JPH0885778A - Adhesive composition and paper tube produced by using the same - Google Patents

Abstract

PURPOSE: To obtain an adhesive composition based on a vinyl acetate resin emulsion, having excellent initial tack and being desirable for, e.g. a paper tube and to prepare a paper tube produced by using the same. CONSTITUTION: This composition either consists mainly of a vinyl acetate resin emulsion obtained by emulsion-copolymerizing 100 pts.wt. vinyl acetate monomer with 0.1-5 pts.wt. hydroxylated (meth)acrylate in the presence of a protective colloid comprising polyvinyl alcohol, or comprises 100 pts.wt. (in terms of solid matter) vinyl acetate resin emulsion obtained by emulsion-(co)polymerizing a vinyl acetate monomer alone or with a monomer copolymerizable therewith in the presence of a protective colloid comprising polyvinyl alcohol and 1-20 pts.wt. (in terms of solid matter) sodium dialkylsulfosuccinate. A paper tube is produced by using either of the above compositions.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an adhesive composition containing a vinyl acetate resin emulsion as a main component, which is used for paper tubes, paper packaging, woodworking, general purposes, etc., and the adhesive composition. The present invention relates to a paper tube made by using the paper tube.

[0002]

2. Description of the Related Art A paper tube is manufactured by winding a strip of paper on a metal core in a plurality of layers and adhering the polymerized portion of the strip of paper with an adhesive. The adhesive used in this case is , Based on one or more of aqueous solutions of starch, polyvinyl alcohol and the like, and vinyl acetate resin emulsions using polyvinyl alcohol as a protective colloid.

On the other hand, an adhesive for paper tubes is required to have an initial adhesive strength to withstand the restoring force of a strip of paper wound around a metal core, an adhesive strength after making a paper tube, water resistance, and pressure resistance. Particularly in recent years, the demand for initial adhesive strength is increasing more and more in order to improve productivity.

Various attempts have been made to meet the above requirements. For example, polyvinyl alcohol having a low degree of polymerization having an average degree of polymerization of about 200 to 800 is used as a protective colloid, and a surfactant and a plasticizer are used in combination. Method for producing vinyl acetate-based resin emulsion adhesive composition for improving initial adhesive strength (Japanese Patent Application Laid-Open No. 57-100107)
Or a paper containing a vinyl acetate resin emulsion having a grafting degree of 50% or more as a main component, which is obtained by emulsion polymerization of a vinyl acetate monomer in the presence of polyvinyl alcohol having a saponification degree of 78 to 98 mol% and a plasticizer. Adhesive (Japanese Patent Publication 4-14
No. 154) has been proposed.

However, in the method proposed by the former method, polyvinyl alcohol having a low degree of polymerization is used as a protective colloid and a surfactant, a plasticizer and the like are used in combination, so that a dry film of the obtained vinyl acetate resin emulsion adhesive composition is obtained. Has a problem that the cohesive force becomes weak and the adhesive force and water resistance are poor, and the method according to the latter proposal is obtained because emulsion polymerization is performed in the coexistence of polyvinyl alcohol and a plasticizer. The dry film of the vinyl acetate resin emulsion has a problem that the cohesive force becomes weak and the adhesive force and the water resistance are poor, and both of them are not practical as an adhesive for paper tubes.

[0006]

SUMMARY OF THE INVENTION In view of the above points, the present invention is an adhesive composition containing a vinyl acetate resin emulsion as a main component, which has an excellent initial adhesive force and is suitable for paper tubes and the like, and It is an object to provide a paper tube manufactured by using the adhesive composition.

[0007]

The adhesive composition according to the invention of claim 1 (hereinafter referred to as "first invention") comprises polyvinyl alcohol as a protective colloid, and contains 100 parts by weight of vinyl acetate monomer and a hydroxyl group ( A vinyl acetate resin emulsion obtained by emulsion copolymerizing 0.1 to 5 parts by weight of (meth) acrylate as a main component,
Thereby, the above object is achieved.

The adhesive composition according to the invention of claim 2 (hereinafter referred to as the "second invention") comprises polyvinyl alcohol as a protective colloid, vinyl acetate monomer alone, or vinyl acetate monomer and the vinyl acetate monomer. 1 to 20 parts by weight of dialkylsulfosuccinic acid ester soda salt is contained per 100 parts by weight of solid content of a vinyl acetate resin emulsion obtained by emulsion (co) polymerizing a copolymerizable monomer with The above-mentioned object is achieved by that.

Further, in a paper tube according to the invention of claim 3 (hereinafter referred to as "third invention"), a strip-shaped paper piece is wound in a tubular shape, and the overlapped portion of the tubular paper piece wound in the tubular shape is It is characterized by being bonded by the adhesive composition according to the first invention or the second invention.

In the vinyl acetate resin emulsion which is the main component of the adhesive composition according to the first invention, 100 parts by weight of vinyl acetate monomer and 0.1 to 5 parts by weight of hydroxyl group-containing (meth) acrylate are emulsified and copolymerized. It is necessary to have In addition, "(meth) acrylate" referred to here
Means "acrylate" or "methacrylate".

Specific examples of the above-mentioned hydroxyl group-containing (meth) acrylate are not particularly limited, but include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Acrylate and the like can be mentioned, and one kind or two or more kinds thereof are preferably used.

If the amount of the above-mentioned hydroxyl group-containing (meth) acrylate is less than 0.1 parts by weight with respect to 100 parts by weight of vinyl acetate monomer, the affinity of the resulting adhesive composition with paper or wood will not be sufficiently improved. However, if the initial adhesive strength is not excellent, and if it exceeds 5 parts by weight, the stability during emulsion copolymerization deteriorates, and a large amount of coarse particles are generated in the vinyl acetate resin emulsion, or emulsion copolymerization is performed. That becomes difficult.

In the vinyl acetate resin emulsion of the first invention, the above hydroxyl group which can be copolymerized with the vinyl acetate monomer used in the second invention to be described later, if necessary, within a range not impairing the object of the present invention. One or more monomers other than the contained (meth) acrylate may be copolymerized.

The monomer copolymerizable with the vinyl acetate monomer used in the vinyl acetate resin emulsion which is the main component of the adhesive composition according to the second invention is not particularly limited, but (meth) acrylic acid may be used. , Methyl (meth) acrylate, ethyl (meth) acrylate,
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol mono (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, glycidyl (meth) acrylate, used in the first invention. Examples thereof include a hydroxyl group-containing (meth) acrylate, and one or more of these are preferably used.

In the vinyl acetate resin emulsion which is the main component of the adhesive composition according to the first and second inventions, it is necessary that polyvinyl alcohol be used as a protective colloid during emulsion (co) polymerization. The polyvinyl alcohol referred to here includes not only ordinary polyvinyl alcohol but also so-called modified polyvinyl alcohol modified with a carboxyl group or the like. The term "emulsion (co) polymerization""used herein means" emulsion polymerization "in the case of emulsion-polymerizing only vinyl acetate monomer, or emulsion-copolymerizing a vinyl acetate monomer and a monomer copolymerizable with the vinyl acetate monomer. In this case, it means "emulsion copolymerization".

The saponification degree of the polyvinyl alcohol is not particularly limited, but is preferably 80 to 99 mol%, and more preferably 94 to 98 mol%. The degree of saponification of polyvinyl alcohol is 80
If it is less than mol%, the water resistance of the dry film of the adhesive composition obtained will be reduced, and if it exceeds 99 mol%, the stability during emulsion (co) polymerization will be poor.

The average degree of polymerization of the polyvinyl alcohol is not particularly limited, but is 1000 to 25.
00 is preferable, and 1500 to 200 is particularly preferable.
It is more preferably 0. When the average degree of polymerization of polyvinyl alcohol is less than 1000, the dry film strength of the obtained adhesive composition becomes weak, and when it exceeds 2,500, the viscosity of the obtained adhesive composition becomes too high.

The amount of the polyvinyl alcohol used is not particularly limited, but the total amount of the vinyl acetate monomer and the hydroxyl group-containing (meth) acrylate is 10
0 to 30 parts by weight, or 100 to 100 parts by weight of vinyl acetate monomer, or 0.1 to 30 parts by weight of polyvinyl alcohol based on 100 parts by weight of the total amount of the vinyl acetate monomer and the monomer copolymerizable with the vinyl acetate monomer. Is preferred, and more preferably 1 to 20 parts by weight. If the amount of polyvinyl alcohol is less than 0.1 parts by weight relative to 100 parts by weight of the above-mentioned monomer, initial polymerization is unlikely to occur, and if it exceeds 30 parts by weight, the dry film strength of the obtained adhesive composition is weak. Become.

Further, in the vinyl acetate resin emulsion according to the first and second inventions, in addition to the above-mentioned polyvinyl alcohol, an α-olefin and an unsaturated carboxylic acid may be added, if necessary, within a range that does not impair the object of the present invention. A water-soluble polymer substance such as a water-soluble product of a basic substance of the copolymer or its derivative may be used together as a protective colloid.

The emulsion (co) polymerization method of the vinyl acetate resin emulsion in the first and second inventions is not special, and the above polyvinyl alcohol is used as a protective colloid and hydrogen peroxide solution or ammonium persulfate or persulfate is used. 100 parts by weight of vinyl acetate monomer and hydroxyl group (meth) are used as a polymerization catalyst using one or more of peroxides such as persulfates such as potassium and sodium persulfate and reducing agents such as tartaric acid, formic acid and oxalic acid. Acrylate 0.1
˜5 parts by weight, or vinyl acetate monomer alone, or a vinyl acetate monomer and a monomer copolymerizable with the vinyl acetate monomer may be emulsion (co) polymerized by a conventional method.

The amount of the above-mentioned polymerization catalyst used is not particularly limited, but is 100 parts by weight of the total amount of vinyl acetate monomer and hydroxyl group-containing (meth) acrylate, or 100 parts by weight of vinyl acetate monomer, or vinyl acetate. The polymerization catalyst is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the total amount of the monomer and the monomer copolymerizable with the vinyl acetate monomer.

Next, the dialkylsulfosuccinic acid ester soda salt used in the adhesive composition according to the second invention is
It is represented by the following general formula (1). (In the formula, R ₁ and R ₂ represent an alkyl group)

Since the above-mentioned sodium dialkylsulfosuccinate ester salt has excellent surface tension lowering ability, wettability, penetrability, etc., when it is contained in the adhesive composition in a small amount, it adheres to an adherend. The wettability of the agent composition is improved, and the initial adhesive strength is remarkably improved.

In the adhesive composition according to the second invention,
Using polyvinyl alcohol as a protective colloid, vinyl acetate monomer alone or a vinyl acetate resin emulsion obtained by emulsion (co) polymerization of vinyl acetate monomer and a monomer copolymerizable with the vinyl acetate monomer is added to 100 parts by weight of solid content. On the other hand, the dialkyl sulfosuccinate soda salt has a solid content of 1 to 20 parts by weight, preferably 5 parts by weight.
It is necessary to contain 10 to 10 parts by weight.

When the content of the dialkyl sulfosuccinate ester soda salt is less than 1 part by weight based on 100 parts by weight of the vinyl acetate resin emulsion, the solid content is less than 1 part by weight.
Since the wettability of the obtained adhesive composition to an adherend is not sufficiently improved, the initial adhesive force is not sufficiently improved, and when it exceeds 20 parts by weight, the water resistance of the obtained adhesive composition is lowered.

The adhesive compositions according to the first and second aspects of the present invention include tackifier resins, surfactants, plasticizers, fillers, pigments, dyes, and deodorizers, if necessary, as long as the objects of the present invention are not impaired. Various additives such as foaming agents, preservatives and organic solvents may be contained.

Needless to say, the adhesive compositions according to the first and second inventions are used not only for paper tubes but also for paper packaging, woodworking, general use and the like.

[0028]

The adhesive composition according to the first invention is based on a vinyl acetate resin emulsion obtained by emulsion copolymerizing 100 parts by weight of vinyl acetate monomer and 0.1 to 5 parts by weight of a hydroxyl group-containing (meth) acrylate. Since the hydroxyl group-containing (meth) acrylate has a hydroxyl group in the molecule,
The resulting adhesive composition has improved affinity with paper, wood, etc., and exhibits excellent initial adhesive strength.

Since the adhesive composition according to the second aspect of the present invention contains 1 to 20 parts by weight of the dialkyl sulfosuccinic acid ester soda salt as a solid content, the solid content of the vinyl acetate resin emulsion is 100 parts by weight. , The wettability with respect to the adherend is improved, and excellent initial adhesive strength is exhibited.

Furthermore, since the paper tube according to the third aspect of the invention is manufactured by using the adhesive composition according to the first aspect or the second aspect of the invention, it has excellent workability during pipe manufacturing and high productivity.

[0031]

EXAMPLES In order to explain the present invention in more detail, examples will be given below. In the examples, "part" means "part by weight" and "%" means "% by weight".

(Example 1)

(1) Weight of vinyl acetate resin emulsion
In a reaction vessel equipped with a combined stirrer, a reflux condenser, a thermometer and a dropping funnel, 128.5 parts of water and polyvinyl alcohol (trade name "Kuraray PVA-CST", saponification degree 96 mol%, average degree of polymerization 1700, Kuraray Co., Ltd. 11 parts), and heated at 90 ° C. for 1 hour with stirring to obtain an aqueous solution of polyvinyl alcohol. Next, the aqueous solution is cooled to 70 ° C.,
To this was added 5 parts of vinyl acetate monomer, 0.1 part of 2-hydroxyethyl methacrylate and a polymerization catalyst (0.1 part of hydrogen peroxide solution and 0.1 part of tartaric acid) to carry out initial polymerization. Next, 95 parts of vinyl acetate monomer, 1.9 parts of 2-hydroxyethyl methacrylate and a polymerization catalyst (0.4 parts of hydrogen peroxide solution and 0.4 parts of tartaric acid) were added dropwise over 3 hours, and emulsion copolymerization was carried out at 70 ° C. After that, aging at 80 ° C. for 1 hour, viscosity (30 ° C.) 6000 cps, solid content 4
A 7% vinyl acetate resin emulsion was obtained.

(2) Preparation of adhesive composition

To 100 parts by weight of the solid content of the vinyl acetate resin emulsion obtained above, 15 parts of dibutyl phthalate (DBP) and water were added and mixed to obtain a viscosity (30
C) 4000 cps, solid content of 45% adhesive composition was obtained.

(3) Evaluation The performance of the vinyl acetate resin emulsion and the adhesive composition obtained above was evaluated by the following methods, and the results are shown in Table 1. In addition, unless otherwise specified, the evaluation is
It was performed in an atmosphere of 20 ° C.-65% RH.

Amount of Coarse Particles 100 g of the vinyl acetate resin emulsion adhesive composition obtained above was diluted with 400 g of water and then filtered through a 180-mesh wire net. Then, the residue remaining on the wire net was dried at 100 ° C. for 3 hours, and the weight was measured to determine the amount of coarse particles (mg / 100 g).

Initial adhesive strength (material breaking time) Two pieces of class B paper tube base paper (manufactured by Okayama Paper Co., Ltd.) cut into 20 mm × 40 mm were used as test pieces, and the adhesive composition obtained above was applied to one surface of one of the test pieces. Application area 20 mm x 30 m
m, the coating amount was 30 g / m ^2, and immediately thereafter, the other test piece was adhered to the coated surface with an adhesion area of 20 mm ×
The pieces were attached to each other so as to have a length of 30 mm, and the attached portions were pressed under a pressure of 70 g / cm ² for 5 seconds to prepare a large number of adhesion test pieces. Then, the adhesive test piece was peeled off by hand every 10 seconds after depressurization, and the shortest time (second) until the fracture area ratio of the adhesive portion of the base paper for class B paper tube reached 100% was measured.

Initial adhesive strength (shear strength) Two sheets of the same base paper for class B paper tubes cut into 25 mm × 50 mm as the above were used as test pieces, and the adhesive composition obtained above was applied to one half of one side of one test piece. Coating area 25 mm x 25 m
m, the coating amount is 0.05 g / (25 mm) ^2, and half of one surface of the other test piece is alternately laminated on this coated surface so that the adhesive area is 25 mm × 25 mm. 4 at a pressure of 1 kg / cm ²
It was crimped for 0 seconds. Immediately thereafter, it was set in a tensile tester and pulled at a pulling speed of 10 mm / min, and the shear strength (kg
/ (25 mm) ² ) was measured.

(Example 2)

In the polymerization of the vinyl acetate resin emulsion, the viscosity (30) was obtained in the same manner as in Example 1 except that the amount of 2-hydroxyethyl methacrylate was 4 parts.
A vinyl acetate resin emulsion having a solid content of 47.4% was obtained. Then, using the vinyl acetate-based resin emulsion obtained above, an adhesive composition having a viscosity (30 ° C.) of 4,200 cps and a solid content of 45% was obtained in the same manner as in Example 1.

(Comparative Example 1)

In the polymerization of the vinyl acetate resin emulsion, the amount of 2-hydroxyethyl methacrylate was adjusted to 0.
A vinyl acetate resin emulsion having a viscosity (30 ° C.) of 6000 cps and a solid content of 46.6% was obtained in the same manner as in Example 1 except that the amount was changed to 05 parts. Then, using the vinyl acetate resin emulsion obtained above, in the same manner as in Example 1, viscosity (30 ° C.) 4000 cps, solid content 45
% Adhesive composition was obtained.

Table 1 shows the results of evaluation of the performance of the vinyl acetate resin emulsion and the adhesive composition obtained in Example 1 and Comparative Example 1 by the same method as in Example 1.

(Comparative Example 2)

Emulsion copolymerization was carried out in the same manner as in Example 1 except that the amount of 2-hydroxyethyl methacrylate was changed to 7 parts by weight in the polymerization of the vinyl acetate resin emulsion. Is bad, and a large amount of coarse particles were generated in the vinyl acetate resin emulsion.
As shown in Table 1, only the amount of coarse particles was measured, and the preparation of the adhesive composition and the evaluation of the initial adhesive force (material breaking time and shear strength) were not performed.

[0047]

[Table 1]

(Example 3)

(1) Weight of vinyl acetate resin emulsion
A reaction vessel equipped with a combined stirrer, a reflux condenser, a thermometer and a dropping funnel was charged with 111 parts of water and 11 parts of polyvinyl alcohol “Kuraray PVA-CST” and stirred at 90 ° C.
It was heated for 1 hour to obtain an aqueous solution of polyvinyl alcohol. Next, this aqueous solution was cooled to 70 ° C., and 8 parts of vinyl acetate monomer and a polymerization catalyst (0.1 part of hydrogen peroxide solution and 0.1 part of tartaric acid) were added thereto to carry out initial polymerization.
Then, 92 parts of vinyl acetate monomer and a polymerization catalyst (0.4 parts of hydrogen peroxide solution and 0.4 parts of tartaric acid) were added dropwise over 3 hours to carry out emulsion polymerization at 70 ° C, followed by aging at 90 ° C for 1 hour. Viscosity (30 ° C) 12,000 cps, solid content 50
% Vinyl acetate resin emulsion was obtained.

(2) Preparation of Adhesive Composition Based on 100 parts of the solid content of the vinyl acetate resin emulsion obtained above, dialkyl sulfosuccinate ester soda salt (trade name "Neocor P", Dai-ichi Kogyo Seiyaku Co., Ltd.) 6 parts by solid content, 15 parts of DBP and water were added and mixed to obtain an adhesive composition having a viscosity (30 ° C.) of 2000 cps and a solid content of 43%.

(3) Evaluation The performance of the adhesive composition obtained above was evaluated by the following method, and the results are shown in Table 2. The evaluation was carried out in an atmosphere of 20 ° C.-65% RH unless otherwise specified.

Initial Adhesive Strength (Material Destruction Time) In the same manner as in Example 1, the shortest time until the fracture area ratio of the bonded portion of the class B paper tube base paper (made by Okayama Paper Co., Ltd.) reaches 100% ( Second) was measured.

Water resistance (falling time) Two sheets of the same base paper for class B paper tubes cut into 25 mm × 50 mm as test pieces were used as test pieces, and the adhesive composition obtained above was applied to half of one side of one test piece. Application area 25 mm x 25 m
m, the coating amount is 0.05 g / (25 mm) ² , half of one surface of the other test piece is laminated alternately on this coated surface, and the bonded portion is 1 kg / (25
mm) ^{2 After} pressure bonding for 60 seconds, 20 ℃ -65%
An adhesive test piece was prepared by curing for 24 hours in an RH atmosphere. Then, apply 1 to the lower end of one of the adhesive test pieces.
A weight of 00 g was suspended and vertically dipped in warm water of 60 ° C., and the shortest time (minute) until the test piece peeled off from the adhesive surface and dropped was measured.

(Example 4)

In the polymerization of the vinyl acetate resin emulsion, the viscosity (30) was obtained in the same manner as in Example 3 except that a mixed monomer of 98 parts of vinyl acetate monomer and 2 parts of ethylene glycol dimethacrylate was used as the monomer.
C) 2100 cps, solid content 43% of the adhesive composition was obtained.

(Comparative Example 3)

A viscosity (3) was obtained in the same manner as in Example 3 except that the dialkylsulfosuccinate ester soda salt "Neocor P" was not added in the preparation of the adhesive composition.
(0 ° C.) 2000 cps, solid content 43% adhesive composition was obtained.

(Comparative Example 4)

In the preparation of the adhesive composition, Example 3 was repeated except that the amount of the dialkyl sulfosuccinate ester soda salt "Neocor P" was 50 parts based on the solid content of 100 parts of the vinyl acetate resin emulsion. Same as above, viscosity (30 ℃) 2200cps, solid content 43%
An adhesive composition of was obtained.

(Comparative Example 5)

In the preparation of the adhesive composition, Example 4 was repeated except that the solid content of dialkylsulfosuccinate ester soda salt "Neocor P" was 50 parts with respect to 100 parts of the solid content of the vinyl acetate resin emulsion. Same as above, viscosity (30 ℃) 2300cps, solid content 43%
An adhesive composition of was obtained.

The results of evaluating the performance of the adhesive compositions obtained in Example 4 and Comparative Examples 3 to 5 by the same method as in Example 3 are shown in Table 2.

[0063]

[Table 2]

[0064]

As described above, the adhesive compositions according to the first and second inventions have excellent initial adhesive strength.
Further, the paper tube according to the third invention produced by using the above-mentioned adhesive composition has excellent workability at the time of producing the tube and high productivity.

Claims (3)

[Claims] 1. A vinyl acetate resin emulsion obtained by emulsion-copolymerizing 100 parts by weight of a vinyl acetate monomer and 0.1 to 5 parts by weight of a hydroxyl group-containing (meth) acrylate as a protective colloid. An adhesive composition comprising: 2. A solid of a vinyl acetate resin emulsion obtained by using polyvinyl alcohol as a protective colloid and emulsion-copolymerizing a vinyl acetate monomer alone or a vinyl acetate monomer and a monomer copolymerizable with the vinyl acetate monomer. An adhesive composition comprising 1 to 20 parts by weight of a solid content of a dialkylsulfosuccinic acid ester soda salt per 100 parts by weight of a component. 3. The strip-shaped paper piece is wound in a tubular shape, and the polymerized portion of the tubular paper piece wound in a tubular shape is adhered by the adhesive composition according to claim 1 or 2. Paper tube.