JP3523679B2 - Polyvinyl alcohol-based resin composition, hot melt adhesive and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having a melting point and a low melt viscosity in a low temperature range, and particularly to a resin composition suitable for a water-soluble or water-dispersible hot melt adhesive.

[0002]

2. Description of the Related Art Hot-melt adhesives can be applied to a wide range of adherends, have a very high adhesion speed, have no toxicity or danger, and are economically advantageous, as compared with other adhesives. For reasons such as bookbinding, packaging, woodworking,
It is widely used for making shoes and adhering fabrics. The hot-melt adhesive is required to meet performances such as adhesiveness, meltability, heat resistance, cold resistance and flexibility, and is generally an ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polyamide, polyester. Is used as the base polymer.

Particularly, as an adhesive in the field of fiber systems such as bookbinding, bag making, box making, and woodworking, adhesiveness, workability,
Ethylene-vinyl acetate copolymers having excellent flexibility are widely used. However, since the resin is hydrophobic, it is the current situation that, for example, when a waste paper is recycled in water, a portion that does not dissolve or disperse in water remains. On the other hand, hot melt adhesives made of a water-soluble polyvinyl alcohol-based resin have recently attracted attention.

[0004]

However, the polyvinyl alcohol-based resin is a resin having a high melting point and a high melt viscosity in a low temperature range, and the resin alone does not have an aptitude for a hot-melt adhesive. Therefore, a plasticizer such as glycerin or ethylene glycol is added to the polyvinyl alcohol resin, but only by adding such a plasticizer,
It is impossible to reduce the melting point and melt viscosity to the target, and the hot-melt adhesive composed of the polyvinyl alcohol resin is unavoidably used at a high temperature (180 ° C. or higher). In the case of melting in the range, the polyvinyl alcohol-based resin is likely to cause thermal decomposition, and the compatibility between the polyvinyl alcohol-based resin and various additives in the hot-melt adhesive that is usually used tends to be lowered. In addition, since the polyvinyl alcohol-based resin is inferior in low-temperature flexibility, there is a problem that the hot melt adhesive portion of the product is extremely brittle, which lowers the product value, especially in a cold region. Therefore, a water-soluble or water-dispersible hot melt adhesive having a low melting point and a low melt viscosity in a low temperature range and having good low temperature flexibility is desired.

[0005]

However, the inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, partial saponification or introduction of a hydrophilic group has made them water-soluble or water-dispersible. met polyvinyl alcohol resin
And a polyvinyl alcohol-based resin composition comprising a hydrophilic polyvinyl alcohol-based resin having an average saponification degree of 30 to less than 90 mol% , a hydroxy fatty acid having 6 or more carbon atoms or a derivative thereof, and a plasticizer meets the above purpose. After finding out the above, the present invention has been completed. In the present invention, by mixing a hydroxy fatty acid having 6 or more carbon atoms, the melting point and melt viscosity of the resin composition in a low temperature region can be sufficiently lowered, and further, the low temperature flexibility can be improved. Hereinafter, the present invention will be described in detail.

As the hydrophilic polyvinyl alcohol-based resin, a polyvinyl alcohol-based resin which is made water-soluble or water-dispersible by partial saponification or introduction of a hydrophilic group is used. The hydrophilic polyvinyl alcohol resin of the present invention is usually produced by a known method. Such a polyvinyl alcohol resin is not only a partially saponified product of polyvinyl acetate but also a monomer copolymerizable with a vinyl ester, such as ethylene, prepylene, isobutylene, α.
-Octene, α-dodecene, olefins such as α-octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, unsaturated acids such as itaconic acid or salts or mono- or dialkyl esters thereof, acrylonitrile, Nitriles such as methacrylonitrile, amides such as acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid or salts thereof, alkyl vinyl ethers, N-acrylamidomethyltrimethylammonium chloride, Allyl trimethyl ammonium chloride, dimethyl diallyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth) allyl ether,
Polyoxyalkylene (meth) allyl ether such as polyoxypropylene (meth) allyl ether, polyoxyethylene (meth) acrylate, polyoxyalkylene (meth) acrylate such as polyoxypropylene (meth) acrylate, polyoxyethylene (meth) Polyoxyalkylene (meth) acrylamides such as acrylamide, polyoxypropylene (meth) acrylamide,
Polyoxyethylene (1- (meth) acrylamide-
1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, etc. To be

Of the above comonomers, the sulfonic acid group-containing monomer and the oxyalkylene group-containing monomer are particularly preferably used as the monomer having a hydrophilic group, but are not necessarily limited thereto. The polyvinyl alcohol resin may be used alone or in combination of two or more. The preferred average degree of polymerization of the hydrophilic polyvinyl alcohol-based resin of the present invention is preferably 50 to 700, particularly 100 to 500, and the preferred average degree of saponification is 30 to 90 mol%, particularly 45 to 70 mol%. . If the average degree of polymerization is less than 50, the adhesive strength is low,
If it exceeds 0, the melt viscosity increases. If the average degree of saponification is less than 30 mol, the blocking property is large and water is insoluble, and if it exceeds 85 mol%, the melting point becomes high.

[0008] The number 6 or more hydroxy fatty acid carbon in the present invention, 2-hydro carboxymethyl-2-methylpentanoic acid,
2-hydro carboxymethyl-5-methyl hexanoic acid, 3-hydro key <br/> shea 2-methylpentanoic acid, 11-hydro carboxy tetradecane acid, 11 hydro carboxy hexadecanoic acid, 14-hydrate
B carboxymethyl hexadecanoic acid, 12-hydro Kishidodekan acid,
16 hydro carboxymethyl hexadecanoic acid, 12-hydro carboxy octadecanoic acid, 9-hydro carboxy octadecanoic acid, 22-
Hydro Kishidokosan acid and alkali salts thereof, are esterified products are mentioned, in particular 12-hydro alkoxy octadecanoic acid practical. The hydroxy fatty acid having 5 or less carbon atoms cannot exert the effect of the present invention. The hydroxy fatty acid is a hydrophilic polyvinyl alcohol resin 10
5 to 100 parts by weight, preferably 10 to 0 parts by weight
80 parts by weight are mixed. If the mixing amount is less than 5 parts by weight, the effect of the present invention cannot be exhibited, and if it exceeds 100 parts by weight, water solubility or water dispersibility is lost.

The plasticizer in the present invention is not particularly limited as long as it is a compound having a plasticizing effect on the above-mentioned hydrophilic polyvinyl alcohol resin, and for example, glycerin, diglycerin, polyglycerin, pentaerythritol, pentamethylene glycol. , Polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, methylpentanetriol, sorbit and mannite, and urea derivatives such as ethylene urea.
The mixing amount of the plasticizer is polyvinyl alcohol resin 1
5 to 50 parts by weight, preferably 10 to 100 parts by weight
40 parts by weight. If the mixing amount is less than 5 parts by weight, the effect as a plasticizer is hardly seen, and if it exceeds 50 parts by weight, tack occurs at room temperature.

As a method for blending the hydrophilic polyvinyl alcohol resin, the hydroxy fatty acid having 6 or more carbon atoms, and the plasticizer to obtain the resin composition of the present invention, a well-known method, that is, a melting can equipped with a stirrer is used. It is melt-mixed by an extruder, a roll kneader, or the like. The order of blending is not particularly limited, and either a method of simultaneously blending three types of resins or a method of blending two types of resins and then the rest of the resins may be used. The melt mixing temperature is preferably about 120 to 180 ° C. Such a resin composition may be blended with another polymer within the range not impairing the gist of the present invention, for example, ethylene-vinyl acetate copolymer, polyester, polypropylene, polyamide, polyester, or vice versa. The above resin composition can also be blended. Also, rosins,
Rosin ester, pinene polymer, hydrogenated petroleum resin,
Various additives such as well-known additives for hot melt adhesives such as hydrocarbon resins, antioxidants, lubricants, fillers, colorants and stabilizers can be added.

After the resin composition is melted, it is molded into an arbitrary shape to obtain a product. For example, in order to commercialize it as a hot melt adhesive, any conventional method can be carried out, and it can be processed into an appropriate shape such as a block, a strip, a biscuit, a pellet, a rope, a powder or a film. The molding method depends on the shape. For example, in the case of forming into a strip shape, the melt obtained by melting and mixing as described above is caused to flow out from a feeder onto a belt plate made of stainless steel or the like, and cooling water is sprayed from the inside of the belt to cool and solidify the strand indirectly discharged. Then, after solidification, a method of cutting into a strip shape with a cutter and molding is mentioned. The hot-melt adhesive thus obtained has a low melting point and has a low melt viscosity in a low temperature range, and therefore is extremely excellent in coating work, and also has low flexibility. It is industrially very advantageous because the production and coating machines for vinyl acetate copolymers can be used as they are.

There is no particular limitation on the adherend of the hot melt adhesive, and it is used for making or box-making cardboard boxes / carton boxes, packaging for pharmaceuticals, confectionery, toys, etc., and binding for telephone directories, catalogs, slips, etc. , Bag making such as top / bottom / body bonding, paper products such as corrugated pallets / fiber cans / paper tubes / labels, sanitary materials such as disposable diapers, woodworking such as furniture / shelf assembly, aluminum For making cans such as polypropylene and polypropylene, for construction such as laminating aluminum sashes and decorative paper on the ceiling, for making shoes such as folding and bottoming, for automobiles such as oil filters and headlamps, hem of coats, leather and fabric For attaching and reinforcing clothing, TV yokes, etc.
It is used for electrical parts such as temporarily fixing speaker coils, and for general work such as do-it-yourself engineering and other repairs. The hot melt adhesive has been described above,
The resin composition of the present invention is not only a hot melt adhesive,
Bottle, film, sheet, hose, tube, container,
It is used for various purposes such as bags, fibers, molded products such as foams, and paper processing agents.

[0013]

[Working] The resin composition of the present invention has a low melting point and a low melt viscosity in a low temperature region, and further has excellent low temperature flexibility. Such a resin composition is particularly effective as a water-soluble or water-dispersible hot melt adhesive.

[0014]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to actual examples. In addition, "part" and "%" are based on weight unless otherwise specified. Example 1 Resin composition The average saponification degree 65 mol%, 100 parts of polyvinyl alcohol having an average degree of polymerization of 250, 12 - were charged 25 parts of hydro carboxymethyl octadecanoic acid, 25 parts of glycerin to melt the can 170
The resin composition was obtained by melt mixing at ℃. The melting point, melt viscosity and low temperature flexibility of the resin composition were measured. The results are summarized in Table 1. (Melting point) PERKIN-ELMER DSC-7 (PERKIN
-Manufactured by ELMER) at a heating rate of 20 ° C / min. (Melt viscosity) According to JAI-7-991, using a Brookfield type rotational viscometer, spindle NO. 29, rotation speed 100
The melt viscosity at 140 ° C. and 170 ° C. was measured at rpm.

(Low temperature flexibility) A sheet having a thickness of 1 mm (width 20 mm x length 80 mm) was prepared in accordance with JAI-7-991, and the sheet was left at -10 ° C for 2 hours or more. The mandrel having a diameter of 1 mm was bent by 180 degrees and the presence or absence of cracks in the bent portion was observed. ○: No cracks at all △: Partially cracked ×: Whole cracked

Hot Melt Adhesive The melt obtained by the above composition was cast in a strand form from a feeder onto a steel belt, and cooling water was sprayed from the inside of the steel belt to cool and solidify the strand. Then, the strand was peeled from the belt, and formed into a strip shape having a length of 20 mm, a width of 20 mm and a thickness of 3 mm with a rotary cutter. The adhesive strength and water solubility or water dispersibility of such hot melt adhesives were measured. The results are summarized in Table 1. (Adhesive strength) The hot melt adhesive is heated and melted,
Kraft paper was coated with a thickness of 100 to 150 μm, a fine paper was placed on the coated surface, and a hot roller at about 150 ° C. was passed to obtain an adhesive paper. Apply this adhesive paper at 20 ℃ × 65% RH, 24
After standing for more than one hour, the 180 ° peel strength was measured under the same conditions at a pulling speed of 30 mm / min. (Water-soluble or water-dispersible) The strip-shaped hot-melt adhesive obtained above was put in water at 20 ° C. and slowly stirred, and 1
The condition after a while was examined.

[0017] Example 2 average saponification degree 70 mol%, 100 parts of polyvinyl alcohol having an average degree of polymerization of 400, 30 parts of 14-hydro carboxymethyl hexadecanoic acid, except that 25 parts of glycerin were melt mixed to obtain a resin composition embodiment The experiment was performed according to Example 1. The results are summarized in Table 1. Example 3 The average saponification degree 75 mol%, average polymerization degree of 100 parts of polyvinyl alcohol was 0.5 mol% modified with allyl sodium sulfonate of 200, 12-hydro Kishidodekan acid 40
Part and 20 parts of triethylene glycol were melt mixed to obtain a resin composition, and an experiment was performed according to Example 1. The results are summarized in Table 1.

[0018] Example 4 average saponification degree 65 mol%, 100 parts of polyvinyl alcohol having an average degree of polymerization of 200, 12 - 25 parts hydro carboxymethyl octadecanoic acid, 20 parts of tetraethylene glycol, vinyl content of 28 wt% ethylene acetate - acetic acid Vinyl copolymer 1
An experiment was conducted according to Example 1 except that 5 parts were melt mixed to obtain a resin composition. The results are summarized in Table 1. Example 5 35 parts of polyvinyl alcohol having an average degree of saponification of 45 mol% and an average degree of polymerization of 250, 65 parts of polyvinyl alcohol having an average degree of saponification of 70 mol% and an average degree of polymerization of 100, and 12- hydroxide
B carboxymethyl 17 parts octadecanoic acid, except that to obtain a resin composition by melt-mixing 25 parts of glycerin were experimented in accordance with Example 1. The results are summarized in Table 1.

[0019] The experiments were carried out in accordance with Example 1 except for Comparative Example 1 12-hydroperoxide carboxymethyl octadecanoic acid. The results are summarized in Table 1. Since this resin composition was brittle, when a hot melt adhesive was molded according to Example 1, it was easily broken during cutting, and an adhesive having a uniform shape could not be obtained. Comparative Example 2 An experiment was performed according to Example 1 except that glycerin was not used. The results are summarized in Table 1. Since this resin composition was brittle, when a hot melt adhesive was molded according to Example 1, it was easily broken during cutting, and an adhesive having a uniform shape could not be obtained.

[0020]

[Table 1] Melting point Melt viscosity (CPS) Low temperature adhesive strength Water-soluble or (℃) 140 ℃ 170 ℃ Flexible (kg / 30mm) Water dispersibility Example 1 85 6000 2500 ○ 0.55 (material break) Complete dispersion 〃 2 79 7000 3000 ○ 0.51 (〃) Complete dispersion 〃 3 82 9500 4000 ○ 0.52 (〃) Complete dispersion 〃 4 80 7000 3500 ○ 0.50 (〃) Complete dispersion 〃 5 80 6000 2000 ○ 0.53 (〃) Complete dispersion Comparative example 1 120 Not measurable 7500 × 0.48 (〃) Complete dispersion 〃 2 125 〃 8500 × 0.46 (〃) Complete dispersion (Note) Complete dispersion means that most of the material is dissolved and the undissolved area is completely evenly dispersed. Say that.

[0021]

INDUSTRIAL APPLICABILITY The resin composition of the present invention has a low melting point and a low melt viscosity in a low temperature range, and further is excellent in low-temperature embrittlement. It is effectively used and is particularly effective as a water-soluble or water-dispersible hot melt adhesive.

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Claims (6)

(57) [Claims] 1. A polyvinyl alcohol resin composition comprising a hydrophilic polyvinyl alcohol resin having an average degree of saponification of 30 to 90 mol%, a hydroxy fatty acid having 6 or more carbon atoms or its derivative, and a plasticizer. 2. A hydrophilic polyvinyl alcohol resin having an average degree of saponification of 30 to 90 mol% has an average degree of polymerization of 50 to 50.
Polyvinyl alcohol-based resin composition of claim 1 wherein the port polyvinyl alcohol resin 700. 3. A hydrophilic polyvinyl alcohol resin having an average degree of saponification of 30 to 90 mol% has an average degree of polymerization of 50 to 50.
The polyvinyl alcohol resin composition according to claim 1, which is a polyvinyl alcohol resin having a hydrophilic group at 700. 4. The polyvinyl alcohol resin composition according to claim 3, wherein the monomer unit having a hydrophilic group is a monomer unit having a sulfonic acid group or an oxyalkylene group. 5. A partially saponified polyvinyl alcohol, or resin der that is to have a water solubility by the introduction of hydrophilic groups
A hot-melt adhesive obtained by melt-mixing a hydrophilic polyvinyl alcohol-based resin having an average saponification degree of 30 to 90 mol% , a hydroxy fatty acid having 6 or more carbon atoms or its derivative, and a plasticizer. In 6. partially saponified or polyvinyl alcohol resin which is to have a water solubility by the introduction of hydrophilic groups
And a hydrophilic polyvinyl alcohol-based resin having an average degree of saponification of 30 to 90 mol% , a hydroxy fatty acid having 6 or more carbon atoms or a derivative thereof, and a plasticizer are melt-mixed, and the melt mixture is placed on a belt. A method for producing a hot melt adhesive, which comprises: running, cooling on the belt, and then cutting.