JP2000230099A - Resin composition for coloration and vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition reduced in the deposition and accumulation of the constituent pigment on the molding machine even in a long-time continuous running and giving a molding having a good appearance by using a pigment and dispersant having a specified acrylic polymeric lubricant and used for dispersing the pigment as the principal components. SOLUTION: The dispersant used is an acrylic polymeric lubricant having a weight-average molecular weight of 10,000-1,000,000 and is used in an amount of, desirably, 1-80 pts.wt. per 100 pts.wt. pigment. The resin composition is added to a vinyl chloride resin to obtain a vinyl chloride resin composition. Desirably, the coloring resin composition is used in an amount of 0.05-20 pts.wt. per 100 pts.wt. vinyl chloride resin. The vinyl chloride resin is desirably a resin obtained by grafting vinyl chloride onto an acrylic copolymer obtained by copolymerizing 50-100 pts.wt. (meth)acrylate monomer giving a homopolymer having a glass transition temperature of -140 to -20 deg.C with 0-50 pts.wt. other radically polymerizable monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition for coloring a thermoplastic resin, and a vinyl chloride resin composition for colored extrusion molding or injection molding.

[0002]

2. Description of the Related Art The vinyl chloride resin described above has mechanical strength,
As a material having characteristics excellent in weather resistance and chemical resistance, it is colored and molded by a coloring agent such as an organic pigment or an inorganic pigment, and is used in many applications such as pipes and joints. However, when used for hard materials, they have a disadvantage of poor impact resistance, and various improvement methods have been proposed. It is generally known that impact resistance can be imparted by mixing a rubbery polymer with a fragile hard resin, and for applications requiring impact resistance and weather resistance, a cross-linked acrylic copolymer can be used. A vinyl chloride resin obtained by graft copolymerizing vinyl chloride (JP-A-60-255813) has been proposed. However, when the rubber component is mixed into the vinyl chloride resin as described above, it becomes tacky under high-temperature molding,
These rubber components serve as a medium, and the colorant with poor compatibility with the matrix resin tends to adhere and accumulate very easily on the resin flow surface in the molding machine such as the screw, cylinder, breaker, and mold. Was. Therefore,
When a conventional colorant is used, deposits containing the colorant as a main component are generated in the molding machine during continuous operation, which not only causes shading and streaks on the surface of the molded product, but also causes uneven coloring and causes molding. There was a problem that the appearance of the product was significantly impaired. On the other hand, a method of adding an acrylic polymer lubricant during molding has been proposed as a method for improving the surface properties and providing long-term running properties of such a resin containing an acrylic rubber (Japanese Patent Application Laid-Open No. 10-231410). Gazette). However, this method has little effect on the build-up of the pigment, and the surface condition of the obtained colored molded product is not satisfactory.

[0003]

SUMMARY OF THE INVENTION The object of the present invention has been made in view of the above-mentioned prior art. Compared with a conventional product, even during continuous operation for a long time, there is less adhesion and accumulation in a molding machine. An object of the present invention is to provide a coloring resin composition which can be uniformly colored to obtain a molded article having a good appearance, and a vinyl chloride resin composition obtained by blending the coloring resin composition.

[0004]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a coloring resin composition using a specific compound as a dispersant has high tackiness at the time of high-temperature melting. It has been found that even with a vinyl chloride resin, there is little adhesion and deposition in the molding machine, and it is possible to obtain a molded product having a uniform appearance and good appearance.

That is, the invention according to claim 1 is a coloring resin composition comprising a pigment and a dispersing agent for dispersing the pigment as a main component, wherein the dispersing agent has a weight average molecular weight of 10,000 to 1,000,000. Characterized in that an acrylic polymer lubricant is used.

According to a second aspect of the present invention, there is provided a vinyl chloride resin composition comprising the coloring resin composition according to the first aspect of the invention mixed with a vinyl chloride resin.
The invention according to claim 3 is the invention according to claim 2, wherein the homopolymer has a glass transition temperature of −140 ° C. to −20 ° C.
C. and 50 to 100 parts by weight of a (meth) acrylate monomer and 0 to 0
Acrylic copolymer obtained by copolymerizing 50 parts by weight,
It is characterized in that a vinyl chloride resin obtained by graft copolymerizing vinyl chloride is used.

First, the present invention will be described in detail. The pigment of the present invention includes organic pigments and inorganic pigments, and known pigments conventionally used for coloring vinyl chloride resins can be used. Examples of such pigments include organic pigments such as azo, anthraquinone, phthalocyanone, quinacridone, isoindolinone, dioxane, berylen, quinophthalone, and berynone, cadmium sulfide, cadmium selenide, There are inorganic pigments such as ultramarine, titanium dioxide, iron oxide, chromate, and carbon black.

The present invention provides a dispersant having a weight average molecular weight of 1
It is characterized by using 10,000 to 1,000,000 acrylic polymer lubricants. The acrylic polymer lubricant is interposed between the coloring resin composition and the vinyl chloride resin composition containing the same during molding and the metal surface of the molding machine, and prevents the coloring resin from adhering to the inside of the molding machine. I do. The acrylic polymer lubricant is not particularly limited in type, but includes, for example, “METABLEN L-1000” manufactured by Mitsubishi Rayon Co., Ltd.

The monomer components constituting the acrylic polymer lubricant include, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-
Examples thereof include butyl (meth) acrylate and isobutyl (meth) acrylate, and a monomer that can be radically copolymerized with these monomers is used as needed.

When the weight average molecular weight of the acrylic polymer lubricant is less than 10,000, it becomes tacky and has insufficient lubricity.
May cause build-up. On the other hand, if the weight average molecular weight of the acrylic polymer lubricant exceeds 1,000,000, the molding load may increase and molding may not be possible.

In the coloring resin composition of the present invention, the content of the acrylic polymer lubricant is preferably 1 to 80 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the pigment. is there.

The coloring resin composition of the present invention may contain a thermoplastic resin as a binder (dispersion medium) for dispersing the pigment. The type of the thermoplastic resin is not particularly limited as long as it is a resin capable of producing a masterbatch. Examples thereof include polyvinyl chloride, polyolefin, polystyrene, polyethylene terephthalate, ABS resin, acrylic resin, polyacetal, polyurethane, and polycarbonate. And copolymers thereof, and a vinyl chloride resin is particularly preferable. The compounding amount of such a thermoplastic resin is preferably from 0 to 70% by weight, more preferably from 0 to 40% by weight, in the coloring resin composition.

The coloring resin composition may further contain a heat stabilizer, a stabilizing aid, a lubricant, a processing aid, an antioxidant, a light stabilizer, a filler, and the like, if necessary. The method of mixing the pigment, acrylic polymer lubricant, and other additives is not particularly limited, but, for example, a Henschel mixer, a hot blend mixing method using a super mixer, a cold blend mixer method,
Extrusion mixing method and the like can be mentioned.

The coloring resin composition of the present invention can be most suitably blended for coloring a vinyl chloride resin. However, the coloring resin composition is not particularly limited to the vinyl chloride resin, and may be polyolefin, polystyrene, polyethylene terephthalate, ABS resin, or the like. Acrylic resin, polyacetal, polyurethane,
It is blended with thermoplastic resins such as polycarbonate and copolymers thereof.

Next, the invention according to claim 2 will be described in detail. According to a second aspect of the present invention, there is provided a vinyl chloride resin composition obtained by blending the coloring resin composition according to the first aspect of the present invention with a vinyl chloride resin. The characteristic feature is that a molded product having a good quality can be obtained.

As the vinyl chloride resin, for example,
Polyvinyl chloride; copolymer of vinyl chloride monomer and monomer copolymerizable with vinyl chloride monomer; vinyl chloride monomer and graft copolymer of vinyl chloride monomer and resin capable of graft copolymerization; copolymerization of polyvinyl chloride Chlorinated polyvinyl chloride and the like, and at least one of them can be used.

The monomers copolymerizable with vinyl chloride are generally known vinyl monomers, for example, olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate and methyl acrylate. (Meth) acrylates such as methacrylate and ethyl acrylate; vinyl ethers such as isobutyl vinyl ether and phenyl vinyl ether; vinyl halides such as vinylidene chloride and vinyl fluoride; and maleimides, and at least one of them can be used.

Examples of the resin which can be graft-copolymerized with the vinyl chloride monomer include ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, chlorinated polyethylene, polyurethane and the like. Can be used.

The polymerization method of the vinyl chloride resin is not particularly limited, and examples thereof include a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and a bulk polymerization method. desirable.

If the degree of polymerization of polyvinyl chloride in the above-mentioned vinyl chloride resin is too small or too large, it is difficult to obtain sufficient moldability of a molded article. 400 to 1600.

The method of mixing the vinyl chloride resin and the coloring resin composition is not particularly limited, but examples thereof include a hot blend mixing method using a Henschel mixer, a super mixer, etc., a cold blend mixer method, Extrusion mixing method and the like can be mentioned.

When the vinyl chloride resin composition of the present invention is molded, a heat stabilizer, a stabilizing aid, a lubricant,
Processing aids, oxidation aids, antioxidants, light stabilizers, fillers,
A pigment or the like is added and used.

Examples of the heat stabilizer include dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin maleate, dibutyltin maleate polymer, dioctyltin malate, dioctyltin maleate polymer, dibutyltin laurate, dibutyltin Organic tin stabilizers such as laurate polymers, lead stabilizers such as lead stearate, dibasic lead phosphite, and tribasic lead sulfate, calcium-zinc stabilizer, barium-zinc stabilizer, barium- Cadmium stabilizers and the like can be mentioned.

Examples of the stabilizing aid include epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, phosphate esters and the like.

Examples of the above lubricant include montanic acid wax, paraffin wax, polyethylene wax,
Stearic acid, stearyl alcohol, butyl stearate and the like can be mentioned.

Examples of the processing aid include an acrylic processing aid which is an alkyl acrylate / alkyl methacrylate copolymer having a weight average molecular weight of 100,000 to 2,000,000, and specific examples thereof include n-butyl acrylate / Examples include a methyl methacrylate copolymer and a 2-ethylhexyl acrylate / methyl methacrylate / butyl methacrylate copolymer.

Examples of the antioxidant include phenolic antioxidants. Examples of the light stabilizer include salicylic acid ester-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers, and hindered amine-based light stabilizers.

Examples of the filler include calcium carbonate, talc and the like. As the pigment, for example, azo-based, phthalocyanine-based, sulene-based, organic pigments such as dye lakes, oxides, molybdenum chromate-based, sulfides / selenide-based, inorganic pigments such as ferrocyanide-based and the like. No.

Further, the vinyl chloride resin composition includes:
A plasticizer may be added for the purpose of improving workability at the time of molding, and examples thereof include dibutyl phthalate, di-2-ethylhexyl phthalate, and di-2-ethylhexyl adipate.

The above additives may be mixed with the vinyl chloride resin composition by hot blending or cold blending. The mixing of the additives may be carried out by adding the vinyl chloride resin to the coloring resin composition. May be performed simultaneously with the step of mixing.

The method for molding the vinyl chloride resin composition is not particularly limited, and examples thereof include an extrusion molding method, an injection molding method, a calendar molding method, and a press molding method.
The mixing ratio of the coloring resin composition to the vinyl chloride resin is 0.05 to 100 parts by weight of the vinyl chloride resin.
20 parts by weight is preferred, and more preferably 0.1 to 5 parts by weight.
Parts by weight.

Next, the invention according to claim 3 will be described in detail. According to a third aspect of the present invention, in the vinyl chloride resin composition according to the second aspect, a vinyl chloride resin obtained by graft-polymerizing vinyl chloride to an acrylic copolymer as the vinyl chloride resin is used. It is characterized in that it not only provides a molded article having a good appearance even in continuous molding for a long time, but also has an excellent impact resistance and weather resistance.

The (meth) acrylate (A), which is a main component of the acrylic copolymer, is used for the purpose of improving the impact resistance of a vinyl chloride resin, and is required to have flexibility at room temperature, so that it has a single weight. The glass transition temperature of the coalescence is -20 ° C
It is necessary that the temperature is not higher than -20 ° C, and the type is not particularly limited as long as it is -20 ° C or lower. However, in view of the glass transition temperature of a polymer generally used industrially, −140 ° C or higher is suitable. Examples of the (meth) acrylate (A) include, for example, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate, sec-butyl acrylate, cumyl acrylate, n-hexyl acrylate, n- Heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-methylheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, 2-methyloctyl acrylate, 2-ethylheptyl acrylate ,
Examples thereof include alkyl (meth) acrylates such as n-decyl (meth) acrylate and lauryl (meth) acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate. These may be used alone or in combination of two or more. it can.

The glass transition temperature of the (meth) acrylate (A) homopolymer having a glass transition temperature of −140 ° C. or higher and −20 ° C. or lower is the same as that of the high polymer published by Baifukan in “High Molecular Data Handbook (Basic Edition) ”etc.

The radical polymerizable monomer (B) copolymerizable with the (meth) acrylate (A) is added for the purpose of improving the mechanical strength, chemical resistance and moldability of the vinyl chloride resin. Is not limited, for example, methyl (meth) acrylate, ethyl methacrylate, n-
Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, sec-butyl methacrylate, t-butyl (meth) acrylate, cumyl methacrylate, n-hexyl methacrylate, cyclohexyl (meth) acrylate, myristyl (meth) acrylate, Alkyl (meth) acrylates such as palmityl (meth) acrylate and stearyl (meth) acrylate; polar group-containing vinyl monomers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-acryloyloxyethyl phthalic acid; styrene; Aromatic vinyl monomers such as methylstyrene, p-methylstyrene and p-chlorostyrene; unsaturated vinyl monomers such as acrylonitrile and methacrylonitrile; Lil, vinyl acetate, vinyl esters such as vinyl propionate and the like, and these can be used singly or in combinations of two or more.

If the amount of the radical polymerizable monomer (B) added to the (meth) acrylate (A) constituting the acrylic copolymer is too large, the flexibility of the acrylic copolymer is lost, and Since the grafting efficiency of a vinyl monomer containing vinyl as a main component is reduced and the impact resistance is reduced, the radical polymerizable monomer (B) is 0 to 49 parts by weight based on 51 to 100 parts by weight of the (meth) acrylate (A). It is appropriate to add.

A polyfunctional monomer may be added to the monomer containing (meth) acrylate as a main component, if necessary. The polyfunctional monomer not only crosslinks the acrylic copolymer latex copolymer and improves the impact resistance of the vinyl chloride resin, but also causes coalescence of the copolymer latex particles during and after production. For example, as di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate ) Acrylate, trimethylolpropane di (meth) acrylate, and the like. Examples of tri (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and pentaerythritol (meth) acrylate. ) Acryle Doors and the like. Other polyfunctional monomers include pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl succinate, triallyl isocyanurate And divinyl compounds such as divinylbenzene and butadiene. These can be used alone or in combination of two or more.

The amount of the polyfunctional monomer to be added to the monomer containing (meth) acrylate as a main component is not particularly limited. However, if the amount is too large, it becomes difficult to obtain impact resistance due to excessive crosslinking density. It is appropriate to add 0 to 30 parts by weight of the polyfunctional monomer to 100 parts by weight of the monomer containing acrylate as a main component, and preferably 0 to 10 parts by weight.

In the present invention, the polymerization method of the acrylic copolymer is not particularly limited, and examples thereof include an emulsion polymerization method and a suspension polymerization method. The emulsion polymerization method is preferred from the viewpoint that the particle size of the acrylic copolymer latex can be easily controlled.

In the emulsion polymerization of the acrylic copolymer of the present invention, an emulsifying dispersant and a polymerization initiator are used as additives. The emulsifying and dispersing agent is added for the purpose of improving the dispersion stability of the mixed monomer in an emulsion and efficiently performing polymerization, for example, an anionic surfactant, a nonionic surfactant, and a partial saponification. Examples thereof include polyvinyl acetate, cellulose dispersants, and gelatin. Particularly preferred are anionic surfactants, such as polyoxyethylene alkyl phenyl ether sulfate.

Examples of the polymerization initiator include water-soluble polymerization initiators such as potassium persulfate, ammonium persulfate, and aqueous hydrogen peroxide, organic peroxides such as benzoyl peroxide and lauroyl peroxide, and azobisisobutyrate. Examples include azo-based initiators such as lonitrile, and redox initiators.

In the emulsion polymerization method, a pH adjuster and an antioxidant may be added as required. The emulsion polymerization method is roughly classified into three methods, namely, a batch polymerization method, a monomer dropping method, and an emulsion dropping method depending on the difference in the monomer addition method, but is not particularly limited.

In the batch polymerization method, for example, water, an emulsifying dispersant, a mixed monomer composed of the acrylic monomer and the polyfunctional monomer are added all at once in a jacketed polymerization reactor, and after oxygen is removed under vacuum, This is a method in which nitrogen is sealed, emulsification is sufficiently performed by stirring under normal pressure conditions, the inside of the vessel is heated to a predetermined temperature by a jacket, and then a polymerization initiator is added to carry out polymerization.

The monomer dropping method means that, for example, water, an emulsifying dispersant, and a polymerization initiator are charged into a jacketed polymerization reactor, oxygen is removed under a vacuum, nitrogen is sealed, and the reaction is carried out under normal pressure. In this method, the inside of the vessel is first heated to a predetermined temperature by a jacket, and then the above-mentioned mixed monomer is added dropwise in a predetermined amount to gradually polymerize.

The emulsion dropping method is, for example,
The above-mentioned mixed monomer, emulsifying dispersant, and water are sufficiently emulsified by stirring to prepare an emulsifying monomer in advance, and then pure water and a polymerization initiator are placed in a jacketed polymerization reactor. Is sealed, and at normal pressure, the inside of the vessel is first heated to a predetermined temperature by a jacket, and then the emulsified monomer is dropped by a predetermined amount to carry out polymerization. Further, in the emulsion dropping method, if a method is used in which a part of the above-mentioned emulsifying monomer is added all at once in the early stage of polymerization (hereinafter referred to as “seed monomer”) and then the remaining emulsifying monomer is dropped, the amount of the seed monomer is changed. Thereby, the particle size of the produced latex can be easily controlled.

The resin solid content of the latex emulsion of the acrylic copolymer obtained by emulsion polymerization is not particularly limited, but is preferably 10 to 60% by weight in view of the productivity of the latex and the stability of the polymerization reaction. Is preferred.

The average particle size of the above-mentioned acrylic copolymer latex is not particularly limited, but if it is too large, the impact resistance and tensile strength of the molded article are both reduced. Is slightly reduced,
Preferably it is 0.01 to 1.0 μm.

The above-mentioned acrylic copolymer latex includes:
For the purpose of improving the mechanical stability of the latex emulsion, a protective colloid agent may be added as required after the completion of the latex polymerization reaction.

In the present invention, a vinyl chloride resin is obtained by graft copolymerizing vinyl chloride alone or a vinyl monomer containing vinyl chloride as a main component to the acrylic copolymer latex.

The proportion of the acrylic copolymer in the vinyl chloride resin is not particularly limited. However, when the proportion is small, it is difficult to obtain sufficient impact resistance, and when the proportion is large, the mechanical strength such as bending strength and tensile strength is low. 1-6
0% by weight, preferably 4 to 30% by weight.

In the present invention, in the method of obtaining a vinyl chloride resin by graft copolymerizing vinyl chloride alone or a vinyl monomer containing vinyl chloride as a main component with the above acrylic copolymer, the method comprises a process containing vinyl chloride as a main component. The monomer means a mixture of 50% by weight or more of vinyl chloride and a vinyl monomer copolymerizable therewith, and the copolymerizable monomer is a generally known vinyl monomer such as vinyl acetate, alkyl ( Examples thereof include (meth) acrylate, alkyl vinyl ether, ethylene, vinyl fluoride, and maleimide, and at least one of them can be used.

The method of graft copolymerizing vinyl chloride alone or a vinyl monomer containing vinyl chloride as a main component with the acrylic copolymer is not particularly limited, and examples thereof include a suspension polymerization method and an emulsion polymerization method. , A solution polymerization method, a bulk polymerization method and the like, and a suspension polymerization method is desirable in order to carry out the present invention advantageously. The suspension polymerization method uses a dispersant and an oil-soluble polymerization initiator.

When graft copolymerizing vinyl chloride,
A coagulant may be added to the acrylic copolymer latex emulsion for the purpose of reducing the scale adhering in the polymerization tank during the polymerization.

The dispersing agent used in the suspension polymerization is added for the purpose of improving the dispersion stability of the acrylic copolymer and efficiently performing the vinyl chloride graft polymerization.
Poly (meth) acrylate, (meth) acrylate-alkyl acrylate copolymer, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose,
Polyethylene glycol, polyvinyl acetate and partially saponified products thereof, gelatin, polyvinylpyrrolidone, starch, maleic anhydride-styrene copolymer, and the like,
These can be used alone or in combination of two or more.

Among the above oil-soluble polymerization initiators, radical polymerization initiators are preferably used because they are advantageous for graft copolymerization. Examples thereof include lauroyl peroxide, t-butylperoxypivalate, and diisopropylperoxydioxide. Carbonate, dioctyl peroxy dicarbonate, t-butyl peroxy neodecanoate,
organic peroxides such as α-cumylperoxy neodecanoate, 2,2-azobisisobutyronitrile,
Azo compounds such as 2,2-azobis-2,4-dimethylvaleronitrile are exemplified. In the above suspension polymerization method, a pH adjuster, an antioxidant and the like may be added as necessary.

As a specific method for producing the vinyl chloride resin in the present invention, for example, a reaction vessel equipped with a stirrer and a jacket is charged with pure water, the acrylic copolymer latex, a dispersant, and an oil-soluble polymerization initiator. And a water-soluble thickener,
After the polymerization degree regulator is charged as required, the air in the polymerization vessel is discharged by a vacuum pump, and then, under stirring conditions, vinyl chloride and other vinyl monomers are charged as needed. Is heated by a jacket to carry out graft copolymerization of vinyl chloride.

Since the graft copolymerization of vinyl chloride is an exothermic reaction, the temperature in the reaction vessel, that is, the polymerization temperature can be controlled by changing the jacket temperature. After the completion of the reaction, unreacted vinyl chloride is removed to form a slurry, which is then dehydrated and dried to produce a vinyl chloride resin.

If the degree of polymerization of polyvinyl chloride in the above-mentioned vinyl chloride resin is too small or too large, it is difficult to obtain sufficient moldability of a molded article. 400 to 1600.

The coloring resin composition according to the first aspect of the present invention is mixed with the vinyl chloride resin in the same manner as in the second aspect of the present invention. Further, similarly to the invention according to claim 2, a heat stabilizer, a stabilizing aid, a lubricant,
Processing aids, antioxidants, light stabilizers, fillers, pigments and the like may be added and used.

The method for molding the composition comprising the vinyl chloride resin, the coloring resin composition, and the additives is not particularly limited, and examples thereof include an extrusion molding method, an injection molding method, a calendar molding method, and a press molding method. Is mentioned.

[0061]

Embodiments of the present invention will be described below. According to the composition shown in Table 1, vinyl chloride resins (PAG-1 to PAG-4) were obtained by the following operation procedure.

(Preparation of Acrylic Copolymer) First, ion-exchanged water (１ ／ of the total amount used), emulsifying dispersant (polyoxyethylene nonylphenyl ether ammonium sulfate), (meth) acrylate and radical polymerizable monomer Was mixed and stirred to prepare an emulsion monomer. On the other hand, the remaining ion-exchanged water (total usage 2/3) was charged into the polymerization tank, and stirring was started. After depressurizing the inside of the polymerization tank and deoxidizing the inside of the vessel, the pressure was returned by nitrogen to perform replacement, and the temperature of the polymerization tank was raised to 70 ° C. Ammonium persulfate (hereinafter referred to as APS) and 20% by weight of the emulsified monomer were collectively charged as a seed monomer into the polymerization vessel in which the temperature was raised, and polymerization was started. After the seed monomer was consumed by polymerization, the rest of the emulsified monomer was added dropwise. The addition of all the emulsified monomers was completed in 3 hours. After an aging period of 1 hour, the polymerization tank was cooled to terminate the polymerization, and an acrylic copolymer latex (hereinafter referred to as latex) having a solid content of about 30% by weight and a particle size of about 0.1 μm was obtained. Obtained.

(Preparation of Vinyl Chloride Resin) Then, ion-exchanged water was placed in a reaction vessel equipped with a stirrer and a jacket.
The latex, a 3% aqueous solution of partially saponified polyvinyl acetate, a 3% aqueous solution of hydroxypropyl methylcellulose,
t-butyl peroxy neodecanoate, α-cumyl peroxy neodecanoate were charged all at once, then the air in the polymerization vessel was discharged with a vacuum pump, and vinyl chloride was further charged under stirring conditions. Polymerization was started at a polymerization temperature of 57 ° C. by controlling the jacket temperature.

The completion of the reaction was confirmed when the pressure in the reactor dropped to a pressure of 6.0 kg / cm ² , and the reactor was cooled and stopped. After that, unreacted vinyl chloride monomer is removed,
By further dehydrating and drying, a vinyl chloride resin having a polymerization degree of vinyl chloride in the vinyl chloride resin of about 1000 was obtained.

[0065]

[Table 1]

N-BA: n-butyl acrylate 2-EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate TMPTA: trimethylolpropane triacrylate APS: ammonium persulfate PVA: partially saponified polyvinyl acetate MPS: hydroxypropyl methylcellulose BPOND: t -Butyl peroxy neodecanoate QPOND: α-cumyl peroxy neodecanoate

Examples 1 to 5 and Comparative Examples 1 to 3 (Preparation of Masterbatch)
Acrylic polymer lubricant ("METABLEN L-1000" manufactured by Mitsubishi Rayon Co., weight average molecular weight: about 200,000), degree of polymerization: 1
000 vinyl chloride resin was supplied to Kawada Seisakusho's "Supermixer" and mixed at room temperature for 3 minutes to obtain a coloring resin composition (hereinafter referred to as "masterbatch").

(Preparation of Vinyl Chloride Resin Composition) According to the composition shown in Table 2, a masterbatch, a vinyl chloride resin, and various additives were supplied to Kawada Seisakusho's "Supermixer", and the resin temperature reached 110 ° C. The mixture was stirred and mixed at high speed to obtain a vinyl chloride resin composition.

The evaluation items and evaluation methods are shown below. [Impact resistance] A Charpy impact test was performed according to JIS K7111. The sample was prepared by kneading the vinyl chloride resin composition at 190 ° C. for 3 minutes with a roll and then 200 ° C.
It was manufactured from a 3 mm-thick press plate obtained by press molding for minutes. The measurement temperature is 23 ° C. Usually, when used for molded products requiring impact resistance, 70 kgf · cm / cm
It is desirable to have a Charpy impact value of ² or more (non-destructive).

[Evaluation of Appearance] The above-mentioned vinyl chloride resin composition was supplied to a biaxial anisotropic extruder having a screw diameter of 50 mm (trade name “BT-50”, manufactured by Plastics Engineering Laboratory Co., Ltd.). The vinyl resin tube was continuously molded for 24 hours. The inner and outer surfaces of the obtained rigid vinyl chloride tube were visually observed, and the time from the start of molding to appearance defects such as burrs, stripes and unevenness was examined. If the surface condition of the tube was good over 24 hours, it was marked as ≧ 24.

[0071]

[Table 2]

As is clear from Table 2, the acrylic resin lubricant is contained in the coloring resin composition according to the present invention, and the vinyl chloride resin composition containing the coloring resin composition is extruded as a resin tube. The surface condition of the tube when molded was good for a long time. It was also confirmed that the adhesion and deposition of the pigment on the molding machine was extremely small. In addition, as is clear from the comparison between Example 1 and Comparative Example 1, it is more preferable that the acrylic polymer lubricant is contained as a pigment dispersant in the coloring resin composition than the compound is added to the compound during molding. It can be seen that it is effective for preventing the adhesion and deposition of the pigment on the machine.

The vinyl chloride resins PAG-1 to PAG-3 used in Examples 1 to 4 were n-BA and 2-vinyl having a glass transition temperature of a homopolymer of -140 ° C. to -20 ° C. Contains 50 parts by weight or more of EHA. For this reason,
PA containing less than 50 parts by weight of these monomers
Examples 1 to 4 exhibit better impact resistance than Example 5 using G-4. Therefore, according to the third aspect of the invention, a molded article having excellent impact resistance can be obtained.

[0074]

According to the first and second aspects of the present invention, the adhesion and deposition of the pigment on the molding machine are extremely small, and the surface condition is excellent even in continuous molding for a long time. The product can be obtained stably.

According to the third aspect of the invention, it is possible to obtain a molded article having further excellent impact resistance. The vinyl chloride resin composition of the present invention can be molded with good fluidity, and a molded article having a good surface condition can be stably obtained. It can be used for such applications, and can also be suitably used for molding window frames, sashes, and the like that require good moldability and surface properties.

Continued on the front page F term (reference) 4F070 AA22 AA32 AC15 AC29 AE04 FB03 FB04 FC02 4J002 AA011 BB011 BC031 BD041 BD051 BD061 BD071 BD081 BD091 BG031 BG042 BG052 BG062 BN081 BN091 DG111 CB111 DEB 016111 EL106 EQ016 EU026 EU056 FD010 FD040 FD060 FD070 FD096 FD170 FD200 FD202

Claims (3)

[Claims] 1. A coloring resin composition comprising a pigment and a dispersant for dispersing the pigment as a main component, wherein an acrylic polymer lubricant having a weight average molecular weight of 10,000 to 1,000,000 is used as the dispersant. A resin composition for coloring characterized by the following. 2. A vinyl chloride resin composition obtained by blending the coloring resin composition according to claim 1 with a vinyl chloride resin. 3. The glass transition temperature of the homopolymer is -140.
(Meth) acrylate monomer 50 having a temperature of
To 100 parts by weight, and an acrylic copolymer obtained by copolymerizing 0 to 50 parts by weight of another copolymerizable radical polymerizable monomer, a vinyl chloride resin obtained by graft copolymerizing vinyl chloride with the vinyl copolymer resin. The vinyl chloride resin composition according to claim 2, which is used as a vinyl chloride resin.