JP2002265779A - Thickener composition and acrylic emulsion type self- adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thickener composition to be added to a water-based emulsion type self-adhesive, having a high thickening power and low temperature dependence and permitting a wide range of satisfactory self-adhesive performances such as water resistance, cissing, viscosity stability during storage, leveling properties, and the like, and further an acrylic emulsion type self-adhesive comprising the thickener composition. SOLUTION: The thickener composition comprises as essential ingredients at least 20 mass% but less than 80 mass% of a connpound A represented by formula (1) having a weight-average molecular weight of at least 10,000 and less than 40,000 and at least 20 mass% but less than 80 mass% of a compound B represented by formula (2) having a weight-average molecular weight of at least 40,000 and less than 140,000. In the formulae, X1 and X2 are each a 15-24C hydrocarbyl group; X3 and X4 are each a 4-24C hydrocarbyl group, Y is a divalent organic residue derived from a diisocyanate compound; OR, OR' and OR" are each a 2-4C oxyalkylene group; (a), (b) and (d) are each an integer of 1-500; and (c) is an integer of at least 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thickener composition. More specifically, the present invention relates to a thickener composition useful for an acrylic emulsion-type pressure-sensitive adhesive, and further relates to an acrylic emulsion-type pressure-sensitive adhesive obtained by blending the thickener composition.

[0002]

2. Description of the Related Art In recent years, conversion from a water-based emulsion type pressure-sensitive adhesive to a solvent-type pressure-sensitive adhesive has been studied from the viewpoint of protection of the global environment. Generally, it is a (meth) acrylic pressure-sensitive adhesive, and a tackifier, a thickener, a preservative, an antifoaming agent, etc. are added to a (meth) acrylic emulsion prepared by emulsion polymerization of a (meth) acrylic acid ester. It is manufactured by blending This (meth) acrylic adhesive is applied to a release substrate by a roll coater, blade coater, air knife coater,
It is coated with a lip coater, die coater, etc., and processed into an adhesive sheet or tape. When applying to the release substrate, there is a problem such as repelling, and in order to solve the problem, a measure is taken to increase the viscosity of the pressure-sensitive adhesive by adding a thickener.

Conventionally, water-soluble polymers have been generally used as thickeners. Many water-soluble polymers are also known as polyvinyl alcohol, carboxymethyl cellulose, polyacrylic acid-based thickeners and thickeners of polyoxyalkylene glycol derivatives.
(Japanese Patent Publication No. 1-55292, JP-A-58-213074)
The repelling problem can be solved by increasing the viscosity of the pressure-sensitive adhesive using these thickeners.

However, these thickeners did not satisfy the performance of the pressure-sensitive adhesive. When a thickener such as polyvinyl alcohol or carboxymethyl cellulose is used, the adhesive strength and water resistance of the pressure-sensitive adhesive tend to decrease, and the stability over time of the viscosity tends to decrease. With respect to polycarboxylic acid-based thickeners, the addition of a small amount can thicken the pressure-sensitive adhesive, but the thixotropy is imparted to the pressure-sensitive adhesive, which leaves problems such as poor leveling property during coating. .

[0005] Thickeners of polyoxyalkylene glycol derivatives have been used to solve the problems of reduced adhesive strength, water resistance, and reduced leveling property. However, these thickeners have the disadvantage that the viscosity increases greatly with temperature and the viscosity of the pressure-sensitive adhesive changes significantly. If the change in viscosity with respect to temperature change (hereinafter referred to as temperature dependency) is large, the viscosity of the pressure-sensitive adhesive changes due to, for example, changes in air temperature in summer and winter, resulting in differences in workability such as mixing and stirring. Also, since the amount of coating changes when applying the adhesive to the release substrate, the operating conditions of the coating machine must be changed each time.
There was a major problem with operability, such as the need to change.

Accordingly, the temperature dependency is low, and
At present, it has been difficult to produce a pressure-sensitive adhesive having excellent pressure-sensitive adhesive properties such as leveling properties, water resistance, and viscosity stability during storage.

[0007]

DISCLOSURE OF THE INVENTION The present invention comprises a water-based emulsion type pressure-sensitive adhesive, which has high viscosity, low temperature dependency, water resistance, repellency, viscosity stability during storage, leveling property, etc. Thickener composition that can satisfy a wide range of adhesive properties,
It is another object of the present invention to provide an acrylic emulsion-type pressure-sensitive adhesive comprising the thickener composition.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to overcome the above-mentioned problems, and as a result, a (meth) acryl-based compound was used in combination with two or more specific polyoxyalkylene glycol compounds having different characteristics. It has been found that adding the compound to the emulsion meets the purpose, and the present invention has been accomplished. That is, in the present invention, the compound A having a weight average molecular weight of 10,000 or more and less than 40,000 represented by the general formula (1) has a weight average molecular weight of 40, A thickener composition comprising as an essential component at least 20% by mass and less than 80% by mass of a compound B of at least 000 and less than 140,000; This is an acrylic emulsion-type pressure-sensitive adhesive that is blended in an amount of from 0.01 to 10% by mass. [Wherein, X 1 and X 2 are hydrocarbon groups having 15 to 24 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR ′, and OR ″ are each a group having 2 to 4 carbon atoms.
Wherein a, b, and d are from 1 to 500.
And c is an integer of 1 or more. ] [In the formula, X3 and X4 are a hydrocarbon group having 4 to 24 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR ′, and OR ″ are those having 2 to 4 carbon atoms. An oxyalkylene group, a, b, and d are integers of 1 to 500, and c is an integer of 1 or more.]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Compound A is a compound represented by the general formula (1), wherein X1 and X2 are a hydrocarbon group having 15 to 24 carbon atoms. It is a hydrocarbon group, more preferably a hydrocarbon group of 18 to 22. X1 and X2 may be the same type or a combination of different types. If the number of carbon atoms is less than 15, the desired viscosity cannot be obtained,
On the other hand, when the number of carbon atoms exceeds 24, the viscosity is increased, but the temperature dependency is reduced, and the cost is high, which is not common. Here, the carbon number refers to a weight average carbon number.

As the hydrocarbon group having 15 to 24 carbon atoms,
Examples thereof include a pentadecyl group, a cetyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henycosyl group, a docosyl group, a tricosyl group and a tetracosyl group. The hydrocarbon may be linear or branched.

The compound B is represented by the general formula (2), wherein X3 and X4 are a hydrocarbon group having 4 to 24 carbon atoms, and preferably a hydrocarbon group having 4 to 22 carbon atoms. More preferably, they are 8 to 14 hydrocarbon groups. X3, X
4 may be the same kind or different kinds of combinations. When the number of carbon atoms is less than 4, the thickening is low, and when the number of carbon atoms exceeds 24, the temperature dependency is reduced, and the cost is high and is not common.
Here, the carbon number refers to a weight average carbon number.

Examples of the alkyl group having 4 to 24 carbon atoms include butyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, tridecyl, pentadecyl, cetyl, heptadecyl, octadecyl, Nonadecyl, icosyl, henycosyl, docosyl, tricosyl, tetracosyl and the like. The hydrocarbon may be linear or branched.

Y in the general formulas (1) and (2) is a divalent organic residue derived from a diisocyanate compound. There is no particular limitation as long as it is a diisocyanate compound. Examples of the diisocyanate compound include an aliphatic diisocyanate compound, an aromatic diisocyanate compound, and an alicyclic diisocyanate compound.

Examples of the aliphatic diisocyanate compound include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, and the like.
Nonamethylene diisocyanate, decamethylene diisocyanate, dipropyl ether diisocyanate, 2,
Examples include 2′-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, 2,2,4-trimethylpentane diisocyanate, 3-butoxyhexane diisocyanate, and 1,4-butylene glycol dipropyl ether diisocyanate.

As for the aromatic diisocyanate compound, for example, metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, biphenyl Diisocyanate, tolidine diisocyanate,
3,3′-dimethoxybiphenyl diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,2-dimethyldiphenylmethane-4,4′-diisocyanate, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate,
4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, 4,4'-diethoxydiphenylmethane-3,3'-diisocyanate, and 2,2'-dimethyl-5,5'-dimethoxydiphenylmethane-4,
4'-diisocyanate and the like.

Examples of the alicyclic diisocyanate compound include cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane-4,4'-diisocyanate.

In the general formulas (1) and (2), OR, OR ',
OR "is an oxyalkylene group having 2 to 4 carbon atoms. Examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group, an oxypropylene group and an oxybutylene group. The oxyethylene group content is 60% by mass.
The above is essential, and the ratio of oxyethylene groups is preferably 80% by mass or more of the ratio of all oxyalkylene groups, and particularly preferably 90% by mass or more of all oxyalkylene groups. When the oxyethylene group content is less than 60% by mass, the viscosity increase is reduced. OR, OR ', and OR "may be those in which two or more oxyalkylene groups are connected in blocks or randomly.

In the general formulas (1) and (2), a, b and d each represent a repeating unit of OR, OR 'and OR ",
It is an integer of 500, preferably 2 to 400, and more preferably 2 to 300. If it is less than 1 or more than 500, the viscosity increases. C in the general formulas (1) and (2) is Is an integer of 1 or more.

The weight average molecular weight of compound A is 10,000.
It is less than 40,000. Preferably 15,000
Not less than 35,000, more preferably 20,000
Not less than 30,000. Weight average molecular weight of 10,
It is not preferable to use those having a molecular weight of less than 000 and 40,000 or more, because the viscosity is reduced.

The weight average molecular weight of compound B is 40,000.
More than 140,000. Preferably 60,00
0 or more and less than 120,000, more preferably 80,0
It is from 00 to 100,000. When the weight average molecular weight is less than 40,000, the temperature dependency is reduced, and the molecular weight is 14
If it is used in an amount of not less than 000, only a low-concentration aqueous solution of the thickener composition can be produced, which is not economical and the viscosity is reduced.

The weight average molecular weights of Compound A and Compound B can be measured by gel permeation chromatography (GPC) using polystyrene and n-propylbenzene of known molecular weight as standard substances. For example, it can be measured under the following conditions using gel permeation chromatography (GPC) of model HLC-8120GPC manufactured by Tosoh Corporation. The columns are Tosoh Corporation Model SuperH-4000x2 and Model SuperH-
Using 3000 × 1 tubes, the column temperature is 40 ° C., the detector is a differential refraction system (RI detector), THF (reagent grade 1, Katayama Chemical Industry) is used as the eluent, and the flow rate is 0.5 ml / m.
in, sample concentration 1% sample solution injection volume 10 μL, Tosoh Corp. as data processor, Model SC-8020, Tosoh Corp. as polystyrene standard substance with known molecular weight
And TSK polystyrene and normal propylbenzene manufactured by Katayama Chemical Industry Co., Ltd. are used. The grade of TSK polystyrene is F128 (weight average molecular weight 1,300,
000), F80 (weight average molecular weight 791,000)
F40 (weight average molecular weight 427,000), F20 (weight average molecular weight 184,000), F10 (weight average molecular weight 98,000), F4 (weight average molecular weight 0), F2 (weight average molecular weight 17,300), F1 (weight average molecular weight) Molecular weight 1
0,100), A5000 (weight average molecular weight 6400)
And A2500 (weight average molecular weight 2,800) and normal propyl benzene (weight average molecular weight 120.19) manufactured by Tokyo Chemical Industry Co., Ltd.

As a method for synthesizing the thickened composition of the present invention, it can be synthesized using a known urethane-forming reaction. For example, polyether monool, polyether diol and diisocyanate are reacted at a reaction temperature of 40 to 130 ° C.
For 2 to 10 hours. For example, when synthesizing from polyether monol, polyether diol and diisocyanate, a synthesis method by batch charging of all may be used, or after reacting polyether diol and diisocyanate, a method of reacting with polyether monool and synthesizing, or A method of reacting polyether monool with diisocyanate and then reacting with polyether diol for synthesis may be used. Although some by-products may be formed by the reaction, the main product is a compound of the general formulas (1) and (2) and can be used in a mixture with the by-products.

The reaction temperature is from 40 to 130 ° C., preferably from 70 to 100 ° C. If the temperature is lower than 40 ° C., the reaction rate is slow and there is a disadvantage that it takes too much time. If the temperature is higher than 130 ° C., an abnormal side reaction occurs, which is not preferable.

In these reactions, a solvent may be used if necessary. The solvent used must not contain active hydrogen, for example, toluene as an aromatic solvent,
Petroleum ether, n-
Cyclohexane, cyclohexanone, decalin, etc. as alicyclic solvents such as hexane, chloroform, carbon tetrachloride, ethylene dichloride, chlorobenzene, etc. as halogen-containing solvents, ethyl acetate as an ester solvent,
Examples of ketone solvents such as butyl acetate and pentyl acetate include methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone.

If necessary, the catalyst used in the urethanization reaction may be, for example, an amine compound such as triethylamine, triethylenediamine, heptamethyldiethylenetriamine, N-methylmorpholine and benzyltriethylammonium hydroxide. Examples include stannous, 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.

Next, an acrylic emulsion-type pressure-sensitive adhesive prepared by blending the thickener composition of the present invention will be described.

The acrylic emulsion-type pressure-sensitive adhesive of the present invention comprises the thickener composition in an amount of 0.01 to 0.01% based on the solid content of the emulsion.
10 to 10% by weight. If the amount is less than 0.01% by weight, no thickening effect is exhibited, and if it exceeds 10% by weight, the viscosity is too high.

The thickener of the present invention may be incorporated directly into the pressure-sensitive adhesive, or may be incorporated after diluting the thickener composition with water or a solvent so as to have an appropriate viscosity before addition. .

The acrylic emulsion for pressure-sensitive adhesive used in the acrylic emulsion type pressure-sensitive adhesive of the present invention is mainly composed of a polymer of (meth) acrylate or a copolymer of (meth) acrylate with another vinyl monomer. Is used.

(Meth) acrylate [(meth) acrylate means acrylate or methacrylate. same as below. ] As, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) Acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-tridecyl (meth) acrylate, isotridecyl (meth) acrylate, n-tetradecyl (meth)
Acrylate and isotetradecyl (meth) acrylate. These alkyl (meth) acrylates may be used alone or in combination of two or more.

Examples of the vinyl monomer copolymerizable with the (meth) acrylic acid ester include carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and crotonic acid, and anhydrides thereof.
Hydroxyl-containing monomers such as -hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, polyoxyethylene mono (meth) acrylate and polyoxyethylene monoallyl ether; other vinyl acetates, acrylonitrile, acrylamide, Examples include styrene and dimethylamino methacrylate.

The acrylic emulsion-type pressure-sensitive adhesive of the present invention further contains known tackifiers, thickeners, preservatives, defoamers, fungicides, dispersants, lubricating / release agents, fillers and the like. May be.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the text, “part” or “%” means “part by mass” or “% by mass”.

The thickener compositions of Production Examples a to z were obtained by the following production methods.

A polyethylene glycol 6000 (molecular weight: 6000) was charged into a four-necked flask having a capacity of 1000 ml equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
Part, n-dodecyl alcohol with ethylene oxide
13.5 parts of the mol-added polyether monol was added at 80 to 90 ° C. under low pressure (500 to 1500 Pa).
After dehydration for an hour, the water content of the system was reduced to 0.03%. Then, the mixture was cooled to 70 ° C., and tetramethylene diisocyanate was added in 1 ml.
6.8 parts were added and reacted at 85-90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). After cooling at room temperature, a reaction product (Production Example a) as a pale yellow viscous solid was obtained. Was.

Ethylene oxide and propylene oxide were added in a weight ratio of 82: 1 to a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
500 parts of a polyether diol having a molecular weight of 8000 and 53.8 parts of a polyether monool obtained by adding 3 moles of ethylene oxide to n-icosyl alcohol at a low pressure (500 to 1500 P).
It dehydrated at 80-90 degreeC for 3 hours in a), and made the water content of the system 0.03%. Then, the mixture was cooled to 70 ° C., and 21.8 parts of tolylene diisocyanate was added.
The reaction was allowed to proceed at 0 ° C. until the isocyanate content became 0% (3 hours). After cooling at room temperature, a reaction product (Production Example b) was obtained as a pale yellow cooled solid.

A polyethylene glycol 6000 (molecular weight: 6000) was charged in a four-necked flask having a capacity of 1000 ml equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
Part, n-icosyl alcohol with 5 parts of ethylene oxide
86.3 parts of the mol-added polyether monool is added at 80 to 90 ° C. under low pressure (500 to 1500 Pa).
After dehydration for an hour, the water content of the system was adjusted to 0.03%. It was then cooled to 70 ° C. and tolylene diisocyanate was added at 23.3
The mixture was further reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). After cooling at room temperature, a light yellow cooled solid reaction product (Production Example c) was obtained.

A polyethylene glycol 20000 (molecular weight: 20,000) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer.
00 parts, 3.9 parts of polyether monool obtained by adding 6 moles of ethylene oxide to n-octyl alcohol are dehydrated under low pressure (500 to 1500 Pa) at 80 to 90 ° C. for 3 hours to reduce the water content of the system to 0. 0.03%. Then, the mixture was cooled to 70 ° C., 4.3 parts of tetramethylene 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). (Production Example d) was obtained.

500 g of polyethylene glycol 6000 (molecular weight: 6000) was placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity.
Parts, 13.0 parts of polyether monool obtained by adding 4 mol of ethylene oxide to n-tetradecyl alcohol, and 80 to 90 ° C. under low pressure (500 to 1500 Pa).
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). Reaction product (Preparation example e)
I got

A 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer was charged with 500 parts of polyethylene glycol having a molecular weight of 8000, and polyether monoether obtained by adding 10 mol of ethylene oxide to n-butyl alcohol. 12.9 parts of oars and low pressure (5
(00 to 1500 Pa) 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 14.1 parts of xylylene diisocyanate was added.
% (3 hours), and after cooling at room temperature, a reaction product (Production Example f) as a pale yellow cooled solid was obtained.

A polyether obtained by adding 500 parts of polyethylene glycol having a molecular weight of 4000 and 5 mol of ethylene oxide to n-docosyl alcohol in a four-necked flask having a capacity of 1000 ml equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. Put 27.3 parts of monool and put it under low pressure (5
(00 to 1500 Pa) 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 26.1 parts of tolylene diisocyanate was added.
The reaction was carried out at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). After cooling at room temperature, a light yellow cooled solid reaction product (Production Example g) was obtained.

A 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer was charged with 500 parts of polyethylene glycol having a molecular weight of 8,000 and poly-mol obtained by adding 4 mol of ethylene oxide to n-tetracosyl alcohol. 13.3 parts of ether monool was added and dehydrated at 80 to 90 ° C. for 3 hours under low pressure (500 to 1500 Pa) to reduce the water content of the system to 0.03%. Then 70 ° C
, And 13.1 parts of tolylene diisocyanate was added.
% (3 hours), and cooled at room temperature to obtain a light yellow cooled solid reaction product (Production Example h).

In a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer, 500 parts of polyethylene glycol having a molecular weight of 6000 and 500 mol of ethylene oxide added to n-tetracosyl alcohol were added. 22.1 parts of ether monool was added, and the mixture was dehydrated at 80 to 90 ° C. for 3 hours under low pressure (500 to 1500 Pa) to reduce the water content of the system to 0.03%. Then 70
C., to which 16.8 parts of tolylene diisocyanate was added.
% (3 hours), and after cooling at room temperature, a pale yellow cooled solid reaction product (Production Example i) was obtained.

A polyether obtained by adding 500 parts of polyethylene glycol having a molecular weight of 6000 and 5 mol of ethylene oxide to n-pentadecyl alcohol in a four-necked flask having a capacity of 1000 ml equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. 74.7 parts of the monol was added and dehydrated at 80 to 90 ° C. for 3 hours under low pressure (500 to 1500 Pa) to reduce the water content of the system to 0.03%. Then 70 ° C
And 28.0 of hexamethylene diisocyanate was added.
The mixture was further reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). After cooling at room temperature, a light yellow cooled solid reaction product (Production Example j) was obtained.

In a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer, 500 parts of polyethylene glycol having a molecular weight of 7,500, and polyether monoether obtained by adding 5 mol of ethylene oxide to n-cetyl alcohol were added. Insert 61.6 parts of oar and put under low pressure (50
0 to 1500 Pa) at 80 to 90 ° C. for 3 hours,
The water content of the system was 0.03%. Then, the mixture was cooled to 70 ° C., 23.2 parts of tolylene diisocyanate was added, and reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). (Production Example k) was obtained.

In a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer, 500 parts of polyethylene glycol having a molecular weight of 6000 and 500 mol of ethylene oxide added to n-octadecyl alcohol were added. 81.7 parts of all were charged and dehydrated at 80 to 90 ° C. for 3 hours under low pressure (500 to 1500 Pa) to reduce the water content of the system to 0.03%. Then 70 ° C
And 28.0 of hexamethylene diisocyanate was added.
The mixture was further reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). After cooling at room temperature, a light yellow cooled solid reaction product (Production Example 1) was obtained.

Polyether monool obtained by adding 500 parts of polyethylene glycol having a molecular weight of 6000 and 5 mol of ethylene oxide to docosyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. 91.0 parts and put under low pressure (500
(1500 Pa) at 80-90 ° C. for 3 hours to reduce the water content of the system to 0.03%. Then, the mixture was cooled to 70 ° C., and 28.0 parts of hexamethylene diisocyanate was added.
% (3 hours). After cooling at room temperature, a reaction product (Production Example m) was obtained as a pale yellow cooled solid.

A polyether monool obtained by adding 500 parts of polyethylene glycol having a molecular weight of 8000 and 4 mol of ethylene oxide to docosyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. Into 66.3 parts under low pressure (500
(1500 Pa) 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., 21.8 parts of tolylene 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). (Production Example n) was obtained.

A 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer was charged with 500 parts of polyethylene glycol having a molecular weight of 6000 and polyether monool obtained by adding 3 mol of ethylene oxide to dodecyl alcohol. 17.7 parts put under low pressure (500
(1500 Pa) at 80-90 ° C. for 3 hours to reduce the water content of the system to 0.03%. Then, the mixture was cooled to 70 ° C., 19.3 parts of tolylene 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). (Production Example o) was obtained.

A 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high viscosity stirrer was charged with 500 parts of polyethylene glycol having a molecular weight of 20,000 and n-
4.1 parts of polyether monool obtained by adding 5 mol of ethylene oxide to dodecyl alcohol is added under low pressure (5
(00 to 1500 Pa) 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., 5.2 parts of tolylene 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). (Production Example p) was obtained.

A 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer was charged with 500 parts of polyethylene glycol having a molecular weight of 6000 and polyether monool obtained by adding 20 mol of ethylene oxide to dodecyl alcohol. 71.7 parts put under low pressure (50
0 to 1500 Pa) at 80 to 90 ° C. for 3 hours,
The water content of the system was 0.03%. Then, the mixture was cooled to 70 ° C, 25.9 parts of isophorone diisocyanate was added, and reacted at 85 to 90 ° C under a nitrogen stream until the isocyanate content became 0% (3 hours). After cooling at room temperature, a pale yellow cooled solid was obtained. A reaction product (Production Example q) was obtained.

A 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer was charged with 500 parts of polyethylene glycol having a molecular weight of 8000 and polyether monool obtained by adding 10 mol of ethylene oxide to dodecyl alcohol. 13.0 parts low pressure (50
0 to 1500 Pa) at 80 to 90 ° C. for 3 hours,
The water content of the system was 0.03%. Then, the mixture was cooled to 70 ° C., and 12.3 parts of hexamethylene diisocyanate was added.
% (3 hours), and cooled at room temperature to obtain a light yellow cooled solid reaction product (Production Example r).

A polyether obtained by adding 500 parts of polyethylene glycol having a molecular weight of 4000 and 10 mol of ethylene oxide to n-icosyl alcohol in a four-necked flask having a capacity of 1000 ml equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. 184.5 parts of the monol was added and dehydrated at 80 to 90 ° C. for 3 hours under low pressure (500 to 1500 Pa) to reduce the water content of the system to 0.03%. Then 70 ° C
, And 43.5 parts of tolylene diisocyanate was added.
% (3 hours), and cooled at room temperature to obtain a light yellow cooled solid reaction product (Production Example s).

A polyether monool obtained by adding 500 parts of polyethylene glycol having a molecular weight of 8000 and 10 mol of ethylene oxide to icosyl alcohol in a four-necked flask having a capacity of 1000 ml equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. 36.9 parts and put under low pressure (50
0 to 1500 Pa) at 80 to 90 ° C. for 3 hours,
The water content of the system was 0.03%. Then, the mixture was cooled to 70 ° C., 15.2 parts of tolylene 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). (Production Example t) was obtained.

A polyether monool obtained by adding 500 parts of polyethylene glycol having a molecular weight of 6000 and 5 mol of ethylene oxide to icosyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. 86.3 parts and put under low pressure (500
(1500 Pa) at 80-90 ° C. for 3 hours to reduce the water content of the system to 0.03%. Then, the mixture was cooled to 70 ° C., 34.8 parts of tolylene 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). (Production Example u) was obtained.

Polyether monool obtained by adding 500 parts of polyethylene glycol having a molecular weight of 6000 and 5 mol of ethylene oxide to icosyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. 34.5 parts and low pressure (500
(1500 Pa) at 80-90 ° C. for 3 hours to reduce the water content of the system to 0.03%. Then, the mixture was cooled to 70 ° C., 20.3 parts of tolylene 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). (Production Example v) was obtained.

In a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer, 500 parts of polyethylene glycol having a molecular weight of 8000 and 500 parts of n-propyl alcohol were added with 5 mol of ethylene oxide. 7.0 parts oar and low pressure (50
0 to 1500 Pa) at 80 to 90 ° C. for 3 hours,
The water content of the system was 0.03%. Then, the mixture was cooled to 70 ° C., and 13.1 parts of tolylene diisocyanate was added. The mixture was reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). (Production Example w) was obtained.

A 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer was charged with 500 parts of polyethylene glycol having a molecular weight of 8000 and polyether monoether obtained by adding 5 mol of ethylene oxide to pentacosyl alcohol. Insert 16.8 parts of oar and put under low pressure (5
(00 to 1500 Pa) 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., 12.6 parts of hexamethylene diisocyanate was added, and reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours).
A pale yellow cooled solid reaction product (Production Example x) was obtained.

In a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer, ethylene oxide and propylene oxide were added in a weight ratio of 54: 5.
500 parts of a polyether diol having a molecular weight of 6000, which was randomly copolymerized in 6, and 8 parts of a polyether monool obtained by adding 5 mol of ethylene oxide to icosyl alcohol.
6.3 Put 80 parts under low pressure (500-1500Pa)
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., 37.1 parts of isophorone diisocyanate was added, and reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours).
After cooling at room temperature, a light yellow cooled solid reaction product (Production Example y) was obtained.

In a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high-viscosity stirrer, 500 parts of polyethylene glycol having a molecular weight of 6000 and 500 mol of ethylene oxide added to pentacosyl alcohol were added. Add 98.0 parts of oar and put under low pressure (5
(00 to 1500 Pa) 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 29.0 parts of tolylene diisocyanate was added.
The reaction was carried out at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours), and after cooling at room temperature, a reaction product (Production Example z) as a pale yellow cooled solid was obtained.

The weight average molecular weights of Production Examples a to z are as shown in Table 1.

[0062]

[Table 1]

Table 2 shows the contents of Examples 1 to 23 and Comparative Examples 24 to 29. In Comparative Example 30, PVA117 (manufactured by Kuraray Co., Ltd.) was used as a thickener polyvinyl alcohol. In Comparative Example 31, CMC Daicel <1190> (manufactured by Daicel Chemical Industries, Ltd.) was used as the thickener carboxymethylcellulose. In Comparative Example 32, SN thickener 618 (San Nopco Co., Ltd.) was used as a polycarboxylic acid thickener.
Was used.

[0064]

[Table 2]

The performance of Examples 1 to 23 and Comparative Examples 24 to 33 was evaluated by the following methods.

Examples 1 to 23 of the present invention and Comparative Examples 24 to 2
No. 9, 30 parts of the thickener composition, 20 parts of butyl triglycol ether and 50 parts of water were uniformly mixed to obtain respective thickener composition solutions. In addition, about Comparative Examples 30-32, since the 30% aqueous solution was not made, the 3% aqueous solution was adjusted, and the following evaluation was performed so that the solid content amount and the butyl triglycol amount of the thickener composition with respect to the emulsion would be the same. . In addition, as Comparative Example 33, the evaluation was performed without adding the thickener composition.

Table 3 shows the evaluation results.

Evaluation of thickening and temperature dependency 120 parts by weight of acrylic emulsion for pressure-sensitive adhesive, water
An acrylic emulsion-type pressure-sensitive adhesive was prepared in which 1 part by weight and 0.9 part by weight of the aqueous solution of the thickener composition were mixed. In addition, what did not mix | blend a thickener composition solution was made into the blank. As a compounding method, an acrylic emulsion for an adhesive, water, and an aqueous solution of a thickener composition are put into a 225 ml glass bottle, and the mixture is subjected to 3000 r with an SMT-made high flex disperser HG-92.
Stirring was carried out until uniform at pm. After standing for 24 hours,
After adjusting to a predetermined temperature, the viscosity at 12 rpm (manufactured by
BM type viscometer manufactured by Tokyo Keiki Co., Ltd.). Thickening: The higher the viscosity at 25 ° C. as compared with the blank, the higher the viscosity. The viscosity is defined as (1
Temperature dependency: The smaller the ratio of viscosity at 2 ° C. to 40 ° C. (viscosity at 40 ° C./value of viscosity at 2 ° C.), the smaller the temperature dependency. The viscosity is a value measured by a BM type viscometer (12 rpm, after 60 seconds).

Each sample was applied to a glass plate with a 10-mil applicator. It was repelled visually, and the leveling property was observed and evaluated in three steps. The symbols in Table 3 indicate ○: good appearance, Δ: slight coating unevenness, ×: large coating unevenness.

Evaluation of Water Resistance The sample after the repelling and leveling evaluation was dried at room temperature for 48 hours. Then, place each glass plate in 40 ° C hot water for 2 hours.
After immersion for 4 hours, whitening, peeling and blisters were observed and evaluated in three steps. The symbols in the table indicate ○: good appearance, Δ: slight blistering, ×: whitening, peeling, and many blisters.

Evaluation of viscosity stability during storage Each sample was allowed to stand in a constant temperature bath at 40 ° C. for one month, and the viscosity was measured. The symbols in the table indicate ○: no viscosity reduction, Δ: slight viscosity tendency, ×: greatly reduced viscosity.

[0072]

[Table 3]

[0073]

Since the present invention is a thickener composition and an acrylic emulsion-type pressure-sensitive adhesive having a small change in viscosity with temperature change, the emulsion-type pressure-sensitive adhesive containing the thickener of the present invention has a low temperature. Stable operation due to low dependence, which suppresses differences in workability such as mixing and stirring even when the temperature during coating changes, and suppresses changes in the amount of coating when coating on a release base. It has the feature to make it. It has a wide range of adhesive properties such as repelling, leveling, water resistance, and viscosity stability during storage.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hirofumi Oi 1 No. 11 Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto F-term in San Nopco Co., Ltd. (Reference) 4J002 CK02W CK02X CK04W CK04X GT00 4J040 DF041 DF051 EF132 GA05 GA07 GA12 GA13 GA15 GA22 JA03 LA01 LA05 LA06 LA07

Claims (2)

[Claims] 1. A weight average molecular weight 1 represented by the general formula (1)
When the amount of the compound A is at least 20% by mass and less than 80% by mass, the amount of the compound B represented by the general formula (2) having a weight average molecular weight of at least 40,000 and less than 140,000 is at least 20% by mass. A thickener composition comprising less than 10% by mass as an essential component. [Wherein, X 1 and X 2 are hydrocarbon groups having 15 to 24 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR ′, and OR ″ are each a group having 2 to 4 carbon atoms.
Wherein a, b, and d are from 1 to 500.
And c is an integer of 1 or more. ] [In the formula, X3 and X4 are a hydrocarbon group having 4 to 24 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR ′, and OR ″ are those having 2 to 4 carbon atoms. An oxyalkylene group, a, b, and d are integers of 1 to 500, and c is an integer of 1 or more.] 2. An acrylic emulsion-type pressure-sensitive adhesive comprising the thickener composition according to claim 1 in an amount of 0.01 to 10% by mass based on the solid content of the emulsion.