JPH0753610A - Latex for coating web offset paper and coating composition for web offset paper - Google Patents

Latex for coating web offset paper and coating composition for web offset paper

Info

Publication number
JPH0753610A
JPH0753610A JP21684693A JP21684693A JPH0753610A JP H0753610 A JPH0753610 A JP H0753610A JP 21684693 A JP21684693 A JP 21684693A JP 21684693 A JP21684693 A JP 21684693A JP H0753610 A JPH0753610 A JP H0753610A
Authority
JP
Japan
Prior art keywords
latex
monomer
weight
chain transfer
coating
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
Application number
JP21684693A
Other languages
Japanese (ja)
Other versions
JP3345979B2 (en
Inventor
Toshio Koike
敏夫 小池
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Nippon Zeon Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Zeon Co Ltd filed Critical Nippon Zeon Co Ltd
Priority to JP21684693A priority Critical patent/JP3345979B2/en
Publication of JPH0753610A publication Critical patent/JPH0753610A/en
Application granted granted Critical
Publication of JP3345979B2 publication Critical patent/JP3345979B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Abstract

PURPOSE:To obtain a latex giving a coated paper having balanced adhesive strength and blister resistance by emulsion polymerizing an aliphatic conjugated diene monomer and an ethylenic unsaturated carboxylic acid monomer using a specific chain transfer agent. CONSTITUTION:This copolymer latex has a gel, content of 15-65wt.% and is produced by the emulsion polymerization of a monomer mixture composed of 15-50wt.% of an aliphatic conjugated diene monomer, 1-6wt.% of an ethylenic: unsaturated carboxylic acid monomer and 44-84wt.% of an ethylenic unsaturated monomer copolymerizable with the these monomers using a chain transfer agent consisting of a t-mercaptan having at least one t-butyl group and a total carbon number of 7-16, such as 2,5,5-trimethylhexane-2-thiol. A latex composition for the coating of a web offset paper is produced by adding a pigment to the latex.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明はオフセット輪転印刷紙塗
工用組成物及びこれに用いるラテックスに関する。更に
詳しくは接着強度及び耐ブリスター性に優れ且つそれら
のバランスに優れる塗工紙を得るためのオフセット輪転
印刷紙塗工用組成物及びこれに用いるラテックスに関す
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an offset rotary printing paper coating composition and a latex used for the composition. More specifically, it relates to a composition for offset rotary printing paper coating for obtaining a coated paper having excellent adhesive strength and blister resistance, and a good balance thereof, and a latex used therefor.

【0002】[0002]

【従来の技術】近年、オフセット輪転印刷技術の急速な
発達に伴い、塗工紙に要求される性能もきびしくなって
おり、例えば、接着強度と耐ブリスター性との相矛盾し
た特性を両方とも向上させ、そのバランスが良好な塗工
紙を得るためのオフセット輪転印刷紙塗工用組成物が求
められている。オフセット輪転印刷紙塗工用組成物に用
いるラテックスとしては、一般にゲル含量の低いラテッ
クスが用いられている。ラテックスのゲル含量を調整す
る方法としては、t−ドデシルメルカプタン、α−メチ
ルスチレンダイマーなどの連鎖移動剤の存在下に、単量
体を重合する方法が知られている。しかし、この方法で
得られるラテックスを塗工して得られる塗工紙は接着強
度と耐ブリスター性とのバランスが不十分で、上記要求
を十分満足するものではなかった。
2. Description of the Related Art In recent years, with the rapid development of rotary offset printing technology, the performance required for coated paper has become severe. For example, both the adhesive strength and the blister resistance are contradictory to each other. Therefore, there is a demand for a composition for offset rotary printing paper coating for obtaining a coated paper having a good balance. As the latex used for the composition for offset rotary printing paper coating, latex having a low gel content is generally used. As a method of adjusting the gel content of the latex, a method of polymerizing a monomer in the presence of a chain transfer agent such as t-dodecyl mercaptan or α-methylstyrene dimer is known. However, the coated paper obtained by applying the latex obtained by this method has an insufficient balance between the adhesive strength and the blister resistance, and thus does not sufficiently satisfy the above requirements.

【0003】[0003]

【発明が解決しようとする課題】本発明の目的は、接着
強度と耐ブリスター性との相矛盾した特性を両方とも向
上させ、そのバランスが良好な塗工紙を得るためのオフ
セット輪転印刷紙塗工用組成物及びこれに用いるラテッ
クスを提供することにある。本発明者らは、上記目的を
達成するために鋭意研究を行った結果、特定の化合物を
連鎖移動剤として用い、乳化重合して得られるラテック
スを用いることによって、本目的を達成できることを見
いだし、本発明を完成するに到った。
SUMMARY OF THE INVENTION An object of the present invention is to provide an offset rotary printing paper coating for improving both the contradictory properties of adhesive strength and blister resistance and obtaining a coated paper having a good balance thereof. An object is to provide an industrial composition and a latex used for the composition. The present inventors have conducted intensive studies to achieve the above objects, and as a result, use of a specific compound as a chain transfer agent, and by using a latex obtained by emulsion polymerization, found that this object can be achieved. The present invention has been completed.

【0004】[0004]

【課題を解決するための手段】かくして本発明によれ
ば、脂肪族共役ジエン単量体15〜50重量%、エチレ
ン性不飽和カルボン酸単量体1〜6重量%及びこれらと
共重合体可能なエチレン性不飽和単量体44〜84重量
%からなる単量体を連鎖移動剤の存在下に乳化重合して
なる、ゲル含量が15〜65重量%である共重合体のラ
テックスであって、該連鎖移動剤として少なくとも1個
の第3級ブチル基を有し且つ全炭素原子数が7〜16個
である第3級メルカプタンを用いて得られることを特徴
とするオフセット輪転印刷紙塗工用ラテックスが提供さ
れる。また、本発明によれば、前記ラテックスと顔料と
を必須成分とするオフセット輪転印刷紙塗工用組成物が
提供される。
Thus, according to the present invention, 15 to 50% by weight of an aliphatic conjugated diene monomer, 1 to 6% by weight of an ethylenically unsaturated carboxylic acid monomer, and a copolymer with them are possible. A latex of a copolymer having a gel content of 15 to 65% by weight, which is obtained by emulsion polymerization of a monomer consisting of 44 to 84% by weight of an ethylenically unsaturated monomer in the presence of a chain transfer agent. An offset rotary printing paper coating obtained by using as the chain transfer agent a tertiary mercaptan having at least one tertiary butyl group and having a total number of carbon atoms of 7 to 16 Latex is provided. Further, according to the present invention, there is provided an offset rotary printing paper coating composition containing the latex and the pigment as essential components.

【0005】本発明のオフセット輪転印刷紙塗工用ラテ
ックスは、少なくとも1個の第3級ブチル基を有し且つ
全炭素原子数が7〜16個である第3級メルカプタンを
連鎖移動剤として用い、脂肪族共役ジエン単量体、エチ
レン性不飽和カルボン酸単量体及びこれらと共重合体可
能なエチレン性不飽和単量体からなる単量体を乳化重合
して得られるものである。
The latex for rotary offset printing paper coating of the present invention uses a tertiary mercaptan having at least one tertiary butyl group and having a total carbon atom number of 7 to 16 as a chain transfer agent. , An aliphatic conjugated diene monomer, an ethylenically unsaturated carboxylic acid monomer, and a monomer composed of an ethylenically unsaturated monomer copolymerizable therewith, which are obtained by emulsion polymerization.

【0006】本発明に用いる連鎖移動剤は、少なくとも
1個の第3級ブチル基を有する第3級メルカプタンであ
る。また、本発明に用いる連鎖移動剤は、その全炭素原
子数が7〜16個、好ましくは10〜13個である。
The chain transfer agent used in the present invention is a tertiary mercaptan having at least one tertiary butyl group. The total number of carbon atoms in the chain transfer agent used in the present invention is 7 to 16, preferably 10 to 13.

【0007】本発明に用いる連鎖移動剤の具体例として
は、2,5,5−トリメチルヘキサン−2−チオール、
2,2,4,6,6−ペンタメチルヘプタン−4−チオ
ール、2,2,4,4,6−ペンタメチルヘプタン−6
−チオール、2,2,4,6,6,8,8−ヘプタメチ
ルノナン−4−チオール、2,2,5,8,8−ペンタ
メチルノナン−5−チオール、2,2,5,5,6,
8,8−ヘプタメチルノナン−6−チオール等が挙げら
れる。
Specific examples of the chain transfer agent used in the present invention include 2,5,5-trimethylhexane-2-thiol,
2,2,4,6,6-pentamethylheptane-4-thiol, 2,2,4,4,6-pentamethylheptane-6
-Thiol, 2,2,4,6,6,8,8-heptamethylnonane-4-thiol, 2,2,5,8,8-pentamethylnonane-5-thiol, 2,2,5,5 , 6,
Examples include 8,8-heptamethylnonane-6-thiol and the like.

【0008】連鎖移動剤の使用量は、全単量体100重
量部に対して、通常、0.05〜4重量部、好ましくは
0.1〜2重量部である。4重量部を超えると塗工紙の
接着強度が低下することがあり、逆に0.05重量%未
満では塗工紙の耐ブリスター性が低下することがある。
The amount of the chain transfer agent used is usually 0.05 to 4 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of all the monomers. If it exceeds 4 parts by weight, the adhesive strength of the coated paper may decrease, and if it is less than 0.05% by weight, the blister resistance of the coated paper may decrease.

【0009】本発明において、前記連鎖移動剤以外に、
連鎖移動効果を有する他の化合物を必要に応じて併用す
ることができる。
In the present invention, in addition to the chain transfer agent,
Other compounds having a chain transfer effect can be used in combination as necessary.

【0010】連鎖移動効果を有する他の化合物として
は、n−オクチルメルカプタン、n−ドデシルメルカプ
タン、t−ドデシルメルカプタン(第3級ブチル基を含
有しない。)、n−ヘキサデシルメルカプタン、n−テ
トラデシルメルカプタン、2,2,4,6,6−ペンタ
メチルヘプタン−4−メチレンチオール、2,4,6−
トリメチルノナン−4−チオールなどのメルカプタン;
ジメチルキサントゲンジスルフィド、ジエチルキサント
ゲンジスルフィド、ジイソプロピルキサントゲンジスル
フィドなどのキサントゲンジスルフィド;テトラメチル
チウラムジスルフィド、テトラエチルチウラムジスルフ
ィド、テトラブチルチウラムジスルフィドなどのチウラ
ムジスルフィド;四塩化炭素、臭化エチレンなどのハロ
ゲン化炭化水素;ペンタフェニルエタンなどの炭化水
素;アクロレイン、メタクロレイン等のα,β−不飽和
アルデヒド;アリルアルコール;2−エチルヘキシルチ
オグリコレート;テルピノーレン、α−テルピネン、β
−テルピネン、γ−テルピネン、ジペンテン等のテルペ
ン;2−4−ジフェニル−4−メチル−1−ペンテン等
のα−メチルスチレンダイマー;2,5−ジヒドロフラ
ンなどが挙げられる。これら化合物のうち、t−ドデシ
ルメルカプタン、テルペン及びα−メチルスチレンダイ
マーが好適に用いられる。t−ドデシルメルカプタンの
量は、全単量体100重量部に対して、通常、0.05
〜3重量部、好ましくは0.1〜1.5重量部であり、
テルペン又はα−メチルスチレンダイマーの量は、全単
量体100重量部に対して、通常、0.1〜3重量部、
好ましくは0.5〜1.5重量部である。
Other compounds having a chain transfer effect include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan (not containing a tertiary butyl group), n-hexadecyl mercaptan, n-tetradecyl. Mercaptan, 2,2,4,6,6-pentamethylheptane-4-methylenethiol, 2,4,6-
Mercaptans such as trimethylnonane-4-thiol;
Xanthogen disulfides such as dimethylxanthogen disulfide, diethylxanthogen disulfide, and diisopropylxanthogen disulfide; thiuram disulfides such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide; halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide; pentaphenyl Hydrocarbons such as ethane; α, β-unsaturated aldehydes such as acrolein and methacrolein; allyl alcohol; 2-ethylhexyl thioglycolate; terpinolene, α-terpinene, β
-Terpinenes such as terpinene, γ-terpinene, and dipentene; α-methylstyrene dimers such as 2-4-diphenyl-4-methyl-1-pentene; and 2,5-dihydrofuran. Among these compounds, t-dodecyl mercaptan, terpene and α-methylstyrene dimer are preferably used. The amount of t-dodecyl mercaptan is usually 0.05 based on 100 parts by weight of the total monomer.
To 3 parts by weight, preferably 0.1 to 1.5 parts by weight,
The amount of the terpene or α-methylstyrene dimer is usually 0.1 to 3 parts by weight, based on 100 parts by weight of all the monomers,
It is preferably 0.5 to 1.5 parts by weight.

【0011】本発明に用いる脂肪族共役ジエン単量体と
しては、1,3−ブタジエン、イソプレン、2,3−ジ
メチル−1,3−ブタジエン、2−エチル−1,3−ブ
タジエン、1,3−ペンタジエン、クロロプレン等を挙
げられる。
Examples of the aliphatic conjugated diene monomer used in the present invention include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene and 1,3. -Pentadiene, chloroprene and the like.

【0012】本発明に用いるエチレン性不飽和カルボン
酸単量体としては、アクリル酸、メタクリル酸、クロト
ン酸、マレイン酸、イタコン酸、マレイン酸モノエチル
などが挙げられる。
Examples of the ethylenically unsaturated carboxylic acid monomer used in the present invention include acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and monoethyl maleate.

【0013】脂肪族共役ジエン単量体およびエチレン性
不飽和カルボン酸単量体と共重合可能な単量体として
は、芳香族ビニル単量体としては、スチレン、α−メチ
ルスチレン、ビニルトルエン、ハロゲン化スチレン等の
芳香族ビニル単量体;アクリロニトリル、メタクリロニ
トリル、フマロニトリル、α−クロロアクリロニトリ
ル、α−シアノエチルアクリロニトリル等のシアノ基含
有エチレン性不飽和単量体;(メタ)アクリル酸メチ
ル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブ
チル、マレイン酸ジブチル等のエチレン性不飽和カルボ
ン酸エステル;(メタ)アクリルアミド、N−メチロー
ル(メタ)アクリルアミド等のエチレン性不飽和アミド
などが挙げられる。これらの単量体は、接着強度、着肉
性などの塗工紙物性を向上させるために適宜組み合わせ
て使用される。
The monomers copolymerizable with the aliphatic conjugated diene monomer and the ethylenically unsaturated carboxylic acid monomer include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, Aromatic vinyl monomers such as halogenated styrene; acrylonitrile, methacrylonitrile, fumaronitrile, α-chloroacrylonitrile, α-cyanoethylacrylonitrile and other cyano group-containing ethylenically unsaturated monomers; methyl (meth) acrylate, ( Examples thereof include ethylenically unsaturated carboxylic acid esters such as ethyl (meth) acrylate, butyl (meth) acrylate and dibutyl maleate; ethylenically unsaturated amides such as (meth) acrylamide and N-methylol (meth) acrylamide. These monomers are used in appropriate combination for improving the physical properties of coated paper such as adhesive strength and inking property.

【0014】本発明に用いる各単量体の量は、全単量体
100重量部のうち、脂肪族共役ジエン単量体が15〜
50重量%、好ましくは20〜45重量%、エチレン性
不飽和カルボン酸単量体が1〜6重量%、好ましくは
1.5〜5重量%及びこれらと共重合可能な単量体が4
4〜84重量%、好ましくは50〜78.5重量%であ
る。これらの範囲外では、接着強度、着肉性などの塗工
紙物性が低下することがある。
The amount of each monomer used in the present invention is such that the aliphatic conjugated diene monomer is 15 to 100 parts by weight based on the total monomers.
50% by weight, preferably 20 to 45% by weight, 1 to 6% by weight of ethylenically unsaturated carboxylic acid monomer, preferably 1.5 to 5% by weight and 4% of monomers copolymerizable therewith.
It is 4 to 84% by weight, preferably 50 to 78.5% by weight. Outside of these ranges, the physical properties of the coated paper such as adhesive strength and inking property may deteriorate.

【0015】本発明のオフセット輪転印刷紙塗工用ラテ
ックスは、それを構成する共重合体のゲル含量が15〜
65重量%、好ましくは20〜60重量%である。15
重量%未満では塗工紙の接着強度が低くなり、逆に65
重量%を超えると塗工紙の耐ブリスター性が低下する。
The latex for the offset rotary printing paper coating of the present invention has a gel content of 15 to 50 in the copolymer constituting the latex.
It is 65% by weight, preferably 20-60% by weight. 15
If it is less than wt%, the adhesive strength of the coated paper will be low, and conversely it will be 65%.
If the content is more than wt%, the blister resistance of the coated paper will decrease.

【0016】本発明のオフセット輪転印刷紙塗工用ラテ
ックスは、前記連鎖移動剤の存在下に前記の単量体を乳
化重合して得られる。連鎖移動剤は反応器に重合開始前
に一括添加し又は重合開始後に一括添加、分割添加ある
いは連続添加する。分割添加あるいは連続添加する場
合、添加量は均等にあるいは一定にすることもでき、重
合の進行段階に応じて変えることもできる。また、連鎖
移動剤は、そのまま単独で添加してもよいし、単量体、
水、重合副資材または有機溶媒に混合し又は溶解して添
加してもよい。
The offset rotary printing paper coating latex of the present invention is obtained by emulsion polymerization of the above monomers in the presence of the chain transfer agent. The chain transfer agent is added to the reactor all at once before the start of polymerization or after the start of polymerization, all at once, dividedly or continuously. In the case of divided addition or continuous addition, the addition amount may be uniform or constant, and may be changed according to the stage of progress of polymerization. Further, the chain transfer agent may be added alone as it is, a monomer,
You may mix and dissolve in water, a polymerization auxiliary material, or an organic solvent, and may add it.

【0017】本発明のオフセット輪転印刷紙塗工用組成
物は、本発明のオフセット輪転印刷紙塗工用ラテックス
と顔料とを必須成分とするものである。
The offset rotary printing paper coating composition of the present invention comprises the offset rotary printing paper coating latex of the present invention and a pigment as essential components.

【0018】本発明に用いる顔料は、紙塗工用として一
般的に用いられる粉粒状物質である。 その具体例とし
てはクレー、炭酸カルシウム、タルク、酸化チタン、サ
チンホワイトなどの無機顔料;プラスチックピグメント
等の有機顔料が挙げられる。
The pigment used in the present invention is a granular material generally used for paper coating. Specific examples thereof include inorganic pigments such as clay, calcium carbonate, talc, titanium oxide and satin white; and organic pigments such as plastic pigments.

【0019】顔料とオフセット輪転印刷紙塗工用ラテッ
クスとの比率は、顔料100重量部に対してオフセット
輪転印刷紙塗工用ラテックス(固形分)が、通常、5〜
30重量部、好ましくは7〜20重量部である。
The ratio of the pigment to the offset rotary printing paper coating latex is usually 5 to 5 parts by weight of the offset rotary printing paper coating latex (solid content) relative to 100 parts by weight of the pigment.
It is 30 parts by weight, preferably 7 to 20 parts by weight.

【0020】また、本発明のオフセット輪転印刷紙塗工
用組成物は、必要に応じて他のラテックスバインダー、
分散剤、水溶性高分子、耐水化剤、消泡剤、染料、滑剤
などを配合したものであってもよい。
In addition, the composition for coating the offset rotary printing paper of the present invention contains, if necessary, another latex binder,
It may be a mixture of a dispersant, a water-soluble polymer, a waterproofing agent, an antifoaming agent, a dye, a lubricant and the like.

【0021】本発明のオフセット輪転印刷紙塗工用組成
物は、オフセット輪転印刷用原紙に塗布して使用する。
塗布の方法は特に限定されず、例えば、ブレードコータ
ー、ロールコーター、エアナイフコーター、ショートド
ウェルコーターなどの塗工装置を用いて塗布する。塗布
量は、通常、組成物が固形分換算で、通常、3〜30g
/m2、好ましくは5〜20g/m2になる範囲である。
また、該組成物を塗布後、それぞれ乾燥することが好ま
しい。
The offset rotary printing paper coating composition of the present invention is applied to an offset rotary printing base paper for use.
The coating method is not particularly limited, and for example, a blade coater, a roll coater, an air knife coater, a short dwell coater or the like is used for coating. The coating amount is usually 3 to 30 g in terms of solid content of the composition.
/ M 2 , preferably 5 to 20 g / m 2 .
Further, it is preferable to dry each of the compositions after coating.

【0022】[0022]

【発明の効果】本発明によれば、良好な接着強度と耐ブ
リスター性とを併せもち且つそれらのバランスに優れる
オフセット輪転印刷塗工紙を得ることができる。
According to the present invention, it is possible to obtain an offset rotary printing coated paper which has good adhesive strength and blister resistance and is excellent in the balance between them.

【0023】[0023]

【実施例】以下、本発明を実施例により、さらに詳細に
説明する。なお、実施例中の部及び%は重量基準であ
る。
EXAMPLES The present invention will now be described in more detail by way of examples. The parts and% in the examples are based on weight.

【0024】ラテックス及びこのラテックスを主成分と
する紙塗工用組成物を塗工して得られた塗工紙につい
て、以下の方法に従って評価した。 (ラテックスの評価) ゲル含量 ラテックスのpHを8.0に調整した後、枠付きガラス
板に流延し、100℃にて減圧乾燥してフィルムを得
た。このフィルム0.5gを80メッシュの金網のかご
に入れて、それを20℃のテトラヒドロフラン100m
lに24時間浸漬した後、金網のかごに残るフィルムを
100℃で減圧乾燥し、残存率を計算してゲル含量を求
めた。 平均粒子径 電子顕微鏡で観察し、重合体ラテックスの粒子径を50
0個測定しその数平均値で示した。
The latex and the coated paper obtained by coating the paper coating composition containing the latex as a main component were evaluated according to the following methods. (Evaluation of Latex) Gel Content After adjusting the pH of latex to 8.0, it was cast on a glass plate with a frame and dried under reduced pressure at 100 ° C. to obtain a film. 0.5g of this film is put in a wire mesh basket of 80 mesh, and it is placed in tetrahydrofuran 100m at 20 ° C.
After being immersed in 1 for 24 hours, the film remaining in the cage of the wire net was dried under reduced pressure at 100 ° C., and the residual rate was calculated to determine the gel content. Average particle size The particle size of the polymer latex is 50 when observed with an electron microscope.
0 pieces were measured and the number average value was shown.

【0025】(塗工紙の評価) ドライピック強度 塗工紙にRIテスター(明石製作所製)を用いて、印刷
インク(タック値14)を4回重ね刷りした後、紙面の
剥がれ(ピッキング)状態を観察し5点法で評価した。
点数の高いほうがドライピックが高い。 ウェットピック強度 塗工紙にモルトンロールを用いて水を塗布した後、RI
テスター(明石製作所製)を用いて、印刷インク(タッ
ク値20)を4回重ね塗りした後、ドライピック強度の
評価方法と同様に5点法で評価した。点数の高いものほ
どウェットピックが高い。 耐ブリスター性 塗工紙を約6%に調湿した後、加熱したオイルバスに投
げ込み、ブリスターの発生する最低オイルバス温度で示
した。
(Evaluation of coated paper) Dry pick strength Using an RI tester (manufactured by Akashi Seisakusho) on coated paper, printing ink (tack value 14) was overprinted four times, and then the surface of the paper was peeled (picking). Was observed and evaluated by the 5-point method.
The higher the score, the higher the dry pick. Wet pick strength After applying water to the coated paper with a Molton roll, RI
Using a tester (manufactured by Akashi Seisakusho Co., Ltd.), printing ink (tack value: 20) was applied four times, and then evaluated by a 5-point method in the same manner as the dry pick strength evaluation method. The higher the score, the higher the wet pick. Blister resistance After controlling the humidity of the coated paper to about 6%, it was thrown into a heated oil bath and indicated by the minimum oil bath temperature at which blisters occur.

【0026】実施例1 1,3−ブタジエン35部、スチレン42部、メタクリ
ル酸メチル15部、アクリロニトリル5部、アクリル酸
1部、イタコン酸2部、2,2,4,6,6−ペンタメ
チルヘプタン−4−チオール1部及びドデシルベンゼン
スルホン酸ナトリウム0.5部を軟水50部に添加し攪
拌混合してモノマーエマルジョンを得た。別に攪拌機付
オートクレーブに軟水34部、過硫酸カリウム0.5
部、ドデシルベンゼンスルホン酸ナトリウム1部を仕込
み、80℃に加熱した後、前記モノマーエマルジョンの
うち10%をオートクレーブに添加し、1時間反応させ
た。次に、過硫酸カリウム1.0部及び軟水20部をオ
ートクレーブに添加した後、残りのモノマーエマルジョ
ンを4時間かけて反応器に添加した。この間オートクレ
ーブは80℃に維持した。モノマーエマルジョン添加終
了後、更に4時間、80℃を維持し反応させた後、水蒸
気を吹き込んで、未反応の単量体を除去し、室温に冷却
し、20%の水酸化ナトリウム水溶液を添加してpHを
8に調整して固形分濃度50%の本発明の重合体ラテッ
クスAを得た。このラテックスの評価結果を表1に示
す。
Example 1 35 parts of 1,3-butadiene, 42 parts of styrene, 15 parts of methyl methacrylate, 5 parts of acrylonitrile, 1 part of acrylic acid, 2 parts of itaconic acid, 2,2,4,6,6-pentamethyl 1 part of heptane-4-thiol and 0.5 part of sodium dodecylbenzenesulfonate were added to 50 parts of soft water and mixed with stirring to obtain a monomer emulsion. Separately, add 34 parts of soft water and 0.5 parts of potassium persulfate to the autoclave with a stirrer.
Parts and 1 part of sodium dodecylbenzenesulfonate were charged and heated to 80 ° C., then 10% of the monomer emulsion was added to an autoclave and reacted for 1 hour. Next, after adding 1.0 part of potassium persulfate and 20 parts of soft water to the autoclave, the remaining monomer emulsion was added to the reactor over 4 hours. During this period, the autoclave was maintained at 80 ° C. After the addition of the monomer emulsion, the reaction was maintained at 80 ° C. for another 4 hours, and then steam was blown to remove unreacted monomers, the mixture was cooled to room temperature, and a 20% aqueous sodium hydroxide solution was added. Then, the pH was adjusted to 8 to obtain a polymer latex A of the present invention having a solid content concentration of 50%. The evaluation results of this latex are shown in Table 1.

【0027】次にカオリンクレー(エンゲルハルド社
製、UW90)70部、炭酸カルシウム(三共製粉社
製、エスカロン#2000)30部、分散剤(東亜合成
社製、アロンT−40)0.15部、水酸化ナトリウム
0.15部、酸化デンプン3部及び重合体ラテックスA
10部(固形分)を混合して攪拌し、固形分濃度65
%、pH9.5の紙塗工用組成物を得た。この組成物を
原紙に塗工量が片面当り12g/m2となるように塗布
し、塗布直後に140℃の熱風で4秒間乾燥し、20
℃、65%R.H.の恒温恒湿室内に一夜放置した。そ
の後温度40℃、線圧40Kg/cmの条件で2回スー
パーカレンダー処理を行った。
Next, 70 parts of kaolin clay (UW90 manufactured by Engelhard), 30 parts of calcium carbonate (Escalon # 2000 manufactured by Sankyo Milling Co., Ltd.), and 0.15 parts of a dispersant (Aron T-40 manufactured by Toagosei Co., Ltd.) , Sodium hydroxide 0.15 parts, oxidized starch 3 parts and polymer latex A
Mix 10 parts (solid content) and stir to obtain a solid content concentration of 65
%, PH 9.5 paper coating composition was obtained. This composition was coated on a base paper so that the coating amount was 12 g / m 2 per side, and immediately after coating, it was dried with hot air at 140 ° C. for 4 seconds, and
C, 65% R.C. H. It was left overnight in a constant temperature and humidity room. After that, super calendering was performed twice under the conditions of a temperature of 40 ° C. and a linear pressure of 40 kg / cm.

【0028】実施例2〜6及び比較例1〜2 表1及び表2に示す処方に変えた他は実施例1と同じ方
法で重合体ラテックスB〜Hを得た。これらのラテック
スについて実施例1と同様に評価し、その結果を表1及
び表2に示した。さらに、重合体ラテックスB〜Hを用
いて実施例1と同様にして塗工用組成物を得、さらに塗
工紙を得た。これらの塗工紙について実施例1と同様に
評価し、その結果を表1及び表2に示した。
Examples 2 to 6 and Comparative Examples 1 to 2 Polymer latexes B to H were obtained in the same manner as in Example 1 except that the formulations shown in Tables 1 and 2 were changed. These latexes were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2. Further, using Polymer Latex B to H, a coating composition was obtained in the same manner as in Example 1, and further coated paper was obtained. These coated papers were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

【0029】[0029]

【表1】 [Table 1]

【0030】[0030]

【表2】 [Table 2]

【0031】表1及び表2から、少なくとも1個の第3
級ブチル基を有し且つ全炭素原子数が7〜16個である
第3級メルカプタン以外の連鎖移動剤を用いた場合(比
較例1及び2)では、ドライピック強度、ウェットピッ
ク強度及び耐ブリスター性が低いことがわかる。一方、
少なくとも1個の第3級ブチル基を有し且つ全炭素原子
数が7〜16個である第3級メルカプタンを用いた場合
(実施例)には、ドライピック強度、ウェットピック強
度及び耐ブリスター性が高く且つそれらのバランスも良
いことがわかる。
From Table 1 and Table 2, at least one third
When a chain transfer agent other than a tertiary mercaptan having a tertiary butyl group and a total number of carbon atoms of 7 to 16 was used (Comparative Examples 1 and 2), dry pick strength, wet pick strength and blistering resistance were obtained. It can be seen that the property is low. on the other hand,
When a tertiary mercaptan having at least one tertiary butyl group and having a total carbon atom number of 7 to 16 is used (Example), dry pick strength, wet pick strength and blister resistance are obtained. It can be seen that these are high and their balance is good.

───────────────────────────────────────────────────── 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 D21H 19/56 19/20 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location D21H 19/56 19/20

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 脂肪族共役ジエン単量体15〜50重量
%、エチレン性不飽和カルボン酸単量体1〜6重量%及
びこれらと共重合体可能なエチレン性不飽和単量体44
〜84重量%からなる単量体を連鎖移動剤の存在下に乳
化重合してなる、ゲル含量が15〜65重量%である共
重合体のラテックスであって、該連鎖移動剤として少な
くとも1個の第3級ブチル基を有し且つ全炭素原子数が
7〜16個である第3級メルカプタンを用いて得られる
ことを特徴とするオフセット輪転印刷紙塗工用ラテック
ス。
1. An aliphatic conjugated diene monomer 15 to 50% by weight, an ethylenically unsaturated carboxylic acid monomer 1 to 6% by weight, and an ethylenically unsaturated monomer 44 copolymerizable therewith.
A latex of a copolymer having a gel content of 15 to 65% by weight, which is obtained by emulsion-polymerizing a monomer consisting of ~ 84% by weight in the presence of a chain transfer agent, and at least one latex as the chain transfer agent. 1. A latex for rotary offset printing paper coating, which is obtained by using a tertiary mercaptan having a tertiary butyl group and having a total carbon atom number of 7 to 16.
【請求項2】 請求項1記載のオフセット輪転印刷紙塗
工用ラテックスと顔料とを必須成分とすることを特徴と
するオフセット輪転印刷紙塗工用組成物。
2. A composition for offset rotary printing paper coating, comprising the latex for offset rotary printing paper coating according to claim 1 and a pigment as essential components.
JP21684693A 1993-08-10 1993-08-10 Latex for web offset printing paper and composition for web offset printing paper Expired - Fee Related JP3345979B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP21684693A JP3345979B2 (en) 1993-08-10 1993-08-10 Latex for web offset printing paper and composition for web offset printing paper

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP21684693A JP3345979B2 (en) 1993-08-10 1993-08-10 Latex for web offset printing paper and composition for web offset printing paper

Publications (2)

Publication Number Publication Date
JPH0753610A true JPH0753610A (en) 1995-02-28
JP3345979B2 JP3345979B2 (en) 2002-11-18

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Country Link
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KR100409076B1 (en) * 2000-12-20 2003-12-11 주식회사 엘지화학 Method for preparing latex in use paper coating
JP2006274144A (en) * 2005-03-30 2006-10-12 Dainippon Ink & Chem Inc Method for producing copolymer latex
USRE41575E1 (en) * 1998-06-02 2010-08-24 Osamu Yamamoto Crystalline turbostratic boron nitride powder and method for producing same
JP2012092485A (en) * 2010-09-30 2012-05-17 Nippon A&L Inc Copolymer latex for paper coating and composition for paper coating
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE41575E1 (en) * 1998-06-02 2010-08-24 Osamu Yamamoto Crystalline turbostratic boron nitride powder and method for producing same
KR100409076B1 (en) * 2000-12-20 2003-12-11 주식회사 엘지화학 Method for preparing latex in use paper coating
JP2006274144A (en) * 2005-03-30 2006-10-12 Dainippon Ink & Chem Inc Method for producing copolymer latex
JP2012092485A (en) * 2010-09-30 2012-05-17 Nippon A&L Inc Copolymer latex for paper coating and composition for paper coating
WO2016017735A1 (en) * 2014-07-31 2016-02-04 日本ゼオン株式会社 Nitrile-group-containing copolymer rubber, crosslinkable rubber composition, and crosslinked rubber
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US20170166672A1 (en) * 2014-07-31 2017-06-15 Zeon Corporation Nitrile group-containing copolymer rubber, cross-linkable rubber composition, and cross-linked rubber
US9932434B2 (en) 2014-07-31 2018-04-03 Zeon Corporation Nitrile group-containing copolymer rubber, cross-linkable rubber composition, and cross-linked rubber
RU2676707C2 (en) * 2014-07-31 2019-01-10 Зэон Корпорейшн Nitrile group-containing copolymer rubber, cross-linkable rubber composition and cross-linked rubber
CN106536580B (en) * 2014-07-31 2020-04-24 日本瑞翁株式会社 Nitrile group-containing copolymer rubber, crosslinkable nitrile rubber composition, and crosslinked rubber product
KR20240005983A (en) * 2014-07-31 2024-01-12 니폰 제온 가부시키가이샤 Nitrile-group-containing copolymer rubber, crosslinkable rubber composition, and crosslinked rubber

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