JPH0489806A - Resin composition - Google Patents

Abstract

PURPOSE:To improve adhesive properties and pigment dispersion by polymerizing a monomer having an alpha,beta-unsatd. double bond in the presence of a specific compsn. and neutralizing the resulting solid resin, if necessary, to convert it into an aq. compsn. CONSTITUTION:A copolymer of a 6C or higher alpha-olefin (e.g. 1-hexene) with maleic anhydride is made to react with at least one compd. selected from the group consisting of a hydroxy acid (e.g. glycolic acid), an amino acid (e.g. glycine), and a nonionic surfactant (e.g. a polyoxyethylene alkyl ether) at 70-180 deg.C for several hr to give a compsn. having an acid value of 80 or higher. In the presence of the compsn., a monomer having an alpha,beta-unsatd. double bond (e.g. methyl acrylate) is polymerized in an org. solvent using a polymn. initiator (e.g. azobisisobutyronitrile) to give a solid resin, which, if necessary, is neutralized with an alkali and thereby converted into an aq. compsn. The compsn. is compounded with a mono-, di-, or trivalent metallic compd. and/or a tackifier resin according to requirements.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Field of Application) The present invention relates to hot melt adhesives having alkali resolubility, solvent-free adhesives, resins for thermal inks, and resins for water-based printing inks. The present invention relates to a resin composition that can be used in a wide range of applications, including solvent-free water-based paints, water-based paints, and adhesives.

(Conventional Technology) In recent years, environmental issues have become more important, and there is a strong desire to reuse resources. For example, recycling of used paper is a particularly important issue. Currently, cardboard and other materials are collected and used to make thin paper, but because the adhesive used for cardboard is acrylic or general real-melt adhesive, which does not re-melt in alkaline aqueous solutions, recycled paper cannot be used. The current situation is that it takes a lot of effort to remove them. Therefore, there is a need for hot melt adhesives or water-based adhesives that have good adhesive properties and can be redissolved in alkali.

On the other hand, waxes such as carnauba wax and the like have been conventionally used as vehicles for thermal inks. However, to make a thermal ink, good pigment dispersibility is required, and antistatic properties are also required. For this purpose, conventionally, emulsifiers with low LB (1) and pigment dispersants that are easily dispersed in waxes and waxes have been used, and antistatic agents and the like have also been mixed.

Since these are low molecules, they often migrate to the surface of a coated film coated in the form of ink, causing blocking and adversely affecting print passability. In addition, water-based printing inks used water-based emulsifiers with good pigment dispersibility, water-soluble acrylic resins, water-soluble polyester resins, etc., but water-based emulsifiers have significantly poor water resistance, and Polyester resins and the like have drawbacks such as the need to select a polymer composition in order to obtain good pigment dispersibility.

(Problems to be Solved by the Invention) As a result of intensive research to overcome the various drawbacks mentioned above, the present inventor has developed a copolymer of an α-olefin having 6 or more carbon atoms and maleic anhydride. A hepatoma having α5β unsaturated double bonds is polymerized in the presence of a composition in which one or more selected from oxyacids, amino acids, and nonionic emulsifiers are reacted, and if necessary, an alkaline component is added. Basically, by neutralizing it with water and making it water-based, it is possible to use hot-melt adhesives that have good adhesion and re-melt in alkali, and also have good pigment dispersibility on their own and can reduce the amount of antistatic agent added.・7 King, we can provide thermal ink that does not adversely affect print passability,
Furthermore, it has become possible to provide a new water-based resin with good pigment dispersibility as a water-based paint.

(Structure of the Invention) (Means for Solving the Problems) The present inventor has developed a copolymer of an α-olefin having 6 or more carbon atoms (C) and maleic anhydride using an oxyacid, an amino acid, and a nonionic emulsifier selected from oxyacids, amino acids, and nonionic emulsifiers. A resin composition obtained by polymerizing monomers having α2β unsaturated double bonds in the presence of a composition in which one or more of them are reacted, and further neutralizing with an alkaline component to make it aqueous, if necessary. It is about things.

In the copolymer of α-olefin and maleic anhydride, α-olefins include 1-hexene, 1-heptene,
1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, l-hexadecene, 1-octadecene, 1-eicosene, ■=tocosene, ■-tetracosene, ■-hexacosene, 1-oftacosene, Examples include I-triacontin, 1-todriacontin, 1-tetratriacontin, 1-hexatriacontin, 1-octatriacontin, 1-tetracontin, and mixtures thereof. The α-olefin is not particularly limited as long as it has 6 or more carbon atoms, and as a mixture of α-olefins, Mitsubishi Kasei's Dialene 20B (C
8), Dialen 30 (C30 or higher), etc. are commercially available. As the α-olefin of the copolymer, an α-olefin having 10 or more carbon atoms is desirable.

The copolymerization method of α-olefin and maleic anhydride may be carried out without a solvent or in combination with a solvent. Further, maleic anhydride may be charged at once with the α-olefin, or may be added gradually to the polymerization system.

These polymerization methods are not particularly limited. Examples of polymerization initiators used in this case include azobis compounds such as azobisisobutyronitrile and azobis2,4-dimethylvaleronitrile, cumene hydroperoxide,
t-butyl hydroperoxide, benzoyl peroxide, diisopropyl peroxycarbonate, di-t
-butyl peroxide, lauroyl peroxide,
t-butyl peroxyhendoate, potassium persulfate,
Examples include peroxides such as ammonium persulfate. Although not particularly limited to these, it is preferable to use organic peroxides and organic azo compounds.

As the oxyacid to be used next, an aliphatic oxyacid or an aromatic oxyacid can be used. For example, aliphatic oxyacids include glycolic acid, lactic acid, hydroacrylic acid, α-oxybutyric acid, glyceric acid, tartronic acid, malic acid, citric acid, 12-hydroxystearic acid, and aromatic oxyacids include salicylic acid and m-oxybutyric acid. Examples include benzoic acid, p-oxybenzoic acid, gallic acid, mandelic acid, trohaic acid, etc., but basically any organic compound that has a carboxyl group and a hydroxyl group in one molecule can be used, but is not necessarily limited to these. It is not something that will be done. However, aliphatic oxyacids are preferred from the viewpoint of reactivity. Further, as the amino acids used here, aliphatic amino acids, amino acids having an aromatic nucleus, amino acids having a heterocyclic ring, etc. can be used.

For example, aliphatic amino acids include glycine, alanine,
Amino acids with aromatic nuclei include valine, leucine, isoleucine, serine, threonine, cysteine, methionine, aspartic acid, glutamic acid, lysine, arginine, β-alanine, T-aminobutyric acid, and phenylalanine, tyrosine, anthranilic acid, -Aminobenzoic acid, P-aminobenzoic acid, etc., and examples of amino acids having a heterocycle include histyrene, tryptophan, proline, oxybucolin, etc. is not necessarily limited to these, as long as it has a carboxyl group and an amino group in the molecule.

Further, the nonionic emulsifier used here includes polyethylene glycol ester, polyethylene glycol ether, etc., but block polymers such as polyoxypropylene glycol ester and ether can also be used as special ones. Specifically, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivatives,
Examples include oxyethylene, oxypropylene block copolymer, sorbitan aliphatic ester, polyoxyethylene sorbitan aliphatic ester, polyoxyethylene sorbitol aliphatic ester, glycerin aliphatic ester, polyoxyethylene aliphatic ester, polyoxyethylene alkylamine, etc. .

The desired product can be obtained by charging the α-olefin, maleic anhydride copolymer, and the above-mentioned components into a reaction vessel and reacting them at a temperature of about 70° C. to 180° C. for several hours.

A solvent may be added if necessary. Further, the final acid value is preferably 80 or more. This is because a resin with an acid value of 80 or less is difficult to exhibit alkali resolubility. Furthermore, the monomers having α,β unsaturated double bonds in the present invention include the following monomers.

(1) Acrylic ester or methacrylic ester having an alkyl group having 1 to 18 carbon atoms, such as methyl acrylate, ethyl acrylate, n-butyl acrylate,
1so-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, cyclohexyl acrylate, etc., methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid n
-butyl, 1SO-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, and cyclohexyl methacrylate. (2) Number of carbons: 2
Hydroxyl alkyl acrylates having ~12 alkyl groups, and hydroxyl methacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 5-hydroxyamyl acrylate 6-hydroxyhexyl acrylate , 8-hydroxyoctyl acrylate, 10-hydroxydecyl acrylate, etc., 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate,
5-hydroxyamyl methacrylate, 6- methacrylate
Hydroxyhexyl, 8-hydroxyoctyl methacrylate, 10-hydroxydecyl methacrylate, etc.
Furthermore, other substituents may be introduced into the alkyl group, examples of which include amino groups, epoxy groups, halide groups, nitrile groups, and amide groups.

(3) Others, such as hydrolyzable silyl group-containing vinyl monomers, silicone acrylate, silicone methacrylate, fluorine acrylate, fluorine methacrylate, acrylonitrile, styrene, vinyltoluene, methacrylonitrile, dialkyl itaconate, dialkyl fumarate, Examples include allyl alcohol, acrylic chloride, vinyl acetate, vinyl chloride, vinylidene chloride, vinylpyridine, vinylpyrrolidone, methyl vinyl ketone, and rosin having a double bond.

In general, polymerization is carried out by dissolving α-olefin, maleic anhydride copolymer, and/or partial reactants in an organic solvent, and then dropping a monomer solution and a polymerization initiator into this solution. Alternatively, the polymerization may be carried out in the presence of a mixture that has been neutralized with an alkaline component to make it aqueous. Furthermore, it is also possible to polymerize in a solvent-free system. At this time, by appropriately selecting synthesis conditions, it is possible to use a solution type, an aqueous dispersion type, or a solvent-free type, and the solid content concentration and viscosity can be freely changed. Further, when polymerization is carried out in an organic solvent having a solubility parameter of 8.3 or less, the resin becomes a so-called non-aqueous dispersion resin. As the initiator used during polymerization, a general polymerization initiator is used. For example, azobisisobutyronitrile, azobis2
4-dimethylvaleronitrile, 4゜4゛-azobis(4
Ab compounds such as -cyanohalelic acid), organic peroxides such as hendiyl peroxide, and lauroyl peroxide are also used. Furthermore, water-soluble initiators such as ammonium persulfate, potassium persulfate, and 2,2'-azobis(2-methylpropionamidine) dihydrochloride can also be used.

Further, when the solid resin obtained in the above reaction is to be made aqueous, it can be easily made aqueous by neutralizing the obtained reaction product with an alkaline component such as a hydroxide or an organic amine. Specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, aqueous ammonia, triethylamine,
Examples include, but are not limited to, triethanolamine and the like.

Furthermore, when used as an adhesive, monovalent to trivalent metal compounds can be used if necessary. For example, sodium compounds, zinc compounds, calcium compounds, aluminum compounds, etc. can be used, but are not necessarily limited to these.

Further, the tackifier resin used as necessary is generally known as a tackifier.

For example, as natural products and derivatives thereof, gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, rosin glycerin ester, hydrogenated rosin pentaerythritol ester, etc. can be used. Furthermore, examples of synthetic resins include petroleum resins, coumaron-indene resins, styrene resins, phenol resins, xylene resins, etc., but are not necessarily limited to these.

Additives such as pigments, fillers, plasticizers, pigment dispersants, solvents, thickeners, preservatives, antifoaming agents, and leveling agents can also be used in the composition of the present invention, if necessary. next,
The present invention will be specifically described with reference to examples.

Production 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.
After purging with nitrogen gas, while heating and stirring at 150°C, 294.2 g of maleic anhydride was added at a rate of 9.8 g every 2 minutes, and 2.1 g of di-t-butyl peroxide was added at a rate of 0.7 g every 20 minutes. were added one by one. After the addition is complete, the temperature of the system is increased to 16
The temperature was maintained at 0°C for 4 hours, and the reaction was continued for an additional 6 hours. 12 more
- 18 by adding 901.5g of hydroxystearic acid
The reaction was carried out at 0''C for 6 hours. After the reaction was completed, the contents were taken out while still hot and cooled to solidify.

Production Example 2 1276 g of Dialene 208, 3.6 g of di-t-butyl peroxide, and 14 g of toluene were charged into a flask.
After purging with nitrogen, while heating and stirring at 150"C, 412 g of maleic anhydride was added at a rate of 13.7 g every 2 minutes, and 1.8 g of di-t-butyl peroxide was added at a rate of 0.5 g every 20 minutes.
9 g each was added. After the addition was completed, 1 g of di-t-butyl peroxide was further added, the temperature of the system was maintained at 160°C, and the reaction was continued for an additional 6 hours. In addition, 26 glutamic acid
4.9g was added and reacted at 180°C for 6 hours. After the reaction was completed, the contents were taken out while still hot and cooled to solidify.

Production Example 3 1,350 g of Dialene 30, 2.7 g of di-t-butyl peroxide, and 14 g of toluene were placed in a flask, and the atmosphere was replaced with nitrogen. While heating and stirring at 150°C, 323 g of maleic anhydride was heated at 10° every 2 minutes. 8 g each, and 2.1 g of di-t-butyl peroxide every 20 minutes.
g each. After the addition was completed, the temperature of the system was maintained at 160°C and the reaction was continued for an additional 6 hours. After that, landing point 90'
C polyoxyethylene nonylphenyl ether 95
0.4g was added and the reaction was further continued for 4 hours. After the reaction was completed, the contents were taken out while still hot and cooled to solidify.

Example: After adding 50 g of 25% ammonia water to 500 g of the resin obtained in Production Example 1, 3283 g of water was added, and 1 g of ammonium persulfate was further added, the temperature was raised to 80"C, and methacrylic acid was added. 250g of methyl, 2-acrylic acid
250 g of ethylxyl was added dropwise over 2 hours. Thereafter, the reaction was continued for another 2 hours to obtain an aqueous dispersion resin with a solid content of 30%.

Example 2 Triethylamine 5 was added to 200 g of the resin obtained in Production Example 3.
After adding 0g, add 1350g of water, further add 1g of ammonium persulfate, raise the temperature to 80°C, and add 200g of 2.2.2-trifluoromethacrylate.
, 200 g of methyl methacrylate was added dropwise over 2 hours. Thereafter, the reaction was continued for another 2 hours to obtain an aqueous dispersion resin with a solid content of 29.7%.

Example 3 100g of the resin obtained in Production Example 2 was charged into a flask,
After melting at 100°C, the atmosphere was replaced with nitrogen. 60 g of vinyl acetate, 32 g of ethyl acrylate, and 8 g of acrylic acid were dissolved, and the 7-mer solution thereof was added dropwise over 1 hour, and 1.6 g of benzoyl peroxide was added 4 times at 0.5 g every 20 minutes. The mixture was further heated and stirred for 2 hours. After the reaction was completed, the contents were taken out while still hot, cooled, and solidified.

Example 4 100g of the resin obtained in Production Example 2 was charged into a flask,
After melting at 100°C, the atmosphere was replaced with nitrogen. 60 g of vinyl acetate, 32 g of ethyl acrylate, and 8 g of acrylic acid were dissolved, and the monomer solution was added dropwise over 1 hour, and 1.6 g of benzoyl peroxide was added 4 times at 0.5 g every 20 minutes. The mixture was further heated and stirred for 2 hours. After the reaction was completed, 36.8g of ammonia water and 630g of water were added to reduce the solid content to 2.
An 8.2% aqueous dispersion resin was obtained.

Example 5 50 g of the resin obtained in Production Example 3 and 50 g of ethylcyclohexane were placed in a flask, and after purging with nitrogen, the temperature was heated to 80°C.
heated to. Vinyl acetate 30g, ethyl acrylate 16
g, 4 g of acrylic acid, 50 g of ethylcyclohexane, and 0.75 g of benzoyl peroxide were melted, and the monomer solution was added dropwise over 1 hour. After the dropwise addition was completed, 0.25 g of benzoyl peroxide was further added, and the mixture was further heated and stirred for 2 hours. A white resin dispersion with a solid content of 49.9% was obtained.

Example 6 50 g of the resin obtained in Production Example 3 and 50 g of ethylcyclohexane were placed in a flask, and after purging with nitrogen, the temperature was 80°C.
heated to. Vinyl acetate 18g, ethyl acrylate 9.
6g, acrylic acid 2.4g, ethylcyclohexane 50
g, and 0.45 g of benzoyl peroxide were dissolved, and the monomer solution was added dropwise over 1 hour. After the dropwise addition was completed, 0.15 g of benzoyl peroxide was further added, and the mixture was further heated and stirred for 2 hours. Then, add 2.5% tetrabutoxytitanium.
After adding g, the mixture was stirred for about 1 hour. After the reaction was completed, the contents were taken out while still hot, cooled, and solidified.

Example 7 50 g of the resin obtained in Production Example 3 and 50 g of ethylcyclohexane were placed in a flask, and after purging with nitrogen, the temperature was 80°C.
heated to. Vinyl acetate 18g, ethyl acrylate 9.
6g, acrylic acid 2.4g, ethylcyclohexane 50
g, and 0.45 g of benzoyl peroxide were dissolved, and the monomer solution was added dropwise over 1 hour. After the dropwise addition was completed, 0.15 g of benzoyl peroxide was further added, and the mixture was further heated and stirred for 2 hours. After the reaction was completed, 20g of rosin ester having a softening point of 80 to 90°C was added, followed by stirring for about 1 hour.

After the reaction was completed, the contents were taken out while still hot, cooled, and solidified.

Comparative example 1 700 g of water, 2 sodium dodecylbenzenesulfonate
g was placed in a flask, the atmosphere was replaced with nitrogen, and the flask was heated to 80°C. Dissolve 0.75 g of potassium persulfate, 150 g of methyl methacrylate, and 1 portion of 2-ethylhexyl acrylate.
A mixed solution of 45 g of acrylic acid and 5 g of acrylic acid was added dropwise over 1 hour. After completing the dropping, add 0.2 more potassium persulfate.
5 g was added, and the mixture was further heated and stirred for 2 hours. An aqueous dispersion resin having a solid content of 29.4% was obtained.

Comparative Example 2 Synthesis was carried out in the same manner as in Production Example 1 except that 12-hydroxystearic acid was reacted. Examples 1 to 7 above,
Table 1 shows the adhesive shear strength, alkali solubility, pigment dispersibility, and antistatic properties of the resins and resin compositions obtained in Comparative Examples 1 and 2.

(Effects of the Invention) The thus obtained resin composition of the present invention can be used as a hot-melt adhesive having alkali resolubility, a solvent-free adhesive,
It has been found that it can be used in a wide range of applications, including resins for thermal inks, resins for water-based printing inks, water-based paints, solvent-free paints, water-based paints, and adhesives, and is extremely useful industrially.

Table 1 (Note 2) 0. The solubility in IN 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. Add 10 parts of phthalocyanine blue to 100 parts of the resin solution, disperse for 20 minutes in a Rhett Devil filled with 60% by volume glass beads with an average particle size of 15 mm, and check the storage stability after 1 week at 50°C in a sedimentation tube. It was measured with

(E4) The electrostatic charge of each test piece was measured using a static electricity meter, Statyron-M (manufactured by Sagetsu Shokai).

30~40kV x 15~30kv △ 0~15kV ○ Patent applicant Toyo Ink Manufacturing Co., Ltd. (Note 1) JIS
The test was conducted according to K6850 using a cardboard piece as a test piece. The resins of Examples 3.5 to 7 and Comparative Example 2 were melted at 180°C, and then applied to test pieces with a spatula.

Claims (1)

[Claims] 1. Existence of a composition in which 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. A resin composition characterized by polymerizing a monomer having an α,β unsaturated double bond as described below, and further neutralizing it with an alkaline component as necessary to make it aqueous. 2. The resin composition according to claim 1, further comprising a monovalent to trivalent metal compound and/or a tackifier resin.