JP3065255B2 - Adhesive composition and paper tube using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive which is preferably used for bonding side edges of a cardboard wound on a metal mandrel when a cardboard is wound around a metal mandrel to manufacture a paper tube. The present invention relates to an agent composition and a paper tube manufactured using the adhesive composition.

[0002]

2. Description of the Related Art A paper tube used as a mandrel for winding a sheet-like article such as paper, foil, woven fabric or the like is usually formed by winding a cardboard spirally around a metal mandrel and adjoining adjacent side edges of the cardboard. It is manufactured by bonding the parts together with an adhesive composition. The adhesive composition used for manufacturing such a paper tube is usually made of starch, polyvinyl alcohol (PV).
A), manufactured based on polyvinyl acetate resin and the like.

[0003] Such an adhesive composition for paper tubes is disclosed, for example, in Japanese Patent Application Laid-Open No. 5-125341.
This adhesive composition is composed of an inorganic filler, PVA, and boric acid based on the solid content of the vinyl acetate resin emulsion.
Each is added at a specific ratio.

[0004]

The adhesive composition used in the manufacture of a paper tube has a pressure resistance so that the paper tube is not damaged by the pressure of a sheet-like article wound on the paper tube. It is required that the film formed by drying has a high elastic modulus and is hard. Also, when manufacturing the paper tube, the initial adhesiveness is excellent so that the cardboard wound around the metal mandrel can be held so as not to spread so that the diameter of each manufactured paper tube becomes constant. It is necessary.

[0005] In the adhesive composition disclosed in the above-mentioned publication, the dried film has a high modulus of elasticity, and the manufactured paper tube has excellent pressure resistance. In addition, the initial adhesive strength is also excellent. However, paper tubes are
Depending on the sheet-like article to be wound, further pressure resistance is required. Therefore, even for the adhesive composition used for the production of the paper tube, both the elastic modulus of the dry film and the initial adhesive strength are further increased. Improved ones are required.

The present invention is intended to solve such a problem, and an object of the present invention is to provide a dried film having a high modulus of elasticity and excellent initial adhesion and water resistance. An object of the present invention is to provide an adhesive composition which is suitably used for an adhesive. Another object of the present invention is to provide a paper tube having a predetermined uniform diameter and exhibiting excellent pressure resistance and water resistance.

[0007] The present invention, based on the solids content of the vinyl acetate resin emulsion, an inorganic filler, mosquito carboxyl group-modified polyvinyl alcohol, starch, and at least one water-soluble polymer selected from the group consisting of dextrin, By adding boric acid in a specific ratio to make the undissolved material of tetrahydrofuran (THF) in the dry film 90% by weight or more, the dry film of the obtained adhesive composition has a high elastic modulus, and It is based on the finding that the initial adhesive strength is also significantly improved.

[0008]

The adhesive composition according to the invention described in claim 1 (hereinafter referred to as "first invention") is used in an amount of 80 to 80 parts by weight based on 100 parts by weight of a solid content of a vinyl acetate resin emulsion. 170 and parts of the inorganic filler, mosquito carboxyl group-modified polyvinyl alcohol 35 to 70 parts by weight of at least one starch is selected from the group consisting of dextrin
An adhesive composition comprising at least one water-soluble polymer and 1 to 5 parts by weight of boric acid, wherein the dried film has 90% by weight or more of an undissolved substance due to tetrahydrofuran. Features.

The adhesive composition according to the second aspect of the present invention (hereinafter referred to as "second invention") is the adhesive composition according to the first aspect, wherein the vinyl acetate resin emulsion comprises Is characterized in that the extraction ratio with acetone is 45% by weight or more.

Further, the adhesive composition according to the invention of claim 3 (hereinafter referred to as "third invention") is the adhesive composition according to the first invention or the second invention, wherein the vinyl acetate resin emulsion is Characterized by being obtained by emulsion copolymerization of 0.1 to 5 parts by weight of an ethylenically unsaturated monomer with respect to 100 parts by weight of a vinyl acetate monomer.

Further, the invention according to claim 4 (hereinafter referred to as "the invention")
The "fourth invention" is defined as follows: when the adhesive composition according to any one of the first to third inventions is used to manufacture a paper tube by winding a cardboard around a mandrel, adjacent side edges of the cardboard are used. It is characterized by being used for bonding.

The invention according to claim 5 (hereinafter referred to as the "fifth invention")
The paper tube according to any one of the first to third aspects of the present invention is manufactured by bonding adjacent side edges of a cardboard wound around a mandrel with the adhesive composition according to any one of the first to third aspects. And

The vinyl acetate resin emulsion used as a main component in the adhesive composition according to the first invention is a vinyl acetate monomer alone or a mixture of a vinyl acetate monomer and a monomer copolymerizable with the vinyl acetate monomer. (Hereinafter referred to as "PVA") as a protective colloid, emulsified in water in the presence of a polymerization initiator (co).
It can be obtained by polymerizing. Here, “(co) polymerization” means “polymerization” or “copolymerization”.

The monomer copolymerizable with the vinyl acetate monomer is not particularly limited, but may be (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Ethylenically unsaturated monomers such as 2-ethylhexyl (meth) acrylate, ethylene glycol mono (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, and glycidyl (meth) acrylate; 2-hydroxyethyl (meth) ) Hydroxy group-containing monomers such as acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate, and one or more of these are suitably used. Here, “(meth) acryl” means “acryl” or “methacryl”.

The protective colloid is not particularly limited, but includes PVA, carboxyl group-modified P
Modified PVA such as VA, a copolymer of α-olefin and unsaturated carboxylic acid such as a copolymer of isobutylene and maleic anhydride, or a water-soluble product of a derivative thereof with a basic substance,
And carboxymethyl cellulose.
Species or two or more species are preferably used. Among them, PVA is more preferably used in that the initial adhesive strength of the obtained adhesive composition is improved.

Further, the polymerization initiator is not particularly limited, but may be, for example, aqueous hydrogen peroxide; a persulfate such as ammonium persulfate, potassium persulfate or sodium persulfate; a reduction of tartaric acid, formic acid, oxalic acid or the like. Agents and the like, and one or more of these are suitably used.

In the adhesive composition according to the first invention,
80-170 parts by weight, preferably 115-150 parts by weight, based on 100 parts by weight of the solid content of the vinyl acetate resin emulsion.
It is necessary that 140 parts by weight of an inorganic filler is added.

Examples of the inorganic filler include, but are not particularly limited to, clay, aluminum hydroxide, calcium carbonate, kaolin, talc and the like.
Species or two or more species are preferably used. Among them, clay is more preferably used in that the dispersibility of the inorganic filler and the film strength of the obtained adhesive composition are improved.

Solid content 1 of vinyl acetate resin emulsion
If the amount of the inorganic filler is less than 80 parts by weight relative to 00 parts by weight, the elasticity of the resulting dried film of the adhesive composition is not sufficiently improved. The initial adhesive strength of the agent composition decreases.

In the adhesive composition according to the first invention, the solid content of the vinyl acetate resin-based emulsion is 100%.
35 to 70 parts by weight, preferably 45 to 70 parts by weight,
60 parts by weight, more preferably Ca Rubo <br/> hexyl group modified PVA 50-55 parts by weight, starch, at least one water soluble polymer selected from the group consisting of dextrin (hereinafter, simply "a water-soluble polymer ") Must be added.

The carboxyl group-modified PVA includes:
For example, those obtained by reacting a carboxylic acid with PVA to introduce a carboxyl group at the end of PVA, and the like are preferably used. Examples of the carboxylic acid used for the above reaction include (meth) acrylic acid, itaconic acid, and (maleic anhydride) maleic acid, but are not particularly limited thereto.

The saponification degree of the above asked carboxyl group-modified PVA include, but are not particularly limited, but is preferably 88 mol% or more, more preferably among them 96 mol% or more. Further, the upper hear carboxyl group-modified PVA
The average degree of polymerization of is not particularly limited,
It is preferably from 2,500 to 2,500, and particularly preferably 150
More preferably, it is 0 to 2000.

Examples of the starch include, but are not particularly limited to, physically modified starch such as raw starch obtained from corn, wheat, potato, rice, tapioca, sweet potato, α-starch, etc., oxidized starch, Chemically modified starch such as esterified starch, etherified starch and the like can be mentioned, and one or more of these are preferably used.

The dextrin is not particularly restricted but includes white dextrin, yellow dextrin, British gum and the like obtained by reacting starch with heat, heat and acid or alkali, enzymes and the like. One or more kinds are suitably used.

Solid content of vinyl acetate resin emulsion 1
When the amount of the water-soluble polymer is less than 35 parts by weight per 100 parts by weight, the elasticity of the dried film of the obtained adhesive composition becomes insufficient. The adhesive strength of the agent composition decreases.

Further, in the adhesive composition according to the first invention, the solid content of the vinyl acetate resin-based emulsion may be 1%.
1 to 5 parts by weight, preferably 2 to 100 parts by weight
3.5 parts by weight of boric acid must be added.

Solid content of vinyl acetate resin emulsion 1
When the amount of the boric acid is less than 1 part by weight based on 00 parts by weight, the water resistance and initial adhesive strength of the obtained adhesive composition are not sufficiently improved. The viscosity stability of the composition over time is reduced.

Further, in the adhesive composition according to the first aspect of the present invention, it is necessary that the undissolved material of tetrahydrofuran (hereinafter referred to as "THF") in the dried film is 90% by weight or more. .

The undissolved matter in THF of the dried film is 9
If the amount is less than 0% by weight, the elastic modulus of the dried film decreases.

The undissolved matter of the above dried film by THF was 9
Although it is not particularly limited to make the content of 0% by weight or more, a vinyl acetate resin emulsion obtained by emulsion polymerization of a vinyl acetate monomer alone is used. better to use the provided that acetic acid vinyl resin emulsion obtained a monomer and a hydroxyl group-containing monomers by emulsion copolymerization is preferable.

The undissolved matter (% by weight) of the above-mentioned dried film by THF is obtained by immersing the dried film of the adhesive composition in 20 times the weight of the dried film of THF at room temperature for 48 hours. After the extraction, it is calculated by the following equation. {(Weight of dry film−dry weight of THF extract) / weight of dry film} × 100

In the adhesive composition according to the first invention,
An inorganic filler which is added to the vinyl acetate resin emulsion, mosquitoes carboxyl group-modified PVA, starch, by the action of at least one water soluble polymer selected from the group consisting of dextrin, a dry film having a high modulus of elasticity Excellent initial adhesion is obtained. Also, excellent initial adhesive strength and water resistance can be obtained by the action of boric acid added to the vinyl acetate resin emulsion. Further, since the undissolved matter of the dried film of the adhesive composition by THF is 90% by weight or more, the elastic modulus and the initial adhesive force of the dried film are further improved.

Next, the adhesive composition according to the second aspect of the present invention is the adhesive composition according to the first aspect of the present invention, wherein the extraction rate of the dried film of the vinyl acetate resin-based emulsion as the main component with acetone is 45% by weight or more. It is necessary that it is.

By setting the extraction ratio of the dried film of the vinyl acetate resin-based emulsion with acetone to 45% by weight or more, the elastic modulus and the initial adhesion of the dried film of the adhesive composition finally obtained are remarkably improved. . In other words, if the extraction ratio of the dried film with acetone is less than 45% by weight, the elasticity and initial adhesive strength of the dried film of the finally obtained adhesive composition are not sufficiently improved.

In order to make the extraction ratio of the dried film of the above-mentioned vinyl acetate resin-based emulsion with acetone at 45% by weight or more, it is necessary to use a vinyl acetate resin-based emulsion obtained by emulsion polymerization of a vinyl acetate monomer alone. better to use the provided that acetic acid vinyl resin emulsion obtained by emulsion copolymerization of ethylenically unsaturated monomers and hydroxyl group-containing monomer mentioned above and the vinyl monomer are preferred.

In the emulsion (co) polymerization of a vinyl acetate resin emulsion, the amount of the monomer at the time of the initial polymerization is set to 10 to 20% by weight of the total monomer amount, and the amount of the polymerization initiator is set to 20% by weight of the total polymerization initiator amount. % Is preferable.

The extraction rate (% by weight) of the above-mentioned dried film with acetone was determined by adding a dried film of a vinyl acetate resin-based emulsion in acetone 20 times the weight of the dried film at room temperature.
After immersion for 8 hours to extract the dissolved substance, it is calculated by the following equation. (Dry weight of acetone extract / weight of dry film) × 10
0

Next, the adhesive composition according to the third invention is the same as the adhesive composition according to the first invention or the second invention, except that the vinyl acetate resin emulsion as the main component is added to 100 parts by weight of the vinyl acetate monomer. On the other hand, it is necessary that the monomer be obtained by emulsion copolymerization of 0.1 to 5 parts by weight of the ethylenically unsaturated monomer.

The ethylenically unsaturated monomers include:
Although not particularly limited, various monomers that can be copolymerized with the vinyl acetate monomer exemplified in the description of the adhesive composition according to the first aspect of the present invention are mentioned, and one or more of them are preferably used. Used.

By emulsion-copolymerizing the ethylenically unsaturated monomer with the vinyl acetate monomer, the resulting vinyl acetate resin-based emulsion has a high grafting ratio, and the extraction rate of the dried film with acetone is 45%.
When the content is not less than 10% by weight, the modulus of elasticity and the initial adhesive strength of the dried film of the finally obtained adhesive composition are remarkably improved.

[0041] When the copolymerization amount of the ethylenically unsaturated monomer to 100 parts by weight of vinyl acetate monomer is less than 0.1 part by weight, the elastic modulus and initial dry film of the adhesive composition obtained in final adhesion If the force or the like is not sufficiently improved, and if the copolymerization amount of the ethylenically unsaturated monomer exceeds 5 parts by weight, the stability of the polymerization becomes poor and coarse particles increase.

The viscosity of the adhesive composition according to the first to third aspects of the present invention is not particularly limited. However, considering the workability of coating at the time of use, the viscosity is about 1000 centipoise (cps) or less at 30 ° C. It is preferred that

The adhesive compositions according to the first to third inventions may contain, if necessary, tackifier resins, surfactants, plasticizers, softeners and pigments within a range not to impair the achievement of the object of the present invention. One or more of various additives such as a dye, an antifoaming agent, a preservative, a fungicide, and an organic solvent may be added.

Next, in the fourth invention, when the cardboard is wound around a mandrel to produce a paper tube, the adhesive composition according to any one of the first to third inventions is applied to the side of the cardboard adjacent to the cardboard. It needs to be used to glue the edges together.

Further, the paper tube according to the fifth aspect of the present invention includes the above-described first type.
It is necessary that the adhesive composition according to any one of the inventions to the third invention be manufactured by bonding adjacent side edges of the cardboard wound around the mandrel.

The adhesive compositions according to the first to third inventions described above are suitably used not only for the above-mentioned paper tubes but also for paper packaging, woodworking, general use and the like.

[0047]

[Action] The adhesive composition according to the first invention, based on vinyl acetate resin emulsion, and the specific amount of the inorganic filler, a specific amount of Ca carboxyl group-modified PVA, starch, at least one selected from the group consisting of dextrin Due to the addition of some water-soluble polymers, the dried film has a high modulus of elasticity and exhibits excellent initial adhesion. Further, since a specific amount of boric acid is added to the vinyl acetate resin-based emulsion, excellent initial adhesive strength and excellent water resistance are exhibited. Further, in the adhesive composition, since the undissolved matter of the dried film by THF is 90% by weight or more, the elastic modulus and the initial adhesive force of the dried film are further improved.

The adhesive composition according to the second aspect of the present invention is the adhesive composition according to the first aspect, wherein the extraction ratio of the dried film of the vinyl acetate resin-based emulsion, which is the main component, with acetone is 45% by weight or more. As a result, the modulus of elasticity and the initial adhesive strength of the dried film are further improved.

Further, the adhesive composition according to the third invention comprises:
In the adhesive composition according to the first or second invention, the vinyl acetate resin emulsion as the main component is obtained by emulsifying and copolymerizing a specific amount of an ethylenically unsaturated monomer with respect to a vinyl acetate monomer. Therefore, the elastic modulus, initial adhesive strength, water resistance and the like of the dried film are remarkably improved.

Next, in the fourth invention, when the cardboard is wound around a mandrel to produce a paper tube, the adhesive composition according to any one of the first to third inventions is applied with the side edge adjacent to the cardboard. Since it is used to bond the parts together, it is possible to easily obtain a paper tube having a predetermined uniform diameter and excellent pressure resistance and water resistance with good workability.

Further, the paper tube according to the fifth invention is manufactured by bonding adjacent side edges of the cardboard wound around the mandrel with the adhesive composition according to any one of the first to third inventions. As a result, it has a predetermined uniform diameter and exhibits excellent pressure resistance and water resistance.

[0052]

I mentioned Comparative Examples and Reference Examples with the following examples for the further illustrate the present invention DETAILED DESCRIPTION OF THE INVENTION Although,
The present invention is not limited to these examples. still,
In the embodiment, numbers 1-3 and numbers 13-15 are missing numbers.
I do. “Parts” in Examples , Comparative Examples and Reference Examples means “parts by weight”, and “%” means “% by weight” unless otherwise specified. The “viscosity” is “viscosity at 30 ° C.”, and the “addition amount” of the inorganic filler, the water-soluble polymer and boric acid is “addition amount of solid content”.

(Reference Example 1)

(1) Polymerization of Vinyl Acetate Resin Emulsion In a reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel, 120 parts of water and polyvinyl alcohol (trade name “Kuraray PVA-CST”, degree of saponification of 96) were added. 11 parts by mole, average polymerization degree 1700, manufactured by Kuraray Co., Ltd. were charged and stirred at 90 ° C. for 1 hour to obtain an aqueous solution of polyvinyl alcohol (hereinafter referred to as “PVA”). Next, this PVA aqueous solution was added to 75
After cooling to 10 ° C., 10 parts of a vinyl acetate monomer and 0.1 part of a polymerization initiator (0.06 part of a hydrogen peroxide solution and tartaric acid 0.1 part) were added.
04 parts) to perform initial polymerization. Next, while adding 90 parts of vinyl acetate monomers dropwise over 3 hours,
0.4 part of a polymerization initiator (0.24 part of hydrogen peroxide solution and 0.16 part of tartaric acid) was added dropwise over 3.5 hours to complete the emulsion polymerization. Furthermore, after the end of the dropping of the vinyl acetate monomer,
Aged at 85 ° C for 1 hour, solid content 48%, viscosity 8000
A vinyl acetate resin emulsion of cps was obtained. Next, a plasticizer, an antifoaming agent, a preservative, and water were added to the obtained vinyl acetate resin emulsion to obtain a solid content of 45%.
% And a viscosity of 4000 cps to give a vinyl acetate resin emulsion (A). The acetone extraction of the dried film of the obtained vinyl acetate resin emulsion (A) was 53%.

(2) Preparation of adhesive composition 125 parts of clay (30% water slurry) as an inorganic filler, 100 parts by weight of the solid content of the vinyl acetate resin emulsion (A) obtained above, P as a conductive polymer
VA (trade name "117", manufactured by Kuraray, 15% aqueous solution)
50 parts, 2.5 parts of boric acid (3% aqueous solution) and water are added,
Stir and mix uniformly, solid content 26%, viscosity 500 cps
Was obtained. The undissolved tetrahydrofuran (THF) content of the dried film of the obtained adhesive composition was 95%.

(3) Evaluation Various properties of the adhesive composition obtained above (tensile strength of the film, elasticity of the film, initial adhesive strength, water resistance,
Viscosity stability over time) was evaluated by the following method. The results were as shown in Table 1. The evaluation was performed in an atmosphere of 20 ° C. and 65% RH unless otherwise specified.

Tensile Strength of Film and Elastic Modulus of Film The adhesive composition is applied on a polyethylene plate, and the coated layer of the adhesive composition is applied under an atmosphere of 20 ° C. and 65% RH.
After curing for days, a dried film having a thickness of 300 to 500 μm was formed, and the formed dried film was punched out with a No. 1 dumbbell to prepare a test piece. Next, the prepared test piece was set in a tensile tester, pulled at a tensile speed of 10 mm / min, and the tensile strength (kg / cm ² ) was measured. Also, the elastic modulus (kg
/ Cm ² ).

Initial adhesive strength (shear adhesive strength) Two B-grade paper tube base papers (made by Fukuyama Paper Co., Ltd.) cut into 40 mm × 100 mm and 50 mm × 100 mm were used as test pieces.
An adhesive test piece was prepared by bonding with the adhesive composition. Next, the initial adhesive strength {shear adhesive strength (kg / cm ² )} was measured using the adhesive test piece. 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 / s, open time: 0.5 seconds, pressing pressure: 3 kg / cm ² , pressing time: 6 seconds, 8 seconds , 10 seconds [Measurement conditions] Leaving time after decompression: 0.5 seconds, pulling speed:
100mm / min

Water resistance (fall time) Two pieces of the same class B paper tube base paper cut to 25 mm x 50 mm were used as test pieces, and the adhesive composition was applied to one half of one side of one test piece with an application area of 25 mm x 25 mm, coating amount (w
et) 0.05 g / (25 mm) ² , half of one surface of the other test piece was stuck alternately on the coated surface, and the stuck portion was 1 kg / (25 m
m) After pressing at a pressure of ² for 60 seconds, 20 ° C-65% R
After curing for 24 hours under an atmosphere of H, an adhesion test piece was prepared. Next, one end of one of the adhesive test pieces was attached to the lower end of the test piece.
While suspending a weight of 00 g, the test piece was immersed vertically in warm water at 40 ° C., and the time (minute) until the test piece peeled off the adhesive surface and dropped was measured.

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

(Reference Example 2) In the preparation of the adhesive composition, the amount of clay added was 90
Parts, except that the 40 parts of the addition amount and the addition amount of boric acid PVA "117" and 1.2 parts in the same manner as in Reference Example 1,
An adhesive composition having a solid content of 25.5% and a viscosity of 450 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 92%.

Reference Example 3 In the preparation of the adhesive composition, the amount of clay added was 165.
Parts, the addition amount of PVA “117” was 65 parts and the addition amount of boric acid was 4.7 parts, in the same manner as in Reference Example 1 ,
An adhesive composition having a solid content of 27% and a viscosity of 600 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 96%.

Example 4 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
A solid content of 2 was obtained in the same manner as in Reference Example 1 except that 50 parts of carboxyl group-modified PVA (trade name “KL-117”, manufactured by Kuraray Co., Ltd.) was added instead of 50 parts of VA “117”.
An adhesive composition having a viscosity of 6% and a viscosity of 550 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 96%.

Example 5 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
Instead of VA "117" 40 parts, ginseng except for adding a carboxyl group-modified PVA "KL-117" 40 parts
Solid content 25.5%, viscosity 480c in the same manner as in Reference Example 2.
PS adhesive composition was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 91%.

Example 6 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
Instead of VA "117" 65 parts, ginseng except for adding a carboxyl group-modified PVA "KL-117" 65 parts
Reference Example 3 were used to give 27% solids, viscosity 660cps
Was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 95%.

Example 7 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
A solid content of 26% and viscosity were obtained in the same manner as in Reference Example 1 except that 50 parts of starch (trade name “Petrocoat C-8”, manufactured by Nichiden Chemical Co., Ltd.) was added instead of 50 parts of VA “117”. 5
An adhesive composition of 00 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 95%.

Example 8 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
An adhesive composition having a solid content of 25.5% and a viscosity of 450 cps was obtained in the same manner as in Reference Example 2 except that 40 parts of starch “Petrocoat C-8” was added instead of 40 parts of VA “117”. Was. THF of the dried film of the obtained adhesive composition
Undissolved material was 90%.

Example 9 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
An adhesive composition having a solid content of 27% and a viscosity of 600 cps was obtained in the same manner as in Reference Example 3 except that 65 parts of starch “Petrocoat C-8” was added instead of 65 parts of VA “117”. The undissolved THF in the dried film of the obtained adhesive composition was 96%.

Example 10 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
A solid content of 2 was obtained in the same manner as in Reference Example 1 except that 50 parts of dextrin (trade name “Akadama dextrin (yellow)”, manufactured by Nissei Chemical Co., Ltd.) was added instead of 50 parts of VA “117”.
An adhesive composition having a viscosity of 6% and a viscosity of 400 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 92%.

Example 11 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
Referenced except that 40 parts of dextrin “Akatama dextrin (yellow)” was added instead of 40 parts of VA “117”
As in Example 2 , solid content 25.5%, viscosity 400 cp
s was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 90%.

Example 12 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
References except that 65 parts of dextrin “Akadama dextrin (yellow)” was added instead of 65 parts of VA “117”
In the same manner as in Example 3 , an adhesive composition having a solid content of 27% and a viscosity of 500 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 96%.

Comparative Example 1 An adhesive composition having a solid content of 25% and a viscosity of 450 cps was prepared in the same manner as in Reference Example 1 except that no clay (inorganic filler) was added in the preparation of the adhesive composition. I got The undissolved THF in the dried film of the obtained adhesive composition is 80%.
%Met.

Comparative Example 2 In the preparation of the adhesive composition, the amount of clay added was 200
Except that the parts are in the same manner as in Reference Example 1, solid content 27
%, And an adhesive composition having a viscosity of 600 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 92%.

Comparative Example 3 A solid content of 24 was prepared in the same manner as in Reference Example 1 except that the amount of the clay was 60 parts in the preparation of the adhesive composition.
%, And an adhesive composition having a viscosity of 550 cps was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 83%.

Comparative Example 4 An adhesive composition having a solid content of 25.5% and a viscosity of 450 cps was prepared in the same manner as in Reference Example 1 except that the amount of PVA “117” was changed to 30 parts in the preparation of the adhesive composition. Agent composition was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 84%.

Comparative Example 5 Adhesion with a solid content of 25.5% and a viscosity of 450 cps was performed in the same manner as in Reference Example 1 except that the amount of PVA “117” was changed to 90 parts in the preparation of the adhesive composition. Agent composition was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 94%.

(Comparative Example 6) A solid content of 25.0% was prepared in the same manner as in Reference Example 1 except that the amount of boric acid was changed to 0.5 part in the preparation of the adhesive composition.
An adhesive composition having 5% and a viscosity of 450 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 86%.

Comparative Example 7 A solid content of 25.5 was prepared in the same manner as in Reference Example 1 except that the amount of boric acid was changed to 6 parts in the preparation of the adhesive composition.
%, And an adhesive composition having a viscosity of 450 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 92%.

(Comparative Example 8) In the preparation of the adhesive composition, clay, PVA "11
Reference except that neither 7 "nor boric acid was added
In the same manner as in Example 1 , an adhesive composition having a solid content of 25% and a viscosity of 350 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 53%.

Comparative Example 9 In the polymerization of a vinyl acetate resin emulsion, 3 parts of a vinyl acetate monomer and 0.025 part of a polymerization initiator (0.015 part of hydrogen peroxide and 0.01 part of tartaric acid) were added. Reference Example except that initial polymerization was carried out, and then emulsion polymerization was carried out by dropping 97 parts of vinyl acetate monomer and 0.475 parts of polymerization initiator (0.285 parts of hydrogen peroxide solution and 0.19 parts of tartaric acid). As in Example 1 , the solid content was 45% and the viscosity was 90.
A vinyl acetate resin emulsion (B) of 00 cps was obtained. The acetone extraction of the dried film of the obtained vinyl acetate resin emulsion (B) was 38%.

In the preparation of the adhesive composition, a solid content of 26% and a viscosity of 50 were obtained in the same manner as in Reference Example 1 except that the vinyl acetate resin emulsion (B) obtained above was used.
An adhesive composition of 0 cps was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 85%.

Comparative Example 10 An adhesive composition having a solid content of 25% and a viscosity of 500 cps was obtained in the same manner as in Example 4 except that no clay was added in the preparation of the adhesive composition. The undissolved THF in the dried film of the obtained adhesive composition was 73%.

Comparative Example 11 An adhesive composition having a solid content of 25% and a viscosity of 450 cps was obtained in the same manner as in Example 7, except that clay was not added in the preparation of the adhesive composition. The undissolved THF in the dried film of the obtained adhesive composition was 71%.

Comparative Example 12 An adhesive composition having a solid content of 25% and a viscosity of 400 cps was obtained in the same manner as in Example 10 except that no clay was added in the preparation of the adhesive composition. The undissolved THF in the dried film of the obtained adhesive composition was 73%.

Examples 4 to 12, Reference Examples 2, 3, and Ratio
Various properties of the 23 types of adhesive compositions obtained in Comparative Examples 1 to 12 were evaluated in the same manner as in Reference Example 1 . The results are shown in Table 1 (Examples 4 to 12 and Reference Examples 1 to 3) and Table 2.
The results were as shown in (Comparative Examples 1 to 12).

[0086]

[Table 1]

[0087]

[Table 2]

(Reference Example 4)

(1) Polymerization of vinyl acetate resin emulsion A reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was charged with 120 parts of water and PVA “Kuraray PVA-CST” 1
One part was charged and stirred at 90 ° C. for 1 hour to obtain an aqueous solution of PVA. Next, the PVA aqueous solution was cooled to 75 ° C., and then 8.16 parts of a mixed monomer composed of 100 parts of vinyl acetate monomer and 2 parts of ethylene glycol dimethacrylate and 0.1 part of polymerization initiator (0.1% of hydrogen peroxide solution). (0.64 parts and tartaric acid 0.04 parts). Next, 93.84 parts of the above-mentioned mixed monomer was added dropwise over 3 hours, and at the same time, 0.4 part of a polymerization initiator (a hydrogen peroxide solution of 0.1 part) was added.
24 parts and tartaric acid 0.16 parts) were added dropwise over 3.5 hours to complete the emulsion copolymerization. After completion of the dropwise addition of the mixed monomer, the mixture was aged at 85 ° C. for 1 hour to obtain a vinyl acetate resin emulsion having a solid content of 48% and a viscosity of 8000 cps. Next, a plasticizer, an antifoaming agent, a preservative and water were added to the obtained vinyl acetate resin emulsion to obtain a vinyl acetate resin emulsion (C) having a solid content of 45% and a viscosity of 4000 cps. The acetone extraction of the dried film of the obtained vinyl acetate resin emulsion (C) was 53%.

(2) Preparation of Adhesive Composition 125 parts by weight of clay (30% water slurry) as an inorganic filler was added to 100 parts by weight of the solid content of the vinyl acetate resin emulsion (C) obtained above. P as a conductive polymer
50 parts of VA "117" (15% aqueous solution), 2.5 parts of boric acid (3% aqueous solution) and water are added, and the mixture is stirred and mixed uniformly.
An adhesive composition having a solid content of 26% and a viscosity of 500 cps was obtained. The undissolved tetrahydrofuran (THF) content of the dried film of the obtained adhesive composition was 95%.

(Reference Example 5) In the preparation of the adhesive composition, the added amount of the clay was 90
Parts, except that the 40 parts of the addition amount and the addition amount of boric acid PVA "117" and 1.2 parts in the same manner as in Reference Example 4,
An adhesive composition having a solid content of 25.5% and a viscosity of 450 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 92%.

(Reference Example 6) In the preparation of the adhesive composition, the amount of added clay was 165.
Parts, the addition amount of PVA “117” was 65 parts and the addition amount of boric acid was 4.7 parts, in the same manner as in Reference Example 4 ,
An adhesive composition having a solid content of 27% and a viscosity of 600 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 96%.

Example 16 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
Instead of VA "117" 50 parts, ginseng except for adding a carboxyl group-modified PVA "KL-117" 50 parts
Reference Example 4 were used to give 26% solids, viscosity 550cps
Was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 96%.

Example 17 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
Instead of VA "117" 40 parts, ginseng except for adding a carboxyl group-modified PVA "KL-117" 40 parts
Solid content 25.5%, viscosity 480c as in Example 5.
PS adhesive composition was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 93%.

Example 18 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
Instead of VA "117" 65 parts, ginseng except for adding a carboxyl group-modified PVA "KL-117" 65 parts
27% solids, viscosity 660 cps as in Example 6.
Was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 97%.

Example 19 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
An adhesive composition having a solid content of 26% and a viscosity of 500 cps was obtained in the same manner as in Reference Example 4 except that 50 parts of starch “Petrocoat C-8” was added instead of 50 parts of VA “117”. The undissolved THF in the dried film of the obtained adhesive composition was 95%.

Example 20 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
An adhesive composition having a solid content of 25.5% and a viscosity of 450 cps was obtained in the same manner as in Reference Example 5 except that 40 parts of starch “Petrocoat C-8” was added instead of 40 parts of VA “117”. Was. THF of the dried film of the obtained adhesive composition
Undissolved material was 91%.

Example 21 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
An adhesive composition having a solid content of 27% and a viscosity of 600 cps was obtained in the same manner as in Reference Example 6 except that 65 parts of starch “Petrocoat C-8” was added instead of 65 parts of VA “117”. The undissolved THF in the dried film of the obtained adhesive composition was 96%.

Example 22 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
Reference: Except that 50 parts of dextrin “Akatama dextrin (yellow)” was added instead of 50 parts of VA “117”
In the same manner as in Example 4 , an adhesive composition having a solid content of 26% and a viscosity of 400 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 96%.

Example 23 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
Referenced except that 40 parts of dextrin “Akatama dextrin (yellow)” was added instead of 40 parts of VA “117”
As in Example 5 , solid content 25.5%, viscosity 400 cp
s was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 93%.

Example 24 In the preparation of the adhesive composition, P was used as the water-soluble polymer.
References except that 65 parts of dextrin “Akadama dextrin (yellow)” was added instead of 65 parts of VA “117”
In the same manner as in Example 6 , an adhesive composition having a solid content of 27% and a viscosity of 500 cps was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 97%.

Comparative Example 13 An adhesive composition having a solid content of 25% and a viscosity of 450 cps was obtained in the same manner as in Reference Example 4 except that clay was not added in the preparation of the adhesive composition. The amount of undissolved THF in the dried film of the obtained adhesive composition was 80%.

(Comparative Example 14) In the preparation of the adhesive composition, the amount of clay added was 200
Except that the parts are in the same manner as in Reference Example 4, solid content 27
%, And an adhesive composition having a viscosity of 600 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 92%.

Comparative Example 15 A solid content of 24 was prepared in the same manner as in Reference Example 4 except that the amount of the clay was 60 parts in the preparation of the adhesive composition.
%, And an adhesive composition having a viscosity of 550 cps was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 83%.

(Comparative Example 16) Adhesion with a solid content of 25.5% and a viscosity of 450 cps was performed in the same manner as in Reference Example 4 except that the amount of PVA “117” was changed to 30 parts in the preparation of the adhesive composition. Agent composition was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 84%.

Comparative Example 17 An adhesive having a solid content of 25.5% and a viscosity of 450 cps was prepared in the same manner as in Reference Example 4 except that the amount of PVA “117” was changed to 90 parts in the preparation of the adhesive composition. Agent composition was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 94%.

(Comparative Example 18) In the preparation of the adhesive composition, the solid content was adjusted to 25.50 in the same manner as in Reference Example 4 except that the amount of boric acid was changed to 0.5 part.
An adhesive composition having 5% and a viscosity of 450 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 86%.

Comparative Example 19 A solid content of 25.5 was prepared in the same manner as in Reference Example 4 , except that the amount of boric acid was changed to 6 parts in the preparation of the adhesive composition.
%, And an adhesive composition having a viscosity of 450 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 92%.

(Comparative Example 20) In the preparation of the adhesive composition, clay, PVA "11
Reference except that neither 7 "nor boric acid was added
In the same manner as in Example 4 , an adhesive composition having a solid content of 25% and a viscosity of 350 cps was obtained. The undissolved THF in the dried film of the obtained adhesive composition was 53%.

Comparative Example 21 In polymerization of a vinyl acetate resin emulsion, 3.06 parts of a mixed monomer composed of 100 parts of vinyl acetate monomer and 2 parts of ethylene glycol dimethacrylate and 0.025 part of a polymerization initiator (hydrogen peroxide solution) (0.015 part and 0.01 part of tartaric acid) were added to carry out initial copolymerization, and then 98.94 parts of the mixed monomer and 0.475 part of polymerization initiator (0.285 parts of hydrogen peroxide solution and 0.1 part of tartaric acid). 19 parts) to obtain a vinyl acetate resin emulsion (D) having a solid content of 45% and a viscosity of 9000 cps, in the same manner as in Reference Example 4 , except that emulsion copolymerization was carried out. The acetone extraction ratio of the obtained dried film of the vinyl acetate resin emulsion (D) was 38%.

The preparation of the adhesive composition was carried out in the same manner as in Reference Example 4 , except that the vinyl acetate resin emulsion (D) obtained above was used, and the solid content was 26% and the viscosity was 50%.
An adhesive composition of 0 cps was obtained. The amount of undissolved THF in the dried film of the obtained adhesive composition was 85%.

Comparative Example 22 An adhesive composition having a solid content of 25% and a viscosity of 450 cps was obtained in the same manner as in Example 16 except that no clay was added in the preparation of the adhesive composition. The undissolved THF in the dried film of the obtained adhesive composition was 78%.

Comparative Example 23 An adhesive composition having a solid content of 25% and a viscosity of 450 cps was obtained in the same manner as in Example 19 except that no clay was added in the preparation of the adhesive composition. The undissolved THF in the dried film of the obtained adhesive composition was 72%.

Comparative Example 24 An adhesive composition having a solid content of 25% and a viscosity of 450 cps was obtained in the same manner as in Example 22 except that no clay was added in the preparation of the adhesive composition. The undissolved THF in the dried film of the obtained adhesive composition was 74%.

Examples 16 to 24, Reference Examples 4 to 6, and
Various properties of the 24 types of adhesive compositions obtained in Comparative Examples 13 to 24 were evaluated in the same manner as in Reference Example 1 . The results were as shown in Table 3 (Examples 16 to 24 and Reference Examples 4 to 6) and Table 4 (Comparative Examples 13 to 24).

[0116]

[Table 3]

[0117]

[Table 4]

[0118]

As described above, the adhesive composition according to the present invention has a high dry film elastic modulus and excellent initial adhesive strength, water resistance, storage stability and the like. It is preferably used.

Further, by using the adhesive composition according to the present invention, a paper tube having a predetermined uniform diameter and excellent in pressure resistance, water resistance, etc. can be easily obtained.

Further, the paper tube manufactured by using the adhesive composition according to the present invention has a predetermined uniform diameter, and exhibits excellent pressure resistance and water resistance, so that it can be suitably used for various applications. Can be

Claims (5)

(57) [Claims] Respect 1. A solid content of 100 parts by weight of vinyl acetate resin emulsion, an inorganic filler 80 to 170 parts by weight, Ca carboxyl group-modified polyvinyl alcohol 35 to 70 parts by weight, starch, the group consisting of dextrin An adhesive composition comprising at least one water-soluble polymer selected from the group consisting of 1 to 5 parts by weight of boric acid, and a dried film having 90% by weight or more of an undissolved substance due to tetrahydrofuran. An adhesive composition characterized in that: 2. The vinyl acetate resin emulsion according to claim 1,
2. The adhesive composition according to claim 1, wherein an extraction ratio of the dried film with acetone is 45% by weight or more. 3. The vinyl acetate resin emulsion according to claim 1,
3. The composition of claim 1, which is obtained by emulsion-copolymerizing 0.1 to 5 parts by weight of an ethylenically unsaturated monomer with respect to 100 parts by weight of a vinyl acetate monomer.
The adhesive composition as described in the above. 4. The method according to claim 1, wherein when the cardboard is wound around a mandrel to produce a paper tube, the cardboard is used for bonding adjacent side edges of the cardboard. Adhesive composition. 5. A paper tube manufactured by bonding adjacent side edges of a cardboard wound around a mandrel with the adhesive composition according to claim 1. .