JPH09143276A - Production of thermoplastic resin composition for coloring - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject composition good in strength, blocking resistance and dispersibility at high concentrations by fusing and granulating a dye or a pigment to a noncrystalline and low-molecular weight thermoplastic polymer having a specific molecular weight and a specified melt viscosity in a high-teinperature state with a high-speed rotating blade stirrer. SOLUTION: A composition obtained by blending (A) at least one or more dyes or pigments (e.g. titanium oxide) with (B) one or more of terpene resins, hydrogenated resins of the terpene resins, modified rosin resins, petroleum resins, hydrogenated petroleum resins, low-molecular weight polystyrene, low-molecular weight styrene copolymers, epoxy resin oligomers, etc., as a noncrystalline low-molecular weight thermoplastic polymer having a number-average molecular weight within the range of 300-5000 and a melt viscosity within the range of 0.1-100P at 200 deg.C is fused and granulated in a high-temperature state with a high-speed rotating blade stirrer to thereby afford the objective low-cost thermoplastic resin composition for coloring, capable of readily carrying out the diversified small-quantity production and good in mechanical strength, blocking resistance and dispersibility at high concentrations.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decoration of a thermoplastic resin with a coloring agent, and further relates to a method for producing a coloring thermoplastic composition, which belongs to improvement of productivity and quality of resin coloring. The obtained coloring thermoplastic composition is suitably used as a masterbatch.

[0002]

2. Description of the Related Art In recent years, a variety of resin types such as office automation equipment, home electric appliances, and housing-related equipment have been diversified, and resin hues have been made into other items.

Conventionally, as a coloring agent for thermoplastic resin,
A powder obtained by mixing and processing a pigment and a dispersant, a dye and a pigment and a thermoplastic resin, which are melt-kneaded by a kneader, an extruder or the like and granulated, are generally used.

However, the processed powder has a problem of scattering during handling, environmental pollution, uneven distribution of colorant, and uneven color. In addition, the melt-kneaded granules are expensive in terms of equipment cost due to the manufacturing method, and require a great deal of labor and materials when switching items.
In addition to the problem of time loss, there are limits to the concentration of dyes and pigments, the reduction in particle size, and the dispersibility in various types of resins in response to the demand for reducing the amount of colorants used.

For example, Japanese Patent Application Laid-Open No. 51-16336 proposes a granulated pigment composition by stirring and mixing and frictional heat, but it has a problem of environmental pollution because the mechanical strength of the particles is small and they are easily pulverized. .

Further, JP-A-51-47922 proposes to reduce the viscosity of a composition of a pigment and a plasticizer or a petroleum solvent, but it is difficult to obtain a granular material.

Further, JP-A-52-91055 discloses a pigment preparation coated with an organic substance, JP-A-58-34833.
Is a powdery colorant composition containing dyes and pigments, low molecular weight polystyrene and low molecular weight polyethylene.
No. 43231 shows a composition of carbon black and petroleum resin, and Japanese Patent Publication No. 53-4538 shows a composition of dye / pigment, polystyrene, and synthetic resin.
Due to the need for other post-processes, etc., it was lacking in high-mix low-volume production and economic efficiency.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides low cost, easy production of a wide variety of products in small quantities, excellent mechanical strength and blocking resistance required for ensuring storage stability, and high dispersibility at high concentration. It is intended to provide a granular thermoplastic composition for coloring.

[0009]

Means for Solving the Problems As a result of intensive investigations by the present inventors, a coloring thermoplastic composition was blended with a dye / pigment and an amorphous low molecular weight thermoplastic polymer, and produced by a high-speed rotary blade agitator. By doing so, the inventors have found that the above problems can be achieved, and have reached the present invention.

That is, the present invention provides the following (1) to (7).
It is.

(1) A) at least one or two or more dyes and pigments, and B) the number average molecular weight is in the range of 300 to 5,000.
A composition prepared by blending one or more non-crystalline low molecular weight thermoplastic polymers having a melt viscosity at 00 ° C. in the range of 0.1 to 100 poises in a high temperature state using a high-speed rotary blade stirrer. A method for producing a thermoplastic composition for coloring, which comprises granulating a dye and a pigment and a thermoplastic polymer by welding.

(2) For coloring according to the above (1), the non-crystalline low molecular weight thermoplastic polymer is a combination of one or more selected from the following a) to g). Method for producing thermoplastic composition.

A) a terpene resin containing, as a main ingredient, a combination of at least one selected from α-pinene and β-pinene-containing monoterpenes, sesquiterpenes, diterpenes, polyterpenes and limonenes b) terpene resins described in a) above Hydrogenated resin c) An organic acid whose main component is a rosin acid containing at least one of abietic acid, diabietic acid, neoabietic acid, levopimaric acid, pimaric acid, dextropimaric acid, and hydrogenated rosin acid is glycerin. Or modified rosin resin esterified with polyhydric alcohol containing pentaerythritol d) Monoolefin containing C ₅ to C ₉ styrene compound, diolefin containing diene compound, coumarone, indene or cyclopentadiene, diester One or more types selected from cyclopentadiene Petroleum resin e) above d) hydrogenation of petroleum resins described resin f) low molecular weight polystyrene or a low molecular weight styrene copolymer g) bisphenol A or brominated bisphenol A which was combined with the main component material
Epoxy resin oligomer containing (3) The weight fraction of the dye / pigment is A, the true specific gravity is a, the weight of the non-crystalline low molecular weight thermoplastic polymer is B, and the true specific gravity is b. ) / (A / a + B / b) is 0.2
It is a range of -0.8, The manufacturing method of the thermoplastic composition for coloring as described in said (1) characterized by the above-mentioned.

(4) The high-speed rotary blade agitator has a rotary agitating blade inside, and has a counter shaft if necessary.
The method for producing a coloring thermoplastic composition according to (1) above, wherein the granules are produced by a batch operation.

(5) The tip speed of the rotary blade of the high speed rotary blade agitator is in the range of 2 m / sec to 40 m / sec, and the temperature for welding necessary for granulation is in the range of 50 ° C to 150 ° C. The method for producing the coloring thermoplastic composition as described in (1) above, which is characterized in that.

(6) A method for producing a coloring thermoplastic composition, characterized in that, in order to satisfy the temperature condition of the above (5), heating is carried out by a high speed rotary blade agitator with a jacket.

(7) A method for producing a thermoplastic composition for coloring, which comprises supplying a heating raw material to a high-speed rotary blade stirrer in order to satisfy the temperature condition of (5) above.

Hereinafter, each component of the composition used in the present invention, a stirring device and the like will be described.

The dyes and pigments are not particularly limited and are all pigments or dyes usually used for coloring thermoplastic resins.
For example, at least one selected from titanium oxide, carbon black, cadmium pigment, iron oxide, dark blue, ultramarine, phthalocyanine, quinacridone, benzidine, azo, perylene, anthraquinone, thioindigo, etc. or 2 It is a combination of at least one kind, and includes a dye and pigment which have been surface-treated with an organic silane coupling agent, an organic titanate or the like, or a lubricant, and a dispersant agent such as a metal soap.

The amorphous low molecular weight thermoplastic polymer is not particularly limited as long as the number average molecular weight and the melt viscosity are within the scope of the present invention. Preferably, a) α-pinene, monoterpene containing β-pinene, sesquiterpene, diterpene, polyterpene, terpene resin starting from limonene, b) hydrogenated resin of these terpene resins, c) abietic acid, diabietic acid, neoabietin. Acid, levopimaric acid, pimaric acid, rosin acid containing dextropimaric acid, and organic acids using hydrogenated products of the organic acid as a raw material, modified rosin resin esterified by polyhydric alcohol containing glycerin or pentaerythritol, d) Low molecular weight petroleum resin made from an unsaturated compound selected from monoolefins containing C ₅ to C ₉ styrene compounds, diolefins containing diene compounds, coumarone, indene, or cyclopentadiene, dicyclopentadiene , E) Hydrogenated petroleum resins of these petroleum resins f) a specific gravity of aromatic epoxy resins containing oligomers low molecular weight polystyrene in the range of 1.1 to 1.0, the low molecular weight styrene copolymer, a or g) of bisphenol A or brominated bisphenol A.

The low molecular weight thermoplastic polymer has a melt viscosity at 200 ° C. in the range of 0.1 to 100 poise, preferably 0.5 to 50, in order to uniformly wet the surface of the dye or pigment.
A range of poise is required, and in order for the dye / pigment in the granular composition to be uniformly dispersed in the thermoplastic resin during molding, it is amorphous and has a number average molecular weight of 300 to 5000,
Preferably, the range of 500 to 3000 is required. Furthermore, in order to prevent agglomeration during the production of granules and ensure high productivity and high quality, a low molecular weight thermoplastic polymer in the above range is required.

The non-crystalline low molecular weight thermoplastic polymer may be used alone or, if necessary, in combination of two or more kinds.

Furthermore, antioxidants, stabilizers, stabilizers such as anti-tarnish agents, etc. which are usually used as additives, light-stable weathering agents containing UV absorbers, lubricants, release agents, halogens, non-halogen flame retardants. It is also possible to contain an antistatic agent, a cross-linking agent, a foaming agent, a coupling agent, and an antibacterial / antifungal agent. The method for obtaining and producing the above resin is not limited. For example, terpene resin and rosin resin are natural products. , Petroleum resin is mainly produced by-product of naphtha crack, and each hydrogenated resin has physical properties of adhesive / tackifier tackifier, printing ink / paint, toner component of PPC copier, rubber / thermoplastic resin. Commercially available as an improving agent. Hydrogenated resins are preferred as the composition components used in the method of the present invention because of the stability of storage discoloration. Low molecular weight polystyrene and low molecular weight copolystyrene are also commercially available for similar applications. Epoxy resin oligomers are generally used as adhesives, paints, plates and sealants in combination with curing agents and reaction catalysts such as polyfunctional amines and aromatic polyfunctional acid anhydrides, and are in a state without a curing agent. Is thermoplastic and is commercially available as a raw material component such as an adhesive.

The high-speed rotary blade agitator used in the present invention has a rotary agitating blade inside, and is, for example, a vertical or horizontal type with an axial direction and a main axis and, if necessary, an auxiliary axis. is there. Typical examples are described in detail in "Granulation Handbook" published by Ohm Co., Ltd., edited by Japan Powder Industry Technology Association. Super mixer, Henschel mixer, Shugi mixer, GRAL-gural, vertical granulator, high granulator. There are speed mixer, Pharma Matrix, etc.

In the present invention, the compounding composition of the dye / pigment and the amorphous low molecular weight thermoplastic polymer is such that the weight of the dye / pigment is A,
The true specific gravity is a, the weight of the amorphous low molecular weight thermoplastic polymer is B, and the true specific gravity is b, and the volume fraction (A / a) /
(A / a + B / b) is preferably in the range of 0.2 to 0.8. If the volume fraction is less than 0.2, the cost reduction effect of the coloring process is small and the practicality is poor, and if it exceeds 0.8, the mechanical strength required for the storage and transportation of the granules is poor and the productivity is remarkably lowered.

The tip speed of the rotary blade of the high speed rotary blade agitator is preferably in the range of 2 m / sec to 40 m / sec. In order to adjust the temperature, for example, a raw material composition that is jacket-heated or pre-heated is supplied, and the granulated colorant composition is batched by setting the temperature condition for welding necessary for granulation to 50 ° C to 150 ° C. Manufactured by the method. When the temperature condition is lower than 50 ° C, it is difficult to granulate, and when the temperature condition is higher than 150 ° C, a large particle size or agglomeration tends to occur.

The granule composition produced in the present invention contains a high proportion of particles having a size of 0.1 mm to 3 mm, which is suitable as a coloring masterbatch, and is usually sieved by passing through a sieve. A more preferable particle size range is 0.3 mm to 1 mm.

The thermoplastic resin which can be colored with the composition produced by the present invention is not particularly limited. For example, commercially available GPP
S, HIPS, AS, ABS, AAS, AES, AC
Polystyrene resins such as S and MBS, block copolymer resins of styrene and gen compounds and elastomers and hydrogenated elastomers, LDPE, LLDPE, HD
Polyethylene resins such as PE and copolymers containing ethylene as the main component, polypropylene resins and copolymers containing ethylene and propylene as the main component and elastomers, polyphenylene ether resins, polyoxymethylene homopolymers and copolymers, N6, N66, N61
0, N612, N12, N46, MDX6 and other polyamide resins, MMA resins, PVC resins, polycarbonate resins, polyarylate resins and two or more of the above resins,
Alternatively, there may be mentioned polymer alloys or blends of the above resins with other resins, various resins already reinforced with glass fiber or the like, various flame-retardant composite resins, and the like.

The number average molecular weight and the melt viscosity of the amorphous low molecular weight thermoplastic polymer were measured by the following methods.

Measurement of number average molecular weight: The number average molecular weight in terms of polystyrene was measured by a GPC device (HLC8020 manufactured by Tosoh Corporation).

Measurement of melt viscosity: A complex viscosity at a frequency of 100 radians / second was measured at a temperature of 200 ° C. with a dynamic analyzer (RDAII manufactured by Rheometrics Co., Ltd.), and this was taken as a melt viscosity.

Further, the particle hardness and blocking resistance evaluated in the examples were measured by the following methods.

Measurement of particle hardness: A granular sample was placed on a paper and rubbed with a fingertip, and the particle hardness was judged by the touch.

This method was based on the method described in "Pigment Handbook" published by Seibundo Shinkosha, edited by Japan Pigment Technology Association.
The measurement indicators are as follows.

◯ (good): Hard to be crushed. Δ (Slightly good): About half crushed. × (Poor): Crushed immediately.

Measurement of blocking resistance: Diameter 6.2 cm
Put 50g of granule sample into the cylindrical flat bottom container of
/ Cm ² load at 80 ℃ for 3 hours, then cooled to room temperature and remove the load to see the fusion state,
The blocking resistance of the granule sample was judged. The measurement indicators are as follows.

◯ (good): fusion bonding ½ or less. × (Poor): Total fusion

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to Examples and Comparative Examples.

Example 1 Titanium oxide (R-TC30 manufactured by Tyoxide Co., specific gravity = 3.9) 50.6 parts by volume, number average molecular weight 2100, 2
Hydrogenated petroleum resin with a melt viscosity of 5 poises at 00 ° C (Arakawa Chemical Co., Ltd. Alcon P115 specific gravity =
1.0) 500 g of 49.4 parts by volume of the compound is added at 120 ° C.
The mixture was put into a jacketed 2 liter high speed mixer (manufactured by Fukae Kogyo Co., Ltd.) and heated at a main shaft blade tip speed of 4.1 m / sec and a side auxiliary shaft blade tip speed of 6.6 m / sec for 20 minutes.

The obtained granules were 56% in the range of 0.3 mm to 1 mm, and the particle hardness and blocking resistance were good.

The granules were converted into polystyrene (GP685 manufactured by Asahi Chemical Industry Co., Ltd.) with a titanium oxide concentration of 5% by weight.
When melted and kneaded with a 30 mm extruder and pelletized, a film was prepared by hot pressing.
The titanium oxide had no color unevenness and had good dispersibility. In the same manner, the granules were blended with ABS and polyamide 6 and melt-kneaded to form a film. As a result, there was no color unevenness and the dispersibility was good.

Example 2 69.3 parts by volume of titanium oxide (R-TC30, specific gravity = 3.9, manufactured by Thai Oxide Co., Ltd.), number average molecular weight 910, 20
Hydrogenated rosin ester having a melt viscosity of 1 poise at 0 ° C (Pine Crystal KE10 manufactured by Arakawa Chemical Industry Co., Ltd.)
0 specific gravity = 1.1) 30.7 parts by volume, 500 g of a mixture obtained by adding 10% by weight of ethylenebisstearylamide as a lubricant to the above mixture was heated to 110 ° C., and a jacketed 2 liter high speed mixer ( Fukae Kogyo Co., Ltd., the main blade tip speed 4.1m / sec,
The side auxiliary shaft blade was stirred for 18 minutes at a tip speed of 6.6 m / sec.

32% of the obtained granules were in the range of 0.3 mm to 1 mm, and the particle hardness and blocking resistance were good.

Example 3 Titanium oxide (R-TC30 manufactured by Thai Oxide Co., specific gravity = 3.9) 50.6 parts by volume, number average molecular weight 1010, 2
Hydrogenated terpene resin with a melt viscosity of 7 poises at 00 ° C (Yasuhara Chemical Co., Ltd. Clearon P115)
(Specific gravity = 1.0) 500 g of 49.4 parts by volume of the compound 12
3. Put into a 2 liter high speed mixer with jacket (Fukae Industry Co., Ltd.) heated to 0 ° C, and make the spindle blade tip speed 4.
1 m / sec, 4 at side vice shaft blade tip speed of 6.6 m / sec
Stirred for 0 minutes. The obtained granules are 0.3 mm to 1 m
The value in the range of m was 48%, and the particle hardness and blocking resistance were good.

Example 4 57.8 parts by volume of titanium oxide (R-TC30, specific gravity = 3.9, manufactured by Thai Oxide Co., Ltd.), number average molecular weight: 790, 20
Low-molecular-weight polystyrene with a melt viscosity of 9 poises at 0 ° C (Haimer ST120 manufactured by Sanyo Kasei Co., Ltd.)
1.0) 20 liter Hensche Mixer (Mitsui Mining Co., Ltd.) in which 5 kg of 42.2 parts by volume of the mixture was heated to 125 ° C.
Manufactured) and stirred for 35 minutes at an upper blade tip speed of 6.3 m / sec and a lower blade tip speed of 6.5 m / sec.

48% of the obtained granules were in the range of 0.3 mm to 1 mm, and the particle hardness and blocking resistance were good.

Example 5 54.5 parts by volume of titanium oxide (R-TC30 manufactured by Taioxide Co., Ltd., specific gravity = 3.9), number average molecular weight of 3000, 2
Epoxy resin having a melt viscosity of 6 poises at 00 ° C. (manufactured by Asahi Kasei Kogyo Co., Ltd., specific gravity = 1.17) 5 liters of compound (5 kg) heated to 135 ° C. 20 liter Henscher mixer (Mitsui Mining Co., Ltd.) ) And was stirred for 25 minutes at an upper blade tip speed of 6.3 m / sec and a lower blade tip speed of 6.5 m / sec.

The obtained granules were 54% in the range of 0.3 mm to 1 mm, and the particle hardness and blocking resistance were good.

Example 6 Phthalocyanine blue (specific gravity: 1.5) 60.9 parts by volume, having a number average molecular weight of 2100 and a melt viscosity of 5 poises at 200 ° C., added with 10% by weight of zinc stearate for dispersion treatment, and a hydrogenated petroleum resin. (Arakawa Chemical Industry Co., Ltd. Alcon P115 specific gravity = 1.0) 39.1 parts by volume of compound 5
00 g was put into a jacketed 2 liter high speed mixer (manufactured by Fukae Industry Co., Ltd.) heated to 120 ° C., and stirred for 15 minutes with a main shaft blade of 5.7 m / sec and a side auxiliary shaft blade of 6.6 m / sec.

The obtained granules were in the range of 0.3 mm to 1 mm with 50%, and the particle hardness and blocking resistance were good.

Comparative Example 1 Titanium oxide (R-TC30 manufactured by Tyoxide Co., Ltd. specific gravity = 3.9) 48.8 parts by volume, a low molecular weight polyethylene having a melt viscosity of 1 poise at 200 ° C. as a crystalline low molecular weight thermoplastic polymer (SANYO) Kasei Sun Wax 151P
Specific gravity = 0.93) 51.2 parts by volume of compound 5 kg
Charged to a jacketed 20 liter Hensche mixer (manufactured by Mitsui Mining Co., Ltd.) heated to 0 ° C., and blade speed 1
The mixture was stirred at 1.3 m / sec for 12 minutes.

When the contents were taken out, the resin component was melted and was on the verge of agglomeration because the crystalline polymer was used.
Small particles could not be obtained stably.

Comparative Example 2 53.0 parts by volume of titanium oxide (R-TC30 manufactured by Tyoxide Co., Ltd., specific gravity = 3.9), number average molecular weight 910, 20
Hydrogenated rosin ester having a melt viscosity of 1 poise at 0 ° C (Pine Crystal KE10 manufactured by Arakawa Chemical Industry Co., Ltd.)
0 specific gravity = 1.1) 5 kg of the compound of 47.0 parts by volume was charged into an unheated 20 liter Hensche mixer (manufactured by Mitsui Mining Co., Ltd.), and the upper blade tip speed was 22.1 m / sec.
The lower blade tip speed was 22.9 m / sec and the mixture was stirred for 90 minutes. Even though the mixture was stirred for a long time, the temperature inside the mixer was less than 50 ° C., so that the amount of the granulated product was 0.3 to 1 mm, which was only 6%.

[0054]

Industrial Applicability As described above, the coloring thermoplastic composition produced by the method of the present invention is low in cost, easy to produce in a variety of small quantities, and has a mechanical strength and a blocking resistance necessary for ensuring storage stability. Granules with excellent properties and high concentration and good dispersion.

The thermoplastic composition for coloring produced by this composition and method is used as a masterbatch in a continuous resin kneader such as an extruder, an extrusion molding machine having a melt kneading function, an injection molding machine or a blow molding machine. It is supplied and preferably used.

Claims (7)

[Claims] 1. A) at least one or more dyes and pigments; and B) a number average molecular weight in the range of 300 to 5,000.
A composition prepared by blending one or more non-crystalline low molecular weight thermoplastic polymers having a melt viscosity at 00 ° C. in the range of 0.1 to 100 poises in a high temperature state using a high-speed rotary blade stirrer. A method for producing a thermoplastic composition for coloring, which comprises granulating a dye and a pigment and a thermoplastic polymer by welding. 2. The coloring thermoplastic resin according to claim 1, wherein the non-crystalline low molecular weight thermoplastic polymer is a combination of one or more selected from the following a) to g). A method for producing a composition. a) A terpene resin containing as a main component a combination of one or more selected from α-pinene and β-pinene-containing monoterpenes, sesquiterpenes, diterpenes, polyterpenes, and limonenes b) Hydrogenated resins of the terpene resins described in a) above. c) Organic acid whose main component is one or more kinds of rosin acid including abietic acid, diabietic acid, neoabietic acid, levopimaric acid, pimaric acid, dextropimaric acid, and hydrogenated rosin acid is glycerin or pentaerythritol. Modified rosin resin esterified with polyhydric alcohol containing d) monoolefin containing C ₅ to C ₉ styrene compound, diolefin containing diene compound, coumarone, indene or cyclopentadiene, dicyclopentadiene Mainly one or more combinations selected from Petroleum resin e) above d) hydrogenation of petroleum resins described resin f) low molecular weight polystyrene or a low molecular weight styrene copolymer g) bisphenol A or brominated bisphenol A and partial raw material
Epoxy resin oligomer containing 3. The volume fraction (A / a) / (of the dye / pigment, where A is the weight of the dye / pigment, a is the true specific gravity, B is the weight of the amorphous low molecular weight thermoplastic polymer, and b is the true specific gravity. A / a + B / b)
Is in the range of 0.2 to 0.8, and the method for producing a coloring thermoplastic composition according to claim 1. 4. The heat for coloring according to claim 1, wherein the high-speed rotary blade agitator has a rotary agitating blade inside and has a counter shaft if necessary, and the granules are produced by a batch operation. A method for producing a plastic composition. 5. The high speed rotary blade agitator has a rotary blade tip speed in the range of 2 m / sec to 40 m / sec, and a temperature for welding necessary for granulation is in the range of 50 ° C. to 150 ° C. The method for producing the coloring thermoplastic composition according to claim 1. 6. A method for producing a coloring thermoplastic composition, characterized in that the thermoplastic resin composition for coloring is heated by a high-speed rotary blade stirrer with a jacket to satisfy the temperature condition of claim 5. 7. A method for producing a coloring thermoplastic composition, characterized in that a heating raw material is supplied to a high-speed rotary blade stirrer in order to satisfy the temperature condition of claim 5.