JP2657109B2 - Method for producing resin, method for producing aqueous resin composition, and method for producing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention relates to a hot-melt adhesive having no alkali resolubility, a solvent-free adhesive, a resin for thermal ink, and a resin for aqueous printing ink. The present invention relates to a resin composition that can be used widely, such as a solvent-free paint such as a water-based paint, a water-based paint, and an adhesive.

(Prior Art) In recent years, environmental issues have been emphasized, and there is a strong demand for resource reuse. For example, recycled paper is a particularly important issue. At present, corrugated cardboard is collected and used for thin paper.However, since the adhesive used for corrugated cardboard is made of acrylic or general hot-melt adhesive that does not redissolve in alkaline aqueous solution, it is used for recycled paper. At present, it is very difficult to remove them. Therefore, a hot-melt adhesive or a water-based adhesive which has good adhesiveness and can be redissolved in an alkali is desired.

On the other hand, as the vehicle for the thermal ink, waxes and waxes typified by carnauba wax have been used. However, a heat-sensitive ink requires good pigment dispersibility and also requires antistatic properties. To this end, conventionally, an emulsifier having a low HLB, a pigment dispersant which is easily dispersed in wax and wax, and an antistatic agent and the like have been mixed. These are often migrated due to low molecular weight on the surface of a coating film applied as an ink and applied thereto, often causing blocking and adversely affecting printability.
In addition, water-based printing inks and the like, an aqueous emulsifier having a good pigment dispersibility, a water-soluble acrylic resin, a water-soluble polyester resin and the like have been used, but the water-based emulsifier has significantly poor water resistance,
In addition, water-soluble acrylic resins, water-soluble polyester resins, and the like have drawbacks such as the need to select a polymer composition to improve pigment dispersibility.

(Problems to be Solved by the Invention) The present inventor has conducted intensive studies to overcome the various disadvantages as described above, and as a result, has found that a copolymer of an α-olefin having 6 or more carbon atoms and maleic anhydride has been obtained. A hot melt that has good adhesion and is re-dissolved in alkali by reacting at least one selected from oxyacids, amino acids and nonionic emulsifiers, and further neutralizing with an alkaline component as required to make aqueous. The adhesive and the pigment itself have good pigment dispersibility, the amount of the antistatic agent added can be reduced, and blocking, it is possible to provide a heat-sensitive ink that does not adversely affect printability. It has become possible to provide a novel aqueous resin having good dispersibility.

[Configuration of the invention]

(Means for Solving the Problems) The present invention provides a copolymer of an α-olefin having 6 or more carbon atoms (C) and maleic anhydride with one or more selected from oxyacids, amino acids and nonionic emulsifiers. The present invention relates to a method for producing a resin characterized by reacting. The present invention also provides a copolymer of an α-olefin having 6 or more carbon atoms and maleic anhydride with one or more selected from oxyacids, amino acids and nonionic emulsifiers, and further neutralizes with an alkaline component. And producing a water-based resin composition. Furthermore, the present invention further comprises reacting a copolymer of an α-olefin having 6 or more carbon atoms with maleic anhydride with one or more selected from oxyacids, amino acids, and nonionic emulsifiers, and then reacting the copolymer with a monovalent to trihydric acid. The present invention relates to a method for producing a resin composition, which comprises adding a valent metal compound and / or a tackifier resin.

In the copolymer of α-olefin and maleic anhydride, α-olefin is 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene , 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacocene, 1-octacocene, 1-triaconten, 1-dotriaconten, 1-tetratriaconten, 1-hexatriaconten, 1- Octatria content, 1-tetra content and the like and a mixture thereof are mentioned. The α-olefin is not particularly limited as long as it is C6 or more, and as a mixture of α-olefins, dialen 208 manufactured by Mitsubishi Chemical Industry Co., Ltd.
8), Dialen 30 (C30 or more) and the like are commercially available. As the α-olefin of the copolymer, α-olefin having 10 or more carbon atoms
Olefins are preferred. The method for copolymerizing the α-olefin and maleic anhydride may be carried out without solvent or in combination with a solvent. Maleic anhydride may be charged together with the α-olefin at a time, or may be gradually added to the polymerization system. There is no particular limitation on these polymerization methods. As a polymerization initiator used in this case, azobisisobutyronitrile, azobis compounds such as azobis 2,4-dimethylvaleronitrile, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, diisopropyl peroxycarbonate,
Examples include peroxides such as di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, potassium persulfate, and ammonium persulfate.
Although not particularly limited to these, it is preferable to use an organic peroxide or an organic azo compound.

The next oxyacid used is an aliphatic oxyacid,
Aromatic oxy acids can be used. For example, aliphatic oxyacids include glycolic acid, lactic acid, hydroacrylic acid, α-
Oxybutyric acid, glyceric acid, tartonic acid, malic acid, citric acid, 12-hydroxystearic acid, and aromatic oxyacids such as salicylic acid, m-oxybenzoic acid, p-oxybenzoic acid, gallic acid, mandelic acid, toroic acid, However, any organic compound having a carboxyl group and a hydroxyl group in one molecule can be basically used and is not necessarily limited thereto. However, aliphatic oxyacids are preferred in terms of reactivity.

In addition, as the amino acid used here, an aliphatic amino acid, an amino acid having an aromatic nucleus, an amino acid having a heterocyclic ring and the like can be used. For example, aliphatic amino acids include glycine, alanine, valine, leucine, isoleucine,
Serine, threonine, cysteine, methionine, aspartic acid, glutamic acid, lysine, arginine, β-alanine, γ-aminobutyric acid, and the like; amino acids having an aromatic nucleus include phenylalanine, tyrosine, anthranilic acid, m-aminobenzoic acid, p -Aminobenzoic acid and the like,
Examples of amino acids having a heterocyclic ring include histidine, tryptophan, proline, and oxyproline.
What is necessary is just to have a carboxyl group and an amino group in a molecule, and it is not necessarily limited to these.

Further, as the nonionic emulsifier used here, polyethylene glycol ester, polyethylene glycol ether and the like can be used. As a special one, a block polymer such as polyoxypropylene glycol ester and ether can also be used. Specifically, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene, oxypropylene block copolymer, sorbitan aliphatic ester, polyoxyethylene sorbitan aliphatic ester, polyoxyethylene sorbitol aliphatic ester Glycerin aliphatic esters, polyoxyethylene aliphatic esters, polyoxyethylene alkylamines, and the like.

The desired product can be obtained by charging a copolymer of α-olefin and maleic anhydride and those described above into a reaction vessel and reacting at a temperature in the range of about 70 ° C. to 180 ° C. for several hours.
A solvent may be added as needed. The final acid value is preferably 80 or more. Acid value 80
This is because alkali resolubility is less likely to be exhibited with less than the resin.

When the aqueous solution is further converted to an aqueous solution, the obtained reaction product can be easily converted to an aqueous solution by neutralizing the reaction product with an alkaline component such as a hydroxide or an organic amine. Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, aqueous ammonia, triethylamine, triethanolamine, and the like, but are not necessarily limited thereto.

When used as an adhesive, a monovalent to trivalent metal compound can be used if necessary. For example, a sodium compound, a zinc compound, a calcium compound, an aluminum compound and the like can be used. However, the present invention is not limited to these.

The tackifier resin used as necessary is generally known as a tackifier. For example, natural products and derivatives thereof include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin,
Polymerized rosin, rosin glycerin ester, hydrogenated rosin pentaerythritol ester and the like can be used. Furthermore, as synthetic resins, petroleum resins, coumarone-indene resins,
Examples include styrene-based resins, phenol-based resins, xylene-based resins, and the like, but are not necessarily limited thereto.

If necessary, additives such as pigments, fillers, plasticizers, pigment dispersants, solvents, thickeners, preservatives, defoamers, leveling agents, and the like can be used in the composition of the present invention.

 Next, the present invention will be specifically described with reference to examples.

Example 1 757.4 g of 1-octadecene, 2.7 g of di-t-butyl peroxide and 10 g of toluene were charged into a flask, and after purging with nitrogen gas, 294.2 g of maleic anhydride was added every 2 minutes while heating and stirring at 150 ° C. 9.8 g and 2.2 g of di-t-butyl peroxide were added in 0.7 g every 20 minutes. After the addition was completed, the temperature of the system was maintained at 160 ° C., and the reaction was further performed for 6 hours. Further, 360.6 g of 12-hydroxystearic acid was added and reacted at 180 ° C. for 6 hours. After the completion of the reaction, the contents were taken out with heating, cooled and solidified.

Example 2 A flask was charged with 17.4 g of 1-octadecene, 2.7 g of di-t-butyl peroxide, and 10 g of toluene. After purging with nitrogen gas, 294.2 g of maleic anhydride was added every 2 minutes while heating and stirring at 150 ° C. 9.8 g and 2.1 g of di-tert-butyl peroxide were added every 20 minutes, 0.7 g each. After completion of the addition, the temperature of the system was maintained at 160 ° C., and the reaction was further performed for 6 hours.
Further, 360.6 g of 12-hydroxystearic acid was added and 18
The reaction was performed at 0 ° C. for 6 hours. After completion of the reaction, 408 g of 25% aqueous ammonia and 2887.1 g of water were added to obtain an aqueous dispersion resin having a solid content of 29.3%.

Example 3 1276 g of Dialen 208, di-t-butyl peroxide
After charging 3.6 g and toluene 14 g into a flask and purging with nitrogen, heating and stirring at 150 ° C., while stirring, 412 g of maleic anhydride was used.
Was added every 2 minutes, and 1.8 g of di-t-butyl peroxide was added every 0.9 minutes. After the addition was completed, 1 g of di-t-butyl peroxide was further added, and the temperature of the system was lowered to 16 ° C.
The reaction was maintained at 0 ° C. for a further 6 hours. Further, 88.3 g of glutamic acid was added and reacted at 170 ° C. for 6 hours. After the completion of the reaction, the contents were taken out with heating, cooled and solidified.

Example 4 1276 g of Dialen 208, di-t-butyl peroxide
After charging 3.6 g and toluene 14 g into a flask and purging with nitrogen, heating and stirring at 150 ° C., while stirring, 412 g of maleic anhydride was used.
Was added every 2 minutes, and 1.8 g of di-t-butyl peroxide was added every 0.9 minutes. After the addition was completed, 1 g of di-t-butyl peroxide was further added, and the temperature of the system was lowered to 16 ° C.
The reaction was maintained at 0 ° C. for a further 6 hours. Further, 88.3 g of glutamic acid was added and reacted at 170 ° C. for 6 hours. After completion of the reaction, 808 g of triethylamine was added, and then water was added to 3290.3.
g was added to obtain an aqueous dispersion resin having a solid content of 29.1%.

Example 5 1350 g of Dialen 30 and di-t-butyl peroxide
2.7 g, toluene 14 g was charged into a flask, and after purging with nitrogen, heated and stirred at 150 ° C., while stirring, maleic anhydride 323 g
Was added every 2 minutes, and 2.1 g of di-tert-butyl peroxide was added 0.7 g every 20 minutes. After the addition was completed, the temperature of the system was maintained at 160 ° C., and the reaction was further performed for 6 hours. Thereafter, 475.2 g of polyoxyethylene nonylphenyl ether having a cloud point of 90 ° C. was added, and the mixture was further reacted for 4 hours. After the completion of the reaction, the contents were taken out with heating, cooled and solidified.

Example 6 1350 g of Dialen 30, di-t-butyl peroxide
2.7 g, toluene 14 g was charged into a flask, and after purging with nitrogen, heated and stirred at 150 ° C., while stirring, maleic anhydride 323 g
Was added every 2 minutes, and 2.1 g of di-tert-butyl peroxide was added 0.7 g every 20 minutes. After the addition was completed, the temperature of the system was maintained at 160 ° C., and the reaction was further performed for 6 hours. Thereafter, 475.2 g of polyoxyethylene nonylphenyl ether having a cloud point of 90 ° C. was added, and the mixture was further reacted for 4 hours. After completion of the reaction, 82.8 g of tetrabutoxytitanium was added. Then, the contents were taken out while hot, cooled, and solidified.

Example 7 1350 g of Dialen 30 and di-t-butyl peroxide
2.7 g, toluene 14 g was charged into a flask, and after purging with nitrogen, heated and stirred at 150 ° C., while stirring, maleic anhydride 323 g
Was added every 2 minutes, and 2.1 g of di-tert-butyl peroxide was added 0.7 g every 20 minutes. After the addition was completed, the temperature of the system was maintained at 160 ° C., and the reaction was further performed for 6 hours. Thereafter, 475.2 g of polyoxyethylene nonylphenyl ether having a cloud point of 90 ° C. was added, and the mixture was further reacted for 4 hours. After completion of the reaction, 529.8 g of a rosin ester having a softening point of 80 to 90 ° C. was added, and the mixture was stirred for about 2 hours. Then, the contents were taken out while hot, cooled and solidified.

Comparative Example 1 A resin was synthesized in the same manner as in Example 1, except that 12-hydroxystearic acid was reacted.

Comparative Example 2 An aqueous dispersion resin having a solid content of 29.8% was synthesized in the same manner as in Example 2, except that 12-hydroxystearic acid was reacted.

Comparative Example 3 50 g of ethylene vinyl acetate resin, 10 g of carnauba wax,
A flask was charged with 40 g of a rosin ester having a softening point of 80 to 90 ° C, and heated and mixed at 180 ° C. Thereafter, the contents were taken out while hot, cooled and solidified.

Comparative Example 4 A flask was charged with 50 g of methyl methacrylate, 40 g of ethyl acrylate, 10 g of acrylic acid, 100 g of isopropyl alcohol, and 1.5 g of benzoyl peroxide.
The mixture was heated and stirred at 80 ° C. One hour later, 0.5 g of benzoyl peroxide was further added, and the mixture was heated and stirred for another 2 hours. After the reaction was completed, 8.4 g of aqueous ammonia was added, and then water 33
0 g was added, and 200 g of the solvent was removed at 100 ° C. for 5 hours. An aqueous dispersion resin having a solid content of 27.2% was obtained.

Table 1 shows the adhesive shear strength, alkali solubility, pigment dispersibility, and antistatic properties of the resins and resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 described above.

〔The invention's effect〕

The resin composition of the present invention thus obtained is a hot-melt adhesive having alkali resolubility, a solventless adhesive,
It can be widely used in non-solvents such as resins for heat-sensitive inks, resins for water-based printing inks, water-based paints, water-based paints and adhesives, and has been found to be extremely useful in industry.

(Note 1) According to JIS K6850, a test was performed using a cardboard piece as a test piece. After the resins of Examples 1, 3, 5 to 7 and Comparative Examples 1 and 3 were melted at 180 ° C., the test pieces were spatulated.

(Note 2) The solubility in a 0.1N aqueous sodium hydroxide solution was tested.

(Note 3) The solid resin was tested by dissolving 50 parts of the resin in 50 parts of toluene. 10 parts of phthalocyanine blue are added to 100 parts of the resin solution, and glass beads having an average particle size of 15 mm
Disperse with let devil filled with 60% for 20 minutes, 50 ℃ 1
The storage stability after a week was measured in a settling tube.

(Note 4) The electrostatic charge of each test piece was measured with a static measurement device STATILON-M (manufactured by Shishido Shokai).

 30-40kV × 15-30kV △ 1-15kV ○

Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 35/00 LHS C08L 35/00 LHS

Claims (3)

(57) [Claims] 1. Production of a resin characterized in that a copolymer of an α-olefin having 6 or more carbon atoms and maleic anhydride is reacted with one or more selected from oxyacids, amino acids and nonionic emulsifiers. Method. 2. A copolymer of an α-olefin having 6 or more carbon atoms and maleic anhydride is reacted with one or more selected from oxyacids, amino acids and nonionic emulsifiers, and further neutralized with an alkaline component. A method for producing an aqueous resin composition, comprising: 3. A copolymer of an α-olefin having 6 or more carbon atoms and maleic anhydride is reacted with one or more selected from oxyacids, amino acids and nonionic emulsifiers, and then mono- or trivalent. A method for producing a resin composition, comprising adding a metal compound and / or a tackifier resin.