DE2749238A1 - DIMENSIONS FOR PAINTING AND PRINTING INKS - Google Patents

Description

PATENT LAWYERS DR. E. WIEGAND DIPL-ING. W. DR. M. KÖHLER DIPL-ING. C. GERNHARDT 27 4 3238

MÖNCHEN HAMBURG

TELEPHONE: 55547 «8000 M 0 N C H E N 2,

TELEGRAMS: KARPATENT *) MATHHDENSTRASSE 12

TELEX: 5 29 0 * 8 KARPO

W. 43 000/77 - Ko / Ja November 3, 1977

Denki Kagaku Kogyo Kabushiki Kaisha, Chiyoda-ku,

Tokyo (Japan)

Compound for paints and printing inks

The invention relates to a composition for paints and printing inks having good coating properties and in particular Compositions for paints and printing inks, which are a block copolymer of vinyl-substituted aromatic Contains hydrocarbons and conjugated diene as binders and good wetting by inorganic pigments and have good dispersibility of these pigments.

According to the invention, block copolymers are made from a vinyl-substituted aromatic hydrocarbon and a conjugated diene, wherein alkali metal atoms with at least linked to one end of the polymer chain by polymerizing vinyl-substituted aromatic carbons · «

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hydrogen and conjugated diene monomers using an alkali metal or an organoalkali metal compound received as initiator. The block copolymer thus obtained is introduced with a polar reactant treated polar groups in the polymer chain end.

There are masses for paints and printing inks by incorporating inorganic pigments into the block copolymer with the terminal polar group.

Styrene-butadiene type resins have heretofore been used as binders for paints for concrete, containers and others Purposes and used for printing inks, taking properties such as water resistance, chemical resistance and abrasion resistance required are.

Since these styrene-butadiene type resins are usually produced by a radical polymerization method, they have a broad molecular weight distribution including a substantial amount of polymers low molecular weight and also have a polymer chain configuration, with styrene and butadiene units are arbitrarily arranged therein. Therefore, the coating or film formed by these resins is of concern the mechanical strength significantly deteriorated and also with regard to such properties as water resistance, Weather resistance and chemical resistance, reduced.

Various methods have been proposed to improve the styrene-butadiene resins in terms of film strength, which, however, are unsuitable for use as binders for paints and printing inks. For example, will a polystyrene of high impact resistance with improved

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Film strength obtained by grafting polystyrene onto elastomeric polymers. However, if this resin in one Solvents, such as xylene, for example, are dissolved and converted into a cast film, separate elastomers Particles on the film surface and the resulting film gives an extremely offensive appearance. In the same way For example, ABS resins obtained by copolymerization with acrylic monomers differ when these resins are dissolved in a solvent such as xylene and processed into a cast film , gelled elastomeric particles are deposited on the film surface, and the film thus obtained is superior in appearance significantly deteriorated.

On the other hand, it is known that block copolymers having a molecular configuration regulated therein by copolymerization of vinyl substituted hydrocarbon and conjugated diene monomers in an anionic living Polymerization method (living polymerization) using an alkali metal or organoalkali metal can be obtained as an initiator. It is also known that block copolymers with different properties by change the molecular weight, the molecular weight distribution and the composition ratio of the monomers can be obtained. For example, when is the styrene / butadiene ratio is in the range from about 25/75 to 50/50, the block copolymer obtained is a transparent thermoplastic Elastomer used for shoe soles, hot melt adhesives, plastic mixtures and other purposes can be.

Also block copolymers with a styrene / butadiene ratio from about 50/50 to 70/30 is a transparent soft

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Resin and can be used for stretch film, toy materials and other purposes. Block copolymers are also used having a styrene / butadiene ratio of about 75/25 to 90/10 is a rigid transparent resin that is resistant to mechanical properties, such as impact resistance and cold resistance is.

There have been studies on the use of styrene-butadiene type resins, which by the anionic living polymerization were produced, carried out for a binder for paints and printing inks, and doing so it has been found that coating compositions which contain these resins as binders produce a coating or film with a smooth Surface without the occurrence of gel formation and that these coating compositions, which are thixotropic, have good coating processability and are suitable as anti-corrosive materials. It was also found that one Printing ink made using these resins as a binder is suitable for a specific printing ink which gives a special matted soft shade.

However, the block copolymers obtained by the anionic living polymerization give a poor one Wetting by inorganic pigments and therefore the dispersibility of pigments in the paints and inks deteriorated. Therefore, when using masses with a practically feasible concentration of pigments, the film or coating obtained in terms of such properties as gloss and water resistance compared to the use of compositions obtained using copolymers obtained by radical polymerization were produced, deteriorated considerably.

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Thus, the styrene / butadiene copolymers obtained by the living polymerization are in terms of mechanical and chemical strength of the resin itself such far superior to that by the radical Polymerization have been obtained, but they are nevertheless limited to a specific field in application to the paint and the ink composition.

Furthermore, U.S. Patents 3,108,994 and 3,135,716 teach a process for producing a terminally reactive Polymers described by reacting living polymers with a suitable reactant, with mercapto, Hydroxy or acid groups are introduced as a reactive group and the terminally reactive polymer obtained for Networking is used.

Dispersions of titanium dioxide particles in toluene, which are stabilized by a partially carboxylated styrene-butadiene block copolymer, are also disclosed in Advan.Chem. Ser., Vol. 99, pp. 379-396 (1971), "Dispersion of Solid Particles in Organic Media "by G.E. Molan and E.H. Richardson described. The carboxylation takes place by adding thioglycolic acid to the main chain of the polymers.

One object of the invention consists in paint and printing ink compositions which have a living by the anionic Polymerization obtained block copolymer of vinyl-substituted aromatic hydrocarbon and conjugated Diene and inorganic pigments include and have good pigment wetting and dispersibility of the pigments.

Another object of the invention consists in paints and printing ink compositions which are composed of a block copolymer vinyl-substituted aromatic hydrocarbon and con-

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have jugated diene and inorganic pigments, wherein the masses form a film or coating which in properties such as gloss, water resistance and weather resistance is improved.

It has now been found that block copolymers which contain no polar groups in the polymer chain and which by the anionic living polymerization are obtained, result in poor wetting by pigments and that too their dispersion stability is reduced and that the wetting by pigments and their dispersibility greatly improved by introducing a limited amount of polar groups into the copolymer at its chain ends will.

According to the invention, a composition for paints and printing inks is specified which:

(A) a block copolymer of vinyl-substituted aromatic hydrocarbon and conjugated diene which Polymers with introduced into the ends of the polymer chain polar groups, which by reaction of a vinyl-substituted aromatic hydrocarbon and conjugated diene constructed block copolymers, wherein Alkali metal atoms are connected to at least one end of the polar chain, with one for reaction with the Alkali atom-capable polar reactant was obtained, the block copolymer with the 'terminal Alkali atoms from polymerization of vinyl substituted aromatic hydrocarbon and conjugated diene monomers using an alkali metal or organoalkali metal as an initiator, and

(B) comprises at least one inorganic pigment.

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The invention is explained with reference to the drawings, in which

Fig. 1 is a graph showing the relationship between pigment concentration and film gloss with reference shows on styrene-butadiene block copolymers in whose polymer chain ends polar groups are introduced,

Fig. 2 is a graph showing the relationship between pigment concentration and film gloss with respect to Shows styrene / butadiene block copolymers with different molecular weights,

Fig. 3 is a graph showing the relationship between pigment concentration and film gloss with respect to Shows block copolymers with different molecular structures

Fig. 4 is a graph showing the relationship

between pigment concentration and film gloss in relation to

with Block copolymers <introduced into the polymer chain end shows different polar groups

Fig. 5 is a graph showing the relationship between pigment concentration, film gloss and content of the polymer with introduced into the polymer chain end shows polar groups with respect to block copolymers,

6 is a photomicrograph of titanium oxide (rutile structure) used as a pigment;

7 is a photomicrograph of a film covered by a non-terminal polymer coating contain polar groups and titanium oxide was formed, and

8 is a photomicrograph of a film formed by a coating composition of carboxyl-terminated polymers and titanium oxide;

reproduce.

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The invention is described below on the basis of preferred embodiments.

According to the invention, when oxygen, nitrogen or sulfur containing polar groups are in the ends of the polymers obtained by an anionic living polymerization are introduced, the wetting of the obtained Polymers significantly increased by pigments and, surprisingly, can have a pronounced effect with regard to the improvement of the dispersibility of inorganic pigments can be found, although the The amount of polar groups contained in the entire polymer is very small. In addition, it can be a remarkable Effect also in terms of improving various physical properties, such as gloss and water resistance of the coating film / composition obtained by compounding a pigment of suitable concentration obtained. Furthermore, when the resin is used as a binder, a composition for printing inks found that significant effects in terms of improving mechanical strength and Gloss of the coating film and the storage stabilization of the printing ink can be achieved.

The vinyl-substituted aromatic hydrocarbon usable includes, for example, styrene and various Alkylstyrenes, such as a-methylstyrene, vinyltoluene, tert-butyl styrene and similar materials and their mixtures. Also include those used conjugates For example, butadiene, isoprene and similar materials and mixtures thereof are used. Furthermore is the polymer that can be used according to the invention, a block copolymer composed of polymers from the

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above-mentioned monomers consists of soft to hard resinous polymer is sufficient and has a block structure as shown below.

The compositional ratio of vinyl substituted aromatic hydrocarbon to conjugated diene In the block copolymer, it is not particularly limited, but ratios of about 50 to 95 to 50 to 5 become preferred.

The structures of the block copolymers are represented by (AB) _n , (A-B) _n -A and (A -B) _n X, where A is a polymer comprising predominantly vinyl-substituted aromatic hydrocarbon units and B is a polymer comprising predominantly conjugated diene units.

However, it may be permissible that a small amount of conjugated diene is polymerized with the sequence A copo3 and a small amount of vinyl-substituted aromatic hydrocarbon is copolymerized with sequence B, η is an integer from 1 to 10 and X is the remainder of a coupling agent with more than two functional ones Residues or a polyfunctional polymerization initiator. The sequences A and B of the structure mentioned above can be linked by a clear cut bond and can also be in the form of a conical copolymer U.S. Patent 3,947,536.

Alkali metals that can be used as polymerization initiators include, for example, lithium, Sodium and potassium. Furthermore, as organoalkali metal compounds, naphthalene complexes of metals such as lithium, Sodium and potassium or alkyl or aryl alkali compounds,

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such as butyllithium can be used. In addition, polyfunctional initiators, such as organodilithium compounds and organopoly lithium compounds can be used.

If the polymerization is carried out using an organomonolithium compound, they have polymers produced by treatment with a polar reactant have a structure in which the polar Group is only introduced into one end of the polymer chains. When using an organodilithium compound show the polymers obtained by reaction with a polar reactant after polymerization have a structure in which polar groups are connected to both ends of the polymer chains.

Furthermore, when a polyfunctional initiator is used, branched star polymers are formed and the have polymers prepared by reacting the branched star polymers with a polar reactant a structure in which polar groups are introduced into each end of the branched polymer chains of the star polymer

be used

are. Furthermore, when polymers / produced by polymerization using an organomonolithium initiator, the polymers obtained with a polyfunctional coupling agent were treated and then the star polymers produced in this way with a polar Reactants treated, polar groups introduced near the center of the polymer chain.

According to the invention, the polymers which contain polar groups at their chain ends include all Polymers which have polar groups at least at one end of the molecule of the polymers with different block structures

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-JT-

Have doors made by polymerization using the initiator and reaction with a polar Reactants are produced. However, the effects of the terminal polar group vary depending on the structure of the block copolymer and the content of polymers with terminal polar groups throughout the polymer. For example, it has been found that when the polymerization is carried out using a polyfunctional initiator to introduce polar groups into many ends of the polymer chains are carried out, the effects of the polar groups introduced become more pronounced, than in the case of introducing a polar group into one end only.

It has also been found that polymers containing the polar group at the center of the polymeric chain, by crosslinking a linear polymer with a polyfunctional coupling agent such as divinylbenzene to produce a star polymer and react of the star polymer with a polar reactant have a smaller effect of the polar group bring about, as polymers which have polar groups at polymer chain ends.

According to the invention, block copolymers can be prepared in an inert atmosphere in the presence of a polymerization solvent.

Usable solvents include benzene, cyclohexane, toluene, xy] ol, ethylbenzene, tetrahydrofuran, ethylcyclohexane, methylcyclohexane and mixtures thereof. Any solvents other than the above in which anionic living polymerization can be carried out can also be used.

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Furthermore, the polymerization temperature can be appropriately selected.

Polar reactants which can be used in accordance with the invention include materials necessary to react with the terminal alkali metal are capable and thereby to a hydrophilic polar group, the Containing oxygen, nitrogen or sulfur lead to the polar ends of the chain.

Examples of these oxygen-, nitrogen- or sulfur-containing reactants are as follows:

1) Reagent for introducing a carboxyl radical: carbon dioxide.

2) Reagent for the introduction of a hydroxyl radical: Oxygen, sulfur dioxide, ethylene oxide, propylene oxide, styrene oxide, aldehydes, ketones, halohydrin and diepoxybutane.

3) Reactive agents for introducing a thiol residue: sulfur, carbon disulfide and alkylene sulfides.

U) Reagent for introducing an amine residue: alkyleneimines.

5) Reagent for the introduction of a sulfon residue: Sulfuryl chloride.

6) Reagent for the addition of an acid anhydride: Maleic anhydride, succinic anhydride and phthalic anhydride.

7) Other reagents for the addition of polar compounds: Phosgene, thionyl chloride, cyanide halides, cyano, toluene

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2,4-diisocyanate, cyclic disulfides, p-bromoaniline, Ethyl adipate and ethyl sebacate.

Furthermore, the terminal introduction of the polar group by polymerizing an anionically polymerizable polar monomer in a. Amount of a few molecules of vinyl-substituted aromatic hydrocarbon-conjugated diene block copolymers whose polymer chain ends are carried out.

Examples of these polar monomers are epoxides, such as for example ethylene oxide and propylene oxide alkylene sulfides such as ethylene sulfide and propylene sulfide, Acrylates such as isopropyl acrylate; Methacrylates e.g. methyl methacrylate, ethyl methacrylate, hexyl methacrylate and allyl methacrylate ·, vinyl pyridine; Siloxanes, e.g., hexamethylcyclotrisiloxane, octamethylcyclotrisiloxane, and octamethylcyclotetrasiloxane; 1,2-dihydronaphthalene, 1-methecryloxy-2-butyne and formaldehyde.

Reference to such polar reactants is contained, for example, in "Synthesis of Block Polymers by Homogeneous Anionic Polymerization ¹¹ LJ Fetters, J. Polymer Sci. Part C, No. 26, pages 1 to 35 (1969).

Polar groups introduced into the polymer chain ends in this way have a great effect, even though they are not inserted in all ends.

For example, in the reaction of terminal alkali metal-containing polymers with polar reactants, a side reaction, such as coupling between polymer molecules, may in some cases depending on the reaction conditions, e.g. the type of polar reaction

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tion agent, the structure of the polymers, the solvents, the reaction temperature and the reaction vessel appear. When such a coupling reaction occurs, polar groups become at the center of the polymer chains introduced.

Further, if the coupling reaction occurs during the reaction with the polar reactant after Polymerization using the polyfunctional Initiator takes place, the polymers obtained gel, so that the degree of conversion between the terminal Alkali metal containing polymers and the polar reactant is significantly reduced. A characteristic kum the. However, the invention resides in that the effect of introducing polar groups can be obtained if polar groups are introduced into at least a portion of the polymer chain ends, even though not all of them Ends are introduced due to the side reaction such as the coupling reaction. For example, if an anionic living polymerization in benzene using an organodilithium initiator to obtain is carried out by polymers with alkali metals at both ends and then polar groups are introduced, by introducing carbon dioxide gas into the obtained polymer solution at around room temperature, the polymer solution can instantly gel so that polar groups are not introduced at all of the ends of the polymer chains.

Thus, in general, the amount of polar groups introduced by this method is extremely small.

However, it has been found that the effects of the introduced polar groups become pronounced when the terminal polar group-containing polymers make up more than about 4 wt. # of the total polymers.

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In addition, when a living polymerization is caused by a side reaction such as chain transfer is carried out in a polymerization solvent such as toluene and then a polar reactant such as carbon dioxide gas into the resulting polymer solution is introduced, the amount of polar groups introduced into the ends of the polymer chain is very small.

It has been found, however, that even in such a case, the effects of the introduced polar groups become significant when the terminal polar group-containing polymers constitute more than about k weight 96 of the total polymers.

It is theoretically possible to produce polymers which contain up to 100% by weight of terminally introduced polar groups although the content of terminal polar groups is usually in the range of about 4 to 60% by weight of the total polymer.

These terminal polar group-containing polymers can be prepared by various methods will.

For example, polymers containing lithium carboxylate at both ends by polymerizing styrene with butadiene in xylene in a nitrogen atmosphere Using an alkyldilithium initiator and supplying carbon dioxide gas into the polymer solution obtained will.

The polymer solution obtained in this way can be compounded with pigments for the production of coating compositions.

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Before the preparation, however, it is expedient to use an excess of water or alcohols or other Lewis acids to add to the polymer chains to lower the viscosity of the polymer solution.

Furthermore, the polymers produced in this way can be removed by precipitation with methanol or stripping with steam are separated and removed as a dry powder to produce a coating mass.

Inorganic pigments to be corapounded various metals, metal oxides, metal sulfates, chromates and metal carbonates and other materials. Examples are titanium oxide, zinc white, lead white, lithopone, white aluminum oxide, precipitated barium sulfate, finely powdered Silicic acid, iron black, red oxide, silver venilion, red copper oxide, molybdate chrome orange, chrome yellow, Zinc chromate, chromium oxide, Prussian blue, ultramarine, aluminum powder and the like.

With regard to carbon black, the same effects as metal oxides can be achieved.

The compounding is carried out in an organic solvent with the help of a commonly used one Stirrer such as a ball mill and attritor mill.

The amount of the inorganic pigment is appropriately chosen depending on the coating film concerned, the Molecular weight of the polymer with polar groups and the materials to be compounded are set. In general the pigment concentration is in the range from 5 to 80 vol. 56, preferably 10 to 50 vol. The solution

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agents for the coating composition are not particularly limited, however, non-polar solvents can achieve particularly beneficial effects. These are, for example, aromatic Vinyl compounds such as xylene, ethylbenzene and toluene, alicyclic compounds such as ethylcyclohexane and Methylcyclohexane and other materials such as petroleum constituents such as ligroin.

The coating composition containing these solvents has massive thixotropic and storage stability (hardly separated). Any solvent that dissolves resins can, of course, can be used, and it is possible to use their mixtures as well.

The invention is illustrated by the following examples.

example 1

AB type block copolymer (A: polystyrene, B: polybutadiene) was prepared by anionic living polymerization in a nitrogen atmosphere using benzene as a polymerization solvent and secondary butyllithium as an initiator. A glass autoclave with a capacity of 2 liters was used as the polymerization vessel. 1200 g of well-dried benzene and 2 *> 5 g of styrene were introduced into the autoclave, and 45 g of purified butadiene were also dissolved in the benzene-styrene mixed solution. A solution of 6.0 millimoles of secondary butyllithium in heptane was added while the temperature in the polymerization vessel was maintained at 20 ^° C. The temperature was raised to 60 ⁰ C.

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After about 60 minutes, the polymerization of butadiene and styrene had ended and the contents were colored red. Furthermore, terminal carboxyl group-containing block copolymer of the BAC type (C: carboxyl group) by introducing carbon dioxide gas into the above red AB-type block copolymer solution at a flow rate of about 10 l / min. Polymer powders were made by separating the polymers from the Polymer solution prepared using the steam stripping method.

As a result of the analysis, it was found that both the AB-type and the BAC-type block copolymer Block copolymers with a numerical average molecular weight of 5 × 10, which consisted of 85% by weight Polystyrene and 15 wt.% Polybutadiene were built up. The BAC type block copolymer gave due to Thin layer chromatography about 50% polymer with terminal carboxyl groups, based on the total polymer. Also based on an NMR analysis, the two block copolymers of the AB type and BAC type are conical BlocR copolymers, which contained a small area built up from any styrene-butadiene copolymers was.

Then two masses were made, each one of the above AB-type and BAC-type block copolymers with titanium oxide (rutile structure) and xylene by means of a ball mill was mixed for about 10 hours. Each of the two masses was placed on a well washed steel plate built up with a film applicator and dried at room temperature for two weeks. It became a mirror reflection measured at 60 ° C (gloss value) with reference to the coating film. The results are shown in FIG.

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It can be clearly seen from FIG. 1 that the polymer containing terminal carboxyl groups (curve BAC) does not have any carboxyl groups in terms of film gloss containing polymers (curve AB) is far superior.

Example 2

There were three BAC-type block copolymers containing terminal polar groups and one numerical average molecular weight of 3 x 10, 5x10 or 10 χ 10 ^, and from 85 wt.% Styrene and 15 wt. # Butadiene were built up, changing the amount of initiator by the same anionic living polymerization, prepared as in Example 1.

For comparison, three block copolymers of the BA type, which contained no terminal carboxyl group, the same composition as the block copolymer of the BAC type and with the same numerical average molecular weight of 3 χ 10 ⁴ , 5x10 * and 10 χ 10 ^ in the prepared in the same way as in Example 1. The respective copolymers were compounded with a titanium oxide pigment (rutile structure) and xylene by means of a ball mill according to the same method as in Example 1. The relationship between pigment concentration and film gloss was measured. The results are shown in FIG.

From Flg. 2 it can be seen that in each case of copolymers of different molecular weight the a carboxyl group at one end of the BAC type polymer containing polymer. Superior film gloss compared to the polymers containing no polar group

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of the AB type with the same pigment concentration.

Example 3

(1) BAC type conical block copolymers, the terminal Contained carboxyl groups, a numerical average molecular weight of 50,000 on and off 85% by weight of styrene and 15% by weight of butadiene were built up, and AB-type conical block copolymers containing no terminal polar group of the same composition were prepared by the same anionic living polymerization method as in Example 1.

(2) CABAC type conical block copolymers containing carboxyl groups at both ends of the polymer and had a numerical average molecular weight of 50 and composed of 85% by weight of styrene and 15% by weight of butadiene were constructed and conical, no terminal polar group-containing block copolymers of the ΑΒΑ-type, the same composition were made using a butadiene oligomer-dilithium initiator by the same anionic living polymerization as in Example 4 prepared.

(3) A star polymer was prepared using a linear polymer using benzene and a secondary butyllithium initiator in a nitrogen atmosphere and a coupling agent was added.

The polymerization was carried out in a glass autoclave with a capacity of 2 liters. 1200g of well-dried benzene and 255g of styrene was fed while maintaining the temperature in the autoclave at 20 ⁰ C and

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a solution of 60 millimoles of sec-butyllithium in heptane was also added. Once the temperature had risen to 6O ⁰ C, the polymerization of styrene proceeded and the contents were red. After the temperature had ^{cooled down to 20 °} C. again, 45 g of purified butadiene were blown into the copolymer solution. The temperature was increased to 60 ^° C. and held for 2 hours. The polymer solution turned a little yellow. Then 480 millimoles of a 10X benzene solution of well-dried divinylbenzene was introduced into the polymer solution with stirring. The contents of the autoclave turned deep red and coupling of linear polymers occurred to give an (AB) ₁₀ -type star block copolymer.

Then, after the above deep red polymer solution was ^{heated to about 80 °} C., carbon dioxide gas was blown in at a flow rate of about 20 l / min and a star block copolymer containing carboxyl groups was obtained. Based on the analysis results, the star block copolymers of (AB) ₁ Q-type and (ABC)% polystyrene proved ₁₀ type as polyverzweigte block copolymers having a number average molecular weight of 5 x 10 consisting of 85 wt. And 15 wt.% Polybutadiene.

(4) About the above-mentioned AB-type conical block copolymers, ΑΒΑ-type conical block copolymers, (AB) _1o -type star block copolymers, BAC-type conical block copolymers, CABAC-type conical block copolymers and (ABC ) ₁₀ type, a pigment (titanium oxide: rutile structure) and a diluent (xylene) were added and compounding was carried out in the same manner as in Example 1.

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The relationship between the pigment concentration and the Film gloss is shown in FIG.

Block copolymer of the AB type Blockcopolyineres ABA type block copolymer of () ₁ Q block copolymer from the BAC-type block copolymer of the CABAC-type block copolymer of ()

Curve a Curve b Curve C. Curve d Curve e Curve f

Figure 3 shows that copolymers containing no polar group (curves a, b and c) gave reduced film gloss at suitable pigment concentrations; Among the polymers containing carboxyl groups, the CABAC type polymers (curve e) containing carboxyl groups at both ends of the polymers had the highest gloss and the film gloss became lower in the order of the BAC type polymers (curve d) and (ABC) ₁₀ -type polymers (curve f).

It is clear from these facts that the introduction of the polar groups into both ends of the polymers is more appropriate is than the introduction into one end of the polymer and that the introduction of polar groups into ends of a linear one Polymer chain provides more favorable effects in terms of film gloss than those in the center of the star polymers.

example H

ΑΒΑ-type polymers were prepared by anionic living polymerization in a nitrogen atmosphere using xylene as the polymerization solvent and butadiene oligomer dilithium as the initiator

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tiator was carried out.

A glass autoclave with a capacity of 2 liters was used as the polymerization vessel. 1200g well dried xylene and 255 g of styrene were charged. Furthermore, 45 g of purified butadiene was dissolved therein.

The temperature in the autoclave was kept at 20 ^° C. and a solution of 6.0 millimoles of butadiene oligomer dilithium in benzene was added.

The temperature was raised to 60 ⁰ C. After about 30 minutes, the polymerization of butadiene and styrene was complete and the contents of the solution were colored red.

In addition, CABAC-type block copolymers containing carboxyl groups at both ends of the polymer chain were prepared by heating the above-mentioned red polymer solution of the ABA-type block copolymer to about 100 ^° C., supplying carbon dioxide gas at a flow rate of 20 l / min, and the obtained polymer solution was poured into a large amount of methanol to precipitate polymers.

After the analysis, it was found that the block copolymer thus produced by the ABA type and CABAC type block copolymers having a number average molecular weight of 5 x 10 consisting of 85 wt.% Polystyrene and 15 wt.% Polybutadiene.

As for the CABAC type block copolymer, the carboxyl group-terminated polymers were about 50% of the total polymers based on thin layer chromatography.

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oL (o

Based on the results of the NMR analysis, it was found that any block copolymers of the ΑΒΑ-type and CABAC-type were conical block copolymers, the one substantial range of random styrene-butadiene copolymers contained.

Next, using the above-mentioned respective CABAC type block copolymers and ΑΒΑ-type two masses with the formulations given below in the same manner as in Example 1 manufactured.

Parts by weight

Block Copolymers 77

Titanium oxide, rutile structure 63

Xylene 178 pigment concentration: 15% by volume

Each of the masses thus prepared was applied to a well washed steel plate with the aid of a film applicator applied and the drawn film was dried at room temperature.

6 relates to a microscope photograph (10 times) of titanium oxide (rutile structure) and FIGS. 7 and 8 concern microscope photographs (10 times) of the coating films obtained from polymers without terminal polar groups and polymers with terminal carboxyl groups, respectively.

The gloss values of the coating films are given in Table I.

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Zl

Table I.

Gloss value % ΑΒΑ-type block copolymer 30th CABAC type block copolymer 100

The gloss value in Table I is indicated by the specular reflection at 60 ° according to JISK method 5A00.

From Table I and in Flg. 7 and 8 it can be seen that the one made from polymers without polar groups The coated film has low gloss and pigment particles are aggregated in the coating film during the off The coating film produced by carboxyl-terminated polymers has high glossiness, and the pigment particles are uniformly dispersed in the coating film are.

Example 5

In a red benzene solution containing living polymers of conical block copolymers of the AB type, which prepared by the same procedure as in Example 1, carbon dioxide gas became about room temperature blown to -COOM groups (M = lithium metal or Hydrogen) at the ends of the polymer chain containing BAC-type polymers.

There were also -OM groups on the ends of the polymer

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Polymers containing prepared by adding a gaseous mixture of oxygen and nitrogen in a benzene solution was blown, which living polymers consisting of conical block copolymers of the AB-type, which in the in the same manner as the above were prepared.

Similarly, SM groups were attached to the polymer ends Polymers containing prepared by adding a 1O? 6 Benzene solution of carbon disulfide was added to a benzene solution, the living polymer, consisting of conical AB-type block copolymers.

In the same way, polymers were made that had an average of 5 molecules of vinyl pyridine at the polymer ends contained by adding a 10% benzene solution of 2-vinylpyridine was placed in a benzene solution, which living polymers, consisting of conical block copolymers from AB type included.

Polymers with -C, HgSi (OCH,), - groups were made in the same way at the polymer ends by adding a 10bigen Benzene solution of γ-chloropropyltrimethoxysilane to a Benzene solution containing living polymers composed of conical AB-type block copolymers was prepared.

A pigment (titanium oxide: rutile structure) and a diluent (xylene) became the above-mentioned conical Block copolymers of the AB type with a numerical average molecular weight of 50,000, consisting of 85% by weight Styrene and 15 wt.% Butadiene was built up or the above mentioned 5 polymers with polar groups at the polymer ends of the same composition and molecular weight, like the AB type polymer added. the

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eft

Compounding was carried out in the same manner as in Example 1. The relationship between pigment concentration and film gloss is shown in Fig. H.

Curve g: block copolymer without terminal polar group

Curve h: block copolymer with a terminal -C ₃ H ₆ SiCOCH ₃ ) ₃ group

Curve i: block copolymer with a terminal -SM group

Curve j: block copolymer with terminal vinylpyridine molecules

Curve k: block copolymer with a terminal -OM group

Curve 1: block copolymer with a terminal -COOM group

From the figure it can be seen that polymers which contain terminal groups, in terms of film gloss Polymers with no terminal polar group were far superior at appropriate concentrations of the pigment. That is, it can be said that the dispersibility of a pigment in any polymer, the terminal polar Contains groups, is obviously more favorable than that of the pigment in polymers without a terminal polar group.

Example 6

It became a conical AB type block copolymer with no terminal polar group prepared by the same procedure as in Example 1.

Then, in the benzene solution thus obtained, which contained living copolymers, carbon dioxide gases among those

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Conditions introduced that the content of polymers containing terminal carboxyl groups, 2%, 5%, 10% and 50% based on the total polymers, respectively.

These polymers were compounded with titanium oxide (rutile structure) and xylene in the same manner as in Example 1. The relationship between pigment concentration and film gloss with reference to the masses is shown in FIG.

Curve m: block copolymer without a terminal carboxyl group

Curve n: content of polymers with terminal carboxyl groups 2%

Curve o: content of polymers with terminal carboxyl groups 5%

Curve p: content of polymers with terminal carboxyl groups 10%

Curve q: content of polymers with terminal carboxyl groups 50%

It can be seen from the figure that the film gloss becomes higher as the content of carboxyl-terminated polymers increases.

Further, when the content of carboxyl-terminated polymers is approximately 2% of the total polymers, the effect on film gloss is imperceptible, but becomes clearly noticeable when it is more than about h% , as can be seen.

η DM840 / 06 14

Example 7

The block copolymers prepared in Example 1 from BAC type laid AB type and a polymer of the same composition with the same viscosity at a 10bigen Xylene solution of the polymer (B-type viscometer at 25PC), prepared by a radical emulsion polymerization method were used for the following Formulation used:

Parts by weight

Polymers

Titanium oxide (rutile structure)

Zinc white

Disparlon D-4200

(Polyethylene oxide type dispersant)

Chlorinated paraffin 10

(Chlorine content 40 #)

Xylene 48

The preparation took place by means of a ball mill for about 10 hours. Each of the three masses thus obtained was applied to a well washed steel plate by means of a film applicator and at room temperature Dried for 2 weeks. Various cold tests were then carried out on the films. The results are given in Table II.

20th 0 20th 2 2, 0,

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Table TI

A * 1) B * 2) C * 3) Mirror gloss at 60 °, % 100 40 100 Adhesion to the substrate * 4) Well very
bad Well Impact resistance * 5) Well Well sahr
bad Resistance to salt
water ^;
6% salt water, 200 hours) Well very
bad bad Resistance to salt
fog * 6)
(5 # salt water spray,
200 hours) Well very
bad bad Accelerated weather resistance
ability 6)
(60 ⁰ C, carbon arc, 100 hours) Well Well very
layer

Remarks:

* 1) Coating film of the mass of polymers with terminal polar groups.

* 2) Coating film of the composition made of polymers having no terminal polar group.

* "3) Coating film of the mass of polymers produced by radical Emulsion polymerization were prepared.

* 4) Measured according to the cross-cut adhesion test.

* 5) Measured by dropping a steel ball from 6.35 mm0 on a steel plate 1 mm thick, which was covered with a test film 50 cm high and Evaluation of the change in the film with the naked eye. Evaluated by observing the film surface with naked eye.

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As is clear from Table II, the coating film according to the invention is the coating film made of copolymers, which do not contain a terminal polar group in terms of gloss, adhesion to the substrate, durability far superior to saline solution and in terms of salt mist resistance.

Further, it can be seen that the coating film of the invention is excellent in impact resistance and the accelerated weather resistance and shows an excellent behavior in the salt solution resistance and salt solution spray resistance in comparison to the coating film of styrene-butadiene copolymers, which have been prepared according to a radical emulsion polymerization method.

Example 8

The block copolymers prepared in Example 1 from BAC type and AB type and an arbitrary copolymer of the same composition with the same viscosity a 30 # xylene solution of the polymer (300 cP, B-type Viscometer at 20 "C) made by radical polymerization were each used as a binder for a blue printing ink.

Using phthalocyanine blue as a pigment, three masses were prepared by means of a ball mill according to the following Formulation made:

Weight point

Pigment (phthalocyanine blue) 3

Calcium carbonate 10

Polymer 20

Solvent (xylene) 67

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27 A 9238

The printing ink compositions obtained in this way have the physical properties given in Table 3.

Table III

^^ copolymers
Own ^^ \ ^
shafts ^ ^{s> v} ^^^ BAC type AB type Products of the
radik.Poly
merization Storage stability
(after 1 day) Well Well very bad Storage stability
(after 1 V / o before) Well sweet
bad very bad Film strength Well Well very bad Film gloss. Well very
bad Well Opacity Well very
bad very bad Graininess not
fixed
represents fixed
represents not fixed
represents

In the printing ink using the radical polymerization product, precipitates of white became Calcium carbonate observed 1 day after the blue ink was made. The blue ink using the AB-type block copolymer as a binder separated into two layers one week after production, i.e., a colorless transparent top layer and a blue bottom layer.

From the table above it can be seen that the block copolymer of the BAC type, which has terminal carboxyl groups

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when the binder had the best storage stability.

Further, using the carboxyl-terminated block copolymer provides the blue ink the best behavior in terms of film strength, film gloss, opacity and graininess in the ink as shown in Table III.

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30. Blank page

Claims (8)

Claims 1. Composition for paints and printing inks, marked by (A) a copolymer of vinyl substituted aromatic hydrocarbon and conjugated diene consisting of Polymers with polar groups introduced into the ends of the molecular chain, which are obtained by reacting a vinyl-substituted aromatic hydrocarbon and conjugated diene constructed block copolymers, with alkali metal atoms are connected to at least one end of the molecular chain, with one for reaction with the alkali metal atom capable polar reactant was obtained, wherein the block copolymer with the terminal alkali atoms through Polymerization of vinyl substituted aromatic hydrocarbon and conjugated diene monomers using an alkali metal or organoalkali metal was obtained as an initiator and (B) at least one inorganic pigment. 2. Composition according to claim 1, characterized in that the block copolymer is represented by the structure (A - B) _n , (A- B) _n -A or (A- B) _n X, wherein A is predominantly composed of a vinyl-substituted aromatic A hydrocarbon polymer, B a polymer consisting predominantly of a conjugated diene, η an integer from 1 to 10 and X a radical of a coupling agent having 2 or more functional radicals or a polyfunctional polymerization initiator. 3. Mass according to claim 2, characterized in that the sequences A and B of the above-mentioned structure by a clear cut bond are linked. V, 0 9iUfl / 06U ORIGINAL INSPECTED - 35 - , / 74Ü238 4. Compounds according to claim 2, characterized in that the block copolymer is a conical block copolymer is. 5. masses according to claim 1 to 4, characterized in that the polar reactant consists of oxygen, There is nitrogen- or sulfur-containing compounds that react with the terminal alkali metal under Are able to bring about polar groups. 6. Compounds according to claim 1 to 5, characterized in that the polar reactant consists of polar ones There is monomers that can be subjected to anionic polymerization. 7. Compounds according to claim 1 to 6, characterized in that the polymers with terminal polar Groups make up greater than about 4 percent by weight of the total polymers. 8. Compounds according to claim 1 to 7, characterized in that the inorganic pigment consists of a metal compound consists. ■: M Λ U / [J b 1 4