JPH09316420A - Water-soluble hot melt adhesive, cigarette filter using the same and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a water-soluble hot melt adhesive excellent in heat stability in a molten state. SOLUTION: This water-soluble hot melt adhesive contains a vinylpyrrolidone- vinyl acetate-based copolymer. A molar ratio of the vinylpyrrolidone to the vinyl acetate in the vinylpyrrolidone-vinyl acetate-based copolymer is (the former/the latter) of about (85/15)-(10/90). The water-soluble hot melt adhesive may contain (a) about 50-300 pts.wt. of a water-soluble or a water-dispersible tackifier (a rosin derivative, etc.), (b) about 10-120 pts.wt. of wax (wax oxide, etc.) and (c) about 40-300 pts.wt. of a water-soluble or a water-dispersible plasticizer (glycerol, etc.) per 100 pts.wt. of the vinylpyrrolidone-vinyl acetate-based copolymer. The adhesive is useful as a lap paste for cigarette filter paper.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble hot-melt adhesive useful as a wrap paste for cigarette filter wrapping paper, a tobacco filter using the water-soluble hot-melt adhesive, and a method for producing the same.

[0002]

2. Description of the Related Art Hot melt adhesives are used in various bonding fields such as paper bonding and woodworking bonding. In particular, in the field of paper adhesion, it is widely used for adhesion of packaging agents, bookbinding, bag making, bonding of cardboard boxes and the like. This hot-melt adhesive is generally composed mainly of an ethylene-vinyl acetate copolymer, an ethylene-based copolymer such as an ethylene-acrylic acid ester copolymer, a thermoplastic resin such as polyamide, polyurethane, or polyester, and a water-based adhesive. Often does not dissolve in.

On the other hand, from the viewpoint of forest protection and pollution problems, recovery and recycling of waste paper is being promoted. However, the hot-melt adhesive that adheres to waste paper generally dissolves in water,
Since it does not disperse, it is difficult to remove from the waste paper,
This is a major obstacle in collecting and recycling waste paper.

Several proposals have been made so far to solve these problems. For example, JP-A-58-
No. 10438 discloses that polyvinyl acetate having a polymerization degree of 200 or less is saponified with an alkali (saponification degree of 30 to 80 mol%).
Degree), and hot melt adhesives containing a flux such as ethylene glycol are disclosed. However, although this hot-melt adhesive is water-soluble, its heat-resistant creep property is insufficient, and the thermal stability of the adhesive itself in the molten state is low. Therefore, it is difficult to use it for hot melt adhesion for a long time.

JP-A-5-5084 discloses a water-containing gel consisting of polyvinyl alcohol (hereinafter sometimes referred to simply as PVA) having an average degree of polymerization of 30 to 3000 and a saponification degree of 60 mol% or more, and water. A hot melt adhesive obtained by adding an organic plasticizer such as glycerin to a gel is disclosed. Although this hot-melt adhesive is also water-soluble, not only the adhesive itself has low thermal stability in the hot-melt state, but also the set time, which is an indicator of initial adhesiveness, is long, which is an advantage of hot-melt adhesives. Not suitable for adhesion and not practical.

JP-A-8-92537 discloses a water-soluble hot-melt adhesive containing polyvinyl alcohol, water-soluble or water-dispersible rosin or a rosin derivative or a salt thereof, and a water-soluble or water-dispersible plasticizer. Has been done.
Although this hot melt adhesive is excellent in initial adhesiveness and thermal stability, it has a drawback that characteristics such as adhesiveness, heat creep resistance, and water solubility are easily changed depending on the degree of polymerization or saponification of polyvinyl alcohol. is there.

On the other hand, a tobacco filter composed of a fiber bundle of cellulose ester is widely used as a tobacco filter which removes harmful components in tobacco smoke and has an excellent taste. In this cigarette filter, in order to maintain the shape of the filter plug and to obtain the hardness necessary for cutting the filter tip from the filter plug,
Usually, plasticizers such as triacetin, triethylene glycol diacetate, triethylene glycol dipropionate, dibutyl phthalate, dimethoxyethyl phthalate and citric acid triethyl ester are used.

However, in the above tobacco filter, the plasticizer has a function as a binder, and the cellulose ester fibers are partially fused to each other by the plasticizer. Takes a long time to collapse, which not only spoils aesthetics but also contributes to environmental pollution.

Further, a paper-made tobacco filter made of wood pulp and processed into a crepe shape, and a tobacco filter made of a regenerated cellulose fiber bundle are also known. These filters have a slightly higher disintegration property in a natural environment and can reduce environmental pollution to some extent, as compared with a filter composed of a fiber bundle of cellulose ester. However, the taste of tobacco is inferior, the selective removal property of phenols required for a filter is extremely lower than that of cellulose ester, and the filter hardness is lower than that of cellulose ester at the same pressure loss.

On the other hand, recently, a tobacco filter which is excellent in taste and filtration performance and is excellent in disintegration in a natural environment has been investigated.

For example, JP-A-8-47385 proposes a tobacco filter containing a cellulose ester composition and manufactured from a sheet-shaped filter material having a papermaking structure and good water dispersibility. Further, JP-A-7-75542 and JP-A-6-319512 disclose a tobacco filter having excellent water dispersibility, which is produced by adhering a cellulose ester fiber bundle with a water-soluble polymer. ing. Further, Japanese Unexamined Patent Publication No.
Japanese Patent No. 999558 discloses a water dispersion produced by adhering a fiber bundle, which is a filter material, with a water-soluble polymer, or cutting a filter wound up without adhering it into short pieces, and further winding up a plurality of them at the same time with a wrapping paper. A tobacco filter having excellent properties is disclosed. Furthermore, it is manufactured by rolling up a cellulose ester fiber bundle containing anatase-type titanium oxide as a photodegradation promoter or a tobacco filter with excellent biodegradability produced by rolling up a cellulose ester fiber bundle with a small degree of substitution. Tobacco filters having excellent photodegradability have also been proposed.

Although these cigarette filters certainly improve the disintegration property of the filter material in the natural environment, in order for the filter material to exhibit sufficient disintegration property in the natural environment, the filter wrapping paper is changed from the filter material. It must be peeled and removed. However, a non-water-soluble hot melt adhesive is usually used as an adhesive for bonding the ends of the filter wrapping paper (hereinafter sometimes referred to as "wrap glue"), so that it is used in a natural environment. Peeling of the filter paper from the filter material is poor. Therefore, it is difficult to peel the filter paper from the filter material, or it takes a very long time,
The original disintegration property of the filter material in the natural environment is not fully exerted.

To solve this problem, US Pat. No. 545314
No. 4 discloses a tobacco filter using a water-sensitive hot melt composition adhesive containing a graft copolymer of polyalkylene oxide and a vinyl monomer as a main component as a wrap paste. In this cigarette filter,
The filter paper is relatively easily peeled off from the filter material by the action of water. However, with the hot-melt adhesive containing the above graft copolymer as the main component, until a proper melt viscosity (for example, about 600 to 1500 centipoise) when a tobacco filter is manufactured using a tobacco filter winding machine is obtained. When heated, the vinyl monomer portion of the graft copolymer may be thermally decomposed, and there is a problem in thermal stability when it is heated and melted for a long time.

Thus, although a water-soluble hot-melt adhesive has been proposed as a wrap paste for adhering a cigarette filter wrapping paper, it has a low thermal stability when melted, so that it is continuously wrapped for a long time. Is difficult to bond. Also, since the set time is long, the wrapping paper cannot be bonded at high speed.

[0015]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a water-soluble hot melt adhesive having excellent heat stability in a molten state.

Another object of the present invention is to provide a water-soluble hot melt adhesive having excellent high speed adhesiveness.

Still another object of the present invention is to provide a water-soluble hot melt adhesive having excellent heat stability in a molten state and high heat creep resistance.

Another object of the present invention is to provide a tobacco filter which is excellent in water-releasing property of a filter wrapping paper in a natural environment and which can be continuously produced stably for a long time, and a method for producing the same.

[0019]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a water-soluble hot-melt adhesive containing a copolymer of vinylpyrrolidone and vinyl acetate is remarkably excellent in thermal stability. Excellent, and when the water-soluble hot-melt adhesive is used as a wrap paste, the filter paper for cigarettes can be easily peeled off by the action of water in a natural environment, and the filter paper can be pasted stably for a long period of time. Then, they have completed the present invention.

That is, the present invention relates to vinylpyrrolidone-
Provided is a water-soluble hot melt adhesive containing a vinyl acetate copolymer. The ratio of vinylpyrrolidone and vinyl acetate in the vinylpyrrolidone-vinyl acetate copolymer is
The former / latter = 85/15 to 10/90 (molar ratio), and the vinylpyrrolidone-vinyl acetate copolymer has a viscosity average molecular weight of 3000 to 300,000. The above water-soluble hot-melt adhesive further comprises (a) a water-soluble or water-dispersible tackifier (for example, a rosin derivative), and (b) a wax (for example, a water-soluble or water-dispersible wax such as an oxidized wax). Wax) and (c) at least one selected from water-soluble or water-dispersible plasticizers.

The present invention is also a cigarette filter comprising a filter material and a wrapping paper for winding the filter material to form a rod shape, wherein at least the wrapping paper has an adhesive applied thereto. The adhesive is claim 1.
Provided is a cigarette filter which is the water-soluble hot melt adhesive described.

The present invention further relates to a method for producing a tobacco filter, which comprises winding a filter material with a wrapping paper and applying an adhesive agent to at least the wrapping paper to form a rod-shaped filter.
Provided is a method for manufacturing a tobacco filter using the above water-soluble hot melt adhesive as the adhesive. In this manufacturing method, a sheet-shaped filter material is wound with a wrapping paper at a winding speed of, for example, about 200 to 1200 m / min.
You may wind up in a rod shape and shape.

[0023]

As the vinylpyrrolidone-vinyl acetate copolymer, various copolymers obtained from a monomer mixture containing vinylpyrrolidone and vinyl acetate as monomers can be used. The ratio of vinylpyrrolidone and vinyl acetate in the copolymer can be appropriately selected within a range that does not impair water solubility and adhesiveness, but usually the former / latter (molar ratio) = 85/15 to 10/90, preferably 80. / 20
~ 15/85, more preferably 75 / 25-18 / 8
About 2. If the proportion of vinylpyrrolidone in the copolymer is too large, the heat-melting property tends to decrease, and conversely, if the proportion of vinyl acetate is too large, the water solubility tends to decrease.

The vinylpyrrolidone-vinyl acetate copolymer may contain a monomer unit other than vinylpyrrolidone and vinyl acetate as long as the properties as a water-soluble adhesive are not impaired. As such a monomer, ethylene,
Olefinic monomers such as propylene and 1-butene;
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Isopropyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth ) Acrylonitrile, (meth) acrylamide, N-methylol acrylamide, diacetone acrylamide, and other acrylic monomers; styrene, vinyltoluene, and other styrene monomers; vinyl chloride; and other vinyl monomers.

In the vinylpyrrolidone-vinyl acetate copolymer, the ester moiety may be partially saponified to the extent that thermal stability is not impaired. The degree of saponification is, for example, 80 mol% or less (0 to 80 mol%), preferably 40 mol%.
Mol% or less (0 to 40 mol%), more preferably 20
It is not more than mol% (0 to 20 mol%), particularly not more than 10 mol% (0 to 10 mol%). In many cases, a substantially unsaponified copolymer is used as the vinylpyrrolidone-vinyl acetate copolymer.

The proportion of both components of vinylpyrrolidone and vinyl acetate in the monomers constituting the vinylpyrrolidone-vinyl acetate copolymer is, for example, 50% by weight or more (50 to 50% by weight).
100% by weight), preferably 70% by weight or more (70 to 1)
00% by weight), more preferably 90% by weight or more (90% by weight)
In most cases, it is 95% by weight or more (for example, substantially 100% by weight).

The viscosity average molecular weight of the vinylpyrrolidone-vinyl acetate copolymer can be in a wide range of values, for example, 3000 to 300,000, preferably 5000 to 200.
000, and more preferably about 8000 to 140000. If the viscosity average molecular weight is too small, the adhesiveness tends to decrease, and conversely, if it is too large, the heat melting property tends to deteriorate.

The water-soluble hot-melt adhesive of the present invention comprises, in addition to the vinylpyrrolidone-vinyl acetate copolymer,
It may contain at least one component selected from (a) water-soluble or water-dispersible tackifier, (b) wax, and (c) water-soluble or water-dispersible plasticizer.

It is generally known that a hot-melt adhesive is admixed with a tackifier such as petroleum resin, styrene resin, terpene resin, phenol resin, coumarone-indene resin, rosin and rosin derivative. There is. However, even if such a tackifier is mixed with a water-soluble resin, not only does the water-solubility not develop, but since the compatibility between the tackifier and the water-soluble resin is small, the adhesive strength is not improved and the melt The thermal stability of the adhesive itself in the state is also not improved.

On the other hand, a vinylpyrrolidone-vinyl acetate copolymer, (a) a water-soluble or water-dispersible tackifier, (b) a wax and (c) a water-soluble or water-dispersible plasticizer are used. When combined with at least one selected,
A high adhesive force can be obtained, and the thermal stability of the adhesive itself in a molten state can be further improved. Further, the moist-heat creep resistance is improved, and peeling under high temperature and high humidity can be suppressed.

The water-soluble or water-dispersible tackifier (a) is not particularly limited as long as it is water-soluble or water-dispersible and can impart tackiness. Examples include dispersible rosin and rosin derivatives (hereinafter sometimes simply referred to as “rosins”). You may use such a tackifier individually or in combination of 2 or more types. The rosin or rosin derivative is remarkably improved in water solubility or water dispersibility by forming a salt. The rosins are excellent in safety and therefore suitable as a component of wrap paste.

Examples of the rosin include gum rosin, wood rosin, tall oil rosin, disproportionated rosin, hydrogenated rosin, polymerized rosin and the like (hereinafter, these may be simply referred to as rosin), and derived from these rosins. Rosin derivatives are included. The rosin derivative is a compound in which a carboxyl group remains or is introduced, for example, an ester of rosin and polyhydric alcohol (rosin ester), a reaction product of rosin and polybasic acid (for example, maleic anhydride) (rosin- Rosin-modified maleic acid resin composed of maleic anhydride adduct, etc., ester of rosin-maleic anhydride adduct and polyhydric alcohol, produced by reacting rosin and maleic anhydride in the presence of polyhydric alcohol Ester (ester type rosin-modified maleic acid resin)
Etc. are included.

Examples of the polyhydric alcohol include diols (alkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol and hexanediol; diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol). Such as polyoxyalkylene glycol); glycerin, pentaristhitol, dipentaerythritol and the like. These polyhydric alcohols can be used alone or in combination of two or more. In addition, you may use together monohydric alcohol for adjustment of the acid value of rosins.

Of these rosins, rosin derivatives,
In particular, a rosin-modified maleic anhydride resin and an ester-type rosin-modified maleic acid resin which is a reaction product of rosin, maleic anhydride and a polyhydric alcohol are often used.

The rosin may be hydrophilic, that is, water-soluble or water-dispersible (preferably water-soluble), and its acid value is, for example, 30 to 400 (mgKOH / g), preferably 40 to 370 ( mgKOH / g), more preferably about 50 to 350 (mgKOH / g), and an acid value of 1
00-340 (mgKOH / g) (for example, 100-3
In most cases, about 30 (mgKOH / g)) rosins are used. If the acid value is less than 30 (mgKOH / g), the water solubility of the hot melt adhesive tends to decrease, and the acid value is 400 (m
If it exceeds gKOH / g), the thermal stability of the hot melt adhesive tends to be lowered. The acid value of rosin is 130-18.
Since it is about 3 (mgKOH / g), rosin may be used alone.

The softening point of the rosins can be selected within a range that does not impair the adhesiveness, the miscibility with the vinylpyrrolidone-vinyl acetate copolymer, and the like, and is, for example, 80 to 200 ° C, preferably 100 to 180 ° C. More preferably 100 to 170
C., and rosins having a softening point of 100 to 140.degree. C. are often used. When the softening point is less than 80 ° C, the high-speed adhesiveness and the heat-resistant creep property are likely to deteriorate, and when it exceeds 200 ° C, sufficient adhesive strength may not be obtained. The softening point of rosin is usually about 60 to 80 ° C, and the softening point of polymerized rosin is about 90 to 100 ° C.

The weight average molecular weight of the rosins is, for example, about 500 to 10,000 in order to increase the heat-resistant creep resistance and shorten the set time which is an index of the initial adhesiveness.
It is preferably about 700 to 5,000, and often has a weight average molecular weight of about 1,000 to 3,000. If rosin having a small molecular weight is used, the heat-resistant creep property is lowered, and the set time may be prolonged, and if the molecular weight is too large, compatibility with vinylpyrrolidone-vinyl acetate copolymer and cold-adhesion resistance are reduced. There are cases.

Bases for forming salts of rosins include
Various organic or inorganic bases can be used. Examples of the organic base include dialkylamines such as dimethylamine and diethylamine; trialkylamines such as trimethylamine and triethylamine; alkanolamines such as dimethylaminoethanol, diethanolamine and triethanolamine; heterocyclic compounds such as morpholine, pyridine and piperidine. Includes amines and the like. Examples of the inorganic base include ammonia; alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; alkali metal carbonates such as sodium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate. The use of salts of rosins can increase the water solubility of the hot melt adhesive.

The amount of the water-soluble or water-dispersible tackifier used can be selected according to the kind of the vinylpyrrolidone-vinyl acetate copolymer, for example, 50 to 100 parts by weight of the copolymer. 300 parts by weight, preferably 60-2
50 parts by weight, more preferably about 80 to 220 parts by weight, and often about 100 to 200 parts by weight.
If the amount of the tackifier used is less than 50 parts by weight, the high-speed adhesiveness and the heat-resistant creep property tend to decrease, and if it exceeds 300 parts by weight, the water solubility may decrease.

(B) As the wax, natural wax,
Either synthetic wax or compounded wax may be used, and they may be used alone or in combination of two or more kinds.
Examples of natural waxes include plant waxes such as candelilla wax, carnauba wax, rice wax, wax, jojoba oil; animal waxes such as beeswax, lanolin and whale wax; montan wax, ozokerite, ceresin and the like. Mineral-based or coal-based wax and the like can be mentioned. Synthetic waxes include synthetic hydrocarbons such as Fischer-Tropsch wax and polyethylene wax;
Montan wax derivative, paraffin wax derivative,
Modified waxes such as microcrystalline wax derivatives; hydrogenated waxes such as hydrogenated castor oil and hydrogenated castor oil derivatives; other synthetic waxes such as higher fatty acids or their esters, amides, phthalic anhydride imides, chlorinated hydrocarbons, etc. . Examples of compounded waxes include natural waxes such as petroleum wax and synthetic waxes and synthetic resins.

Preferred waxes include water soluble or water dispersible waxes. The water-soluble or water-dispersible wax includes various waxes having a hydrophilic group such as a hydroxyl group and a carboxyl group. When a vinylpyrrolidone-vinyl acetate copolymer is combined with a water-soluble or water-dispersible wax, the adhesive strength and thermal stability can be remarkably improved while maintaining high water solubility.

As the water-soluble or water-dispersible wax, for example, petroleum wax (paraffin wax, microcrystalline wax etc.), coal wax (Montan wax etc.), synthetic hydrocarbon wax (polyethylene wax, Fischer-Tropsch wax etc.) An oxidized wax obtained by oxidizing a wax composed of an aliphatic hydrocarbon such as; a wax composed of an acid such as a higher hydroxy acid or a salt thereof and / or a higher alcohol obtained by saponifying an oil-based wax such as hydrogenated castor oil; Examples include natural waxes containing higher fatty acids or higher alcohols (eg, wool wax, beeswax, etc.). Examples of the acid salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt, calcium salt and barium salt; transition metal salts such as zinc salt.

Water-soluble or water-dispersible waxes include those having only one hydrophilic group (for example, hydroxyl group, carboxyl group, etc.) in the molecule, and those having a plurality of identical or different hydrophilic groups. included. The carbon number of the water-soluble or water-dispersible wax is usually 16 to 50, preferably about 18 to 36. The oxidized wax obtained by oxidizing the synthetic hydrocarbon wax often has more than 50 carbon atoms. For example, the carbon number of oxidized wax obtained by oxidizing polyethylene wax is about 50 to 900,
The viscosity average molecular weight is about 800 to 12,000. The carbon number of the oxidized wax obtained by oxidizing Fischer-Tropsch wax is about 33 to 120.

Among the water-soluble or water-dispersible waxes, oxidized waxes are preferable. When a wax composed of an aliphatic hydrocarbon is oxidized, a carboxyl group, a hydroxyl group, a carbonyl group, etc. are produced. for that reason,
The oxidized wax is usually a mixture containing higher fatty acids or salts or esters thereof corresponding to the above-mentioned aliphatic hydrocarbons, higher alcohols, higher ketones, and, in some cases, unreacted aliphatic hydrocarbons. Examples of the higher fatty acid salt include the salts exemplified above. The total content of the fatty acid component or its salt and the alcohol component in the oxidized wax is, for example, about 30 to 100% by weight, preferably about 50 to 100% by weight (for example, 60 to 95% by weight). The oxidized wax containing higher alcohol as a constituent is known as an alcohol wax. Preferable oxidized waxes include oxidized waxes obtained by oxidizing waxes composed of linear saturated aliphatic hydrocarbons such as paraffin wax.

The melting point of the wax is, for example, 50 to 120.
C, preferably 55 to 110 C, more preferably 60.
˜105 ° C., often 60˜100 ° C. If the melting point of the wax is less than 50 ° C, it may be softened by the heat of cigarette smoke, and if it exceeds 120 ° C, the cold resistance is likely to decrease.

The amount of wax used is vinylpyrrolidone-
It can be appropriately selected depending on the type of the vinyl acetate copolymer, and is, for example, 10 to 120 parts by weight, preferably 15 to 100 parts by weight with respect to 100 parts by weight of the vinylpyrrolidone-vinyl acetate copolymer.
100 parts by weight, more preferably about 20 to 80 parts by weight, 25 to 70 parts by weight (for example, 30 to 65 parts by weight)
Often used to some extent. The amount of the wax used is 10
If it is less than 100 parts by weight, the high-speed adhesiveness, heat creep resistance and thermal stability cannot be improved so much, and if it exceeds 120 parts by weight, the water solubility of the hot melt adhesive may be impaired. Wax such as oxidized wax is also excellent in safety.

The water-soluble or water-dispersible (hydrophilic) plasticizer (c) may be any one that can impart plasticity to the vinylpyrrolidone-vinyl acetate copolymer, and examples thereof include ethylene glycol and propylene glycol. 1,3-butanediol, alkylene glycol such as tetramethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polyoxyalkylene glycol such as ethylene oxide-propylene oxide copolymer, glycerin, triglyceride Methylol propane, trimethylol ethane, pentalithritol,
Polyhydric alcohols such as dipentaerythritol and sorbitol and their derivatives (for example, cellosolves such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, carbitols, adducts of the polyhydric alcohols and alkylene oxides (ethylene oxide, etc.) Etc.); esters of polyhydric alcohol and boric acid (for example, boric acid ethylene glycol ester, etc.), ethylene urea, urea and the like. These plasticizers may be used either individually or in combination of two or more.

When a hydrophilic plasticizer, particularly a water-soluble plasticizer, is used, the hot melt adhesive property of the hot melt adhesive is improved, and the adhesion failure due to the volume shrinkage of the hot melt adhesive after adhesion can be suppressed and the flexibility is improved. There is an advantage that can be given. Among these plasticizers, water-soluble polyhydric alcohols, for example, polyhydric alcohols having two or more hydroxyl groups, particularly polyhydric alcohols having polyoxyethylene units and glycerin are preferable. By using such a plasticizer, particularly glycerin, the heat resistance and flexibility of the hot melt adhesive can be improved.

The amount of the plasticizer used can be selected within a range that does not impair the adhesiveness, heat resistance, etc., and is, for example, from 40 to 100 parts by weight of the vinylpyrrolidone-vinyl acetate copolymer.
300 parts by weight, preferably 50 to 250 parts by weight, more preferably about 70 to 220 parts by weight, 80 to 20 parts by weight
It is often about 0 parts by weight (for example, 70 to 160 parts by weight). When the amount of the plasticizer used is less than 40 parts by weight, the hot-melt adhesive has insufficient heat-melting property, which tends to cause defective adhesion and also tends to reduce water solubility. On the other hand, if it exceeds 300 parts by weight, the heat-resistant creep resistance and the adhesiveness are likely to deteriorate.

(A) Water-soluble or water-dispersible tackifier, (b) Water-soluble or water-dispersible wax, and (c)
Each of the water-soluble or water-dispersible plasticizers may be contained in the water-soluble hot melt adhesive alone, but (a) to
It is preferable to use two or more of (c) together. In particular, the combined use of the three types of (a) to (c) markedly improves the adhesiveness and the thermal stability of the adhesive itself in the molten state.

The water-soluble hot melt adhesive of the present invention may contain various antioxidants (stabilizers) in order to further improve stability, particularly thermal stability. For the details of these stabilizers, see "Practical Handbook of Additives for Plastics and Rubber", published by Chemical Industry Co., Ltd., 1970, No. 14
Reference can be made to pages 7 to 304 and pages 1041 to 1054.

Examples of the stabilizer include stabilizers generally used in thermoplastic resins, such as 2,6-di-t-butyl-p-cresol and 2,2'-methylenebis (4-methyl-6). -T-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol),
Stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane , Triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene,
1,1,3-tris (2-methyl-4-hydroxy-5)
-T-butylphenol) butane and other phenolic antioxidants; 4,4'-thiobis (3-methyl-6-t-)
Butyl ether), 2,2′-thiobis (4-methyl-6-t-butylphenol) and other thioether antioxidants; phenyl-α-naphthylamine, phenyl-
β-naphthylamine, N, N′-di-2-phenyl-p
-Phenylenediamine, N, N'-di-2-naphthyl-
Amine-based antioxidants such as p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine; dimyristylthiodipropionate,
Sulfur-based antioxidants such as dilauryl thiodipropionate and distearyl thiodipropionate; triisodecyl phosphite, triphenyl phosphite, 2,2
-Phosphorus antioxidants such as methylenebis (4,6-di-t-butylphenyl) octyl phosphite; 2,5-
Hydroquinone antioxidants such as di-t-butylhydroquinone and 2,5-di-t-amylhydroquinone; Quinoline antioxidants such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline Other antioxidants such as mercaptohenzoimidazole are included. These stabilizers can be used alone or in combination of two or more kinds. When two or more stabilizers are used in combination, the thermal stability of the hot melt adhesive can be improved. Preferred stabilizers include phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, and at least two of these (eg, phenolic antioxidants and phosphorus antioxidants, phenolic antioxidants, It is preferable to use an antioxidant, a phosphorus-based antioxidant and a thioether-based antioxidant together.
The ratio of the phenol-based antioxidant, the phosphorus-based antioxidant, and the thioether-based antioxidant is, for example, 100 parts by weight of the phenol-based antioxidant and 0 to 2 of the phosphorus-based antioxidant.
000 parts by weight (preferably 10 to 1000 parts by weight,
More preferably 30 to 300 parts by weight), thioether antioxidant about 0 to 1000 parts by weight (preferably 0 to 300 parts by weight).
500 parts by weight, more preferably 30 to 300 parts by weight)
It is.

The amount of the stabilizer to be used can be selected within a range that does not adversely affect the adhesiveness, for example, 0 to 8 parts by weight, preferably 0.1 to 7 parts by weight, per 100 parts by weight of the water-soluble hot melt adhesive. Parts, more preferably about 0.2 to 6 parts by weight (for example, 0.3 to 5 parts by weight). If the amount of the stabilizer added exceeds 8 parts by weight per 100 parts by weight of the water-soluble hot melt adhesive, the heat creep resistance tends to be impaired, and
It tends to be economically expensive.

Further, the water-soluble hot melt adhesive may contain other components such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, etc. within a range that does not impair adhesiveness, heat stability and the like. Polymers for water-insoluble or water-soluble hot melt adhesives such as polyamide resins and polyester resins, tackifiers (for example, petroleum resins,
Terpene resin, rosin ester and other rosin derivatives),
A deterioration inhibitor such as an ultraviolet absorber, a lubricant, a water-insoluble wax, a filler, a coloring agent (pigment or dye), and a fragrance may be added.

The melt viscosity of the water-soluble hot melt adhesive is
Depending on the type of adherend, it can be selected within a range that does not impair adhesiveness and adhesive workability. For example, at 180 ° C., 100
-1000 centipoise, preferably 150-800 centipoise, more preferably 200-600 centipoise, and more often 300-500 centipoise. If the melt viscosity at 180 ° C. is less than 100 centipoise, adhesion failure may occur, or, for example, when applied to a filter wrapping paper, the amount of bleeding on the back surface of the filter wrapping paper may increase, resulting in contamination of the winding machine and eventually a cigarette filter. The workability of winding up may deteriorate. Further, when the melt viscosity at 180 ° C. exceeds 1000 centipoise, for example, a suitable melt viscosity range (for example, 600 to 1) for operating a cigarette filter hoist or the like.
The heating temperature range to reach (500 centipoise) is narrowed, and it becomes necessary to operate at a high temperature. Therefore, high thermal stability may not be obtained. When the melt viscosity at 180 ° C. is set within the above range, the melt viscosity of the hot melt adhesive is set to an appropriate melt viscosity range for operating the cigarette filter hoist at a relatively low temperature of, for example, 150 ° C. or lower. Can be adjusted.

The water-soluble hot melt adhesive can be prepared by a conventional method. For example, the vinylpyrrolidone-vinyl acetate copolymer may be added, if necessary, to (a) a water-soluble or water-dispersible tackifier, (b) a water-soluble or water-dispersible wax, and (c) a water-soluble wax. Alternatively, a hot-melt adhesive can be obtained by heating and melting the mixture with a water-dispersible plasticizer, a stabilizer (antioxidant) and an additive, and uniformly mixing the mixture, followed by cooling. The heating and melting temperature of the adhesive composition including the above components can be selected according to the type and composition ratio of each component, and for example, the melting temperature to 200 ° C, preferably 100 to 180 ° C, more preferably 130 to 170.
The temperature can be selected from the range of about 0 ° C, and the adhesive composition is often heated and melted at about 130 to 180 ° C. If the heating and melting temperature exceeds 200 ° C., decomposition may start at the constituent site of the vinylpyrrolidone-vinyl acetate-based copolymer corresponding to vinyl acetate. The cooling temperature may be the melting temperature of the adhesive composition or lower, and is usually room temperature or lower from the viewpoint of workability.

The form of the hot melt adhesive is not particularly limited, and may be various shapes such as powder particles, pellets, films, tapes, strings, and rods.

The hot-melt adhesive is applied to an adherend by a conventional method, for example, by hot-melting the hot-melt adhesive in the form described above and using a hot-melt adhesive machine equipped with a nozzle or roller type coater. The adherend can be adhered by coating and cooling. Alternatively, a hot melt adhesive in the form of powder, a film, a tape, a string, or the like may be interposed between the adherends and bonded by heat pressing.

Since the water-soluble hot melt adhesive of the present invention contains a specific resin called vinylpyrrolidone-vinyl acetate copolymer, it is excellent in initial adhesiveness and heat creep resistance, and has a remarkable thermal stability in a molten state. high. For example,
Even when the water-soluble hot melt adhesive of the present invention is melted at a high temperature of about 180 ° C. for a long period of time, it hardly discolors, and phase separation, carbonization, and “skinning” are extremely unlikely to occur. Therefore, it does not impair the aesthetics of the adhesive surface or adherend, and even when using a hot melt adhesive machine, it can be operated stably and continuously for a long time without blocking the piping, greatly improving the adhesive workability. it can. Moreover, since the set time is short, the high-speed adhesiveness is excellent, and the adherend can be adhered in a short time.
Furthermore, since it is excellent in heat-resistant creep resistance, high adhesive strength can be maintained even when a heavy object or a container containing a heavy object is adhered. Therefore, the water-soluble hot-melt adhesive of the present invention is useful for adhering various adherends such as papers, textiles, plastics, metals, ceramics including ceramics, concrete, cement products, glass and wood. In particular, it is suitable as an adhesive for high-speed adhesion and an adhesive when the bonding step (work) is continuously performed for a long time.

The water-soluble hot-melt adhesive of the present invention is excellent in water-solubility, so that it is desired to bond paper that is desired to be collected and recycled as waste paper (bag making, bookbinding, pasting of cardboard boxes, etc.). It is also extremely useful for adhering adherends (cigarette filter wrapping paper, cigarette wrapping paper, etc.) that require water-peelability in a natural environment. That is, since it is highly water-soluble,
The adhesive attached to the waste paper can be easily dissolved or dispersed in water, and the waste paper can be efficiently collected and recycled. Further, the adhesive attached to the filter wrapping paper or the like is easily dissolved or dispersed by the action of water such as rainwater in a natural environment, and the filter wrapping paper or the like is easily detached from the filter or the like. The disintegrating property possessed by the natural environment can be effectively exhibited, and environmental pollution can be reduced.

In the tobacco filter of the present invention, the filter material is not particularly limited, and is a material that is commonly used as a tobacco filter material and has a disintegrating property in a natural environment, for example, water dispersibility, photodegradability or raw material. A degradable material can be used.

Materials constituting the filter material include, for example, cellulose ester fibers (fibers such as cellulose acetate, cellulose propionate and cellulose butyrate); natural cellulose fibers (wood pulp, seed hair fibers, gin skin fibers, leaf fibers). Etc.) and regenerated cellulose fiber (viscose rayon, copper ammonia rayon, etc.)
Cellulose fibers such as; and synthetic fibers such as polypropylene fibers. These may be used alone or in combination of two or more. Preferred materials constituting the filter material include cellulose ester fibers such as cellulose acetate fibers, natural cellulose fibers such as wood pulp, synthetic fibers such as polypropylene fibers, and mixed fibers of cellulose ester fibers and natural cellulose fibers (for example, cellulose acetate. Mixed fibers of fibers and wood pulp) and the like.

The shape of the filter material is not particularly limited, but may be fiber, fiber bundle (eg, cellulose ester fiber bundle, regenerated cellulose fiber bundle, polypropylene fiber bundle, etc.) or sheet (eg, wood pulp, or wood pulp and cellulose ester). It is often used in the form of a sheet having a papermaking structure in which other fibers such as fibers are produced. Sheet-shaped material, through the filter plug,
In order to allow the smoke to pass smoothly and uniformly while suppressing the channeling, it is preferable that it is creped or embossed.

Preferred filter materials having excellent disintegration properties in a natural environment include cellulose ester fiber bundles which are not adhered by a plasticizer; cellulose ester fiber bundles which are adhered by using a water-soluble polymer or a biodegradable polymer. Cellulose ester fiber bundles with a low degree of substitution; Cellulose ester fiber bundles containing photodegradation promoters and biodegradation promoters;
A sheet-like material or the like obtained by making wood pulp or other fibers such as wood pulp and cellulose ester fiber into paper and creping or embossing as necessary is included. The tobacco filter of the present invention is an additive for improving tobacco taste by selective removal of gas phase components, for example, activated carbon,
It may contain an adsorbent such as zeolite. The adsorbent may be fibrous, but is often used in the form of powder. Further, the adsorbent may be a granulated product granulated using a binder, such as granulated activated carbon.

The average particle size of the particulate adsorbent can be selected from a wide range that does not impair the taste and the integrity of the filter constituent material, and is, for example, 0.1 to 1000 μm, preferably 5 to 500 μm, more preferably 10. It is about 300 μm. The average particle size of the powdery adsorbent is, for example, 1
It is often 6 to 200 mesh, preferably 20 to 150 mesh, and more preferably 28 to 60 mesh.

The specific surface area of the adsorbent can be selected within a range that does not impair the efficiency of removing harmful components such as phenols, and is, for example, 200 to 4000 m ² / g, preferably 300 to 3.
000 m ² / g, more preferably 500-2500 m
² / g, and often 1000 to 2000 m ² / g.

The amount of the adsorbent added to the filter material can be appropriately selected in consideration of the efficiency of removing harmful components and the taste, and for example, 1 to 200 parts by weight, preferably 10 parts by weight with respect to 100 parts by weight of the filter material. ~ 150 parts by weight,
More preferably 25 to 120 parts by weight (for example, 30 to
100 parts by weight), and often about 50 to 100 parts by weight.

In the adsorbent, in order to enhance the selective removal property against harmful components, a non-volatile agent, for example, an acid component such as an organic acid or an inorganic acid, a base component such as an organic base or an inorganic base is added, if necessary. May be supported.

The adsorbent may be uniformly distributed throughout the filter material, or may be non-uniform or partially present. When the adsorbent is partially distributed in the filter material, for example, it may be present in the central portion or the outer peripheral portion along the axial direction of the filter material, and is distributed in an appropriate shape such as a ring shape or a spiral shape. Or it may exist.

The adsorbent can be included in the tobacco filter by conventional addition equipment. For example, to add the powdery adsorbent, an activated carbon powder addition device or the like mounted on a device for manufacturing a tobacco activated carbon addition filter can be used.

As the wrapping paper around which the filter material is wound (filter wrapping paper), a paper conventionally used as a wrapping paper for a cigarette filter (for example, plain paper) can be used.

The main feature of the cigarette filter of the present invention is that the water-soluble hot melt adhesive is used as an adhesive (wrap paste) applied to a wrapping paper. This adhesive has only to be applied to at least the wrapping paper, and may be used not only for bonding the wrapping papers but also for bonding the wrapping paper and the filter material. Even if the wrapping paper and the filter material are adhered by the water-soluble hot-melt adhesive, they are easily separated by the action of rainwater or the like in the natural environment, so that the filter material has a disintegrating property in the natural environment. Can be effectively exerted.

The cigarette filter of the present invention can be manufactured by winding a filter material with a wrapping paper and applying the adhesive to at least the wrapping paper to form a rod shape.
More specifically, for example, the water-soluble hot-melt adhesive is heated and melted in a container such as a hot-melt applicator tank of a cigarette filter hoist, and the end of the filter paper is applied by applying means such as a hot-melt gun nozzle. Apply to. Then, the filter-wrapping paper can be wrapped by rolling up the sheet-shaped filter material with a filter-wrapping paper in a rod shape (stick shape), adhering both ends of the filter-wrapping paper, and cooling with a cooler or the like.
The hoisting speed of the filter material is usually 200 to 12
00 m / min (for example, about 200 to 800 m / min), preferably about 300 to 600 m / min. The water-soluble hot melt adhesive has a short set time and excellent initial adhesiveness, and is suitable for such high speed adhesion. It is also possible to obtain a rod-shaped cigarette filter by winding a rod-shaped filter material with a wrapping paper and applying the adhesive.

The cigarette filter of the present invention may constitute a part of the filter or the entire filter when attached to the cigarette. That is, the tobacco filter of the present invention may be used alone or may be used in combination with one or more other filters.

In the cigarette filter of the present invention, the specific water-soluble hot melt adhesive is used as an adhesive for gluing the filter paper. This adhesive has excellent meltability and remarkably high thermal stability in a molten state.
Therefore, the operation of adhering the filter wrapping paper and the production of the cigarette filter can be stably performed continuously for a long time. Further, since the water-soluble hot-melt adhesive is excellent in water solubility, even if it is accidentally disposed of in the natural environment after smoking, the filter wrapping paper adhered by the adhesive is easily treated by the action of water such as rainwater. It is peeled off and removed from the tobacco filter. Therefore, the disintegration property and the dispersibility of the filter material in the natural environment can be effectively exhibited. Further, since the hot melt adhesive is excellent in safety, it is preferable in terms of safety and hygiene.

[0076]

The water-soluble hot melt adhesive of the present invention is
Since it contains a specific resin called vinylpyrrolidone-vinyl acetate copolymer, it has excellent stability in the molten state, especially high thermal stability, and a short set time.
The adherend can be bonded in a short time. Further, since it has excellent heat resistance and creep resistance, high adhesive strength can be maintained even when a heavy article or a container containing a heavy article is adhered.

In the cigarette filter of the present invention, since the above specific water-soluble hot melt adhesive is used for pasting the filter wrapping paper, the filter wrapping paper is quickly detached from the filter material by the action of water such as rainwater. , Removed. Therefore, the original disintegration property of the filter material in the natural environment can be effectively exerted, and environmental pollution can be reduced. Further, since the tobacco filter of the present invention has high stability in the molten state of the adhesive, particularly high thermal stability,
Stable continuous production is possible for a long time.

According to the method for producing a cigarette filter of the present invention, since the above specific water-soluble hot melt adhesive is used, the excellent cigarette filter as described above can be produced continuously, efficiently and stably for a long period of time. .

[0079]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, in an Example and a comparative example, a part and% show a weight part and weight%, respectively. Moreover, vinylpyrrolidone may be abbreviated as "PVP", vinyl acetate as "VA", and vinylpyrrolidone-vinyl acetate copolymer as "PVP-VA copolymer".

The melt viscosity, heat melting property, heat stability, water solubility, set time, adhesive strength of the hot melt adhesive,
The heat creep resistance, filter paper peeling property, filter disintegration property and tobacco taste were measured and evaluated by the following methods.

(1) Melt viscosity of hot melt adhesive: 1
The melt viscosity at 80 ° C. and 150 ° C. was measured with a B type rotational viscometer.

(2) Thermal meltability of hot melt adhesive: 1
The sample was placed on a stainless steel plate heated to 80 ° C., the molten state after 30 minutes was observed, and evaluated according to the following criteria.

◯: Completely melted Δ: Partially melted or phase separated into two phases ×: Not melted (3) Thermal stability of hot melt adhesive: heated to 180 ° C. Place the sample on the stainless steel plate, observe the change in color tone of the sample after 8 hours, the occurrence of carbide and the presence of skin,
Evaluation was made according to the following criteria.

◯: Slightly colored, but no skin or charcoal is observed. Δ: Darkly colored, but no skin or charcoal is observed. X: Generation of charcoal or skin is recognized. (4) Water solubility of hot melt adhesive: distilled water at 30 ° C 1
1 g of the sample was put in 00 g, and the dissolved state was observed every hour while gently stirring, and evaluated according to the following criteria.

◯: Completely dissolved within 4 hours Δ: Completely dissolved within 8 hours ×: Not dissolved even after 8 hours passed (5) Set time of hot melt adhesive: coating temperature 1
A hot-melt adhesive is applied to a 25 mm wide K liner paper under the conditions of 80 ° C. and a coating amount of 3 g / m, and is stuck with an open time of 2 seconds and pressed with a load of 2 kg / 25 mm × 25 mm to obtain a test piece. Was produced.

When peeling was carried out by changing the pressing time, the time until four or more test pieces out of the five test pieces failed was defined as the set time. If the set time is within 5 seconds, it is suitable for high-speed bonding.

(6) Adhesive strength of hot melt adhesive: A hot melt adhesive was applied to a 25 mm wide K liner paper under the conditions of a coating temperature of 180 ° C. and a coating amount of 3 g / m, and an open time was 2 seconds. Pasted together with 2kg / 25mm × 25m
A test piece was produced by pressing with a load of m for 10 seconds. After curing the test piece at 20 ° C and 65% RH for 24 hours, 180 °
The peeling state of the adhesive portion was observed by peeling, and the following criteria were evaluated. It should be noted that if material breakage occurs, it can be said that the adhesive strength has no practical problem.

◯: Paper was broken Δ: Part of the paper was broken ×: Peeled at the interface (7) Heat-resistant creep resistance of the hot melt adhesive: Hot under the conditions of a coating temperature of 180 ° C. and a coating amount of 3 g / m 2. The melt adhesive was applied to a K-liner paper having a width of 25 mm, adhered with an open time of 2 seconds, and pressed with a load of 2 kg / 25 mm × 25 mm for 10 seconds to prepare a test piece. 2 test pieces
After curing at 0 ° C and 65% RH for 24 hours, leave it in a constant temperature bath at 40 ° C for 10 minutes, then fix the upper end for 180 ° peeling, apply a load of 100g to the lower end, and raise the temperature at 1 ° C. The temperature was raised at a rate of / minute. Then, the temperature at which the bonded portion broke was evaluated as the heat-resistant creep resistance. Heat creep resistance is 5
If it is 0 ° C. or higher, practically no problem occurs.

◯: 50 ° C. or more Δ: 40 ° C. or more and less than 50 ° C. ×: less than 40 ° C. (8) Filter paper peeling property A tobacco filter sample cut to a length of 25 mm was
Put in a 100 ml beaker containing 75 ml of water,
It was shaken at a constant speed of 150 times / min with a shaker having a stroke width of 2.5 cm, the peeled state from the filter material of the filter paper was observed every 30 minutes, and evaluated according to the following criteria.

◯: The filter wrapping paper was peeled off from the filter material within 30 minutes. Δ: The filter wrapping paper was peeled off from the filter material within 60 minutes after the lapse of 30 minutes. X: The filter wrapping paper was peeled off from the filter material even after 60 minutes. (9) Filter disintegration property: A tobacco filter sample cut to a length of 10 mm was left on the land surface within the site of Filter Research Laboratory (Sakai City, Osaka Prefecture) of Daicel Chemical Industries,
The shape change after 6 months was observed and evaluated according to the following criteria.

A: The filter wrapping paper is peeled off, and the filter material is almost completely collapsed. B: The filter wrapping paper is peeled off, and the filter material is crushed to the extent that the original shape is not retained. C: The filter wrapping paper is peeled off. Although the filter material remains in its original shape more than half D: The filter paper is peeled off, but the filter material is almost in its original shape E: The filter paper is peeled off about half, but the filter material is almost The original shape is retained F: The filter paper is not peeled off, and the filter material is almost in the original shape.

(10) Eating taste For a cigarette filter sample cut to a length of 25 mm and connected to a tobacco portion of a commercially available tobacco (highlight manufactured by Japan Tobacco Inc.), the taste was determined by 10 panelists as follows. It was evaluated according to the standard.

◯: All admitted that it was about the same as commercially available cigarettes ×: At least one person admitted that it was inferior to commercially available cigarettes In addition, the evaluation (8) to the above tobacco filter
Regarding (10), the sample was left standing in an atmosphere of 23 ° C. and 65% RH for 24 hours or more to adjust the humidity, and then used.

Example 1 25 parts of PVP-VA copolymer having a PVP / VA molar ratio of 60/40 and a viscosity average molecular weight of 135,000 and a rosin derivative having an acid value of 330 (manufactured by Arakawa Chemical Co., Ltd .; KE- 6
04) 35 parts, 30 parts of glycerin, oxidation wax (alcohol type wax) having a melting point of 63 ° C. (Nippon Seiwa Co., Ltd.)
NPS-9125) 10 parts, phenolic stabilizer (Asahi Denka Kogyo KK; AO-70) 0.3 part, phosphorus stabilizer (Asahi Denka KK; PEP-36) 0. 3 parts and thioether stabilizer (Asahi Denka Kogyo KK; A
O-412S) 0.3 part was heated at 160 ° C., melt-mixed, and then cooled to 25 ° C. to obtain a hot-melt adhesive.

Example 2 25 parts of PVP-VA copolymer having a PVP / VA molar ratio of 20/80 and a viscosity average molecular weight of 8000, and an acid value of 1
40 rosin derivatives (Arakawa Chemical Co., Ltd .; Marquide N)
o. 32) 35 parts, oxidized wax (alcohol type wax) having a melting point of 75 ° C. (manufactured by Nippon Seiro Co., Ltd .; NPS-92)
10) 10 parts, glycerin 30 parts, phenolic stabilizer (Asahi Denka Kogyo KK; AO-70) 3.6 parts and phosphorus stabilizer (Asahi Denka Kogyo KK; PEP-36) 0.
A hot melt adhesive was obtained in the same manner as in Example 1 using 4 parts.

Example 3 20 parts of PVP-VA copolymer having a PVP / VA molar ratio of 70/30 and a viscosity average molecular weight of 38,000, and a rosin derivative having an acid value of 330 (manufactured by Arakawa Chemical Co., Ltd .; Marked No. .33) 26 parts, melting point 100 ° C. oxidized wax (alcohol type wax) (manufactured by Nippon Seiro Co., Ltd .; OX-0)
20T) 14 parts, glycerin 40 parts, phenolic stabilizer (Asahi Denka Kogyo KK; AO-70) 0.1 part, phosphorus stabilizer (Asahi Denka KK; PEP-36) 0.1 Parts and thioether stabilizer (Asahi Denka Co., Ltd .; AO
-412S) was used in the same manner as in Example 1 to obtain a hot melt adhesive.

Example 4 30 parts of PVP-VA copolymer having a PVP / VA molar ratio of 60/40 and a viscosity average molecular weight of 55,000, and a rosin derivative having an acid value of 330 (manufactured by Arakawa Chemical Co., Ltd .; KE- 60
4) 30 parts, 25 parts of glycerin, an oxidation wax (alcohol type wax) having a melting point of 63 ° C. (manufactured by Nippon Seiro Co., Ltd .;
NPS-9125) 15 parts, phenolic stabilizer (Asahi Denka Kogyo KK; AO-70) 1.6 parts, phosphorus stabilizer (Asahi Denka KK; PEP-36) 1.6 parts and thioether. System stabilizer (Asahi Denka Co., Ltd .; AO-412)
A hot melt adhesive was obtained in the same manner as in Example 1 using 1.6 parts of S).

Example 5 20 parts of PVP-VA copolymer having a PVP / VA molar ratio of 60/40 and a viscosity average molecular weight of 77,000, and a rosin derivative having an acid value of 140 (manufactured by Arakawa Chemical Co., Ltd .; Marked No. .32) 40 parts, glycerin 35 parts, oxidation wax (alcohol type wax) having a melting point of 63 ° C. (manufactured by Nippon Seiro Co., Ltd .; NPS-9125) 5 parts, phenolic stabilizer (manufactured by Asahi Denka Kogyo KK; AO-70) 3.6 parts and phosphorus-based stabilizer (Asahi Denka Kogyo KK; PEP-36)
A hot melt adhesive was obtained in the same manner as in Example 1 using 0.4 part. The melt viscosity of the obtained hot melt adhesive is 500 centipoise at 180 ° C and 990 at 150 ° C.
It was centipoise.

Example 6 25 parts of PVP-VA copolymer having a PVP / VA molar ratio of 60/40 and a viscosity average molecular weight of 135,000, and a rosin derivative having an acid value of 330 (manufactured by Arakawa Chemical Co., Ltd .; KE- 6
04) 35 parts, glycerin 35 parts, oxidation wax (alcohol type wax) having a melting point of 63 ° C. (Nippon Seiwa Co., Ltd.)
NPS-9125) 10 parts, phenol-based stabilizer (Asahi Denka Kogyo KK; AO-70) 0.3 part, phosphorus-based stabilizer (Asahi Denka Kogyo KK; PEP-36) 0. 3 parts and thioether stabilizer (Asahi Denka Kogyo KK; A
O-412S) was used in the same manner as in Example 1 to obtain a hot melt adhesive. The melt viscosity of the obtained hot melt adhesive is 330 centipoise at 180 ° C., 15
It was 630 centipoise at 0 degreeC.

Example 7 25 parts of PVP-VA copolymer having a PVP / VA molar ratio of 70/30 and a viscosity average molecular weight of 8000, and an acid value of 1
40 rosin derivatives (Arakawa Chemical Co., Ltd .; Marquide N)
o. 32) 35 parts, glycerin 30 parts, oxidation wax (alcohol type wax) having a melting point of 75 ° C. (manufactured by Nippon Seiro Co., Ltd .; NPS-9120) 10 parts, phenolic stabilizer (manufactured by Asahi Denka Co., Ltd .; AO -70) 3.6 parts and phosphorus-based stabilizer (Asahi Denka Kogyo KK; PEP-36)
A hot melt adhesive was obtained in the same manner as in Example 1 using 0.4 part. The melt viscosity of the obtained hot melt adhesive is 350 centipoise at 180 ° C and 700 at 150 ° C.
It was centipoise.

Comparative Example 1 25 parts of polyvinylpyrrolidone having a viscosity average molecular weight of 630000 and an ester gum having an acid value of 20 (manufactured by Arakawa Chemical Co., Ltd .;
Super ester A-125) 35 parts, glycerin 30
Parts and melting point 63 ° C. Oxidized wax (alcohol type wax) (Nippon Seiwa Co., Ltd .; NPS-9125) 10
A hot melt adhesive was obtained in the same manner as in Example 1 except that the parts were used.

Comparative Example 2 29 parts of polyvinyl alcohol having a saponification degree of 45 mol% and a polymerization degree of 480, MFR standardized by JIS K6730.
5 parts of ethylene-vinyl acetate copolymer having a (melt flow rate) of 2500 and a vinyl acetate content of 28% by weight,
45 parts of hydrogenated petroleum resin with acid value 0 (Arakawa Chemical Co., Ltd .; Alcon M-135), 20 parts of glycerin, melting point 75 ° C.
Paraffin wax (manufactured by Nippon Seiro Co., Ltd .; HNP-
9) 1 part, phenolic stabilizer (Asahi Denka Kogyo KK:
AO-70) 0.3 part, phosphorus stabilizer (Asahi Denka Kogyo KK; PEP-36) 0.3 part and thioether stabilizer (Asahi Denka Kogyo KK; AO-412S) 0.
A hot melt adhesive was obtained in the same manner as in Example 1 using 3 parts. The melt viscosity of the obtained hot melt adhesive is 1
It was 850 centipoise at 80 ° C and 7400 centipoise at 150 ° C.

Table 1 shows the evaluation results of the hot melt adhesives, thermal stability, water solubility, set time, adhesive strength and heat creep resistance of the hot melt adhesives obtained in Examples 1 to 7 and Comparative Examples 1 and 2 above. Shown in. The hot melt adhesive of Comparative Example 1 was poor in heat melting property and a uniform molten mixture could not be obtained. Therefore, other evaluation tests were not performed.

[0104]

[Table 1] Example 8 Cellulose acetate short fibers (fineness: 3.3 denier,
Cross-sectional shape: Y-shaped, fiber length 4 mm, degree of substitution: 2.45)
60 parts and 40 parts of softwood bleached kraft pulp with a beating degree of 45 ° SR were uniformly dispersed in 300,000 parts of water, wet-processed using a cylinder paper machine, dehydrated and dried.
Slit to a width of 0 mm, the basis weight is 33 g / m ² , the density is 0.
A filter material sheet having a thickness of 37 g / cm ³ and a thickness of 0.09 mm was obtained.

Using a hoisting machine for producing a filter made of a cigarette paper (CU-20 made by Decofre / KDF2 made by Hawny), a crepe roller temperature of 1 was added to the sheet for the filter material.
At 30 ° C., crepe processing was performed with a crepe depth of 0.50 mm. This crepe-processed filter material sheet is used as plain paper for filter wrapping paper (manufactured by Mishima Paper Co., Ltd .:
(26.5 plug plain paper) was used as a wrapping paper, and the hot melt adhesive of Example 5 heated and melted at 150 ° C. was used as a wrap paste to wind up at a wrapping speed of 400 m / min. The obtained filter rod was cut into a length of 100 mm with a cutter to obtain a tobacco filter.

Example 9 A tobacco filter was obtained in the same manner as in Example 1 except that the hot melt adhesive of Example 6 was used as the wrap paste.

Example 10 A tobacco filter was obtained in the same manner as in Example 1 except that the hot melt adhesive of Example 7 was used as the wrap paste.

Example 11 Tow of cellulose acetate fiber (filament fineness:
4.0 denier, total fineness: 35,000 denier,
Cross-sectional shape: Y-shaped, degree of substitution: 2.45) width of about 20 cm
Was opened. On the surface of the opened tow, a winding machine for manufacturing a filter for adding active carbon for tobacco (KDF2 / AC1 manufactured by HAUNI)
/ AF1) activated carbon powder addition device, as a water-soluble polymer adhesive, polyalkylene oxide resin of 15% by weight to tow (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; Paogen PP-15; melting point 55 ° C.) ) Powder (average particle size 80μ
m) was sprinkled. The tow sprinkled with the water-soluble polymer adhesive was supplied to a paper wrapping device, and was wound at the wrapping speed of 400 m / min using the same filter wrapping paper and wrap paste as in Example 1. The length of the obtained filter rod is 100 with a cutter.
After cutting to mm, 10 in an oven set at 70 ° C
The water-soluble polymer adhesive in the filter rod was melted by heating for 1 minute, and then cooled and solidified to obtain a tobacco filter to which the tow was adhered.

Example 12 Instead of the water-soluble polymer adhesive, a polycaprolactone-based resin (manufactured by Daicel Chemical Industries Ltd .; PCL-H7; melting point 60 ° C.) as a biodegradable polymer adhesive (average particle size) A cigarette filter was obtained in the same manner as in Example 11, except that the diameter was 200 μm).

Example 13 Example 11 except that no water soluble polymer adhesive was added.
The same operation was performed to obtain a cigarette filter.

Example 14 A tobacco filter was obtained in the same manner as in Example 13 except that a tow of cellulose acetate fiber having a degree of substitution of 2.14 was used.

Example 15 As a photodegradation accelerator, fine particles anatase type titanium oxide having photocatalytic activity (manufactured by Teika Co., Ltd .; average particle size 0.0)
A tobacco filter was obtained in the same manner as in Example 13, except that a tow of cellulose acetate fiber containing 0.5% by weight of 3 μm) was used.

Comparative Example 3 Water-insoluble lapping paste (manufactured by Daido Kasei Co., Ltd .; Daicarac S-1101S; melt viscosity 740 centipoise (1
The same operation as in Example 13 was carried out except that 80 ° C.) was used to obtain a tobacco filter.

Comparative Example 4 Instead of the water-soluble polymer adhesive, triacetin (Daicel Chemical Industry Co., Ltd.), which is a plasticizer of cellulose acetate, was used.
Hoisting machine (made by HAUNI,
KDF2 / AF1) plasticizer addition device was used to add 15% to the tow, and as a wrap paste, a water-insoluble wrap paste (manufactured by Daido Kasei Co., Ltd .; DAIKALAC S-1101S; melt viscosity) 740 cm Poise (18
The same operation as in Example 11 was carried out except that 0 ° C.) was used to obtain a tobacco filter.

Comparative Example 5 A tobacco filter was obtained in the same manner as in Example 13 except that the hot melt adhesive of Comparative Example 2 was used as the wrap paste. The melting temperature of the wrap paste is 150
When the temperature was set to ° C, the melt viscosity was remarkably high at 7400 centipoise, and it was out of the proper melt viscosity range in the operation of the hoist. Then, the melting temperature of the wrap paste was set to 180 ° C. and the winding machine was operated to produce a cigarette filter so that the melt viscosity was appropriate.

However, during the operation of the hoist, the hot melt adhesive was phase-separated into two phases in the hot melt applicator tank of the hoist, so that stable operation for a long time was difficult.

With respect to the tobacco filters obtained in Examples 8 to 15 and Comparative Examples 3 to 5, Table 2 shows the evaluation results of filter paper peeling property, filter disintegration property and taste.

[0118]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location A24D 3/16 A24D 3/16 C09J 131/04 JCZ C09J 131/04 JCZ

Claims (22)

[Claims] 1. A water-soluble hot-melt adhesive containing a vinylpyrrolidone-vinyl acetate copolymer. 2. The water-soluble hot melt according to claim 1, wherein the ratio of vinylpyrrolidone to vinyl acetate in the vinylpyrrolidone-vinyl acetate copolymer is former / latter = 85/15 to 10/90 (molar ratio). adhesive. 3. The water-soluble hot melt adhesive according to claim 1, wherein the vinylpyrrolidone-vinyl acetate copolymer has a viscosity average molecular weight of 3,000 to 300,000. 4. Further comprising at least one selected from (a) water-soluble or water-dispersible tackifier, (b) wax and (c) water-soluble or water-dispersible plasticizer. The water-soluble hot melt adhesive described. 5. The water-soluble hot melt according to claim 4, wherein the water-soluble or water-dispersible tackifier (a) is contained in an amount of 50 to 300 parts by weight based on 100 parts by weight of the vinylpyrrolidone-vinyl acetate copolymer. adhesive. 6. The water-soluble hot melt adhesive according to claim 4, wherein the water-soluble or water-dispersible tackifier (a) is a rosin derivative. 7. The acid value of the rosin derivative is 30 to 400 (m
The water-soluble hot melt adhesive according to claim 6, which is gKOH / g). 8. The wax (b) is vinylpyrrolidone-
10-12 based on 100 parts by weight of vinyl acetate copolymer
The water-soluble hot melt adhesive according to claim 4, which contains 0 part by weight. 9. The water-soluble hot melt adhesive according to claim 4, wherein the wax (b) is a water-soluble or water-dispersible wax. 10. The melting point of the wax (b) is 50 to 120.
The water-soluble hot melt adhesive according to claim 9, which has a temperature of ° C. 11. The water-soluble hot melt adhesive according to claim 4, wherein the water-soluble or water-dispersible plasticizer (c) is contained in an amount of 40 to 300 parts by weight based on 100 parts by weight of the vinylpyrrolidone-vinyl acetate copolymer. Agent. 12. A water-soluble or water-dispersible tackifier, 60 to 250 parts by weight, and a water-soluble or water-dispersible wax, 15 to 100 parts by weight per 100 parts by weight of a vinylpyrrolidone-vinyl acetate copolymer. The water-soluble hot melt adhesive according to claim 4, which comprises 50 parts by weight to 50 parts by weight of a water-soluble or water-dispersible plasticizer. 13. A viscosity average molecular weight of 5,000 to 20,000.
0, the ratio of vinylpyrrolidone and vinyl acetate is the former / the latter = 80/20 to 15/85 (molar ratio), based on 100 parts by weight of the vinylpyrrolidone-vinyl acetate copolymer, an acid value of 40 to 370, 80 to 220 parts by weight of a water-soluble or water-dispersible rosin derivative having a softening point of 80 to 180 ° C., and 20 to 80 parts by weight of an oxidized wax having a melting point of 55 to 110 ° C.
The water-soluble hot melt adhesive according to claim 12, further comprising 70 to 220 parts by weight of a water-soluble or water-dispersible plasticizer and an antioxidant. 14. The melt viscosity at 180 ° C. is 100 to 100.
The water-soluble hot melt adhesive according to claim 1, which is 1000 centipoise. 15. A filter material, and a wrapping paper for winding the filter material to form a rod shape,
A tobacco filter in which an adhesive is applied to at least the wrapping paper, wherein the adhesive is the water-soluble hot-melt adhesive according to claim 1. 16. The tobacco filter according to claim 15, wherein the filter material is composed of at least one selected from the group consisting of cellulose ester fiber, wood pulp, regenerated cellulose fiber and polypropylene fiber. 17. The tobacco filter according to claim 15, wherein the filter material is water dispersible, photodegradable or biodegradable. 18. The tobacco filter according to claim 15, wherein the adsorbent is contained in an amount of 1 to 200 parts by weight based on 100 parts by weight of the filter material. 19. The tobacco filter according to claim 18, wherein the adsorbent is activated carbon or zeolite. 20. A filter material is wound with a wrapping paper,
A method for manufacturing a tobacco filter, which comprises applying an adhesive agent to at least a wrapping paper to form a rod shape, wherein the water-soluble hot-melt adhesive agent according to claim 1 is used as the adhesive agent. 21. The method for producing a tobacco filter according to claim 20, wherein a sheet-shaped filter material is wound into a rod shape with a wrapping paper to be molded. 22. The method for producing a tobacco filter according to claim 21, wherein the winding speed is 200 to 1200 m / min.