JPH06172664A - Coloring agent composition for thermoplastic elastomer - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of a pigment, a specific aminoalkoxy-silane compound and a low-molecular weight thermoplastic resin containing acid group, free from plate-out tendency, having good moldability and useful for the coloring of a thermoplastic elastomer. CONSTITUTION:The objective composition is produced by kneading and grinding under thermal plasticizing condition (A) a pigment, (B) an aminoalkoxysilane compound expressed by formula (X is 1-4C alkoxy; A and C are benzene ring or 1-3C hydrocarbon group which may contain benzene ring; B is N; Me is methyl; R is H, lower alkyl or lower alkenyl; (n) is 1-3; (m) is 1 or 2; (p) and (s) are 0 or 1; (q) and (r) are 1-3) (e.g. gamma aminopropyltriethoxysilane) and (C) a low-molecular weight thermoplastic resin having acid group. The thermoplastic elastomer to be colored with the composition is preferably polyolefin elastomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorant composition for a thermoplastic elastomer, which does not plate out a pigment to a molding device during molding.

[0002]

2. Description of the Related Art Plastics have been used for various purposes while substituting natural materials because they have a low specific gravity, excellent mechanical properties, and are easy to mold. However, changes in raw material prices, molding methods, health and safety, etc. Due to changes such as environmental protection, the material of plastics is changing every time even for the same purpose.

In recent years, thermoplastic elastomers have been used in a wide range of applications such as injection molding, extrusion molding or calender molding from the viewpoints of improving performance such as molding cost and heat resistance, and being easy to recycle and having little environmental pollution. It is used as a packing material, tube, sheet, etc.

Generally, coloring of plastics is carried out for the purpose of imparting various properties such as decorativeness to a molded product, and the pigments and dyes are processed in a state in which they are easily dispersed at the stage of injection molding, extrusion molding or calender molding. It is made of powdered, liquid, and granular coloring agents. The colorant can be obtained by adding a dispersion aid to a pigment or dye, or by adding a resin and simply mixing or melt-kneading, but the coloring component depends on the material and application of the plastic. Is generally changed in various ways.

Conventionally, when a coloring component or coloring agent devised in this way is used, the molding processability is generally not impaired, but in the PVC processing field, the inner wall of the mold cavity is colored by injection molding. There was a phenomenon in which contaminants adhered to the die roll of the extruder during extrusion molding and on the surface of the processing roll during calendar molding. This phenomenon is called "plate-out", but once this happens, the mold transferability to the molded product deteriorates, causing defects in the appearance such as streaks on the molded product, dirt on the surface, and change in gloss. Had caused it.

Therefore, although the work of removing the contaminants during the molding is performed, the work of stopping the molding operation is complicated and the molding cost is increased. or,
Since contaminants are presumed to be PVC compounding components such as dyes, pigments, lubricants or stabilizers or their thermal decomposition products, a method of changing the combination of metal soaps as stabilizers in PVC as a plate-out prevention method, Methods for adding silicon oxide-based inorganic substances, known literature (Plastic compounding theory and practice, Plastic Age Co., Ltd., 1971 edition)
Various methods have been devised, such as a method of adding an extreme pressure lubricant containing P, S, and Cl shown in FIG. However, although changing the combination of metal soaps and adding a silicon oxide-based inorganic material has been put to practical use, the method of adding an extreme pressure lubricant has not been put to practical use.

[0007]

On the other hand, when the thermoplastic elastomer is also colored and molded, plate-out similar to that of PVC occurs, resulting in deterioration of quality and processability of the molded product. Therefore, a method for preventing plate-out carried out by PVC has been studied, but the method of adding a metal soap or a silicon oxide-based inorganic material has a problem that its effect is poor, and a new method has been demanded.

[0008]

Under the circumstances, the inventors of the present invention have earnestly studied a method having a high prevention effect, and as a result, have found an effective method of preventing pigment plate-out. That is, it was found that a composition prepared by adding a specific silane compound and a low molecular weight resin having an acid group to a pigment and kneading and grinding treatment extremely reduces the plate out of the pigment to a molding apparatus.

Conventionally, an organic silane compound is applied to a surface treatment in addition to an organic pigment to be applied to a method of preventing molding shrinkage or deformation of a colored molded product of an olefin resin, or a similar treatment to disperse an inorganic pigment into a resin. It has been applied to ways to improve.

However, this treatment alone does not have a plate-out preventing effect, and another method has been required. on the other hand,
Low molecular weight thermoplastics with acid groups are used to control the lubricity of vinyl chloride resins and improve the processability, compatibilizers between different resins, or the adhesiveness of resins to multiple substances. Although it has been used for improvement, it was used for the surface treatment of pigments and did not show a plate-out preventing effect.

According to the present invention, by treating these pigments in combination with these two kinds of compounds, a pigment plate-out preventing effect, which cannot be predicted from each of them, can be obtained. The effect is exhibited by surface-treating with a silane compound, and kneading and grinding with a melt of a low molecular weight thermoplastic resin having an acid group.

The aminoalkoxysilane compound used in the present invention is a compound represented by the following general formula 1.

[0013]

Embedded image General formula 1: (In the formula, X is an alkoxy group having 1 to 4 carbon atoms, A
And C are a benzene ring or a hydrocarbon group having 1 to 3 carbon atoms which may contain a benzene ring, B is nitrogen, Me is a methyl group,
R is hydrogen or a lower alkyl or alkenyl group, n = 1, 2 or 3, m = 1 or 2, p and s = 0 or 1, q and r = 1, 2 or 3. )

[0014] Specifically, .gamma.-aminopropyltriethoxysilane, (EtO) 3 Si (CH 2) 3 NH 2 γ- aminopropyltrimethoxysilane, (MeO) 3 Si (CH 2) 3 NH 2 β- aminoethyl tripropoxysilane, (ProO) 3 Si (CH 2) 2 NH 2 N- (γ- aminopropyl) .gamma.-aminopropyltriethoxysilane, (EtO) 3 Si (CH 2) 3 NH (CH 2) 3 NH ₂ N- (β- aminoethyl) .gamma.-aminopropyltrimethoxysilane, (MeO) 3 Si (CH 2) 3 NH (CH 2) 2 NH 2

3- [N-allyl-N- (2-aminoethyl)] aminopropyltrimethoxysilane, NN Bis [3- (methyldimethoxysilyl) propyl] ethylenediamine, [(MeO) 2 MeSi
_{(CH 2) 3] 2 N} (CH 2) 2 NH 2 p- [N- (2- aminoethyl) aminomethyl] phenethyltrimethoxysilane, (MeO) 3 Si (CH 2) 2 φCH 2 NH (CH 2 ) 2
NH ₂ N - [(3- trimethoxysilyl) propyl] m-
Phenylenediamine, (MeO) 3 Si (CH 2) 3 NHφNH 2 (10) N - [(3- trimethoxysilyl) propyl] diethylenetriamine, (MeO) 3 Si (CH 2) 3 [NH (CH 2) 2] 2 N
_{H 2 (11) N - [} (3- trimethoxysilyl) propyl] triethylenetetramine _{(MeO) 3 Si (CH 2} ) 3 [NH (CH 2) 2] 3 N
H ₂ (wherein Et is an ethyl group, Me is a methyl group, P is
ro represents a propyl group, φ represents a benzene ring) and the like. These examples are preferable examples from the viewpoints of action and effect, availability, etc., but of course the present invention is not limited to these examples.

These are conventionally used as modifiers for improving water resistance, heat resistance and chemical resistance in the field of paints, and as a material for improving adhesion between an inorganic filler and an organic matrix in the field of reinforced plastics. ing.

Since these silane compounds have a function of contributing to the bond at the interface between the inorganic material and the organic material by the hydrolysis of the alkoxy group, they act as a surface treatment agent for the pigment, and the olefin resin is colored. It is known to prevent molding shrinkage and deformation of molded products.

On the other hand, the low molecular weight thermoplastic resin having an acid group used in the present invention is a thermoplastic resin having a molecular weight of 1,000 to tens of thousands, and radical groups or graft copolymerizations of acid groups are carried out at the synthesis stage. The resin that is included in the chemical structure and the resin that is not included in the synthesis stage but is included in the molecule after the post-treatment such as oxidation.

The low molecular weight resins usually used are olefinic resins and styrene resins, and the acid group is often α, β-unsaturated carboxylic acid or its anhydride. The acid group is, for example, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, hymic acid, hymic acid anhydride, and the like. Ethylene-acrylic acid copolymer of Chemical Co., or A-C polyethylene wax of oxidation type polyethylene, maleic anhydride polyethylene or polypropylene of Umex (trade name) of Sanyo Chemical Industry Co., Ltd., acid of Mitsui Petrochemical Co., Ltd. Examples include modified polyethylene or oxidized polyethylene Mitsui High Wax (trade name).

The important point in the present invention is that even if each of the pigments is treated with an aminoalkoxysilane compound or a low molecular weight resin having an acid group, the effect of preventing the plate-out of the pigment in the thermoplastic elastomer is not exerted. It is that the plate-out preventing effect can be obtained only by performing the melt grinding treatment.

The amount of the aminoalkoxysilane compound added to the pigment is not particularly limited,
A range of 0.1 parts by weight or more, preferably 5 to 30 parts by weight can be selected.

The low molecular weight resin having an acid group has an acid value (mg K
Any of those having an OH / gr of 1 or more can be used, but the amount used can be appropriately changed according to the amount of the silane compound added to the pigment.

It is preferable to adjust the amount of the low molecular weight resin added so that the acid amount does not exceed the reaction equivalent of the added silane compound with the amino group. To treat the pigment, 1) charge the pigment in a high-speed stirrer such as a Henschel mixer, add a silane compound or a hydrolysis solution of the silane compound and mix well, and then leave it for a long time or heat-treat it to react with the silane compound. Next, a method of kneading the pigment with a low-molecular-weight resin having an acid group by heating and kneading with a kneader such as a kneader, a heating three-roll, an extruder, etc. 2) Directly kneading machine described above Among them, a method of mixing and kneading a pigment, a low molecular weight resin and a silane compound can be mentioned. In any case, the pigment should be processed by melt kneading.
A low molecular weight resin is required to be 10 parts by weight or more with respect to 100 parts by weight, and 40 parts by weight or more is desirable for efficient kneading.

However, since the amount of the low molecular weight resin having an acid group is restricted by the amount of the silane compound treated, when the amount of the silane compound treated is small or when the low molecular weight resin having a large acid value is used, the acid group is used. Since the amount of the low molecular weight resin having OH is reduced and the resin cannot be efficiently kneaded, it is possible to appropriately increase the amount by diluting with another low molecular weight resin. As the low molecular weight resin for increasing the amount of dilution, a thermoplastic resin having a molecular weight of 1,000 to tens of thousands can be used in the same manner as the low molecular weight resin having an acid group.

The pigments used in the present invention are known in the field of plastic processing, and include inorganic pigments such as titanium oxide, zinc oxide, rouge, titanium oxide calcined pigments, ultramarine blue, cobalt aluminate and carbon black, and azo pigments. , Quinacridone, perylene, anthraquinone,
Organic pigments such as phthalocyanine type, quinophthalone type, isoindolinone type, slene type and diketopyrrolopyrrole type and extender pigments such as barium sulfate, calcium carbonate and talc.

The colorant composition of the present invention is obtained by melt-kneading a powdery colorant obtained by further finely pulverizing a melt-kneaded and ground product or a thermoplastic resin containing a thermoplastic elastomer, depending on the purpose of use. The particulate colorant may be in any form, and these coloring compositions are usually added in an amount of 0.1 to 20 parts by weight based on the thermoplastic elastomer.

The main constituents of the coloring composition for a thermoplastic elastomer of the present invention and the method for producing the same are as described above, but a heat stabilizer and a light stabilizer are added to improve suitability for use other than plate-out prevention and molding processability. Agents, flame retardants, plasticizers or fillers can be added as required.

The thermoplastic elastomer to be colored in the present invention is a flexible component (soft phase) having rubber elasticity in the molecule.
Any thermoplastic polymer having a molecular constraining component (hard phase) for preventing plastic deformation may be used.

As specific commercial products, the trade names thereof are, for example, Kraton of Shell Chemical Co., which uses polystyrene as a hard phase and polybutadiene or polyisoprene or hydrogenated polybutadiene as a soft phase, and Tuffrene of Asahi Kasei Kogyo Co., Ltd. J of Nippon Synthetic Rubber Co., Ltd.
Styrenic elastomer such as SR TR: MILASTOMER of Mitsui Petrochemical Co., Ltd., Sumitomo TPE of Sumitomo Chemical Co., Ltd. with polyethylene or polypropylene as the hard phase and ethylene propylene rubber, ethylene-propylene terpolymer, etc. as the soft phase Or olefinic elastomer such as Santprene N from Mitsubishi Monsanto Kasei Co., Ltd .: Urethane elastomer such as Pandex manufactured by Dainippon Ink and Chemicals Co., Ltd. with polyurethane as hard phase and polyether or polyester as soft phase: polyester Elastomers such as DuPont Japan Limited's Hytrel with hard phase as the soft phase and polyether as the soft phase: Amide elastomers with polyamide as the hard phase and polyester or polyether as the soft phase: crystalline poly Ethylene was styrene and hard phase - vinyl acetate copolymer or ethylene - ethyl acrylate copolymer and the like elastomers soft phase.

Usually, when a thermoplastic elastomer composition is obtained, a polymer similar to the basic structure of the elastomer, bleeding, blooming, heat resistance, weather resistance, etc. is added to improve the processability and suitability for use of these thermoplastic elastomers. Considering this, mineral oils, plasticizers, heat stabilizers, light stabilizers, etc. are further added at the molding stage.

The coloring composition of the present invention does not impair the plate-out preventing effect even if it is blended in such a manner, but the olefinic elastomer has a particularly remarkable effect among the thermoplastic elastomers.

[0032]

EXAMPLES The present invention will now be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and has a wide range of applications. All parts and percentages in the examples and comparative examples are based on weight.

Examples 1 to 4 and Comparative Examples 1 to 6 50 parts of phthalocyanine blue (monochloro α-type), 0 to 50 parts of acid-modified low molecular weight polyolefin and 50 to 0 part of low molecular weight polyethylene shown in Table 1 were mixed in a small mixer. After mixing, 10 to 20 parts of the aminoalkoxysilane compound shown in Table 1 previously diluted with isopropyl alcohol to 50% was added little by little and mixed to obtain a total of 100 to 120 parts of mixture.

Next, the mixture was taken out of the mixer, exposed to the outside air at room temperature and left standing for 6 hours, and then processed into a fine flake-shaped kneaded product by a small three-roll mill heated to 110 to 120 ° C.

The obtained kneaded product was mixed with 52 to 60 parts of low-density polyethylene (MFR = 7) so that the pigment concentration was 20%.
After adding 40 to 48 parts and mixing with a small mixer, the mixture was melt-kneaded with a 30 mmφ twin-screw extruder whose temperature was set at 160 ° C. and shaped into a pellet colorant.

In order to confirm the occurrence of plate-out, a shaped pellet-shaped coloring agent was added to an olefinic thermoplastic elastomer (Mitsui Petrochemical Co., Ltd. Miralastomer 5030N) 1
4 parts was added to 00 parts, and the mixture was well kneaded with a 6-inch two roll heated at 180 ° C. for 5 minutes under the conditions of a roll rotation number of 24 rpm and a roll interval of 0.6 mm, and then the kneaded product was removed from the roll.
The occurrence of plate-out was observed by observing the contamination state of the roll surface after removing the kneaded material, and the same amount of hard polyvinyl chloride compound (PVC degree of polymerization 1050,
It was judged by observing the coloring state of the polyvinyl chloride sheet obtained by kneading well for 5 minutes with a stabilizer).

As shown in Table 1, the composition obtained by adding the aminoalkoxysilane compound of the present invention and the acid-modified low-molecular-weight polyolefin to the pigment and then heat-melting and kneading the mixture does not have pigment plate-out.

The evaluation criteria in Table 1 are as follows. Plate-out prevention effect 5: No contamination is observed on the roll surface, and the polyvinyl chloride sheet is not colored. 4: Contamination on the roll surface is difficult to recognize, and coloring of the polyvinyl chloride sheet is difficult to recognize by itself, but coloring is recognized when it is attached to a non-colored sheet. 3: Contamination of the roll surface is recognized and the polyvinyl chloride sheet is colored. 2: The entire surface of the roll is contaminated and the polyvinyl chloride sheet is considerably colored. 1: The entire roll surface is heavily stained and the polyvinyl chloride sheet is markedly colored.

The compounding ingredient names in Table 1 are as follows. The composition is parts by weight. Additive name-Aminoalkoxysilane compound (diluted with 50% IPA) A: γ-aminopropyltriethoxysilane Nuc A-1100 (manufactured by Nippon Unicar Co., Ltd.) B: N- (β-aminoethyl) -γ-aminopropyl Methyldimethoxysilane TSL-8345 (manufactured by Toshiba Silicone Co., Ltd.) C: p- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane TSL-8205 (manufactured by Toshiba Silicone Co., Ltd.)

Low molecular weight polyolefin D: maleic acid modified type (molecular weight 4000, acid value 51 mg
KOH / gr) Umex 1010 (manufactured by Sanyo Kasei Co., Ltd.) E: Maleic acid modified type (molecular weight 3000, acid value 30 mg
KOH / gr) Yumex 2000 (manufactured by Sanyo Kasei Co., Ltd.) F: Unmodified (molecular weight 5000) Sunwax 161P (manufactured by Sanyo Kasei Co., Ltd.)

[0041]

[Table 1]

Examples 5 and 6 and Comparative Examples 7 to 12 Pigment quinacridone red (dimethyl type) 10 parts and iron oxide
Example 1 except that 50 parts of a mixture of 30 parts and 10 parts of titanium oxide (rutile type) was used and a 50% dilute solution of various alkoxysilane compounds containing an aminoalkoxysilane compound was used as the alkoxysilane compound.
The occurrence of pigment plate-out was observed by the same method as that described in No. 4 and Comparative Examples 1 to 6.

Table 2 shows the composition ratios of the Examples and Comparative Examples and the results of plate-out evaluation. They are whitish except that the aminoalkoxysilane compound and the acid-modified low molecular weight polyolefin are used in combination as shown in the table. A plate-out product of reddish purple pigment was generated on the surface of the two rolls heated, and the plate-out preventing effect was not shown.

The compounding ingredient names in Table 2 are as follows. The composition is parts by weight. Additive name-Alkoxysilane compound (diluted with 50% IPA) A: Same as in Table 1. G: N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane TSL-8340 (manufactured by Toshiba Silicone Co., Ltd.) H: γ-chloropropyltrimethoxysilane TSL-8320 (manufactured by Toshiba Silicone Co., Ltd.) I : Γ-glycidoxypropyltrimethoxysilane TSL-8350 (manufactured by Toshiba Silicone Co., Ltd.) J: γ-methacryloxypropyltrimethoxysilane TSL-8370 (manufactured by Toshiba Silicone Co., Ltd.) K: γ-mercaptopropyltrimethoxy Silane TSL-8380 (manufactured by Toshiba Silicone Co., Ltd.)

Low molecular weight polyolefin D: same as in Table 1. L: Acid-modified (molecular weight 1500, acid value 60 mg KOH
/ Gr) High wax 1105A (manufactured by Mitsui Petrochemical Co., Ltd.) F: Same as in Table 1.

[0046]

[Table 2]

Examples 7 and 8 and Comparative Examples 13 and 14 The aminoalkoxysilane compounds described in Table 3
% Isopropyl alcohol solution is added to 0 to 20 parts of oxidized low molecular weight polyolefin 100 to 80 parts and mixed with a small mixer.

Next, to 50 parts of this mixture, 5 parts of titanium oxide (rutile type), 5 parts of carbon black (furnace type), 2 parts of titanium yellow (Cr-Sb-Tioxide) were added as pigments.
Add 38 parts of phthalocyanine blue (β type), 120-130 ℃
The mixture was melt-kneaded for 15 minutes in a small kneader heated to above, and then the melt was solidified and ground while cooling with water.

The obtained pulverized product had 28.5 to 30 parts of polypropylene (homo, MFR =) so that the pigment concentration became 15%.
9) In addition to 71.5-70 parts, mix with a small mixer, then 20
The mixture was melt-kneaded with a 30 mmφ twin-screw extruder whose temperature was set to 0 ° C. and shaped into a pellet colorant.

In order to observe the occurrence of plate-out, the obtained pellet-like colorant was mixed with an olefinic thermoplastic elastomer (MILASTOMER 8030N manufactured by Mitsui Petrochemical Co., Ltd.) 80.
And 20 parts of low-density polyethylene (MFR = 7) were added and mixed, and then the sheet was extruded for 60 minutes at a screw rotation speed of 45 rpm at a set temperature of 200 ° C. with a 20 mmφT die extruder.

Furthermore, low density polyethylene (MFR = 7)
Was extruded as a cleaning agent for 5 minutes, the die portion was decomposed, and the state of adhesion of the coloring matter on the inner wall of the die was examined. As shown in Table 3, the pigment composition treated with the aminoalkoxysilane compound and the oxidized low molecular weight polyolefin showed almost no generation of blue deposits.

The evaluation criteria in Table 3 are as follows. Plate-out prevention effect 5: No adherence of colored matter. 4: Colored material is slightly attached to one place. 3: Colored matter clearly adhered to one place. 2: Colored material is attached here and there. 1: Colored material is attached to the entire surface.

The compounding ingredient names in Table 3 are as follows. The composition is parts by weight. Additive name-Alkoxysilane compound (diluted with 50% IPA) A: Same as in Table 1.

Low molecular weight polyolefin M: oxidation type (molecular weight 3000, acid value 1 mg KOH / g
r) High wax 320MP (manufactured by Mitsui Petrochemical Co., Ltd.) N: Oxidized type (molecular weight 2600, acid value 17 mg KOH /
gr) High Wax 4202E (Mitsui Petrochemical Co., Ltd.)

[0055]

[Table 3]

[0056]

EFFECTS OF THE INVENTION By using a coloring composition characterized by kneading and grinding an aminoalkoxysilane compound and a low molecular weight resin having an acid group, a molding device for molding a thermoplastic elastomer composition can be obtained. It is possible to prevent the plate out of contaminants.

As a result, the processability of extrusion molding, injection molding and calender molding is improved, and a molded product having an excellent appearance can be obtained.

Claims (5)

[Claims] 1. A colorant composition for a plate-free thermoplastic elastomer comprising a pigment, an aminoalkoxysilane compound represented by the following general formula 1 and a low molecular weight thermoplastic resin having an acid group. Embedded image General formula 1: (In the formula, X is an alkoxy group having 1 to 4 carbon atoms, A
And C are a benzene ring or a hydrocarbon group having 1 to 3 carbon atoms which may contain a benzene ring, B is nitrogen, Me is a methyl group,
R is hydrogen or a lower alkyl or alkenyl group, n = 1, 2 or 3, m = 1 or 2, p and s = 0 or 1, q and r = 1, 2 or 3. ) 2. A method for producing a coloring composition for a thermoplastic elastomer, which is produced by kneading and grinding the coloring composition of claim 1 under heat plasticization. 3. A thermoplastic elastomer composition having no plate-out, which is obtained by incorporating the colorant composition according to claim 1 in a thermoplastic elastomer. 4. The composition according to claim 3, wherein the thermoplastic elastomer is a polyolefin-based elastomer. 5. The composition according to claim 3 or 4, which is a molding material used for injection molding, extrusion molding or calender molding.