JP4524564B2 - Wallpaper paste - Google Patents

Description

  The present invention relates to a paste for wallpaper.

Conventionally, a water-soluble starch solution called “cooking paste” has been used for wallpaper paste. Since this paste requires about 20% by mass in terms of solid content at the time of use, it becomes a concentrated starch paste solution and is difficult to use as it is. For this reason, the starch paste solution is usually used by diluting it several times to 10 times with water.
In general, when the wallpaper becomes very dirty or damaged due to a part of the wallpaper being torn, the old wallpaper is replaced with a new one.

However, since the wallpaper once pasted with the paste is firmly adhered to the base material, it cannot be easily peeled off in many cases. In this case, there is a problem that the wallpaper that has been partially peeled off must be left as it is, and a new wallpaper must be pasted thereon, which makes it impossible to replace it with a good appearance.
In addition, although the above-mentioned paste for wallpaper is also marketed as a solution, there is a concern about the influence on the human body and the environment because formalin and preservatives are added to this solution to enable long-term storage. .

In view of this, a paste comprising a water-soluble cellulose ether powder or granular material of an immediately soluble type in consideration of environmental problems has been developed (Patent Document 1: Japanese Patent Publication No. 48-6622), which is dissolved at the time of use. The method used for the paste is widespread.
As an advantage of using a paste consisting of water-soluble cellulose ether of immediate dissolution type, it can be stored as a solid until just before use, so it is safer without the need to add preservatives, etc. For example, the amount used may be as low as several mass% due to the viscosity.

  However, in the case of wallpaper paste containing only water-soluble cellulose ether, the stickiness of the solution is large, so the coating thickness of the paste becomes unnecessarily thick, or uneven coating can occur when applied at once with a brush or roller. In addition to the drawbacks of the conventional starch paste, the problem that the wallpaper is difficult to peel off at the time of replacement has not been improved.

Japanese Patent Publication No. 48-6622

  The present invention has been made in view of the above circumstances, and provides a wallpaper paste that not only reduces coating unevenness during application, but can easily peel off the wallpaper when the applied wallpaper is replaced. For the purpose.

〔式中、Ａは少なくとも両末端に水酸基を有し、数平均分子量が４００〜１００，０００のＨＯ−Ａ−ＯＨで示される水溶性ポリアルキレンポリオールに由来する二価のポリオキシアルキレン残基を示す。ＢはＯＣＮ−Ｂ−ＮＣＯで示される全炭素数が３〜１８のポリイソシアナートに由来する二価の有機残基を示す。Ｄは下記一般式（３）〜（５）から選ばれるジヒドロキシ化合物に由来する二価の有機残基を示す。

（式中、Ｒ¹及びＲ⁴は炭素数１〜２０の非置換又はハロゲン置換一価炭化水素基、Ｒ²、Ｒ³、Ｒ⁵及びＲ⁶は互いに同一でも異なっていてもよい炭素数４〜２１の非置換又はハロゲン置換一価炭化水素基、Ｙ及びＹ’は互いに同一でも異なっていてもよい水素原子、メチル基又はＣＨＣｌ₂基、Ｚ及びＺ’は酸素原子、硫黄原子又はＣＨ₂基であり、ｎはＺが酸素原子の場合は０〜１５の整数、Ｚが硫黄原子又はＣＨ₂基の場合は０、ｎ’はＺ’が酸素原子の場合は０〜１５の整数、Ｚ’が硫黄原子又はＣＨ₂基の場合は０であり、ｎ及びｎ’は互いに同一でも異なっていてもよい。Ｘ、Ｘ’及びＸ”は互いに同一でも異なっていてもよい炭素数２〜１０のアルキレン基、Ｒ⁷は炭素数２〜１０のアルキレン基であり、ｋは０〜１５の整数である。Ｒ⁸及びＲ⁹は互いに同一でも異なっていてもよく、それらの炭素数の合計が２〜２０の一価炭化水素基、Ｒ¹⁰及びＲ¹¹は互いに同一でも異なっていてもよい炭素数４〜２１の一価炭化水素基、Ｒ¹²は炭素数２〜７のアルキレン基である。）〕
２．さらに、水溶性セルロースエーテルを含むことを特徴とする１の壁紙用糊剤、
３．前記一般式（３）又は（４）で示されるジヒドロキシ化合物が、一般式（６）又は（７）で示されるジヒドロキシ化合物であることを特徴とする１又は２の壁紙用糊剤、

〔式中、Ｒ¹³は炭素数４〜１８の直鎖状又は分岐状アルキル基、Ｒ¹⁴及びＲ¹⁵は互いに同一又は異なっていてもよい炭素数４〜１８の直鎖状又は分岐状アルキル基、Ｒ¹⁶は炭素数１〜１８のアルキル基、Ｒ¹⁷及びＲ¹⁸は互いに同一の炭素数４〜２１の非置換又はハロゲン置換一価炭化水素基である。Ｒ¹⁹は１，２−エチレン基、１，３−プロピレン基又は１，４−ブチレン基である。〕
４．前記水溶性セルロースエーテルが、アルキルセルロース又はヒドロキシアルキルアルキルセルロースであることを特徴とする２又は３の壁紙用糊剤
を提供する。 The present inventor has conducted intensive investigations to achieve the above object, a predetermined polyoxyalkylene polyol derivative obtained by using the comb-shaped diol and wallpaper pastes containing a water-soluble cellulose ethers as necessary, coated The present invention has been completed by finding that there is little unevenness in coating, and that it is easy to peel off when wallpaper applied with this paste is replaced.
Therefore, the present invention
1. It has a repeating unit U-1 represented by the general formula (1) and a repeating unit U-2 represented by the general formula (2), and U-1 / U-2 = 0.5 / 0.5 to 0.99. wallpaper glue agent characterized in that it comprises a polyoxyalkylene polyol derivative is /0.01 (mol ratio),

[In the formula, A represents a divalent polyoxyalkylene residue derived from a water-soluble polyalkylene polyol represented by HO-A-OH having hydroxyl groups at both ends and having a number average molecular weight of 400 to 100,000. Show. B represents a divalent organic residue derived from a polyisocyanate having a total carbon number of 3 to 18 represented by OCN-B-NCO. D represents a divalent organic residue derived from a dihydroxy compound selected from the following general formulas (3) to (5).

(In the formula, R ¹ and R ⁴ are unsubstituted or halogen-substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R ² , R ³ , R ⁵ and R ⁶ may be the same or different from each other. 21 to 21 unsubstituted or halogen-substituted monovalent hydrocarbon group, Y and Y ′ may be the same or different from each other, hydrogen atom, methyl group or CHCl ₂ group, Z and Z ′ are oxygen atom, sulfur atom or CH ₂ N is an integer of 0 to 15 when Z is an oxygen atom, 0 when Z is a sulfur atom or a CH ₂ group, n ′ is an integer of 0 to 15 when Z ′ is an oxygen atom, Z When 'is a sulfur atom or CH ₂ group, it is 0, and n and n ′ may be the same or different. X, X ′ and X ″ may be the same or different from each other. alkylene group, R ⁷ is an alkylene group having 2 to 10 carbon atoms, k is an integer of 0 to 15 .R ⁸及R ⁹ may be the same or different from each other, their sum 2-20 monovalent hydrocarbon radical of carbon number one of R ¹⁰ and R ¹¹ are 4 to 21 carbon atoms, which may be the same or different Valent hydrocarbon group, R ¹² is an alkylene group having 2 to 7 carbon atoms.)]
2. Furthermore, 1 paste for wallpaper characterized by including water-soluble cellulose ether,
3. The wallpapering paste according to 1 or 2, wherein the dihydroxy compound represented by the general formula (3) or (4) is a dihydroxy compound represented by the general formula (6) or (7);

[Wherein, R ¹³ is a linear or branched alkyl group having 4 to 18 carbon atoms, and R ¹⁴ and R ¹⁵ are linear or branched alkyl groups having 4 to 18 carbon atoms which may be the same or different from each other. , R ¹⁶ is an alkyl group having 1 to 18 carbon atoms, and R ¹⁷ and R ¹⁸ are the same unsubstituted or halogen-substituted monovalent hydrocarbon group having 4 to 21 carbon atoms. R ¹⁹ is a 1,2-ethylene group, a 1,3-propylene group or a 1,4-butylene group. ]
4). 2 or 3 wallpapering pastes characterized in that the water-soluble cellulose ether is alkyl cellulose or hydroxyalkyl alkyl cellulose.

According to the present invention, a predetermined polyoxyalkylene polyol derivative, because it is wallpaper pastes containing a water-soluble cellulose ethers as necessary, coating unevenness in the adhesive application is hardly made using comb diol In addition, the wallpaper can be easily peeled off when the wallpaper pasted with the paste is replaced.

Hereinafter, the present invention will be described in more detail.
Polyoxyalkylene polyol derivative in wallpaper pastes of the present invention has a repeating unit represented by the general formula (1) and (2), units U-1 of the formula (1), units of formula (2) Is U-2, U-1 / U-2 satisfies the range of 0.5 / 0.5 to 0.99 / 0.01 (molar ratio).

  In the formula (1), A is a HO-A- having hydroxyl groups at both ends and having a number average molecular weight of 400 to 100,000, preferably 500 to 80,000, more preferably 1,000 to 50,000. 2 shows a divalent polyoxyalkylene residue derived from a water-soluble polyalkylene polyol represented by OH. This water-soluble polyalkylene polyol is an alkylene oxide polymer having hydroxyl groups at both ends. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, pentylene oxide, and hexylene oxide. Etc. These alkylene oxides can be used singly or in combination of two or more. In addition, the said number average molecular weight is a measured value by GPC-MALLS method.

In the formulas (1) and (2), B is a divalent derivative derived from a polyisocyanate having a total carbon number of 3 to 18, preferably 3 to 16, more preferably 4 to 15 represented by OCN-B-NCO. Organic residues are shown. As this polyisocyanate, a chain or cyclic aliphatic polyisocyanate and an aromatic polyisocyanate can be appropriately selected and used.
Examples of chain aliphatic diisocyanates include methylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, 1-methylethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane. -1,4-diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, 2,2'-dimethylpentane-1,5-diisocyanate, lysine diisocyanate methyl ester (LDI), Octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate, nonamethyl diisocyanate, 2,4,4- Trimethylhexane-1,6-diisocyanate Decamethylene diisocyanate, undecamethylene diisocyanate, dodecamethylene diisocyanate, tridecamethylene diisocyanate, tetradecamethylene diisocyanate, pentadecamethylene diisocyanate, hexadecamethylene diisocyanate, trimethylhexamethylene diisocyanate Narto etc. are mentioned.

  Cycloaliphatic polyisocyanates include cyclohexane-1,2-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-methylcyclohexane-2,4-di Isocyanate, 1-methylcyclohexane-2,6-diisocyanate, 1-ethylcyclohexane-2,4-diisocyanate, 4,5-dimethylcyclohexane-1,3-diisocyanate, 1,2-dimethylcyclohexane -Ω, ω'-diisocyanate, 1,4-dimethylcyclohexane-ω, ω'-diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethylmethane 4,4'-diisocyanate, dicyclohexyldi Tylmethane-4,4'-diisocyanate, 2,2'-dimethyldicyclohexylmethane-4,4'-diisocyanate, 3,3'-dimethyldicyclohexylmethane-4,4'-diisocyanate, 4,4 '-Methylene-bis (isocyanatocyclohexane), isopropylidenebis (4-cyclohexylisocyanate) (IPCI), 1,3-bis (isocyanatomethyl) cyclohexane, hydrogenated tolylene diisocyanate (HTDI), hydrogenated 4 4,4'-diphenylmethane diisocyanate (HMDI), hydrogenated xylylene diisocyanate (HXDI), norbornane diisocyanate methyl (NBDI), and the like.

  Aromatic polyisocyanates include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate (2,4-TDI), 1-methyl-2,6. -Phenylene diisocyanate (2,6-TDI), 1-methyl-2,5-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate Narate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl -2,5-phenylene diisocyanate, m-xylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene di Sodiumate, 1-methyl-3,5-diethylbenzene-2,4-diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4 -Diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methylnaphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene- 2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, diphenylmethane-4 4'-diisocyanate (MDI), diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4'-diisocyanate, and the like xylylene diisocyanate (XDI).

  In the formula (2), D represents a divalent organic residue derived from a dihydroxy compound selected from the following general formulas (3) to (5).

In the above formula, R ¹ and R ⁴ are unsubstituted or halogen-substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, preferably 2 to 18 carbon atoms, and R ² , R ³ , R ⁵ and R ⁶ are the same or different from each other. An unsubstituted or halogen-substituted monovalent hydrocarbon group having 4 to 21 carbon atoms, preferably 5 to 18 carbon atoms, Y and Y ′ may be the same or different from each other, a hydrogen atom, a methyl group or a CHCl ₂ group, Z And Z ′ is an oxygen atom, a sulfur atom or a CH ₂ group, n is an integer of 0 to 15, preferably 2 to 12 when Z is an oxygen atom, and 0 when Z is a sulfur atom or a CH ₂ group, n ′ is an integer of 0 to 15, preferably 4 to 8 when Z ′ is an oxygen atom, and 0 when Z ′ is a sulfur atom or a CH ₂ group, and n and n ′ are the same or different from each other. Also good. X, X ′ and X ″ may be the same or different from each other, and may be an alkylene group having 2 to 10 carbon atoms, preferably 4 to 8 carbon atoms, and R ⁷ is an alkylene group having 2 to 10 carbon atoms, preferably 4 to 8 carbon atoms. , K is an integer of 0 to 15, preferably 2 to 12. R ⁸ and R ⁹ may be the same as or different from each other, and the total number of carbon atoms thereof is 2 to 20, preferably 2 to 16. A valent hydrocarbon group, R ¹⁰ and R ^{11, which} may be the same or different, each having 4 to 21 carbon atoms, preferably 4 to 18 monovalent hydrocarbon groups, and R ¹² has 2 to 7 carbon atoms, preferably 3 to 3 carbon atoms. 9 is an alkylene group.

In the above formula, examples of the unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl groups, butyl bromide, and propyl bromide groups. Examples include halogenated alkyl groups.
Examples of the unsubstituted or halogen-substituted monovalent hydrocarbon group having 4 to 21 carbon atoms include, for example, the groups having 4 to 20 carbon atoms mentioned above for the unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Hexyl, cyclohexyl groups and the like.

Examples of the alkylene group having 2 to 10 carbon atoms include ethylene, propylene, butylene, amylene, and hexylene groups.
Examples of the combination of two monovalent hydrocarbon groups having 2 to 20 carbon atoms in total include a methyl group and a methyl group, a methyl group and an ethyl group, a methyl group and a propyl group, and a methyl group and a butyl group.
Examples of the alkylene group having 2 to 7 carbon atoms include the same groups as the groups having 2 to 7 carbon atoms among the above-described alkylene groups having 2 to 10 carbon atoms.

  In this case, in particular, the dihydroxy compound represented by the following general formula (6) or (7) is used as the dihydroxy compound represented by the formula (3) or (4) from the viewpoint of reactivity at the time of polyisocyanate formation. It is preferable.

In the above formula, R ¹³ has 4 to 18 carbon atoms, preferably 4 to 12 linear or branched alkyl groups, and R ¹⁴ and R ¹⁵ may have the same or different carbon numbers 4 to 18, preferably Is a linear or branched alkyl group having 4 to 12 carbon atoms, R ¹⁶ is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and R ¹⁷ and R ¹⁸ are the same carbon atoms having 4 to 21 carbon atoms, preferably Is a 4-16 unsubstituted or halogen substituted monovalent hydrocarbon group. R ¹⁹ is a 1,2-ethylene group, a 1,3-propylene group or a 1,4-butylene group.

Here, examples of the linear or branched alkyl group having 4 to 18 carbon atoms include 2-methyl-butyl and 2,3-dimethyl-butyl groups.
Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, and nonyl groups.
Examples of the monovalent hydrocarbon group having 4 to 21 carbon atoms include the same groups as those described above for the unsubstituted or halogen-substituted monovalent hydrocarbon group having 4 to 21 carbon atoms.

In the present invention, the unit U-1 and the molar ratio of the unit U-2 of the formula (2) in equation (1) constituting the polyoxyalkylene polyol derivative, U-1 / U-2 is 0.5 / 0. It is 5-0.99 / 0.01, Preferably it is 0.6 / 0.4-0.8 / 0.2.
If this ratio is less than the lower limit of the above range, the viscosity may be low and the gel-like characteristics may be lost, and if it exceeds the upper limit, it may be difficult to dissolve in water.

The weight average molecular weight of the polyoxyalkylene polyol derivative is not particularly limited, from the viewpoint of imparting adequate viscoelastic glue agents containing them, several tens of thousand to several million, preferably 10,000～300, 000 is desirable. This weight average molecular weight can be measured by gel permeation chromatography (GPC), and polyethylene oxide, pullulan and the like can be obtained as standard molecular weight substances.
Viscosity at 20 ° C. of a 2 wt% aqueous solution of the polyoxyalkylene polyol derivative, from the viewpoint of imparting good viscosity as wallpaper pastes, when measured at 10rpm by BH type viscometer, 5～10,000MPa · S, particularly those in the range of 15 to 10,000 mPa · s are preferred.
Specific examples of the polyoxyalkylene polyol derivative include compounds used in mortar thickeners described in JP-A No. 2001-348256.

On the other hand, the water-soluble cellulose ether is not particularly limited, but alkyl cellulose and hydroxyalkylalkyl cellulose are preferred in view of exhibiting good paste and fluidity as wallpaper paste. Specifically, methyl cellulose, human loxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose and the like can be used, and these can be used alone or in combination of two or more.
The viscosity at 20 ° C. of a 2 wt% aqueous solution of the water-soluble cellulose ether, from the viewpoint of exerting the proper viscosity and adhesiveness as wallpaper pastes, when measured at 10rpm by BH type viscometer, number The thing of about 100 mPa * s is preferable and it is more preferable that it is 50-10,000 mPa * s.

Water-soluble alkyl cellulose and hydroxyalkyl alkyl cellulose have a hydrophilic hydroxyalkyl group or hydroxyl group in the molecule and a hydrophobic alkyl group, and therefore have a surfactant activity and a chain structure of cellulose ether as a skeleton. As molecules spread over a wide area in water, they become entangled and create viscosity. Due to this viscosity, there is a possibility that uneven brush coating is likely to occur when a high concentration of water-soluble alkyl cellulose or the like is used to obtain a high concentration paste.
On the other hand, the polyoxyalkylene polyol derivative, although having a surface activity, the adhesive strength is weak, and because the aqueous solution is also not very high gel viscosity, which although itself is usable as sizing agent, the flow It is not a good idea to use this component in too large amounts when considering the properties and adhesion.

These light, in wallpaper pastes of the present invention, the mixing ratio of the water-soluble cellulose ether and a polyoxyalkylene polyol derivative, typically 99 / 1-1 / 99, preferably 95 / 5-20 / 80 (mass Ratio), more preferably in the range of 70/30 to 30/70 (mass ratio). When the blending amount of the water-soluble cellulose ether is increased from the above range, the surface active ability shows strong adsorption on the wallpaper and the adhesive surface, so that it may be difficult to peel off the wallpaper at the time of replacement. There is also a possibility that uneven brush coating may occur. On the other hand, when the polyoxyalkylene polyol derivative is increased than the above range, there is a possibility that it becomes difficult to obtain a fluidity and adhesive strength required degree as wallpaper pastes as described above.

The total amount of the components of the water-soluble cellulose ethers and polyoxyalkylene polyol derivative is not particularly limited, considering that to improve the bonding force of wallpaper pastes, relative to the whole picture for sizing agent It is preferable that it is 1-30 mass%, especially 5-20 mass%.
The wallpaper paste of the present invention may optionally contain optional components generally added to the paste, such as fillers and color formers. In this case, the total amount of these components is the wallpaper It is about 5-50 mass% with respect to the whole paste.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
[1] Synthesis of dihydroxy compound [Synthesis Example 1] Synthesis of dihydroxy compound 1 To a 500 ml round bottom flask equipped with a magnetic stirrer, thermometer and dropping funnel, 64.6 g of 2-ethylhexylamine (manufactured by Kanto Chemical Co., Inc.). And the inside of the flask was replaced with nitrogen. After heating the flask to 60 ° C. in an oil bath, 220.0 g of 2-ethylhexyl glycidyl ether (Asahi Denka Co., Ltd., Adeka Glycilol ED518, Epoxy value 220) was added dropwise over 40 minutes while stirring. did. After completion of dropping, the temperature of the oil bath was raised to 80 ° C., and the flask was heated at this temperature for 10 hours. Thereafter, the temperature of the oil bath was raised to 120 ° C., and a small amount of unreacted material was distilled off under reduced pressure at a vacuum degree of 400 Pa using a vacuum pump. Dihydroxy compound 1 (average molecular weight 532 based on OH value) in which 2-ethylhexyl glycidyl ether was added at a ratio of 2 mol to 1 mol of 2-ethylhexylamine was obtained in a yield of 90%.

Synthesis Example 2 Synthesis of Dihydroxy Compound 2 3- (dodecyloxy) -1-propylamine (manufactured by Koei Chemical Co., Ltd.) was added to a 500 ml round bottom flask equipped with a magnetic stirrer, thermometer and dropping funnel. 7 g was charged and the inside of the flask was replaced with nitrogen. While heating the flask to 60 ° C. in an oil bath and stirring, 188.0 g of 2-ethylhexyl glycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., Denacol EX-121, epoxy value 188) is added dropwise over 40 minutes while stirring. did. After completion of dropping, the temperature of the oil bath was raised to 80 ° C., and the flask was heated for 10 hours. Thereafter, the temperature of the oil bath was raised to 120 ° C., and a small amount of unreacted substances were distilled off under reduced pressure at a vacuum degree of 400 Pa using a vacuum pump. Dihydroxy compound 2 (average molecular weight 620 from OH value) in which 2-ethylhexyl glycidyl ether was added at a ratio of 2 mol to 1 mol of 3- (dodecyloxy) -1-propylamine was obtained in a yield of 85%.

[2] Synthesis of polyoxyalkylene polyol derivatives [Synthesis Example 3] Polyoxyalkylene polyol commercially available polyethylene glycol into a SUS-made separable flask of synthetic 1000ml derivatives 1 (PEG # 6000, manufactured by Sanyo Chemical Industries, Ltd., number average 200 g of molecular weight 8,630) was charged and melted at 150 ° C. under a nitrogen seal. This was stirred for 3 hours under reduced pressure (400 Pa) with stirring. At this time, the residual moisture was 200 ppm.
The temperature was lowered to 70 ° C., and the flask was filled with 101 kPa of nitrogen. 300 ppm of BHT (di-tert-butylhydroxytoluene) was added as an antioxidant. While stirring the flask, 1.70 g of the dihydroxy compound 1 obtained in Synthesis Example 1 and 4.35 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged (NCO / OH = 0.98 mol). / Mol). When 0.05 g of DBTDL was added as a catalyst, the viscosity increased rapidly in about 10 minutes. Stopped stirring, allowed to react for 2 hours at 70 ° C., kept at a constant temperature for 30 minutes the temperature was raised to 120 ° C., to obtain a polyoxyalkylene polyol derivative 1 having a melting point of about 60 ° C..

[Synthesis Example 4] polyoxyalkylene polyol derivative commercially available PEG # 6000 made of SUS separable flask 1000ml of 2 (Sanyo Chemical Industries, Ltd., number average molecular weight 8,630) and 200g were charged, under a blanket of nitrogen Melted at 150 ° C. This was stirred for 3 hours under reduced pressure (400 Pa) with stirring. Residual moisture was 200 ppm.
The temperature was lowered to 70 ° C., and the flask was filled with 103 kPa of nitrogen. 300 ppm of BHT (di-tert-butylhydroxytoluene) was added as an antioxidant. While stirring the flask, 1.90 g of the dihydroxy compound 1 obtained in Synthesis Example 1 and 4.41 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged (NCO / OH = 0.98 mol). / Mol). When 0.05 g of DBTDL was added as a catalyst, the viscosity increased rapidly in about 10 minutes. Stopped stirring, allowed to react for 2 hours at 70 ° C., kept at a constant temperature for 30 minutes the temperature was raised to 120 ° C., to obtain a polyoxyalkylene polyol derivative 2 having a melting point of about 60 ° C..

[Synthesis Example 5] polyoxyalkylene polyol derivative 3 commercial PEG # 6000 made of SUS separable flask 1000ml of (Sanyo Chemical Industries, Ltd., number average molecular weight 8,630) and 200g were charged, under a blanket of nitrogen Melted at 150 ° C. This was stirred for 3 hours under reduced pressure (400 Pa) with stirring. Residual moisture was 200 ppm.
The temperature was lowered to 70 ° C., and the flask was filled with 103 kPa of nitrogen. 300 ppm of BHT (di-tert-butylhydroxytoluene) was added as an antioxidant. While stirring the flask, 1.208 g of dihydroxy compound 2 obtained in Synthesis Example 2 and 3.995 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged (NCO / OH = 0.955 mol). / Mol). When 0.05 g of DBTDL was added as a catalyst, the viscosity increased rapidly in about 10 minutes. It stopped stirring, allowed to react for 2 hours at 70 ° C., held for 30 minutes constant temperature by raising the temperature to 120 ° C., to obtain a polyoxyalkylene polyol derivative 3, mp about 60 ° C..

[Synthesis Example 6] Synthesis dihydroxy compounds of the polyoxyalkylene polyol derivative 4 2 / polyethylene glycol = 0.80 (wt%), so that the NCO / OH = 0.995 (molar ratio), a dihydroxy compound 2 and hexamethylene except for substituting the amount of diisocyanate, to obtain a polyoxyalkylene polyol derivative 4 in the same manner as in synthesis example 5.

[Synthesis Example 7] Synthesis dihydroxy compounds of the polyoxyalkylene polyol derivative 5 2 / polyethylene glycol = 0.50 (wt%), so that the NCO / OH = 0.995 (molar ratio), a dihydroxy compound 2 and hexamethylene except for substituting the amount of diisocyanate, to obtain a polyoxyalkylene polyol derivative 5 in the same manner as in synthesis example 5.

For polyoxyalkylene polyols derivative obtained in Synthesis Example 3-7, the dihydroxy compound / polyethylene glycol (mass%), NCO / OH (mole ratio), U-1 / U- 2 ( mol ratio), weight average molecular weight and The viscosity of 2% by mass aqueous solution is summarized in Table 1 below.

In Table 1, the weight average molecular weight and the 2 mass% aqueous solution viscosity were determined by the following methods.
(1) Weight average molecular weight It is the pullulan conversion value of the value measured on condition of the following using gel permeation chromatography (GPC-MALLS, Showa Denko Co., Ltd. product).
Detector: DAWN-DSP, Shodex RI-71, all manufactured by Showa Denko KK Column used: Shodex SB-806MHQ, Showa Denko KK Solvent used: 0.1M NaNO ₃
Measurement temperature: 40 ° C
(2) 2 mass% aqueous solution viscosity 2 mass% aqueous solution was prepared about each polyoxyalkylene polyol derivative, and the viscosity of the said aqueous solution in 20 degreeC was measured at 10 rpm using BH type | mold viscosity meter.

[Examples 1 to 10, Comparative Examples 1 and 2]
Table 1 using the respective polyoxyalkylene polyol derivative and a water-soluble cellulose ether shown in Table 2 (all manufactured by Shin-Etsu Chemical Co., Ltd.) shown in, it was blended in proportions shown in Table 3, wallpaper pastes Was prepared.
The obtained paste for wallpaper is soaked in the brush, coated once on fine paper of thickness 0.03mm, length 27cm, width 45cm, then pasted on gypsum board, dried at room temperature and left for 1 month did. After leaving, the wallpaper was peeled off, and the case where the fine paper remained on the gypsum board without being peeled off was evaluated as “X”, and the case where it did not remain was evaluated as “◯”. Further, when the application was high, the viscosity of the aqueous solution was high, and the case where it could not be applied onto the paper sufficiently with a brush was evaluated as “x”, and the case where it was applied uniformly was evaluated as “◯”. These results are shown in Table 4.

  In Table 2, the weight average molecular weight was measured under the same conditions as described above. Moreover, the 2 mass% aqueous solution viscosity was measured on the same conditions as the above with a BH type viscometer.

As shown in Table 4, at least polyoxyalkylene polyol derivative obtained by blending a wallpaper pastes of the above embodiments, almost no unevenness in brushing, and peeling from the substrate wallpaper once attached It can be seen that the properties are also good. On the other hand, in the wallpaper pastes of Comparative Examples not blended polyoxyalkylene polyol derivative, it is understood that also insufficient with brushing properties and peelability.

Claims (4)

It has a repeating unit U-1 represented by the general formula (1) and a repeating unit U-2 represented by the general formula (2), and U-1 / U-2 = 0.5 / 0.5 to 0.99. /0.01 wallpaper sizing agent which comprises a polyoxyalkylene polyol derivative is a (mol ratio).

[In the formula, A is a divalent polyoxyalkylene residue derived from a water-soluble polyalkylene polyol represented by HO-A-OH having hydroxyl groups at both ends and having a number average molecular weight of 400 to 100,000. Indicates. B represents a divalent organic residue derived from a polyisocyanate having a total carbon number of 3 to 18 represented by OCN-B-NCO. D represents a divalent organic residue derived from a dihydroxy compound selected from the following general formulas (3) to (5).

(In the formula, R ¹ and R ⁴ are unsubstituted or halogen-substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R ² , R ³ , R ⁵ and R ⁶ may be the same or different from each other. 21 to 21 unsubstituted or halogen-substituted monovalent hydrocarbon group, Y and Y ′ may be the same or different from each other, hydrogen atom, methyl group or CHCl ₂ group, Z and Z ′ are oxygen atom, sulfur atom or CH ₂ N is an integer of 0 to 15 when Z is an oxygen atom, 0 when Z is a sulfur atom or a CH ₂ group, and n ′ is an integer of 0 to 15 when Z ′ is an oxygen atom. , Z ′ is 0 when it is a sulfur atom or a CH ₂ group, n and n ′ may be the same or different. X, X ′ and X ″ may be the same or different from each other 10 alkylene group, R ⁷ is an alkylene group having 2 to 10 carbon atoms, k is an integer of 0 to 15. R ⁸ and R ⁹ may be the same or different from each other, and the total carbon number thereof is a monovalent hydrocarbon group having 2 to 20 carbon atoms, and R ¹⁰ and R ¹¹ may be the same or different from each other. 21 monovalent hydrocarbon groups, R ¹² is an alkylene group having 2 to 7 carbon atoms.)]   The wallpaper paste according to claim 1, further comprising a water-soluble cellulose ether. The wallpaper paste according to claim 1 or 2, wherein the dihydroxy compound represented by the general formula (3) or (4) is a dihydroxy compound represented by the general formula (6) or (7).

[Wherein R ¹³ is a linear or branched alkyl group having 4 to 18 carbon atoms, and R ¹⁴ and R ¹⁵ are linear or branched alkyl groups having 4 to 18 carbon atoms which may be the same or different from each other. R ¹⁶ is an alkyl group having 1 to 18 carbon atoms, and R ¹⁷ and R ¹⁸ are the same unsubstituted or halogen-substituted monovalent hydrocarbon group having 4 to 21 carbon atoms. R ¹⁹ is a 1,2-ethylene group, a 1,3-propylene group or a 1,4-butylene group. ]   4. The wallpaper paste according to claim 2, wherein the water-soluble cellulose ether is alkyl cellulose or hydroxyalkyl alkyl cellulose.