JP2002194311A - Thickener and adhesive composition - Google Patents
Thickener and adhesive compositionInfo
- Publication number
- JP2002194311A JP2002194311A JP2000392078A JP2000392078A JP2002194311A JP 2002194311 A JP2002194311 A JP 2002194311A JP 2000392078 A JP2000392078 A JP 2000392078A JP 2000392078 A JP2000392078 A JP 2000392078A JP 2002194311 A JP2002194311 A JP 2002194311A
- Authority
- JP
- Japan
- Prior art keywords
- thickener
- coating
- adhesive composition
- diisocyanate
- pressure
- 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
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は増粘剤に関する。さ
らに詳しくは粘着剤用アクリル系エマルションに有用な
増粘剤に関するものである。TECHNICAL FIELD The present invention relates to a thickener. More specifically, the present invention relates to a thickener useful for an acrylic emulsion for an adhesive.
【０００２】[0002]
【従来の技術】従来粘着剤用アクリル系エマルションの
増粘剤としてはカルボキシメチルセルロ−ス、ポリビニ
ルアルコ−ル、ポリアクリル酸系誘導体、ポリオキシア
ルキレングリコ−ル誘導体などが知られている。カルボ
キシメチルセルロ−ス、ポリビニルアルコ−ル、ポリア
クリル酸系誘導体を増粘剤として使用した場合、エマル
ションのチキソトロピ−性が大きくなるため塗工の際の
レベリング性に劣ることや、保存時にエマルションの凝
集を引き起こすなどして経日保存安定性が悪化するなど
の問題がある。これに対し、ポリオキシアルキレングリ
コ−ル誘導体を増粘剤として使用した場合、エマルショ
ンのチキソトロピ−性が大きくなるのを抑え塗工の際の
レベリング性を改善する。また保存時のエマルションの
凝集を起こさず経日保存安定性の悪化を改善する。一
方、ポリオキシアルキレングリコ−ル誘導体としては、
ウレタン変成ポリオキシアルキレングリコ−ル（特公昭
５２−２５８４０号、特公平１−５５２９２号、特開昭
５８−２１３０７４）、エステル変成ポリオキシアルキ
レングリコ−ル（特開昭５９−４１３７７）、エポキシ
変成ポリオキシアルキレングリコ−ル（特開昭５８−１
６４６７１、特開平２−１７５７２４）などが知られて
いる。2. Description of the Related Art Conventionally, carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid derivatives, polyoxyalkylene glycol derivatives and the like have been known as thickeners for acrylic emulsions for pressure sensitive adhesives. When carboxymethyl cellulose, polyvinyl alcohol, or a polyacrylic acid-based derivative is used as a thickener, the thixotropy of the emulsion becomes large, so that the leveling property at the time of coating is inferior, or the There are problems such as deterioration in storage stability over time due to aggregation and the like. On the other hand, when a polyoxyalkylene glycol derivative is used as a thickener, the thixotropic property of the emulsion is suppressed from increasing, and the leveling property during coating is improved. In addition, it does not cause aggregation of the emulsion during storage, and improves deterioration in storage stability over time. On the other hand, as polyoxyalkylene glycol derivatives,
Urethane-modified polyoxyalkylene glycol (Japanese Patent Publication No. 52-25840, Japanese Patent Publication No. 1-55292, JP-A-58-213074), ester-modified polyoxyalkylene glycol (JP-A-59-41377), epoxy modification Polyoxyalkylene glycol (JP-A-58-1)
64671, JP-A-2-175724) and the like.
【０００３】[0003]
【発明が解決しようとする課題】ブレ−ドコ−タ−、リ
ップコ−タ−、ダイコ−タ−、コンマコ−タ−などの塗
工装置で粘着剤組成物を塗工する場合、増粘剤として従
来のポリオキシアルキレングリコ−ル誘導体を使用して
も、高速塗工の場合、せん断速度が高くなるため塗工時
の粘度低下が大きくなり希望通りの塗工量が得られなか
ったり、また塗工速度の変化によりせん断速度が変化す
るため粘度の変化が大きくなり、塗工量が変化してしま
うという問題があった。When the pressure-sensitive adhesive composition is applied by a coating apparatus such as a blade coater, a lip coater, a die coater, a comma coater, etc., it is used as a thickener. Even when a conventional polyoxyalkylene glycol derivative is used, in the case of high-speed coating, the shear rate becomes high, so that the viscosity decrease during coating becomes large, and the desired coating amount cannot be obtained, or Since the shear rate changes with the change in the processing speed, the change in viscosity increases, and there is a problem that the coating amount changes.
【０００４】[0004]
【発明が解決しようとする手段】本発明は、実際の高速
塗工条件下（高せん断速度下）において、粘度低下が小
さく、高塗工量が実現でき、かつ塗工速度（せん断速
度）が変化しても粘度が変化せず、一定の塗工量を得る
増粘剤並びにそれを配合してなる粘着剤組成物、それを
塗工、乾燥してなる粘着剤シートを提供することを目的
とする。According to the present invention, under actual high-speed coating conditions (under a high shear rate), the viscosity decrease is small, a high coating amount can be realized, and the coating rate (shear rate) is low. It is an object of the present invention to provide a thickener which does not change the viscosity even when it changes and obtains a constant coating amount, a pressure-sensitive adhesive composition comprising the same, and a pressure-sensitive adhesive sheet obtained by coating and drying the same. And
【０００５】[0005]
【発明の実施の形態】本発明者らは鋭意検討の結果、特
定の要件を備えた化合物が目的に合致することを見出し
本発明に至った。すなわち、本発明の増粘剤は、支持体
上にアクリル系エマルションを主成分とする粘着剤組成
物を塗工、乾燥して得られる粘着剤シートにおいて、質
量平均粒子径が０．１〜１．５μｍであるアクリル系エ
マルションに配合される、一般式（１）で示され、かつ
重量平均分子量が８０，０００〜１４０，０００である
ことを特徴とする増粘剤である。 ［式中、Ｘ、Ｚは炭素数４〜２４の直鎖炭化水素基であ
り、Ｙはジイソシアネ−ト化合物から導かれる２価の有
機残基であり、ＯＲ、ＯＲ’、ＯＲ”は炭素数２〜４の
オキシアルキレン基であり、ａ、ｂ、ｄは１〜５００の
整数であり、ｃは１以上の整数である。］BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies, the present inventors have found that a compound having specific requirements is suitable for the purpose, and have reached the present invention. That is, the thickener of the present invention has a mass average particle diameter of 0.1 to 1 in a pressure-sensitive adhesive sheet obtained by applying and drying a pressure-sensitive adhesive composition containing an acrylic emulsion as a main component on a support. A thickener which is represented by the general formula (1) and has a weight average molecular weight of 80,000 to 140,000, which is blended with an acrylic emulsion having a size of 0.5 μm. [In the formula, X and Z are linear hydrocarbon groups having 4 to 24 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR 'and OR "are carbon atoms. 2 to 4 oxyalkylene groups, a, b, and d are integers of 1 to 500, and c is an integer of 1 or more.]
【０００６】また、本発明は支持体上にアクリル系エマ
ルションを主成分とする粘着剤組成物を塗工、乾燥して
得られる粘着剤シートにおいて、粘着剤組成物中に、全
アクリル系エマルション１００質量部に対し、上記記載
の増粘剤を０．０１〜１０質量部配合させることを特徴
とする高速塗工用粘着剤組成物である。The present invention also relates to a pressure-sensitive adhesive sheet obtained by applying a pressure-sensitive adhesive composition containing an acrylic emulsion as a main component on a support and drying the pressure-sensitive adhesive composition. It is a pressure-sensitive adhesive composition for high-speed coating, characterized by blending 0.01 to 10 parts by mass of the above-mentioned thickener with respect to parts by mass.
【０００７】さらに、本発明は上記記載の高速塗工用粘
着剤組成物を塗工、乾燥して得られる粘着剤シートであ
る。Further, the present invention is a pressure-sensitive adhesive sheet obtained by applying and drying the above-described pressure-sensitive adhesive composition for high-speed coating.
【０００８】一般式（１）中のＸ、Ｚは、炭素数４〜２
４の直鎖炭化水素基である。炭素数４〜２４の直鎖炭化
水素基としては、例えばｎ−ブチル基、ｎ−ペンチル
基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル
基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、
ｎ−ドデシル基、ｎ−トリデシル基、ｎ−テトラデシル
基、ｎ−ペンタデシル基、ｎ−セチル基、ｎ−ヘプタデ
シル基、ｎ−オクタデシル基、ｎ−ノナデシル基、ｎ−
イコシル基、ｎ−ヘンイコシル基、ｎ−ドコシル基、ｎ
−トリコシル基、ｎ−テトラコシル基などがあげられ
る。なお、ここでいう炭素数とは、質量平均炭素数を表
わす。また、ｎは直鎖を表わす。X and Z in the general formula (1) each have 4 to 2 carbon atoms.
And 4 straight-chain hydrocarbon groups. Examples of the linear hydrocarbon group having 4 to 24 carbon atoms include n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group,
n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-cetyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-
Icosyl group, n-henicosyl group, n-docosyl group, n
-Tricosyl group, n-tetracosyl group and the like. In addition, the carbon number here represents a mass average carbon number. N represents a straight chain.
【０００９】これらのうち好ましくは炭素数８〜２０の
直鎖炭化水素基であり、さらに好ましくは炭素数１０〜
１８の直鎖炭化水素基である。Ｘ、Ｚは同一の直鎖炭化
水素基でもよく、異なる直鎖炭化水素基の組み合わせで
もよい。炭素数４未満では高せん断速度下での粘度低下
が大きく、炭素数２４を越えるとせん断速度の変化に対
する粘度変化が大きくなり、かつ原料が高価でコストパ
フォ−マンスに劣る。[0009] Of these, straight-chain hydrocarbon groups having 8 to 20 carbon atoms are preferred, and more preferred are those having 10 to 20 carbon atoms.
18 straight-chain hydrocarbon groups. X and Z may be the same linear hydrocarbon group or a combination of different linear hydrocarbon groups. If the number of carbon atoms is less than 4, the decrease in viscosity under a high shear rate is large. If the number of carbon atoms is more than 24, the change in viscosity with respect to the change in the shear rate is large, and the raw materials are expensive and the cost performance is poor.
【００１０】一般式（１）中のＹはジイソシアネ−ト化
合物から導かれる２価の有機残基であり、ジイソシアネ
−ト化合物としては特に限定されない。ジイソシアネ−
ト化合物としては例えば、脂肪族系ジイソシアネ−ト化
合物、芳香族系ジイソシアネ−ト化合物、脂環族系ジイ
ソシアネ−ト化合物などがあげられる。[0010] Y in the general formula (1) is a divalent organic residue derived from a diisocyanate compound, and the diisocyanate compound is not particularly limited. Diisocyanate
Examples of the compound include an aliphatic diisocyanate compound, an aromatic diisocyanate compound, and an alicyclic diisocyanate compound.
【００１１】脂肪族系ジイソシアネ−ト化合物として
は、例えばメチレンジイソシアネ−ト、ジメチレンジイ
ソシアネ−ト、トリメチレンジイソシアネ−ト、テトラ
メチレンジイソシアネ−ト、ペンタメチレンジイソシア
ネ−ト、ヘキサメチレンジイソシアネ−ト、ヘプタメチ
レンジイソシアネ−ト、オクタメチレンジイソシアネ−
ト、ノナメチレンジイソシアネ−ト、デカメチレンジイ
ソシアネ−ト、ジプロピルエ−テルジイソシアネ−ト、
２，２−ジメチルペンタンジイソシアネ−ト、３−メト
キシヘキサンジイソシアネ−ト、２，２，４−トリメチ
ルペンタンジイソシアネ−ト、３−ブトキシヘキサンジ
イソシアネ−ト、１，４−ブチレングリコ−ルジプロピ
ルエ−テルジイソシアネ−ト、メタキシリレンジイソシ
アネ−ト、パラキシリレンジイソシアネ−ト、テトラメ
チルキシリレンジイソシアネ−トなどがあげられる。Examples of the aliphatic diisocyanate compound include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate and pentamethylene diisocyanate. , Hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate
G, nonamethylene diisocyanate, decamethylene diisocyanate, dipropyl ether diisocyanate,
2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, 2,2,4-trimethylpentane diisocyanate, 3-butoxyhexane diisocyanate, 1,4- Butylene glycol dipropyl ether diisocyanate, metaxylylene diisocyanate, paraxylylene diisocyanate, tetramethyl xylylene diisocyanate, and the like.
【００１２】芳香族系ジイソシアネ−ト化合物として
は、例えばメタフェニレンジイソシアネ−ト、パラフェ
ニレンジイソシアネ−ト、２，４−トリレンジイソシア
ネ−ト、２，６−トリレンジイソシアネ−ト、ジメチル
ベンゼンジイソシアネ−ト、エチルベンゼンジイソシア
ネ−ト、イソプロピルベンゼンジイソシアネ−ト、ビフ
ェニルジイソシアネ−ト、トリジンジイソシアネ−ト、
３，３’−ジメトキシビフェニルジイソシアネ−ト、ナ
フタレンジイソシアネ−ト、４，４’−ジフェニルメタ
ンジイソシアネ−ト、２，２’−ジメチルジフェニルメ
タン−４，４’−ジイソシアネ−ト、３，３’−ジメト
キシジフェニルメタン−４，４’−ジイソシアネ−ト、
４，４’−ジメトキシジフェニルメタン−３，３’−ジ
イソシアネ−ト、４，４’−ジエトキシジフェニルメタ
ン−３，３’−ジイソシアネ−ト、２，２’−ジメチル
−５，５’−ジメトキシジフェニルメタン−４，４’−
ジイソシアネ−トなどがあげられる。Examples of the aromatic diisocyanate compound include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate,
3,3'-dimethoxybiphenyldiisocyanate, naphthalenediisocyanate, 4,4'-diphenylmethanediisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate, , 3'-dimethoxydiphenylmethane-4,4'-diisocyanate,
4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, 4,4'-diethoxydiphenylmethane-3,3'-diisocyanate, 2,2'-dimethyl-5,5'-dimethoxydiphenylmethane- 4,4'-
Diisocyanate and the like.
【００１３】脂環族系ジイソシアネ−ト化合物として
は、例えばシクロヘキシルジイソシアネ−ト、水添キシ
リレンジイソシアネ−ト、イソホロンジイソシアネ−
ト、ジシクロヘキシルメタン−４，４’−ジイソシアネ
−トなどがあげられる。Examples of the alicyclic diisocyanate compound include cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate.
And dicyclohexylmethane-4,4'-diisocyanate.
【００１４】一般式（１）中のＯＲ、ＯＲ’、ＯＲ”
は、炭素数２〜４のオキシアルキレン基である。炭素数
が２未満および４を越えると高せん断速度下での粘度低
下が大きくなり、かつ原料が高価でコストパフォ−マン
スに劣る。。炭素数２〜４のオキシアルキレン基として
はオキシエチレン基、オキシプロピレン基およびオキシ
ブチレン基などがあげられる。これらのうちオキシエチ
レン基は必須である。オキシエチレン基の割合は、好ま
しくは全オキシアルキレン基の６０質量％以上、さらに
好ましくは全オキシアルキレン基の８０質量％以上、特
に好ましくは全オキシアルキレン基の９０質量％以上で
ある。オキシエチレン基が６０質量％未満では高せん断
速度下での粘度低下が大きくなる。ＯＲ、ＯＲ’、Ｏ
Ｒ”は２種以上のオキシアルキレン基をブロックまたは
ランダムに繋いだものでも良い。（ＯＲ）ａ、（Ｏ
Ｒ’）ｂ、（ＯＲ”）ｄは同一のオキシアルキレン基で
もよく、異なるオキシアルキレン基の組み合わせでもよ
い。OR, OR ', OR "in the general formula (1)
Is an oxyalkylene group having 2 to 4 carbon atoms. If the number of carbon atoms is less than 2 or more than 4, the decrease in viscosity under a high shear rate becomes large, and the raw material is expensive and the cost performance is poor. . Examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Of these, the oxyethylene group is essential. The proportion of oxyethylene groups is preferably at least 60% by mass of all oxyalkylene groups, more preferably at least 80% by mass of all oxyalkylene groups, particularly preferably at least 90% by mass of all oxyalkylene groups. If the oxyethylene group content is less than 60% by mass, the decrease in viscosity under a high shear rate becomes large. OR, OR ', O
R ″ may be a block in which two or more oxyalkylene groups are linked or randomly. (OR) a, (O)
R ′) b and (OR ″) d may be the same oxyalkylene group or a combination of different oxyalkylene groups.
【００１５】一般式（１）中のａ、ｂ、ｄは、各々、Ｏ
Ｒ、ＯＲ’、ＯＲ”の繰り返し単位を表わし、１〜５０
０の整数であり、好ましくは２〜４００であり、さらに
好ましくは２〜３００である。１未満および５００を越
えると高せん断速度下での粘度低下が大きくなる。A, b and d in the general formula (1) each represent O
Represents a repeating unit of R, OR ', OR ", and represents 1 to 50
It is an integer of 0, preferably 2 to 400, and more preferably 2 to 300. If it is less than 1 or more than 500, the decrease in viscosity under a high shear rate becomes large.
【００１６】 内の繰り返し単位を表わし、１以上の整数である。[0016] And represents an integer of 1 or more.
【００１７】本発明の増粘剤の重量平均分子量は、８
０，０００〜１４０，０００であり、好ましくは９０，
０００〜１３０，０００、さらに好ましくは１００，０
００〜１２０，０００である。重量平均分子量が８０，
０００未満では高せん断速度下での粘度低下が大きくな
り、１４０，０００を越えるとせん断速度の変化に対す
る粘度変化が大きくなり、かつ合成時に粘度が高くなり
すぎて製造が困難である。The weight average molecular weight of the thickener of the present invention is 8
000 to 140,000, preferably 90,
000 to 130,000, more preferably 100,0
00 to 120,000. Weight average molecular weight of 80,
If it is less than 000, the decrease in viscosity under a high shear rate becomes large. If it exceeds 140,000, the change in viscosity with respect to the change in shear rate becomes large, and the viscosity becomes too high at the time of synthesis, making production difficult.
【００１８】本発明の増粘剤の重量平均分子量は、分子
量既知のポリスチレンを標準物質としてゲルパ−ミエ−
ションクロマトグラフィ（Ｇ．Ｐ．Ｃ．）を用いて測定
することができる。例えば、東ソ−（株）製、型式ＨＬ
Ｃ−８１２０ＧＰＣのゲルパ−ミエ−ションクロマトグ
ラフィ（Ｇ．Ｐ．Ｃ．）を用いて以下の条件で測定でき
る。カラムには東ソ−製、型式ＳｕｐｅｒＨ−４０００
×２本と型式ＳｕｐｅｒＨ−３０００×１本を用い、カ
ラム温度は４０℃、検出器は示差屈折計（ＲＩ検出
器）、溶離液としてＴＨＦ（試薬１級、片山化学工業
製）を用い、流速は０．５ｍｌ／ｍｉｎ．、試料濃度は
１％、試料溶液注入量は１０μｌ、デ−タ処理機は東ソ
−（株）製、型式ＳＣ−８０２０、分子量既知のポリス
チレンの標準物質として東ソ−（株）製、ＴＳＫ標準ポ
リスチレンを用いる。ＴＳＫ標準ポリスチレンの重量平
均分子量は次の通りである。Ａー５００：５３０、Ａー
１０００：９５０、Ａ−２５００：２，８００、Ａー５
０００：６，４００、Ｆー１：１０，１００、Ｆー２：
１７，３００、Ｆー４：４３，０００、Ｆー１０：９
８，９００、Ｆー２０：１８４，０００、Ｆー４０：４
２７，０００、Ｆー８０：７９１，０００、Ｆー１２
８：１，３００，０００。The weight average molecular weight of the thickener of the present invention is determined by gel permeation using polystyrene having a known molecular weight as a standard substance.
It can be measured by using chromatography (GPC). For example, model HL manufactured by Tosoh Corporation
It can be measured under the following conditions by using gel permeation chromatography (GPC) of C-8120GPC. The column is manufactured by Tosoh Corporation, Model SuperH-4000
× 2 tubes and model SuperH-3000 × 1 tube, column temperature was 40 ° C., detector was a differential refractometer (RI detector), THF was used as eluent (reagent grade 1, Katayama Chemical Industry), and flow rate was Is 0.5 ml / min. The sample concentration was 1%, the sample solution injection volume was 10 μl, the data processor was Toso Corporation, model SC-8020, and the standard material of polystyrene with a known molecular weight was Toso Corporation, TSK. Use standard polystyrene. The weight average molecular weight of TSK standard polystyrene is as follows. A-500: 530, A-1000: 950, A-2500: 2,800, A-5
000: 6,400, F-1: 10,100, F-2:
17,300, F-4: 43,000, F-10: 9
8,900, F-20: 184,000, F-40: 4
27,000, F-80: 791,000, F-12
8: 1,300,000.
【００１９】本発明の増粘剤を合成する方法としては、
公知のウレタン化反応を用いて合成することができる。
例えばポリエ−テルモノオ−ル、ポリエ−テルジオ−ル
およびジイソシアネ−トを２〜１０時間反応して合成で
きる。例えば、ポリエ−テルモノオ−ル、ポリエ−テル
ジオ−ルおよびジイソシアネ−トから合成する場合、一
括仕込みによる合成方法でもよく、またポリエ−テルジ
オ−ルとジイソシアネ−トを反応させた後ポリエ−テル
モノオ−ルと反応させ合成する方法、あるいはポリエ−
テルモノオ−ルとジイソシアネ−トを反応させた後ポリ
エ−テルジオ−ルと反応させ合成する方法でもよい。反
応により一部副生成物ができる場合があるが、主生成物
は一般式（１）の化合物であり、副生成物との混合物で
使用できる。The method for synthesizing the thickener of the present invention includes:
It can be synthesized using a known urethanation reaction.
For example, it can be synthesized by reacting polyether monool, polyetherdiol and diisocyanate for 2 to 10 hours. For example, when synthesizing from polyether monool, polyether diol, and diisocyanate, a synthesis method by batch charging may be used, or polyether monoole may be reacted after reacting polyether diol with diisocyanate. To react and synthesize
A method in which termonool and diisocyanate are reacted and then reacted with polyetherdiol to synthesize them may be used. Although some by-products may be formed by the reaction, the main product is a compound of the general formula (1) and can be used as a mixture with the by-products.
【００２０】反応温度は４０〜１３０℃であり好ましく
は７０〜１００℃である。４０℃未満では反応が遅く時
間がかかりすぎる欠点があり、また、１３０℃より高い
温度では異常な副反応が起こり好ましくない。[0020] The reaction temperature is 40 to 130 ° C, preferably 70 to 100 ° C. If the temperature is lower than 40 ° C., the reaction is slow and takes too much time. If the temperature is higher than 130 ° C., an abnormal side reaction occurs, which is not preferable.
【００２１】これらの反応において、必要に応じて使用
される溶剤としては、活性水素を含有しないことが必要
であり、例えば芳香族系溶剤としてトルエン、キシレン
など、脂肪族系溶剤として石油エ−テル、ｎ−ヘキサン
など、脂環式系溶剤としてシクロヘキサン、シクロヘキ
サノン、デカリンなど、ハロゲン含有溶剤としてクロロ
ホルム、四塩化炭素、エチレンジクロライド、クロルベ
ンゼンなど、エステル系溶剤として酢酸エチル、酢酸ブ
チル、酢酸ペンチルなど、ケトン系溶剤としてメチルエ
チルケトン、ジエチルケトン、メチルイソブチルケトン
などがあげられる。In these reactions, it is necessary that the solvent used if necessary does not contain active hydrogen, such as toluene and xylene as aromatic solvents, and petroleum ether as aliphatic solvents. , N-hexane, etc., cyclohexane, cyclohexanone, decalin, etc. as alicyclic solvents, chloroform, carbon tetrachloride, ethylene dichloride, chlorobenzene, etc. as halogen-containing solvents, ethyl acetate, butyl acetate, pentyl acetate, etc. as ester solvents, Examples of the ketone solvent include methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and the like.
【００２２】また必要に応じてウレタン化反応に使用さ
れる触媒としては、例えばアミン系化合物としてトリエ
チルアミン、トリエチレンジアミン、ヘプタメチルジエ
チレントリアミン、Ｎ−メチルモルホリン、ベンジルト
リエチルアンモニウムハイドロオキサイドなど、金属含
有化合物として塩化第１スズ、塩化第２スズ、オクチル
酸スズ、オクチル酸鉛、ジブチルチンジラウレ−ト、ナ
フテン酸コバルト、ナフテン酸鉛、ナフテン酸カリウ
ム、三塩化アンチモンなどがあげられる。触媒添加量は
仕込み全重量に対し、０．００１〜１質量％である。ま
た添加方法は通常反応初期に加えるが反応中に分割して
添加してもよい。If necessary, the catalyst used in the urethanation reaction may be, for example, an amine compound such as triethylamine, triethylenediamine, heptamethyldiethylenetriamine, N-methylmorpholine, benzyltriethylammonium hydroxide, or the like. Examples thereof include stannous tin, stannic chloride, tin octylate, lead octylate, dibutyltin dilaurate, cobalt naphthenate, lead naphthenate, potassium naphthenate, and antimony trichloride. The amount of the catalyst added is 0.001 to 1% by mass based on the total weight of the charged components. The addition method is usually added at the beginning of the reaction, but may be added in portions during the reaction.
【００２３】次に本発明の増粘剤を配合してなる高速塗
工用粘着剤組成物について説明する。Next, the pressure-sensitive adhesive composition for high-speed coating comprising the thickener of the present invention will be described.
【００２４】本発明の増粘剤を配合してなる高速塗工用
粘着剤組成物は、増粘剤をアクリル系エマルション１０
０質量部に対して０．０１〜１０質量部配合したもので
あり、好ましくは０．０５〜５質量部配合したものであ
る。配合量が０．０１質量部未満では高せん断速度下で
の粘度低下が大きくなり、１０質量部を越えるとせん断
速度の変化に対する粘度変化が大きくなり、かつ単価が
高くなりコストパフォ−マンスに劣る。ここで示す高速
塗工用粘着剤組成物とはアクリル系エマルショに増粘剤
を配合したものを表わす。The high-pressure coating pressure-sensitive adhesive composition containing the thickener of the present invention comprises a thickener comprising an acrylic emulsion 10
It is a compounded amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 0 parts by mass. If the compounding amount is less than 0.01 part by mass, the viscosity decrease under a high shear rate becomes large, and if it exceeds 10 parts by mass, the change in viscosity with respect to the change in shear rate becomes large, and the unit price becomes high, resulting in poor cost performance. . The pressure-sensitive adhesive composition for high-speed coating shown here is obtained by blending a thickener with an acrylic emulsion.
【００２５】本発明の増粘剤の添加方法としては、アク
リル系エマルションに直接配合してもよく、また添加前
に適当な粘度になるように水あるいは溶剤で増粘剤を希
釈してから配合してもよい。As a method of adding the thickener of the present invention, the thickener may be directly added to the acrylic emulsion, or the thickener may be diluted with water or a solvent so as to have an appropriate viscosity before addition. May be.
【００２６】本発明の高速塗工用粘着剤組成物に用いる
アクリル系エマルションの質量平均粒子径としては０．
１〜１．５μｍであり、質量平均粒子径が０．１μｍ未
満ではせん断速度の変化に対する粘度変化が大きくな
り、質量平均粒子径が１．５μｍを越えると高せん断速
度下での粘度低下が大きくなる。The acrylic emulsion used in the pressure-sensitive adhesive composition for high-speed coating of the present invention has a mass average particle diameter of 0.1.
When the mass average particle diameter is less than 0.1 μm, the viscosity change with respect to the change in the shear rate is large, and when the mass average particle diameter exceeds 1.5 μm, the viscosity decrease under a high shear rate is large. Become.
【００２７】本発明の高速塗工用粘着剤組成物に用いる
アクリル系エマルションとしては一般的な乳化重合、懸
濁重合などの方法で調製することができ、特に限定され
ず、アルキル（メタ）アクリレ−ト系の単独重合体また
はアルキル（メタ）アクリレ−トと他のビニルモノマ−
との共重合体を主成分とするものであればよい。The acrylic emulsion used in the pressure-sensitive adhesive composition for high-speed coating of the present invention can be prepared by general methods such as emulsion polymerization and suspension polymerization, and is not particularly limited. -Homopolymer or alkyl (meth) acrylate and other vinyl monomers
What is necessary is just what has a copolymer of these as a main component.
【００２８】アルキル（メタ）アクリレ−トとしては、
例えばメチル（メタ）アクリレ−ト、エチル（メタ）ア
クリレ−ト、ｎ−プロピル（メタ）アクリレート、イソ
プロピル（メタ）アクリレート、ｎ−ブチル（メタ）ア
クリレ−ト、イソブチル（メタ）アクリレート、ｎ−ペ
ンチル（メタ）アクリレート、イソペンチル（メタ）ア
クリレート、ｎーヘキシル（メタ）アクリレート、イソ
ヘキシル（メタ）アクリレート、ｎーヘプチル（メタ）
アクリレート、イソヘプチル（メタ）アクリレート、２
−エチルヘキシル（メタ）アクリレ−ト、イソオクチル
（メタ）アクリレ−ト、ｎ−オクチル（メタ）アクリレ
−ト、ｎ−ノニル（メタ）アクリレ−ト、イソノニル
（メタ）アクリレ−ト、ｎ−デシル（メタ）アクリレ−
ト、イソデシル（メタ）アクリレ−ト、ｎ−ドデシル
（メタ）アクリレ−ト、イソドデシル（メタ）アクリレ
−ト、ｎ−トリデシル（メタ）アクリレ−ト、イソトリ
デシル（メタ）アクリレ−ト、ｎ−テトラデシル（メ
タ）アクリレ−ト、イソテトラデシル（メタ）アクリレ
−トなどがあげられる。これらのアルキル（メタ）アク
リレ−トは単独で用いてもよく、複数種組み合わせて用
いてもよい。As the alkyl (meth) acrylate,
For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (Meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, isohexyl (meth) acrylate, n-heptyl (meth)
Acrylate, isoheptyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meta) ) Acryle
, Isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, isododecyl (meth) acrylate, n-tridecyl (meth) acrylate, isotridecyl (meth) acrylate, n-tetradecyl ( (Meth) acrylate, isotetradecyl (meth) acrylate and the like. These alkyl (meth) acrylates may be used alone or in combination of two or more.
【００２９】アルキル（メタ）アクリレ−トと共重合可
能なビニルモノマ−としては、例えば（メタ）アクリル
酸、マレイン酸、フマル酸、イタコン酸などのカルボキ
シル基含有ビニルモノマ−またはその無水物、２−ヒド
ロキシエチル（メタ）アクリレ−ト、ヒドロキシプロピ
ル（メタ）アクリレ−ト、４−ヒドロキシブチルアクリ
レ−ト、ポリオキシエチレン（メタ）アクリレ−ト、ポ
リオキシプロピレン（メタ）アクリレ−ト、カプロラク
トン変成（メタ）アクリレ−トなどの水酸基含有ビニル
モノマ−、その他、酢酸ビニル、アクリルニトリル、ア
クリルアマイド、スチレン、ジメチルアミノエチル（メ
タ）アクリレ−トなどがあげられる。Examples of the vinyl monomer copolymerizable with the alkyl (meth) acrylate include, for example, a vinyl monomer having a carboxyl group such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid, or an anhydride thereof; Ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, modified caprolactone (meth) ) Hydroxyl-containing vinyl monomers such as acrylate, and others, vinyl acetate, acrylonitrile, acrylamide, styrene, dimethylaminoethyl (meth) acrylate and the like.
【００３０】本発明の高速塗工用粘着剤組成物には消泡
剤、防腐剤、防かび剤、他の増粘剤、分散剤、界面活性
剤、耐水化剤などを含んでもよい。The pressure-sensitive adhesive composition for high-speed coating of the present invention may contain an antifoaming agent, a preservative, a fungicide, another thickener, a dispersant, a surfactant, a water-proofing agent and the like.
【００３１】本発明の高速塗工用粘着剤組成物の塗工に
用いる塗工装置としては一般に用いられているものであ
り、例えばブレ−ドコ−タ−、リップコ−タ−、ダイコ
−タ−、コンマコ−タ−などの塗工装置があげられる。
本発明の高速塗工用粘着剤組成物はとりわけ、高せん断
速度になる高速塗工作業時により大きな効果を発揮す
る。ここで高速塗工とは塗工速度が５０ｍ／分以上の時
の塗工を意味する。また、高せん断速度とは塗工速度が
５０ｍ／分以上の塗工速度で塗工する時のせん断速度を
意味する。The coating apparatus used for coating the pressure-sensitive adhesive composition for high-speed coating of the present invention is one generally used, for example, a blade coater, a lip coater, a die coater. And a coating device such as a comma coater.
The pressure-sensitive adhesive composition for high-speed coating of the present invention exerts a particularly large effect at the time of high-speed coating operation at a high shear rate. Here, high-speed coating means coating when the coating speed is 50 m / min or more. Further, the high shear rate means a shear rate when coating is performed at a coating rate of 50 m / min or more.
【００３２】本発明の粘着剤シートは上記の高速塗工用
粘着剤組成物を塗工、乾燥して得られる。乾燥方式とし
ては通常のロールサポート方式、フローティング方式な
どがあげられる。The pressure-sensitive adhesive sheet of the present invention is obtained by coating and drying the above-mentioned pressure-sensitive adhesive composition for high-speed coating. Examples of the drying method include a normal roll support method and a floating method.
【００３３】本発明の粘着剤シートの用途としては、ラ
ベル、粘着テ−プ、両面粘着テ−プ、ステッカ−、シ−
ル、ワッペン、配送伝票などがあげられる。The adhesive sheet of the present invention is used for labels, adhesive tapes, double-sided adhesive tapes, stickers, and seals.
And emblems and delivery slips.
【００３４】本発明の増粘剤は、アクリル系エマルショ
ン以外のエマルションにも利用できる。アクリル系エマ
ルション以外のエマルションとしてはエチレン酢酸ビニ
ル系樹脂エマルション、酢酸ビニル系樹脂エマルショ
ン、酢酸ビニルアクリル系樹脂エマルションなどがあげ
られる。The thickener of the present invention can be used in emulsions other than acrylic emulsions. Emulsions other than acrylic emulsions include ethylene vinyl acetate resin emulsions, vinyl acetate resin emulsions, and vinyl acetate acrylic resin emulsions.
【００３５】本発明の増粘剤の用途としては、本発明の
通り、粘着剤のみならず、紙、革および繊維工業に対す
る水系塗料組成物、インク、水系塗料、無機顔料スラリ
ー、洗浄剤、接着剤、ワックス、磨き剤、化粧品、洗面
用化粧品、医薬品、農薬などがあげられる。As the use of the thickener of the present invention, as in the present invention, not only the pressure-sensitive adhesive but also the water-based coating composition, ink, water-based coating, inorganic pigment slurry, detergent, adhesive for paper, leather and textile industries. Agents, waxes, polishes, cosmetics, toiletries, pharmaceuticals, pesticides and the like.
【００３６】以下、実施例により本発明を更に説明する
が、本発明はこれに限定されるものではない。文中に部
または％とあるのは質量部または質量％の意味である。Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. In the text, “part” or “%” means “part by mass” or “% by mass”.
【００３７】（実施例Ａ〜Ｇ）製造例Ａ〜Ｇにより本発
明の実施例Ａ〜Ｇの増粘剤を得た。(Examples A to G) The thickeners of Examples A to G of the present invention were obtained from Production Examples A to G.
【００３８】（製造例Ａ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル１００００（分子量１０
０００）を５００部、ｎ−ブチルアルコ−ルにエチレン
オキサイドを２０モル付加したポリエ−テルモノオ−ル
を３２部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜
９０℃で３時間脱水し、系の水分含量を０．０３％とし
た。次いで、７０℃に冷却しトリレンジイソシアネ−ト
を１１．６部加え、窒素気流下８０〜８５℃でイソシア
ネ−ト含量が０％になるまで反応させ（２時間）、淡黄
色粘稠液状の反応生成物（実施例Ａ）を得た。(Production Example A) A polyethylene glycol 10,000 (molecular weight: 10) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
000) and 32 parts of polyether monool obtained by adding 20 moles of ethylene oxide to n-butyl alcohol, and 80 to 80 under low pressure (5 to 10 mmHg).
After dehydration at 90 ° C. for 3 hours, the water content of the system was adjusted to 0.03%. Then, the mixture was cooled to 70 ° C, 11.6 parts of tolylene diisocyanate was added, and the mixture was reacted at 80 to 85 ° C under a nitrogen stream until the isocyanate content became 0% (2 hours). (Example A) was obtained.
【００３９】（製造例Ｂ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル６０００（分子量６００
０）を５４０部、ｎ−ドデシルアルコ−ルにエチレンオ
キサイドを２モル付加したポリエ−テルモノオ−ルを１
２部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０
℃で３時間脱水し、系の水分含量を０．０３％とした。
次いで、７０℃に冷却しヘキサメチレンジイソシアネ−
トを１８．９部加え、窒素気流下８５〜９０℃でイソシ
アネ−ト含量が０％になるまで反応させ（３時間）、淡
黄色粘稠液状の反応生成物（実施例Ｂ）を得た。(Production Example B) A polyethylene glycol 6000 (molecular weight: 600) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer for high viscosity.
(0) and 540 parts of n-dodecyl alcohol and 1 mol of polyethermonool obtained by adding 2 mol of ethylene oxide to n-dodecyl alcohol.
2 parts, 80-90 under low pressure (5-10mmHg)
The system was dehydrated at 3 ° C. for 3 hours to bring the water content of the system to 0.03%.
Then, the mixture was cooled to 70 ° C. and hexamethylene diisocyanate was added.
18.9 parts, and reacted under a nitrogen stream at 85 to 90 ° C. until the isocyanate content becomes 0% (3 hours) to obtain a pale yellow viscous liquid reaction product (Example B). .
【００４０】（製造例Ｃ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル６０００（分子量６００
０）を４８０部、ｎ−ドコシルアルコ−ルにエチレンオ
キサイドを１５モル付加したポリエ−テルモノオ−ルを
３２部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９
０℃で３時間脱水し、系の水分含量を０．０３％とし
た。次いで、７０℃に冷却しキシリレンジイソシアネ−
トを１８部加え、窒素気流下９０〜９５℃でイソシアネ
−ト含量が０％になるまで反応させ（３時間）、淡黄色
粘稠液状の反応生成物（実施例Ｃ）を得た。(Production Example C) Polyethylene glycol 6000 (molecular weight 600) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
480 parts of 0) and 32 parts of polyether monool obtained by adding 15 moles of ethylene oxide to n-docosyl alcohol are added under low pressure (5 to 10 mmHg).
After dehydration at 0 ° C. for 3 hours, the water content of the system was adjusted to 0.03%. Then, the mixture was cooled to 70 ° C.
Then, the mixture was reacted at 90-95 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours) to obtain a pale yellow viscous liquid reaction product (Example C).
【００４１】（製造例Ｄ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル２００００（分子量２０
０００）を６００部、ｎ−セチルアルコ−ルにエチレン
オキサイドを５０モル付加したポリエ−テルモノオ−ル
を７３部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜
９０℃で３時間脱水し、系の水分含量を０．０３％とし
た。次いで、７０℃に冷却しテトラメチレンジイソシア
ネ−トを６．３部加え、窒素気流下８０〜８５℃でイソ
シアネ−ト含量が０％になるまで反応させ（２時間）、
淡黄色粘稠液状の反応生成物（実施例Ｄ）を得た。(Production Example D) Polyethylene glycol 20000 (molecular weight: 20) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer for high viscosity.
000) and 73 parts of polyether monool obtained by adding 50 moles of ethylene oxide to n-cetyl alcohol, and 80 to 80 under low pressure (5 to 10 mmHg).
After dehydration at 90 ° C. for 3 hours, the water content of the system was adjusted to 0.03%. Next, the mixture was cooled to 70 ° C., 6.3 parts of tetramethylene diisocyanate was added, and reacted at 80 to 85 ° C. under a nitrogen stream until the isocyanate content became 0% (2 hours).
A pale yellow viscous liquid reaction product (Example D) was obtained.
【００４２】（製造例Ｅ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル１０００（分子量１００
０）を１００部、ｎ−オクタデシルアルコ−ルにエチレ
ンオキサイドを４６０モル付加したポリエ−テルモノオ
−ルを４１０部入れ、低圧下（５〜１０ｍｍＨｇ）にて
８０〜９０℃で３時間脱水し、系の水分含量を０．０３
％とした。次いで、７０℃に冷却し水添キシリレンジイ
ソシアネ−トを２１．１部加え、窒素気流下８５〜９０
℃でイソシアネ−ト含量が０％になるまで反応させ（２
時間）、淡黄色粘稠液状の反応生成物（実施例Ｅ）を得
た。(Production Example E) A 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer was charged with polyethylene glycol 1000 (molecular weight: 100).
100 parts of n-octadecyl alcohol and 410 parts of polyethermonool obtained by adding 460 mol of ethylene oxide to n-octadecyl alcohol, and dehydrated under low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours. Water content of 0.03
%. Then, the mixture was cooled to 70 ° C., 21.1 parts of hydrogenated xylylene diisocyanate was added, and the mixture was cooled to 85 to 90 under a nitrogen stream.
At 200 ° C. until the isocyanate content becomes 0% (2
H), to obtain a pale yellow viscous liquid reaction product (Example E).
【００４３】（製造例Ｆ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、エチレンオキサイドとプロピレンオキサイドを重
量比８２：１８の割合でランダム共重合させた分子量６
４００のポリエ−テルジオ−ルを５１５部、ｎ−デシル
アルコ−ルにエチレンオキサイドを８モル付加したポリ
エ−テルモノオ−ルを１６部入れ、低圧下（５〜１０ｍ
ｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含
量を０．０３％とした。次いで、７０℃に冷却しトリレ
ンジイソシアネ−トを１６．７部加え、窒素気流下８０
〜８５℃でイソシアネ−ト含量が０％になるまで反応さ
せ（３時間）、淡黄色粘稠液状の反応生成物（実施例
Ｆ）を得た。(Production Example F) Ethylene oxide and propylene oxide were randomly copolymerized in a weight ratio of 82:18 in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. Molecular weight 6
515 parts of polyetherdiol of 400 and 16 parts of polyethermonool obtained by adding 8 mol of ethylene oxide to n-decyl alcohol were added under low pressure (5 to 10 m).
(mHg) at 80 to 90 ° C. for 3 hours to reduce the water content of the system to 0.03%. Then, the mixture was cooled to 70 ° C., and 16.7 parts of tolylene diisocyanate was added.
The reaction was carried out at -85 ° C until the isocyanate content became 0% (3 hours) to obtain a pale yellow viscous liquid reaction product (Example F).
【００４４】（製造例Ｇ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、エチレンオキサイドとブチレンオキサイドを重量
比８８：１２の割合でランダム共重合させた分子量６０
００のポリエ−テルジオ−ルを４８０部、ｎ−ドデシル
アルコ−ルにエチレンオキサイドを２０モル付加したポ
リエ−テルモノオ−ルを４３部入れ、低圧下（５〜１０
ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分
含量を０．０３％とした。次いで、７０℃に冷却しヘキ
サメチレンジイソシアネ−トを１６．８部加え、窒素気
流下８５〜９０℃でイソシアネ−ト含量が０％になるま
で反応させ（３時間）、淡黄色粘稠液状の反応生成物
（実施例Ｇ）を得た。(Production Example G) Ethylene oxide and butylene oxide were randomly copolymerized at a weight ratio of 88:12 in a four-neck flask having a capacity of 1000 ml equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. Molecular weight 60
480 parts of polyetherdiol of No. 00 and 43 parts of polyethermonool obtained by adding 20 mol of ethylene oxide to n-dodecyl alcohol were added under low pressure (5 to 10).
(Hg) at 80 to 90 ° C. for 3 hours to reduce the water content of the system to 0.03%. Then, the mixture was cooled to 70 ° C., 16.8 parts of hexamethylene diisocyanate was added, and the mixture was reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). A liquid reaction product (Example G) was obtained.
【００４５】（比較例Ｈ〜Ｎ）製造例Ｈ〜Ｎにより本発
明の比較例Ｈ〜Ｎの増粘剤組成物を得た。Comparative Examples H to N The thickener compositions of Comparative Examples H to N of the present invention were obtained from Production Examples H to N.
【００４６】（製造例Ｈ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル４０００（分子量４００
０）を４８０部、ｎ−プロピルアルコ−ルにエチレンオ
キサイドを５モル付加したポリエ−テルモノオ−ルを１
０部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０
℃で３時間脱水し、系の水分含量を０．０３％とした。
次いで、７０℃に冷却しテトラメチレンジイソシアネ−
トを１９．２部加え、窒素気流下８５〜９０℃でイソシ
アネ−ト含量が０％になるまで反応させ（３時間）、淡
黄色粘稠液状の反応生成物（比較例Ｈ）を得た。(Production Example H) A polyethylene glycol 4000 (molecular weight: 400) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
0), and 1 part of polyether monool obtained by adding 5 mol of ethylene oxide to n-propyl alcohol.
0 parts, 80-90 under low pressure (5-10mmHg)
The system was dehydrated at 3 ° C. for 3 hours to bring the water content of the system to 0.03%.
Then, the mixture was cooled to 70 ° C and tetramethylene diisocyanate was added.
19.2 parts of the reaction mixture was added and reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours) to obtain a pale yellow viscous liquid reaction product (Comparative Example H). .
【００４７】（製造例Ｉ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル２００００（分子量２０
０００）を５００部、ｎ−ヘキシルアルコ−ルにエチレ
ンオキサイドを２０モル付加したポリエ−テルモノオ−
ルを１６部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０
〜９０℃で３時間脱水し、系の水分含量を０．０３％と
した。次いで、７０℃に冷却しヘキサメチレンジイソシ
アネ−トを５．６部加え、窒素気流下８５〜９０℃でイ
ソシアネ−ト含量が０％になるまで反応させ（３時
間）、淡黄色粘稠液状の反応生成物（比較例Ｉ）を得
た。(Production Example I) Polyethylene glycol 20000 (molecular weight: 20) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
000) and 20 moles of ethylene oxide to n-hexyl alcohol.
16 parts, 80 under low pressure (5-10 mmHg)
The system was dehydrated at ~ 90 ° C for 3 hours to bring the water content of the system to 0.03%. Then, the mixture was cooled to 70 ° C., 5.6 parts of hexamethylene diisocyanate was added, and the mixture was reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). A liquid reaction product (Comparative Example I) was obtained.
【００４８】（製造例Ｊ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル２００００（分子量２０
０００）を６００部、ｎ−オクタデシルアルコ−ルにエ
チレンオキサイドを２０モル付加したポリエ−テルモノ
オ−ルを６９部入れ、低圧下（５〜１０ｍｍＨｇ）にて
８０〜９０℃で３時間脱水し、系の水分含量を０．０３
％とした。次いで、７０℃に冷却しキシリレンジイソシ
アネ−トを１１．３部加え、窒素気流下９０〜９５℃で
イソシアネ−ト含量が０％になるまで反応させ（３時
間）、淡黄色粘稠液状の反応生成物（比較例Ｊ）を得
た。(Production Example J) A polyethylene glycol 20000 (molecular weight: 20) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
000) and 69 parts of polyether monool obtained by adding 20 moles of ethylene oxide to n-octadecyl alcohol, and dehydrated at 80 to 90 ° C. under low pressure (5 to 10 mmHg) for 3 hours. Water content of 0.03
%. Then, the mixture was cooled to 70 ° C, 11.3 parts of xylylene diisocyanate was added, and reacted at 90 to 95 ° C under a nitrogen stream until the isocyanate content became 0% (3 hours). (Comparative Example J) was obtained.
【００４９】（製造例Ｋ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル６０００（分子量６００
０）を４８０部、炭素数３０の飽和脂肪族１級アルコ−
ルにエチレンオキサイドを１０モル付加したポリエ−テ
ルモノオ−ルを３５部入れ、低圧下（５〜１０ｍｍＨ
ｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を
０．０３％とした。次いで、７０℃に冷却しトリレンジ
イソシアネ−トを１７．４部加え、窒素気流下８０〜８
５℃でイソシアネ−ト含量が０％になるまで反応させ
（３時間）、淡黄色粘稠液状の反応生成物（比較例Ｋ）
を得た。(Production Example K) Polyethylene glycol 6000 (molecular weight: 600) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
0) is 480 parts, a saturated aliphatic primary alcohol having 30 carbon atoms.
35 parts of polyether monool with 10 moles of ethylene oxide added thereto were added under low pressure (5 to 10 mmH).
In g), dehydration was performed at 80 to 90 ° C. for 3 hours to reduce the water content of the system to 0.03%. Then, the mixture was cooled to 70 ° C., and 17.4 parts of tolylene diisocyanate was added.
The reaction was carried out at 5 ° C. until the isocyanate content became 0% (3 hours), and the reaction product was a pale yellow viscous liquid (Comparative Example K).
I got
【００５０】（製造例Ｌ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、エチレンオキサイドとプロピレンオキサイドを重
量比５０：５０の割合でランダム共重合させた分子量７
０００のポリエ−テルジオ−ルを４２０部、ｎ−オクチ
ルアルコ−ルにエチレンオキサイドを２０モル付加し、
次いでプロピレンオキサイドを２０モル付加したポリエ
−テルモノオ−ルを６５部入れ、低圧下（５〜１０ｍｍ
Ｈｇ）にて８０〜９０℃で３時間脱水し、系の水分含量
を０．０３％とした。次いで、７０℃に冷却し水添キシ
リレンジイソシアネ−トを１４．４部加え、窒素気流下
８５〜９０℃でイソシアネ−ト含量が０％になるまで反
応させ（３時間）、淡黄色粘稠液状の反応生成物（比較
例Ｌ）を得た。(Production Example L) Ethylene oxide and propylene oxide were randomly copolymerized at a weight ratio of 50:50 in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer. Molecular weight 7
2,000 polyetherdiols and 20 moles of ethylene oxide to n-octyl alcohol,
Next, 65 parts of polyether monool to which 20 moles of propylene oxide had been added was added, and under low pressure (5 to 10 mm).
Hg) at 80 to 90 ° C. for 3 hours to reduce the water content of the system to 0.03%. Then, the mixture was cooled to 70 ° C, 14.4 parts of hydrogenated xylylene diisocyanate was added, and the mixture was reacted at 85 to 90 ° C under a nitrogen stream until the isocyanate content became 0% (3 hours). A thick liquid reaction product (Comparative Example L) was obtained.
【００５１】（製造例Ｍ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル１００００（分子量１０
０００）を５００部、炭素数１０のセカンダリ−アルコ
−ルにエチレンオキサイドを１００モル付加したポリエ
−テルモノオ−ルを１１４部入れ、低圧下（５〜１０ｍ
ｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含
量を０．０３％とした。次いで、７０℃に冷却しトリレ
ンジイソシアネ−トを１０．９部加え、窒素気流下８０
〜８５℃でイソシアネ−ト含量が０％になるまで反応さ
せ（２時間）、淡黄色粘稠液状の反応生成物（比較例
Ｍ）を得た。(Production Example M) A polyethylene glycol 10,000 (molecular weight: 10) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
000) and 114 parts of polyether monool obtained by adding 100 moles of ethylene oxide to a secondary alcohol having 10 carbon atoms, and the mixture was placed under low pressure (5 to 10 m).
(mHg) at 80 to 90 ° C. for 3 hours to reduce the water content of the system to 0.03%. Then, the mixture was cooled to 70 ° C., and 10.9 parts of tolylene diisocyanate was added.
The reaction was carried out at -85 ° C until the isocyanate content became 0% (2 hours) to obtain a pale yellow viscous liquid reaction product (Comparative Example M).
【００５２】（製造例Ｎ）温度計、窒素導入管および高
粘度用攪拌機を付した容量１０００ｍｌの４つ口フラス
コに、ポリエチレングリコ−ル６０００（分子量６００
０）を４８０部、ノニルフェノ−ルにエチレンオキサイ
ドを５０モル付加したポリエ−テルモノオ−ルを７７部
入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で
３時間脱水し、系の水分含量を０．０３％とした。次い
で、７０℃に冷却しヘキサメチレンジイソシアネ−トを
１６部加え、窒素気流下８５〜９０℃でイソシアネ−ト
含量が０％になるまで反応させ（３時間）、淡黄色粘稠
液状の反応生成物（比較例Ｎ）を得た。(Production Example N) A polyethylene glycol 6000 (molecular weight: 600) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer for high viscosity.
480 parts of nonylphenol and 77 parts of polyether monool obtained by adding 50 moles of ethylene oxide to nonylphenol, and dehydrated at 80 to 90 ° C. under low pressure (5 to 10 mmHg) for 3 hours to obtain a water content of the system. Was set to 0.03%. Subsequently, the mixture was cooled to 70 ° C, 16 parts of hexamethylene diisocyanate was added, and the mixture was reacted at 85 to 90 ° C under a nitrogen stream until the isocyanate content became 0% (3 hours), to give a pale yellow viscous liquid. A reaction product (Comparative Example N) was obtained.
【００５３】本発明の増粘剤の実施例Ａ〜Ｇ、比較例Ｈ
〜Ｎの重量平均分子量を表１に示した。Examples A to G and Comparative Example H of the thickener of the present invention
Table 1 shows the weight average molecular weights of N.
【００５４】[0054]
【表１】 [Table 1]
【００５５】実施例Ａ〜Ｇ、比較例Ｈ〜Ｎの性能を以下
の方法により評価した。結果を表２に示した。The performance of Examples A to G and Comparative Examples H to N was evaluated by the following methods. The results are shown in Table 2.
【００５６】本発明の実施例Ａ〜Ｇ、比較例Ｈ〜Ｎの増
粘剤３０部、ブチルトリグリコ−ルエ−テル２０部と水
５０部を均一配合し各々の増粘剤溶液を得た。30 parts of the thickeners of Examples A to G and Comparative Examples H to N of the present invention, 20 parts of butyl triglycol ether and 50 parts of water were uniformly mixed to obtain respective thickener solutions. .
【００５７】評価例：高速塗工用粘着剤組成物のハイシ
ィア増粘性、ハイシィアニュ−トニアン性評価 0 粘着剤用アクリル系エマルション（濃度：６３％、質量
平均粒子径：０．２μｍ）１００部、消泡剤（サンノプ
コ製、デヒドラン１６２０）０．１部、増粘剤溶液２．
５部、水２．６部なる配合で固形分６０％の粘着剤組成
物を作成した。上記の配合で、ホモジナイザ−にて４０
００ｒｐｍで１０分間攪拌した後、１２時間静置させ
た。その後作成した高速塗工用粘着剤組成物をハ−キュ
レス粘度計（Ｆボブ、８８００ｒｐｍ）にて測定し、４
４００ｒｐｍでの粘度、５００ｒｐｍと４４００ｒｐｍ
での粘度比を計算した。 ハイシィア増粘性：高せん断速度下での粘度値で表わ
す。４４００ｒｐｍでの粘度値が高い程ハイシィア増粘
性は高い。 ハイシィアニュ−トニアン性：高せん断速度下でのせん
断速度の変化に対する粘度変化の割合で表わす。５００
ｒｐｍと４４００ｒｐｍでの粘度比が小さい程ハイシィ
アニュ−トニアン性に優れる。Evaluation example: Evaluation of high shear viscosity and high shear Newtonian property of high pressure coating adhesive composition 0 100 parts of acrylic emulsion for adhesive (concentration: 63%, mass average particle diameter: 0.2 μm), 100 parts 0.1 part of foaming agent (manufactured by San Nopco, Dehydran 1620), thickener solution
A pressure-sensitive adhesive composition having a solid content of 60% was prepared by mixing 5 parts and 2.6 parts of water. With the above composition, 40 with a homogenizer
After stirring at 00 rpm for 10 minutes, the mixture was allowed to stand for 12 hours. Thereafter, the pressure-sensitive adhesive composition for high-speed coating prepared was measured with a Hercules viscometer (F Bob, 8800 rpm).
Viscosity at 400 rpm, 500 rpm and 4400 rpm
The viscosity ratio at was calculated. High shear thickening: Expressed as a viscosity value under a high shear rate. The higher the viscosity value at 4400 rpm, the higher the high shear thickening. High shear Newtonian property: expressed as a ratio of a change in viscosity to a change in shear rate under a high shear rate. 500
The smaller the viscosity ratio between rpm and 4400 rpm, the better the high shear Newtonian property.
【００５８】[0058]
【表２】 [Table 2]
【００５９】[0059]
【発明の効果】本発明の効果は、実際の高速塗工条件下
（高せん断速度下）において、粘度低下が小さく、高塗
工量が実現でき、かつ塗工速度（せん断速度）が変化し
ても粘度が変化せず、一定の塗工量が塗工可能な増粘剤
並びに当該増粘剤を配合してなる高速塗工用粘着剤組成
物、高速塗工用粘着剤組成物を塗工、乾燥して得る粘着
剤シートを提供したことにある。本発明の増粘剤を含有
する粘着剤組成物を塗工装置にて塗工する場合、支持体
上に希望通りの塗工量を塗工できかつ一定の塗工量で塗
工できるという特徴を有する。The effect of the present invention is that under actual high-speed coating conditions (under high shear rate), the viscosity decrease is small, a high coating amount can be realized, and the coating rate (shear rate) changes. Even when the viscosity does not change, a thickener that can be applied at a constant coating amount, a high-speed coating pressure-sensitive adhesive composition containing the thickener, and a high-speed coating pressure-sensitive adhesive composition are coated. Another object of the present invention is to provide a pressure-sensitive adhesive sheet obtained by processing and drying. When the pressure-sensitive adhesive composition containing the thickener of the present invention is applied by a coating apparatus, a characteristic feature is that a desired amount of coating can be applied on a support and that a constant amount of coating can be applied. Having.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大井 裕文 京都市東山区一橋野本町11番地 サンノプ コ株式会社内 Ｆターム(参考） 4J004 AA10 AB01 4J040 DF001 DF002 JA03 JA09 JB09 LA03 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hirofumi Oi 11F, Nonocho, Higashiyama-ku, Higashiyama-ku, Kyoto Sannopco Co., Ltd. F-term (reference) 4J004 AA10 AB01 4J040 DF001 DF002 JA03 JA09 JB09 LA03
Claims (3)
成分とする粘着剤組成物を塗工、乾燥して得られる粘着
剤シートにおいて、質量平均粒子径が０．１〜１．５μ
ｍであるアクリル系エマルションに配合される、一般式
（１）で示され、かつ重量平均分子量が８０，０００〜
１４０，０００であることを特徴とする増粘剤。 ［式中、Ｘ、Ｚは炭素数４〜２４の直鎖炭化水素基であ
り、Ｙはジイソシアネ−ト化合物から導かれる２価の有
機残基であり、ＯＲ、ＯＲ’、ＯＲ”は炭素数２〜４の
オキシアルキレン基であり、ａ、ｂ、ｄは１〜５００の
整数であり、ｃは１以上の整数である。］1. A pressure-sensitive adhesive sheet obtained by applying and drying a pressure-sensitive adhesive composition containing an acrylic emulsion as a main component on a support, and having a mass average particle diameter of 0.1 to 1.5 μm.
m, represented by the general formula (1) and having a weight average molecular weight of 80,000 to
A thickener characterized by being 140,000. [In the formula, X and Z are linear hydrocarbon groups having 4 to 24 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR 'and OR "are carbon atoms. 2 to 4 oxyalkylene groups, a, b, and d are integers of 1 to 500, and c is an integer of 1 or more.]
ョン１００質量部に対し、請求項１記載の増粘剤を０．
０１〜１０質量部配合させることを特徴とする高速塗工
用粘着剤組成物。2. The pressure-sensitive adhesive composition contains the thickener according to claim 1 in an amount of 100 parts by mass of the acrylic emulsion.
An adhesive composition for high-speed coating characterized by being mixed in an amount of from 0.01 to 10 parts by mass.
を塗工、乾燥して得られる粘着剤シート。3. A pressure-sensitive adhesive sheet obtained by applying and drying the pressure-sensitive adhesive composition for high-speed coating according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000392078A JP2002194311A (en) | 2000-12-25 | 2000-12-25 | Thickener and adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000392078A JP2002194311A (en) | 2000-12-25 | 2000-12-25 | Thickener and adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002194311A true JP2002194311A (en) | 2002-07-10 |
Family
ID=18858124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000392078A Pending JP2002194311A (en) | 2000-12-25 | 2000-12-25 | Thickener and adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002194311A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002265779A (en) * | 2001-03-14 | 2002-09-18 | San Nopco Ltd | Thickener composition and acrylic emulsion type self- adhesive composition |
| JP2005187813A (en) * | 2003-12-10 | 2005-07-14 | Rohm & Haas Co | Nonionic associative thickener containing condensation polymer main chain |
| JP2011225812A (en) * | 2010-03-29 | 2011-11-10 | Dic Corp | Water dispersion type acrylic adhesive composition, and method for manufacturing adhesive layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002265779A (en) * | 2001-03-14 | 2002-09-18 | San Nopco Ltd | Thickener composition and acrylic emulsion type self- adhesive composition |
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| JP2011225812A (en) * | 2010-03-29 | 2011-11-10 | Dic Corp | Water dispersion type acrylic adhesive composition, and method for manufacturing adhesive layer |
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