JPH0563501B2 - - Google Patents

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a thermoplastic resin with wax uniformly and finely dispersed, which has excellent transparency, and which can be used as a molding material, adhesive,
The present invention relates to a resin composition suitable for application to coating materials, colored toners, dispersion aids, compatibilizers, and other fields. (Prior Art) Natural or synthetic waxes generally have a low number average molecular weight of about 300 to 10,000, and therefore have excellent compatibility with various thermoplastic resins, so they are used in various fields by being added to thermoplastic resins. ing. Conventionally, methods for dispersing wax in thermoplastic resin include a method using a kneader, or in special cases, a method in which both are dissolved in a solvent, mixed, and then the solvent is removed. (Problems to be Solved by the Invention) However, in the kneading method, it is difficult to uniformly and finely disperse wax, and as a result, the resulting resin composition becomes opaque.
It has the disadvantage that it cannot be used when transparency or colored hue is required. In addition, the method of mixing solvents is not preferable because it requires complicated equipment and is complicated to operate, and also has environmental problems caused by the solvent and problems associated with its removal. Therefore, it is considered that it is better to achieve fine dispersion by a simple kneading method. Therefore, in order to strengthen the compatibility between the thermoplastic resin and the wax and improve the fine dispersibility, it is possible to consider, for example, a method of grafting the wax with styrene and blending it with a styrenic polymer. When simply kneaded, the resin composition was not sufficiently finely dispersed, and a resin composition with satisfactory transparency could not be obtained. (Means for Solving the Problems) The present invention aims to obtain a resin composition consisting of a thermoplastic resin and wax with sufficient transparency. This was accomplished by discovering that this objective could be achieved by dispersing the particles to a particle size of 1μ or less. That is, the present invention provides polypropylene waxes 2 to 2.
An aqueous suspension containing 85 parts by weight, 98 to 15 parts by weight of an aromatic and/or acrylic acid ester vinyl monomer, and a radical generator in a proportion of 0.05 to 30% by weight based on the vinyl monomer. Modified polypropylene wax obtained by subjecting to polymerization reaction conditions 4.2 to 30% by weight
and a thermoplastic resin consisting of one or more selected from the group of aromatic vinyl monomer resins, acrylic resins, polyesters, and polycarbonates.
A polymer obtained by kneading 95.8 to 70% by weight of polypropylene wax, in which the polypropylene wax component is substantially 1μ
The present invention is a resin composition having a finely dispersed phase, characterized in that it comprises a dispersed phase of m or less. Here, "substantially" means a state in which 80% by weight or more of the dispersed phase satisfies the conditions, and "modified polypropylene wax" refers to a condition in which vinyl monomer is polymerized in the presence of polypropylene wax. The term "polypropylene wax component" refers to the entire polymer obtained by subjecting the polypropylene wax component to polypropylene wax derived from modified polypropylene. It is a mixture of pure polypropylene wax. (Function) The thermoplastic resin used in the present invention includes aromatic vinyl monomer resin, acrylic resin, polyester,
One or two selected from the group of polycarbonate
It is a mixture of more than one species. Aromatic vinyl monomer resins include polystyrene, styrene-(meth)acrylate copolymer, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), styrene- Examples include butadiene-styrene block copolymer. Examples of acrylic resins include polyacrylonitrile and methyl methacrylate resin. Among these thermoplastic resins, styrene resins and polyesters are preferable in terms of transparency, and among them, styrene resins have a glass transition temperature of 30 to 105°C and a number average molecular weight of 1000 to 150,000, particularly 2000 to 100,000. system resin and solvent-soluble polyester, i.e., amorphous or low crystallinity (crystallinity by X-ray analysis is 5% or less), softening degree is 40 to 150
℃, especially 60 to 130℃, and a number average molecular weight of 500 to 30,000, particularly 1,000 to 20,000, is preferable from the viewpoint of fine dispersion of the wax. Note that polyester is obtained by polycondensation of commonly used polybasic acids and polyhydric alcohols. Here, polybasic acids include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, and trimellitic acid;
Aliphatic carboxylic acids such as adipic acid, hexahydroterephthalic acid, succinic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, n-octylsuccinic acid, isooctylsuccinic acid, n-butylsuccinic acid; maleic acid,
Examples include unsaturated carboxylic acids such as fumaric acid and their anhydrides. Alcohol components include ethylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol, 2,2,
4,4-tetramethylene glycol, glycerin, trimethylolpropane, bisphenol A, hydrogenated bisphenol A, sorbitol or their etherified hydroxyl compounds, such as polyoxyethylene (10) sorbitol, polyoxypropylene (5) glycerin , polyoxyethylene (4) pentaerythritol, polyoxypropylene (2,2)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene (2)-2,
Examples include 2-bis(4-hydroxyphenyl)propane. Polypropylene wax is used to produce the modified wax used in the present invention because it is less prone to gelation during denaturation, and waxes with a number average molecular weight of 900 to 5000 are suitable for homogeneity and during subsequent denaturation. This is preferable in that gelation is less likely to occur. The polypropylene wax preferably has a ratio of weight average molecular weight to number average molecular weight of 1.05 or more, more preferably 1.15 or more from the viewpoint of homogeneity. Further, different types of waxes may be blended and used as long as they are within the above range and homogeneity is not impaired. Further, the vinyl monomer used for modification is at least one type of vinyl monomer selected from the group of aromatic vinyl monomers and acrylate vinyl monomers. Here, the aromatic vinyl monomer is preferably, for example, styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorstyrene, α-methylstyrene, α-ethylstyrene, etc.; Suitable monomers include, for example, acrylic acid esters such as methyl, ethyl, butyl, and 2-ethylhexyl, as well as methacrylic acid esters such as methyl, ethyl, and butyl. These vinyl monomers can be copolymerized and used. Preferred examples include, for example, a combination of styrene and ethyl acrylate or styrene and butyl methacrylate. Further, other monomers copolymerizable with each vinyl monomer can be used in coexistence in an amount not exceeding a majority weight. Other monomers include, for example, acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylic acid amide,
Unsaturated organic acids such as maleic anhydride (acids, salts,
unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate; and unsaturated mono- to dihalides such as vinyl chloride and vinylidene chloride. These may be used in combination. The method for obtaining a modified polypropylene wax (hereinafter simply referred to as modified wax) by subjecting a polypropylene wax (hereinafter simply referred to as wax) and a vinyl monomer to modification conditions is sufficient to exhibit the effects of the present invention. In order to obtain a highly modified wax, and taking into consideration equipment problems, environmental problems, and solvent removal problems when using solvents, we developed a method using aqueous suspension polymerization that does not have such problems, namely ( 1) A method in which wax particles are suspended in water, a vinyl monomer is added thereto, and the mixture is impregnated and then reacted. (2) Wax particles dissolved in vinyl monomer are suspended in water as droplets. A method is adopted in which the reaction occurs under the conditions. A polymerization initiator is usually used in this reaction. As the polymerization initiator, those used in general radical polymerization can be used, but considering the temperature of the polymerization reaction, the decomposition temperature is 45 to 110℃, especially 50℃.
It is preferable to choose from those in the range of ~105°C. The decomposition temperature here means the temperature at which the decomposition rate of the radical generator becomes 50% when 0.1 mol of a polymerization initiator is added to benzene 1 and the mixture is left at a certain temperature for 10 hours. Specific examples of such things include, for example:
2,4-dichlorobenzoyl peroxide (54
℃), t-butyl peroxypivalate (56℃),
o-methylbenzoyl peroxide (57°C),
Bis-3,5,5-trimethylhexanoyl peroxide (60℃), octanoyl peroxide (61℃), lauroyl peroxide (62℃),
Benzoyl peroxide (74℃), t-butylperoxy-2-ethylhexanoate (74℃),
1,1-bis(t-butylperoxy)-3,3,
5-trimethylcyclohexane (91°C), cyclohexanone peroxide (97°C), 2,5-dimethyl-2,5-dibenzoyl peroxyhexane (100°C), t-butyl peroxybenzoate (104°C), di- Organic peroxides such as t-butyl-diperoxyphthalate (105°C), methyl ethyl ketone peroxide (109°C), dicumyl peroxide (117°C), di-t-butyl peroxide,
Azobisisobutyronitrile (65℃), azobis(2,4-dimethylvaleronitrile) (68℃), 2
-t-butylazo-2-cyanopropane (79℃)
Water-soluble peroxides such as hydrogen peroxide and potassium persulfate (approximately 70°C) can be mentioned. Here, the temperature in parentheses indicates the decomposition temperature. These can also be used in combination. The proportions of each component used during this modification are 2 to 85 parts by weight, preferably 2 to 70 parts by weight of wax, 98 to 15 parts by weight, preferably 98 to 30 parts by weight of vinyl monomer, and the use of a polymerization initiator. The amount is from 0.05 to 30% by weight, preferably from 0.1 to 10% by weight relative to the vinyl monomer.
% by weight. The ratio of the thermoplastic resin to the modified wax is 30% by weight or less of the modified polypropylene wax so that the wax component forms a dispersed phase, and 4.2% by weight or more from the viewpoint of the modification effect. The method for producing the composition of the present invention is carried out by sufficiently homogeneously kneading the above components using a conventional resin kneading machine such as an extruder, roll, or Banbury mixer. In some cases, a dry blend using a high-speed mixer, tumbler mixer, etc. may be directly subjected to molding or the like. What is important here is to keep the particle size of the wax component in the dispersed phase to substantially 1μ or less, preferably
The thickness should be 0.5μ or less. Good transparency can only be achieved when this condition is satisfied. In addition, in the present invention, in addition to the above-mentioned essential components, additional components such as antioxidants, neutralizers, ultraviolet absorbers, antistatic agents, foaming agents, lubricants, and colorants may be used to inhibit the effects of the invention. It can be added within the range. (Example) Example 1 [Manufacture of modified polypropylene wax] 60 g of tricalcium phosphate and sodium dodecylbenzenesulfonate in an autoclave with a capacity of 10
0.06 g and 3 kg of pure water were added and thoroughly stirred. Then t
8.6 g of -butyl peroxypivalate (the above-mentioned "Perbutyl PV") and 6 g of benzoyl peroxide were dissolved in a mixed solution of 380 g of styrene and 220 g of n-butyl methacrylate, and the solution was added to an autoclave.
After thorough stirring, 900 g of polypropylene wax (the above-mentioned "Viscol 550P") was added, and the mixture was further stirred thoroughly. Afterwards, the inside of the autoclave was replaced with nitrogen.
The system temperature was raised to 50° C. and maintained at this temperature for 3 hours to impregnate the vinyl monomer into the wax.
Subsequently, the system temperature was maintained at 65°C for 2 hours, at 75°C for 3 hours, and further at 90°C for 3 hours to complete polymerization. After cooling, the contents were treated with acid and washed with water to obtain 1.5 kg of modified wax particles. When this product was analyzed for composition using infrared spectroscopy, it was found that the reaction progressed almost quantitatively. [Production of styrene-n-butyl methacrylate copolymer] In the modification method in Example 1, only styrene and n-butyl methacrylate were copolymerized at a weight ratio of 63:37 without using polypropylene wax,
A styrene-n-butyl methacrylate copolymer was produced. Next, 8.4 parts by weight of the modified polypropylene wax obtained in the above production and 91.6 parts by weight of styrene-n-butyl methacrylate copolymer were blended and melt-kneaded at 140°C in a vented twin-screw extruder to form a composition. I got it. The evaluation of this product is shown in Table 1. Example 2 [Manufacture of modified polyester particles] Amorphous and non-waxy polyester (linear saturated polyester,
Glass transition temperature 51.1℃, molecular weight approximately 3000) 600g,
880g styrene and n-butyl methacrylate
520g was added and heated to 60°C while stirring to dissolve.
The solution viscosity at this time was 115 centipoise.
To this, 20 g of t-butyl peroxypivalate (the above-mentioned "Perbutyl PV") and 7 g of benzoyl peroxide were added as a radical generator and dissolved, and further 8 g of polyvinyl alcohol and 4 kg of water were added and stirred.
Performed a phase reversal. Thereafter, the inside of the autoclave was purged with nitrogen, and the temperature inside the system was raised to 75°C, and this temperature was maintained for 4 hours, and then the temperature was further raised to 90°C and held for 2 hours to complete polymerization. After cooling, the contents were taken out and washed with water to obtain 2 kg of modified polyester particles. Next, 91.6 parts by weight of the modified polyester particles obtained in the above production and the modified polypropylene wax particles obtained in Example 1 [Production of modified wax particles]
Blend 8.4 parts by weight and heat at 140℃ in a vented twin-screw extruder.
The mixture was melt-kneaded to obtain a composition. The evaluation of this product is shown in Table 1. Example 3 Modified polypropylene wax particles obtained in Example 1 [Production of modified polypropylene wax]
4.2 parts by weight of the same polypropylene wax used in Example 1 and 2.5 parts by weight of the styrene-n-butyl methacrylate copolymer obtained in Example 1 [Production of styrene-n-butyl methacrylate copolymer] 93.3 parts by weight, vented 2,
A composition was obtained by melt-kneading at 140°C using a screw extruder.
The evaluation of this product is shown in Table 1. Comparative Example 1 5 parts by weight of the same polypropylene wax used in Example 1 and 95 parts by weight of the styrene-n-butyl methacrylate copolymer obtained in Example 1 [Production of styrene-n-butyl methacrylate copolymer] The components were blended and melt-kneaded at 140°C in a vented twin-screw extruder to obtain a composition. The evaluation of this product is shown in Table 1. Comparative Example 2 4 kg of toluene was placed in an autoclave with an internal capacity of 10 and heated to 65°C. Next, 100 g of polypropylene wax (the above-mentioned "Viscol 550P") was added and stirred for 1 hour to dissolve. The inside of the autoclave was replaced with nitrogen, and 1.2 kg of styrene, 700 g of n-butyl methacrylate, and t-butyl peroxypivalate (as described above) were added as a radical generator.
27.1 g of vinyl monomer (PV) and 19 g of benzoyl peroxide were added dropwise for 2 hours to polymerize. Thereafter, the system temperature was raised to 75°C for 3 hours, and further raised to 90°C and held for 3 hours to complete polymerization. Next, the reaction product, which had been concentrated by removing toluene under reduced pressure, was added little by little into methanol under vigorous stirring to reprecipitate the polymer. Furthermore, unreacted substances and soluble substances were removed by washing twice with methanol. After air drying the cleaning resin, vacuum dry it to 1.8Kg.
modified wax particles were obtained. When the composition of this product was analyzed by infrared spectroscopy, the amount of modification of the polypropylene wax was found to be small. Further, the obtained modified polypropylene wax was mixed with the styrene-n-butyl methacrylate copolymer obtained in Example 1 in the proportions shown in Table 1, and the results were evaluated as shown in Table 1. 【table】

Claims (1)

[Claims] 1 2 to 85 parts by weight of polypropylene wax, 98 to 15 parts by weight of aromatic and/or acrylic acid ester vinyl monomer, and a radical generator at a ratio of 0.05 to 30% by weight based on the vinyl monomer. 4.2 to 30% by weight of a modified polypropylene wax obtained by subjecting an aqueous suspension containing the same to polymerization reaction conditions, and one type selected from the group of aromatic vinyl monomer resins, acrylic resins, polyesters, and polycarbonates. or a composition obtained by kneading 95.8 to 70% by weight of two or more thermoplastic resins, characterized in that the polypropylene wax component substantially constitutes a dispersed phase of 1 μm or less. A resin composition having a dispersed phase.