オレフィン混合物を実施例1に準じて
異性化反応を行なわせて、α−オレフィンを6チ含有す
る直鎖型内部オレフィン混合物を得た。これを実施例1
と同一条件で無水マレイン酸と反応させ、生成物を苛性
カリ水溶液でけん化して固形分40チのサイズ剤を得た
。Example 8 Cg 11.1'14%'C912-396, C1
o 17.1%, C1,14,7%, C1゜15.4
An n-α-olefin mixture having a composition of 96% CI314.3% and Cl415.1% was subjected to an isomerization reaction according to Example 1 to obtain a linear internal olefin mixture containing 6 α-olefins. I got it. Example 1
The product was reacted with maleic anhydride under the same conditions as above, and the product was saponified with an aqueous caustic potassium solution to obtain a sizing agent with a solid content of 40 inches.
実施例1〜8および比較例1〜5により得られた各サイ
ズ剤について、下記試験法により「硬水分散性」および
「サイズ効果」を試験した。The sizing agents obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were tested for "hard water dispersibility" and "size effect" using the following test method.
「硬水分散性試験」
30°DH(Ca+2214 ppm )の硬水でサイ
ズ剤を90 ppmに希釈した時のコロイド状態を観察
した。"Hard Water Dispersibility Test" The colloidal state was observed when the sizing agent was diluted to 90 ppm with hard water of 30° DH (Ca+2214 ppm).
「サイズ効果試験」
抄紙法(1)
パル7′1′(LBKP 430m1 C,S、F、)
を水道水(5゜DH)に分散させて1%スラリーとし、
これにサイズ剤を0.2wt%、次いで硫酸ばん土を2
.5wt%(いずれも対・やルゾ)を添加し、用水とし
て水道水(5°DH%pH4,5)を用いて、タノピス
タンダードシートマシンで坪量60f/nt”となるよ
うに抄紙した。湿紙を圧縮脱水後、80°Cで5分間乾
燥し、次いで20°C165%RHの雰囲気で24時間
調湿した紙料について、ステキヒト法(JIS P 8
122)によりサイズ効果を測定した。"Size effect test" Paper making method (1) Pal 7'1' (LBKP 430m1 C, S, F,)
was dispersed in tap water (5°DH) to make a 1% slurry,
Add 0.2wt% of sizing agent to this, and then add 2% of sulfuric acid.
.. 5 wt % (in both cases) and using tap water (5° DH% pH 4,5) as water, paper was made with a Tanopi standard sheet machine to a basis weight of 60 f/nt. After compressing and dehydrating the wet paper, the stock was dried at 80°C for 5 minutes and then conditioned for 24 hours in an atmosphere of 20°C and 165% RH.
The size effect was measured by 122).
抄紙法(2)
用水として硬水(20°DH%pH4,5)’に使用す
る他は上記抄紙法(1)と同様に行なった。Paper-making method (2) The same method as the above-mentioned paper-making method (1) was carried out except that hard water (20° DH% pH 4,5)' was used as the water.
結果を以下の表にまとめて示す。The results are summarized in the table below.
表
表から明らかなように、本発明のサイズ剤はサイズや果
が優れているばかりでなく、硬水分散性にも優れたもの
であることがわかる。As is clear from the table, it can be seen that the sizing agent of the present invention not only has excellent size and fruit, but also has excellent hard water dispersibility.
特許出願人 日本石油化学株式会社Patent applicant: Japan Petrochemical Co., Ltd.
Claims (4)
ンに無水マレイン酸を付加することによって得られる生
成物の水溶性塩および/または該生成物の水素添加物の
水溶性塩からなる紙サイズ剤、R1−C)T = CM
−R2・・・・・(I)上式(I)中、R1およびR
2はそれぞれ炭素数1から11の直鎖アルキル基であり
、かつR1とR2の炭素数の合計は6から12である。(1) Consists of a water-soluble salt of a product obtained by adding maleic anhydride to a linear internal olefin represented by the following general formula (1) and/or a water-soluble salt of a hydrogenated product of the product. Paper sizing agent, R1-C) T = CM
-R2... (I) In the above formula (I), R1 and R
2 is a linear alkyl group having 1 to 11 carbon atoms, and the total number of carbon atoms in R1 and R2 is 6 to 12.
がそれぞれ1から9で、かつR1とR2の炭素数の合計
が8から10である特許請求の範囲第1項記載の紙サイ
ズ剤。(2) The paper sizing agent according to claim 1, wherein in the formula (1), each of R1 and R2 has a carbon number of 1 to 9, and the total number of carbon atoms of R1 and R2 is 8 to 10. .
ン−5である特許請求の範囲第1項記載の紙サイズ剤。(3) The paper sizing agent according to claim 1, wherein the linear internal olefin of formula (1) is n-decene-5.
セン−6である特許請求の範囲第11項記載の紙サイズ
剤。(4) The paper sizing agent according to claim 11, wherein the linear internal olefin of formula (1) is n-dodecene-6.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13174581A JPS5836297A (en) | 1981-08-22 | 1981-08-22 | Paper size agent |
DE19823231106 DE3231106A1 (en) | 1981-08-22 | 1982-08-20 | PAPER SIZING AGENT |
GB08224012A GB2108111B (en) | 1981-08-22 | 1982-08-20 | A maleic anhydride derivative used as a paper sizing agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13174581A JPS5836297A (en) | 1981-08-22 | 1981-08-22 | Paper size agent |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS5836297A true JPS5836297A (en) | 1983-03-03 |
Family
ID=15065190
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13174581A Pending JPS5836297A (en) | 1981-08-22 | 1981-08-22 | Paper size agent |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPS5836297A (en) |
DE (1) | DE3231106A1 (en) |
GB (1) | GB2108111B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8506615D0 (en) * | 1985-03-14 | 1985-04-17 | British Petroleum Co Plc | Scale inhibitors |
JPH08113892A (en) * | 1994-10-14 | 1996-05-07 | Mitsubishi Oil Co Ltd | Alkenylsuccinic acid emulsion sizing agent |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3821069A (en) * | 1973-01-02 | 1974-06-28 | Nat Starch Chem Corp | Process of sizing paper with a reaction product of maleic anhydride and an internal olefin |
JPS5328526A (en) * | 1976-08-30 | 1978-03-16 | Nippon Kokan Kk | Process and apparatus for producing steel pipe having zenccplated outer surface |
JPS5438903A (en) * | 1977-06-28 | 1979-03-24 | Tenneco Chem | Paper sizing agent and method |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL129371C (en) * | 1961-09-08 | |||
US3139373A (en) * | 1962-06-08 | 1964-06-30 | Allied Chem | Process for the internal sizing of paper with a salt of a substituted succinic acid |
-
1981
- 1981-08-22 JP JP13174581A patent/JPS5836297A/en active Pending
-
1982
- 1982-08-20 DE DE19823231106 patent/DE3231106A1/en not_active Withdrawn
- 1982-08-20 GB GB08224012A patent/GB2108111B/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3821069A (en) * | 1973-01-02 | 1974-06-28 | Nat Starch Chem Corp | Process of sizing paper with a reaction product of maleic anhydride and an internal olefin |
JPS5328526A (en) * | 1976-08-30 | 1978-03-16 | Nippon Kokan Kk | Process and apparatus for producing steel pipe having zenccplated outer surface |
JPS5438903A (en) * | 1977-06-28 | 1979-03-24 | Tenneco Chem | Paper sizing agent and method |
Also Published As
Publication number | Publication date |
---|---|
GB2108111B (en) | 1985-09-18 |
DE3231106A1 (en) | 1983-03-10 |
GB2108111A (en) | 1983-05-11 |
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