JP2000204340A - Adhesive composition and paper tube by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive composition having an excellent initial adhesive force and a good preservation stability, and exhibiting various performances such as an excellent adhering force, compression resistant strength, wet resistant strength, heat resistance, etc., after formed as a paper tube, and the paper tube prepared by using the above adhesive composition. SOLUTION: This adhesive composition contains 80-170 pt.wt. inorganic filler, 35-70 pt.wt. polyvinyl alcohol containing carbonyl group and 0.2-5 pt.wt. hydrazine compound based on 100 pts.wt. resin portion of an acrylic resin emulsion and also >=50 pt.wt. amine compound based on 100 pts.wt. the above hydrazine compound. A paper tube is prepared by winding a belt like paper strip as a tubular state, and adhering the overlapping parts of the tubularly wound belt like paper strip with the above adhesive composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition preferably used mainly for paper tubes, and a paper tube produced using the adhesive composition.

[0002]

2. Description of the Related Art Generally, a paper tube used as a mandrel for winding a sheet-like article such as paper, foil, woven fabric or the like is formed by spirally winding a band-shaped paper strip around a metal mandrel in a plurality of layers, and overlapping the band-shaped paper strip. It is manufactured by bonding with an adhesive. As such an adhesive for paper tubes, an adhesive composition mainly containing an aqueous solution of a water-soluble polymer such as starch or polyvinyl alcohol, a vinyl acetate resin-based emulsion, or the like is generally used.

[0003] On the other hand, the adhesive for a paper tube includes an initial adhesive force capable of withstanding the restoring force of a strip of paper wound around a metal mandrel, a pressure resistance after being formed into a paper tube, a moisture resistance, a water resistance, and the like. Excellent heat resistance is required.

[0004] In general, in order to improve the pressure resistance after being formed into a paper tube, a method of increasing the elastic modulus of a dry film of the adhesive composition to impart strength has been adopted.
Japanese Patent No. 2757113 discloses that “a monomer comprising 80 to 90% of 85 to 95% by weight of vinyl acetate and 5 to 15% by weight of ethylene in the presence of 10 to 20% by weight of polyvinyl alcohol containing 5 to 20% by weight of acrylic acid. An adhesive for paper tubes mainly comprising an ethylene-vinyl acetate copolymer resin emulsion obtained by emulsion polymerization of parts by weight "is disclosed.

However, as disclosed in the above disclosure, ethylene-
An adhesive containing a vinyl acetate copolymer resin emulsion as a main component has a problem that the strength of a paper tube is remarkably reduced under high temperature and high humidity because the dry film has insufficient moisture resistance and heat resistance.

That is, it has excellent initial adhesive strength, and
At present, after being formed into a paper tube, a paper tube adhesive exhibiting various properties such as excellent adhesive strength, pressure resistance, moisture resistance, water resistance and heat resistance has not yet been put to practical use.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems by providing an excellent initial adhesive force and a good storage stability, and an excellent after being formed into a paper tube. It is an object of the present invention to provide an adhesive composition exhibiting various properties such as adhesive strength, pressure resistance, moisture resistance, water resistance, heat resistance, and the like, and a paper tube manufactured using the adhesive composition. .

[0008]

The adhesive composition according to the invention described in claim 1 (hereinafter referred to as "first invention")
80 to 170 parts by weight of an inorganic filler, 35 to 70 parts by weight of a carbonyl group-containing polyvinyl alcohol and 0.2 to 5 parts by weight of a hydrazine compound are contained with respect to 100 parts by weight of a resin component of the acrylic resin emulsion, and The amine compound 5 was added to 100 parts by weight of the hydrazine compound.
It is characterized by containing not less than 0 parts by weight.

The invention according to claim 2 (hereinafter referred to as “second
The paper tube according to the invention is formed by winding a strip of paper into a tube, and the overlapping portion of the strip of paper wound by the tube is adhered by the adhesive composition according to the invention of claim 1 above. It is characterized by the following.

The acrylic resin emulsion used as a main component of the adhesive composition according to the first invention is an acrylic resin emulsion obtained by emulsion polymerization of an alkyl (meth) acrylate or an alkyl (meth) acrylate. An acrylic resin-based emulsion obtained by emulsion copolymerization of an alkyl (meth) acrylate and a copolymerizable monomer. Here, “alkyl (meth) acrylate” means “alkyl acrylate” or “alkyl methacrylate”.

The alkyl (meth) acrylate is not particularly limited, but is preferably an alkyl (meth) acrylate having an alkyl group having 2 to 12 carbon atoms, such as ethyl (meth) acrylate and n-butyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and the like are preferably used.

The above alkyl (meth) acrylates may be used alone or in combination of two or more.

When the alkyl (meth) acrylate has less than 2 carbon atoms in the alkyl group, the adhesiveness of the resulting adhesive composition to the adherend and the initial adhesive strength may be insufficient. When the carbon number of the alkyl group exceeds 12, the elastic modulus of the dried film of the obtained adhesive composition becomes low, and the pressure resistance and heat resistance may be insufficient.

The monomer copolymerizable with the above-mentioned alkyl (meth) acrylate is not particularly limited. For example, (meth) acrylic acid, methyl (meth) acrylate, ethylene glycol mono (meth) acrylate , Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Glycidyl (meth) acrylate, propylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, vinyl acetate, styrene, α-methylstyrene, acrylonitrile, acrylamide, and the like are used, and are preferably used.

The monomers copolymerizable with the alkyl (meth) acrylate may be used alone or in combination of two or more.

The copolymerization ratio of the alkyl (meth) acrylate and the monomer copolymerizable with the alkyl (meth) acrylate is not particularly limited, but is preferably 50 to 98% by weight of the alkyl (meth) acrylate and 50% by weight of the alkyl (meth) acrylate. Monomer 50 copolymerizable with (meth) acrylate
It is preferably about 2% by weight.

In the above copolymerization ratio, when the amount of the alkyl (meth) acrylate is less than 50% by weight or the amount of the copolymerizable monomer exceeds 50% by weight, the adhesion of the obtained adhesive composition to the adherend is reduced. In some cases, the adhesiveness and the initial adhesive strength may be insufficient. On the other hand, when the content of the alkyl (meth) acrylate exceeds 98% by weight or the amount of the copolymerizable monomer is less than 2% by weight, the obtained adhesive composition The elastic modulus of the dried film of the product becomes low, and the pressure resistance and heat resistance may be insufficient.

The method for producing the acrylic resin emulsion used in the first invention is not particularly limited. For example, hydrogen peroxide, ammonium persulfate, potassium persulfate can be prepared by using an ordinary emulsion polymerization apparatus and using water as a solvent. , A predetermined amount of alkyl (meth) acrylate or a mixture of alkyl (meth) acrylate and a monomer copolymerizable with the alkyl (meth) acrylate, using a peroxide such as benzoyl peroxide or dicumyl peroxide as a polymerization catalyst. The desired acrylic resin-based emulsion can be obtained by emulsion (co) polymerizing each predetermined amount according to a conventional method. Here, “(co) polymerization” means “polymerization” or “copolymerization”.

The resin content of the acrylic resin-based emulsion obtained above is not particularly limited, but is preferably 30 to 70% by weight in consideration of performance balance and workability.

The resin content of the acrylic resin emulsion is 3
If the amount is less than 0% by weight, storage efficiency and transport efficiency may be deteriorated. Conversely, if the resin content of the acrylic resin-based emulsion exceeds 70% by weight, the storage stability and mechanical properties of the obtained adhesive composition may be reduced. Stability and the like may decrease.

In the adhesive composition according to the first invention,
It is necessary that the inorganic filler is contained in an amount of 80 to 170 parts by weight, preferably 115 to 140 parts by weight, based on 100 parts by weight of the resin component of the acrylic resin emulsion.

By adding the above-mentioned specific amount of the inorganic filler to the acrylic resin-based emulsion, an adhesive having excellent initial adhesive strength, a dried film having a high elastic modulus, and exhibiting excellent pressure resistance and heat resistance can be obtained. Agent composition can be obtained.

The inorganic filler is not particularly restricted but includes clay, aluminum hydroxide, calcium carbonate, kaolin, talc and the like.
Among them, clay is more preferably used because it is excellent in dispersibility in an acrylic resin emulsion and has a large effect of improving the elastic modulus of a dried film of the obtained adhesive composition.

The above-mentioned inorganic fillers may be used alone or in combination of two or more.

Resin content of acrylic resin emulsion 10
When the content of the inorganic filler relative to 0 parts by weight is less than 80 parts by weight, the elasticity of the dry film of the obtained adhesive composition is not sufficiently improved, so that the pressure resistance after being formed into a paper tube or the like. When the heat resistance becomes insufficient and the content of the inorganic filler with respect to 100 parts by weight of the resin component of the acrylic resin emulsion exceeds 170 parts by weight, the adhesiveness of the obtained adhesive composition to the adherend and the initial Adhesive strength becomes insufficient.

The method of adding the inorganic filler to the acrylic resin-based emulsion is not particularly limited, and the inorganic filler may be added as it is and uniformly dispersed. To do so, it is preferable to add the inorganic filler in advance as a water slurry.

In the adhesive composition according to the first invention, carbonyl group-containing polyvinyl alcohol (hereinafter referred to as "carbonyl group-containing PVA") 35 to 7 is added to 100 parts by weight of the resin component of the acrylic resin emulsion.
It is necessary to contain 0 parts by weight, preferably 45 to 60 parts by weight.

By containing the above-mentioned specific amount of carbonyl group-containing PVA to the acrylic resin emulsion, the initial adhesive strength is excellent, the dry film has a high elastic modulus, and excellent adhesive strength, pressure resistance, heat resistance, etc. Can be obtained.

The carbonyl group-containing PVA is obtained by reacting ordinary PVA with a carbonyl group-containing compound such as a carboxylic acid to introduce a carbonyl group into the PVA molecule. ,
For example, (meth) acrylic acid, itaconic acid, (anhydride) maleic acid and the like can be mentioned, but not particularly limited thereto. The introduction position of the carbonyl group in the PVA molecule may be at the terminal of the molecule or at any position in the molecule, and is not particularly limited.

The saponification degree of the carbonyl group-containing PVA is as follows:
Although not particularly limited, it is preferably at least 88 mol%, more preferably at least 96 mol%. The average degree of polymerization of the carbonyl group-containing PVA,
Although it is not particularly limited, it is preferably 1000 to 2500, more preferably 1500 to 200.
0.

The above carbonyl group-containing PVA may be used alone or in combination of two or more.

Resin content of acrylic resin emulsion 10
When the content of the carbonyl group-containing PVA to 0 parts by weight is 3
When the amount is less than 5 parts by weight, the elasticity of a dried film of the obtained adhesive composition is not sufficiently improved, so that the pressure resistance and heat resistance after being formed into a paper tube become insufficient. When the carbonyl group-containing PVA content exceeds 70 parts by weight based on 100 parts by weight of the resin component of the resin emulsion,
The initial adhesive strength, moisture resistance, water resistance, etc. decrease.

The method of adding the carbonyl group-containing PVA to the acrylic resin emulsion is not particularly limited, and the carbonyl group-containing PVA may be added as it is and dissolved uniformly. In order to dissolve in water, it is preferable to add the carbonyl group-containing PVA in advance as an aqueous solution.

Further, in the adhesive composition according to the first invention, the acrylic resin emulsion has a resin content of 10%.
It is necessary that 0.2 to 5 parts by weight of the hydrazine compound be contained with respect to 0 parts by weight, and preferably 1 to 2 parts by weight.

By including the above specific amount of the hydrazine compound in the acrylic resin emulsion, it has good storage stability and, after being formed into a paper tube, more excellent moisture resistance and water resistance. It becomes possible to obtain an adhesive composition exhibiting heat resistance and the like.

The hydrazine compound is not particularly limited, and examples thereof include adipic acid monohydrazide, adipic acid dihydrazide, maleic acid monohydrazide, maleic acid dihydrazide, hydrazine phosphate, neutral hydrazine sulfate, and the like. It is preferably used, and among them, adipic dihydrazide is more preferably used.

The above hydrazine compounds may be used alone or in combination of two or more.

The adipic dihydrazide more preferably used is a white crystalline adipic acid derivative represented by the chemical formula (CH ₂ ) ₄ (CONHNH ₂ ) ₂ .
It can be synthesized by a method of heating adipic acid ethyl ester with hydrazine hydrate or a method of reacting hydrazine with adipic acid chloride or adipic anhydride.

Resin content of acrylic resin emulsion 10
If the content of the hydrazine compound is less than 0.2 part by weight with respect to 0 part by weight, the effect of improving moisture resistance, water resistance, heat resistance, etc. cannot be sufficiently obtained, and conversely, the resin content of the acrylic resin emulsion is 100 parts by weight. When the content of the hydrazine compound per part by weight exceeds 5 parts by weight, the storage stability of the adhesive composition decreases.

The method of adding the hydrazine compound to the acrylic resin-based emulsion is not particularly limited, and the hydrazine compound may be added as it is and dissolved uniformly. It is preferable to add the hydrazine compound in advance as an aqueous solution.

Further, in the adhesive composition according to the first aspect of the invention, 100 parts by weight of the hydrazine compound is used.
It is necessary that at least 50 parts by weight of the amine compound is contained, and preferably 100 to 150 parts by weight.

By including the specific amount of the amine compound in the adhesive composition, the storage stability of the adhesive composition can be remarkably improved.

Examples of the amine compound include, but are not limited to, isopropanolamine,
Ethanolamine, diethanolamine, ethylamine, butylamine, isopropylamine and the like,
It is preferably used, and among them, isopropanolamine is more preferably used.

The above-mentioned amine compounds may be used alone or in combination of two or more.

Isopropanolamine, which is more preferably used, is a water-soluble compound obtained by reacting propylene oxide with ammonia. Depending on the molar ratio of propylene oxide to ammonia, monoisopropanolamine, diisopropanolamine and triisopropanolamine are used. There are three types of compounds.

The above three kinds of isopropanolamines are
Each of them may be used alone, or two or more of them may be used in combination.

If the content of the amine compound in the adhesive composition is less than 50 parts by weight based on 100 parts by weight of the hydrazine compound, a sufficient effect of improving storage stability cannot be obtained.

The method for adding the amine compound to the adhesive composition is not particularly limited, and the amine compound may be added as it is and dissolved uniformly.
For more uniform dissolution, it is preferable to add the amine compound in advance as an aqueous solution.

In order to further improve the storage stability of the adhesive composition, acetone may be used in combination with the amine compound, but the content of acetone is preferably as small as possible. As the content of acetone increases,
Odor problems occur.

In the adhesive composition according to the first invention, in addition to the above essential components, a water-soluble polymer other than the carbonyl group-containing PVA, One or more of various additives such as a resin, a surfactant, a plasticizer, a softener, a pigment, a dye, an antifoaming agent, a preservative, a fungicide, and an organic solvent may be contained.

Although the viscosity of the adhesive composition according to the first invention is not particularly limited, it is preferably not more than 1000 mPa · s at 30 ° C. in consideration of workability at the time of coating.

It is needless to say that the adhesive composition according to the first invention may be used not only for paper tubes but also for paper packaging, woodworking, general use and the like.

Next, in the paper tube according to the second aspect of the invention, the strip of paper is wound in a tubular shape, and the overlapping portion of the strip of paper wound in a tubular shape is bonded by the adhesive composition according to the first aspect of the invention. Become.

[0054]

The adhesive composition according to the first aspect of the present invention comprises a specific amount of an inorganic filler, a specific amount of a carbonyl group-containing PVA and a specific amount of a hydrazine compound with respect to an acrylic resin emulsion as a main component. Therefore, due to their interaction, it has excellent initial adhesive strength, and the film after drying shows a high elastic modulus, so after being made into a paper tube, it has excellent pressure resistance, moisture resistance, and water resistance. Exhibits various performances such as heat resistance. Also, since it contains a specific amount of the amine compound, storage stability is also good.

Further, since the paper tube according to the second invention is manufactured using the adhesive composition according to the first invention, various properties such as excellent adhesive strength, pressure resistance, moisture resistance, water resistance and heat resistance are provided. Combined.

[0056]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”, and “%” means “% by weight” unless otherwise specified. The “viscosity” is “viscosity at 30 ° C.”, and an inorganic filler, a carbonyl group-containing PV
A, "Addition amount" of hydrazine compound and amine compound
Is the “addition amount of solid content”.

(Example 1)

(1) Preparation of Adhesive Composition Acrylic resin emulsion (trade name “ESDINE # 1”)
68, manufactured by Sekisui Chemical Co., Ltd.) and clay as an inorganic filler for 100 parts of resin ("ASP60")
0 ", manufactured by Tsuchiya Kaolin Co., Ltd., (40% water slurry) $ 1
25 parts, carbonyl group-containing PVA (trade name “D-Polymer”, manufactured by Unitika Ltd., (15% aqueous solution)) 55 parts, adipic dihydrazide (10% aqueous solution) as a hydrazine compound, 3 parts, isopropanolamine (10 % Aqueous solution) and 7.5 parts of acetone, and the mixture was uniformly stirred and mixed.
An adhesive composition having 0 mPa · s and a solid content of 27% was obtained.

(2) Evaluation The performance (initial adhesive strength,
Ring crush strength, water resistance, heat resistance, and storage stability) were evaluated by the following methods. The results were as shown in Table 1. In addition, evaluation is unless otherwise noted.
The test was performed under an atmosphere of 20 ° C. and 65% RH.

Initial adhesive strength (tensile shear strength) Two B-grade paper tube base papers (made by Fukuyama Paper Co., Ltd.) cut into a size of 40 mm × 100 mm and 50 mm × 100 mm were bonded with an adhesive composition, and an adhesive test piece was prepared. It was created. Then, using an initial adhesive force measuring device (manufactured by JT Toshi),
Initial adhesive strength of this adhesive test piece / tensile shear strength (kg / c
m ² )｝ was measured. The bonding conditions and measurement conditions at this time were as follows. [Adhesion conditions] Coating amount (wet): 30 g / m ² , coating speed: 0.6 m / sec, open time: 2 seconds, pressing pressure: 3 kg / cm ² , pressing time: 6 seconds, 8 seconds, 10 [Measurement conditions] Leaving time after decompression: 2 seconds, tensile speed: 100
mm / min

Ring Crush Strength In accordance with JIS P-8126 “Testing Method for Compressive Strength of Paperboard (Ring Crash Method)”, the ring crush strength in the vertical direction of the class B paper tube base paper as in the case of the above is as follows. Measured. Two sheets of B-grade paper core base paper are prepared, the adhesive composition is applied to one paper core base paper at a coating amount (wet) of 30 g / m ² , and the other paper core base paper is bonded. Pressure bonding at a pressure of 70 g / cm ² , 20 ° C-65%
After curing under RH atmosphere for 24 hours, width 12.7m
m, and cut to a length of 152.4 mm to prepare an adhesion test piece. Then, the adhesive test piece was measured at 20 ° C. for normal strength measurement.
After being cured in an atmosphere of -65% RH for 72 hours, it was set in a compression tester, compressed at a compression speed of 10 mm / min, and the ring crush strength (kgf) was measured. Further, the adhesive test piece was left in an atmosphere of 50 ° C.-95% RH for humidity resistance measurement, and after adjusting the humidity so that the water content was 12 to 13%, in the same manner as in the case of the normal strength measurement, The ring crush strength (kgf) was measured.

Water resistance (fall time) Two pieces of the same class B paper tube base paper as in the case of cutting into 25 mm × 50 mm were used as test pieces, and the adhesive composition was applied on one half of one side of one test piece, and the coated area was 25 mm. × 25 mm, coating weight (wet) 0.05g / (25mm) was coated to a ^2, bonding a half of one surface of the other specimen to the coated surface, the bonding portion 1 kg / (25 mm) ² And then cured for 24 hours in an atmosphere of 20 ° C. and 65% RH to prepare an adhesion test piece. Next, a weight of 100 g was immersed in warm water at 40 ° C. while being suspended at a 90 ° angle peeling direction at the lower end of one test piece of the adhesive test piece, and the test piece was peeled off at the bonding surface. The time (time) until falling was measured.

An adhesive test piece prepared in the same manner as in the case of
After pressurizing with a 00 ° C. iron for 30 seconds, the piece was immediately peeled off with tweezers, and the material rupture rate (area%) of the bonded portion was measured.

Storage stability (viscosity stability over time) After the adhesive composition was left under an atmosphere of 40 ° C. for one month,
The viscosity was measured and compared with the initial viscosity (the viscosity before standing) to calculate the degree of increase in viscosity (times).

Example 2 In the preparation of the adhesive composition, the addition amount of clay “ASP600” was 90 parts, the addition amount of carbonyl group-containing PVA “D-polymer” was 40 parts,
The procedure of Example 1 was repeated, except that the addition amount of adipic dihydrazide was 2.2 parts, the addition amount of isopropanolamine was 4.4 parts, and the addition amount of acetone was 5.5 parts.
An adhesive composition having a viscosity of 450 mPa · s and a solid content of 28% was obtained.

Example 3 In the preparation of the adhesive composition, the amount of the clay “ASP600” was 165 parts and the amount of the carbonyl group-containing PVA “D-polymer” was 65.
Parts, the addition amount of adipic dihydrazide was 3.6 parts, the addition amount of isopropanolamine was 7.2 parts, and the addition amount of acetone was 9 parts.
An adhesive composition having a viscosity of 430 mPa · s and a solid content of 26% was obtained.

Example 4 The procedure of Example 1 was repeated except that the amount of isopropanolamine was changed to 1.5 parts and the amount of acetone was changed to 3 parts in the preparation of the adhesive composition. s, an adhesive composition having a solid content of 27% was obtained.

Comparative Example 1 An adhesive composition having a viscosity of 450 mPa · s and a solid content of 30% was prepared in the same manner as in Example 1 except that clay “ASP600” was not added in the preparation of the adhesive composition. I got

(Comparative Example 2) A viscosity of 500 mPa · s was obtained in the same manner as in Example 1 except that the amount of the clay “ASP600” was 200 parts in the preparation of the adhesive composition.
s, an adhesive composition having a solid content of 32% was obtained.

Comparative Example 3 In the preparation of the adhesive composition, the addition amount of the carbonyl group-containing PVA “D-polymer” was 20 parts, and the addition amount of adipic dihydrazide was 1.1.
Example 1, except that the amount of isopropanolamine was 2.2 parts and the amount of acetone was 2.75 parts.
In the same manner as in the above, an adhesive composition having a viscosity of 430 mPa · s and a solid content of 27% was obtained.

Comparative Example 4 In the preparation of the adhesive composition, the addition amount of the carbonyl group-containing PVA “D-polymer” was 90 parts, and the addition amount of adipic dihydrazide was 4.9.
Parts, the amount of isopropanolamine added was 9.8 parts, and the amount of acetone was 12.25 parts, except that the viscosity was 430 mPa · s and the solid content was 27%.
Was obtained.

Comparative Example 5 In the preparation of the adhesive composition, the addition amount of adipic dihydrazide was 0.1 part, the addition amount of isopropanolamine was 0.2 part, and the addition amount of acetone was 0.25 part. Otherwise in the same manner as in Example 1, an adhesive composition having a viscosity of 380 mPa · s and a solid content of 27% was obtained.

Comparative Example 6 Example 1 was repeated except that the amount of adipate dihydrazide was changed to 6 parts, the amount of isopropanolamine was changed to 12 parts, and the amount of acetone was changed to 15 parts in the preparation of the adhesive composition. In the same manner as in the above, an adhesive composition having a viscosity of 380 mPa · s and a solid content of 28% was obtained.

Comparative Example 7 A viscosity of 420 mPa · s was obtained in the same manner as in Example 1 except that the amount of isopropanolamine was changed to 1.2 parts in the preparation of the adhesive composition.
Thus, an adhesive composition having a solid content of 28% was obtained.

Comparative Example 8 The procedure of Example 1 was repeated, except that no clay, carbonyl group-containing PVA, adipic dihydrazide, isopropanolamine and acetone were added in the preparation of the adhesive composition.
An adhesive composition having a viscosity of 100 mPa · s and a solid content of 55% was obtained.

The performances of the 11 types of adhesive compositions obtained in Examples 2 to 4 and Comparative Examples 1 to 8 were evaluated in the same manner as in Example 1. The results were as shown in Table 1.

[0077]

[Table 1]

As is clear from Table 1, the adhesive compositions of Examples 1 to 4 according to the present invention have any of initial adhesive strength, ring crush strength (normal pressure resistance and humidity pressure resistance), water resistance and heat resistance. , And storage stability was also good, showing an excellent balance of performance.

On the other hand, the adhesive composition of Comparative Example 1 containing no inorganic filler (clay) had extremely poor heat resistance and poor ring crush strength. The adhesive composition of Comparative Example 2, in which the content of the inorganic filler (clay) was more than 170 parts by weight based on 100 parts by weight of the resin component of the acrylic resin-based emulsion, was extremely poor in the initial adhesive strength.

The adhesive composition of Comparative Example 3 in which the content of the carbonyl group-containing PVA was less than 35 parts by weight based on 100 parts by weight of the resin component of the acrylic resin emulsion was as follows:
The water resistance was extremely poor, and the ring crush strength was also poor. Further, the adhesive composition of Comparative Example 4 in which the content of the carbonyl group-containing PVA was more than 70 parts by weight based on 100 parts by weight of the resin component of the acrylic resin-based emulsion had low initial adhesive strength, heat resistance and storage stability. Was also inferior.

Further, the adhesive composition of Comparative Example 5, in which the content of the hydrazine compound (adipic dihydrazide) was less than 0.2 part by weight based on 100 parts by weight of the resin component of the acrylic resin emulsion, was extremely water-resistant. It was bad.
Also, a hydrazine compound (adipic dihydrazide) based on 100 parts by weight of the resin component of the acrylic resin emulsion.
The adhesive composition of Comparative Example 6, which contained more than 5 parts by weight, had poor storage stability.

Further, the adhesive composition of Comparative Example 7 in which the content of the amine compound (isopropanolamine) was less than 50 parts by weight based on 100 parts by weight of the hydrazine compound (adipic dihydrazide) was extremely poor in storage stability. Was.

The adhesive composition of Comparative Example 8, which did not contain any of the inorganic filler (clay), carbonyl group-containing PVA, hydrazine compound (adipic dihydrazide) and amine compound (isopropanolamine), had a water resistance. The heat resistance was extremely poor, and the ring crush strength was also poor.

[0084]

As described above, the adhesive composition according to the present invention has excellent initial adhesive strength and good storage stability, so that it has good workability and excellent adhesive strength after drying. Since it exhibits various properties such as pressure resistance, moisture resistance, water resistance, heat resistance, etc., it is suitably used as an adhesive for various uses including paper tubes.

Further, since the paper tube according to the present invention is manufactured by using the above-mentioned adhesive composition, the workability at the time of forming the tube is good, and finally, the adhesive strength, pressure resistance and moisture resistance are excellent. Since it exhibits various properties such as water resistance and heat resistance, it is suitably used as a paper tube for winding various sheet-like articles.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C09J 129/04 C09J 129/04 A F-term (Reference) 3E075 AA09 BA72 BA77 DD02 3E078 CC22 4J040 DD022 DF041 DF051 HA136 HA196 HA356 HC01 HC03 HC09 HC15 JA03 KA42 LA05 LA06 LA07 LA08 MA09 MB06

Claims (2)

[Claims] 1. A resin component 1 of an acrylic resin emulsion
With respect to 00 parts by weight, 80 to 170 parts by weight of an inorganic filler,
35 to 70 parts by weight of a carbonyl group-containing polyvinyl alcohol and 0.2 to 5 parts by weight of a hydrazine compound, and 50 parts by weight or more of an amine compound with respect to 100 parts by weight of the hydrazine compound. An adhesive composition characterized by the following: 2. A paper tube, wherein a strip of paper is wound in a tubular shape, and an overlapping portion of the strip of paper wound in a tubular shape is bonded with the adhesive composition according to claim 1.