JPS61130363A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent thermal stability, weather resistance and extrudability, consisting of a vinyl chloride resin, an alpha-methylstyrene resin and an organotin stabilizer. CONSTITUTION:0.5-10.0pts.wt. organotin stabilizer (e.g. dibutyltin laurate) is blended with 100pts.wt. mixture of 45-95wt% vinyl chloride resin (A) obtd. by graft-copolymerizing 99-70pts.wt. vinyl chloride onto 1-30pts.wt. acrylic copolymer composed of an alkyl (meth)acrylate whose homopolymer has a second-order transition temp. of -10 deg.C or below and a monomer whose homopolymer has a second-order transition temp. of 0 deg.C or above, and 5-55wt% alpha-methylstyrene resin (B) having an alpha-methylstyrene content of at least 50wt%.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a vinyl chloride resin composition, and more specifically, a vinyl chloride resin composition for profile extrusion molding, which is suitable for coloring and has a tin stabilizer pigment added thereto. relating to things.

(Prior Art) Vinyl chloride resin has excellent physical and mechanical properties and has many uses such as hard, semi-hard, and soft. However, when a vinyl chloride homopolymer is used for hard materials, it has the disadvantage of poor impact resistance and weather resistance.

In order to improve these drawbacks, the use of polymer blends of vinyl chloride homopolymers and various elastomers and the use of resins in which cyclized vinyl is graft copolymerized to various elastomers have been developed.

However, although polymer blends with various elastomers can improve impact resistance, they have the drawbacks of reduced weather resistance and flexural modulus. In addition, the impact resistance of various elastic bodies simply graft-polymerized with vinyl chloride is improved compared to the above-mentioned polymer blend of a homopolymer and an elastic body, but depending on the processing conditions, the impact resistance 1 flexural modulus It had the defect that it was affected.

Therefore, in order to overcome the above-mentioned drawbacks, the present inventors have developed an alkyl acrylate and/or alkyl methacrylate whose second-order transition temperature of the homopolymer is -10°C or lower, and a second-order transition temperature of the homopolymer. Using a vinyl chloride resin made by graft copolymerizing vinyl chloride to a copolymer with a monomer that has a temperature of 0°C or higher, it is blended with lead-based stabilizers and titanium white, resulting in less deterioration of physical properties and good weather resistance and impact resistance. The present invention provides a vinyl chloride resin composition which has excellent properties and processability (Japanese Patent Application No. 59-211027).

(Problems to be Solved by the Invention) However, the above-mentioned vinyl chloride resin composition proposed by the present inventors has excellent weather resistance and impact resistance, so it is suitable for use in profile extrusion molding for building materials such as window frames and decking materials. However, it is essential to use a lead-based stabilizer, which has a large thermal stability effect, and titanium white as a pigment, so only white products can be obtained. .

Nowadays, products made of vinyl chloride resin colored with colored pigments are required depending on the intended use. As a stabilizer for obtaining such a colored product, an organic tin stabilizer is used because it is required to have a strong thermal stability effect, excellent weather resistance and extrusion processability.

However, although it is certainly possible to extrude colored products using these stabilizers, the melt viscosity of the resin is significantly different from extrusion molding using lead-based stabilizers, so it is difficult to extrude colored products using the same mold. Co-birth was difficult. Therefore, it is necessary to prepare one set of molds for each stabilizer system, which is very economically disadvantageous.

(Means for Solving the Problems) As a result of extensive studies in order to improve the above-mentioned drawbacks, the present inventors have discovered that an alkyl acrylate and/or alkyl acrylate whose homopolymer has a secondary transition temperature of 110°C or less A vinyl chloride resin obtained by graft copolymerizing vinyl chloride to a copolymer of methacrylate and a monomer whose homopolymer has a secondary transition temperature of 01 or higher, an α-methylstyrene resin of a predetermined composition, and an organotin stabilizer. If a polyvinyl chloride resin composition is mainly blended with PVC resin and is further colored with a pigment, and profile extrusion molding is performed, a vinyl chloride resin composition containing the above vinyl chloride resin with a lead-based stabilizer and titanium white as a main ingredient can be obtained. The inventors have discovered that the same mold used for profile extrusion molding can be used to achieve the present invention.

That is, the present invention provides (a) acrylic copolymers 1 to 30
α- containing 45 to 95% by weight of a vinyl chloride resin obtained by graft copolymerizing 98 to 70 parts by weight of vinyl chloride and 50 or more parts by weight of an α-methylstyrene component based on the weight part
(b) 0.5 parts by weight of an organotin stabilizer per 100 parts by weight of a mixture containing 5 to 55% by weight of a methylstyrene resin.
The object of the present invention is to provide a vinyl chloride-based resin composition with excellent processability, characterized in that it contains 10.0 parts by weight of polyvinyl chloride.

The acrylic copolymer used in the present invention is a copolymer mainly composed of alkyl acrylate and/or alkyl methacrylate with other monomers.

As the alkyl acrylate and/or algylme tafrylate, those having a secondary transition temperature of 110°C or less when made into a homopolymer are advantageous because of their excellent impact resistance.
For example, ethyl acrylate, n-propyl acrylate, iso-butyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl 7-acrylate, n-decyl acrylate, n-octyl methacrylate, n- -decyl methacrylate, n-dodecyl methacrylate, lauryl methacrylate, and the like.

Alkyl acrylate and/or alkyl methacrylate acts as a soft segment in both the acrylic copolymer and the graft copolymer, and the amount used is preferably 95 to 95% by weight of Go in the acrylic copolymer.
If it exceeds 70% by weight, no improvement in the flexural modulus can be expected, and if it is less than 70% by weight, the impact resistance decreases, which is not preferable.

In addition, other monomers can be copolymerized with alkyl acrylate and/or alkyl methacrylate to form a hard segment in an acrylic copolymer or a graft copolymer, and can cause secondary transition in a homocopolymer. Temperatures of 0° C. or higher are advantageous, and examples include monofunctional heptamines such as ethylene, fluoropylene, and hexene, aromatic vinyls such as styrene, α-methylstyrene, and vinyltoluene, acrylonitrile, Unsaturated nitriles such as methacrylates, vinyl esters such as vinyl #acid and vinyl propionate, vinyl ethers such as butyl vinyl ether, octyl vinyl ether, and lauryl vinyl ether, alkyl 7-acrylates such as methyl acrylate, methyl methacrylate, and ethyl methacrylate. , full-thousand methacrylates such as propyl methacrylate; examples of polyfunctional methacrylates include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, ethylene glycol dimethacrylate,
(Poly)alkylene glycol acrylates or methacrylates such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene gelicold dimethacrylate, Examples include polyallyl compounds such as diallyl phthalate, diallyl maleate, diallyl fumarate, and diallyl succinate, divinylbenzene, butadiene, and the like.

The amount of this monomer used is preferably 1 to 40% by weight in the acrylic copolymer; if it is less than 1% by weight, no improvement in the flexural modulus can be expected, and if it exceeds 40% by weight, the impact resistance will deteriorate. Among these monofunctional monomers, methyl methacrylate, methyl acrylate,
Acrylonitrile and styrene are preferably used, and each is preferably used alone or in combination with a polyfunctional hetamine.

The copolymer of alkyl acrylate and/or alkyl methacrylate and monomer used in the present invention is produced by polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization using generally known emulsifiers, dispersants, catalysts, etc. In order to advantageously carry out the present invention, it is desirable to employ emulsion polymerization.

As a method for obtaining a copolymer by a general emulsion polymerization method, 1. For example, pure water, an anionic emulsifier, and a water-soluble polymerization catalyst are placed in a jacketed polymerization reactor, the air inside the can is removed, and then the alkyl acrylate is And/or an alkyl methacrylate and a 7-mer are charged, and after emulsification, the inside of the can is heated by a jacket to start a copolymerization reaction. This copolymerization reaction is an exothermic reaction, and if necessary, the internal temperature is controlled through the jacket. After the reaction is complete, unreacted heptamers are removed from the outside of the can, and the acrylic copolymer is
Ru.

The charging method to the polymerization reactor is not limited, and if necessary, a particle size regulator for the acrylic copolymer, a decomposition accelerator for the catalyst, etc. may be added to control the copolymerization reaction. Also good.

Next, in the present invention, the acrylic copolymer thus obtained is used as a backbone polymer to carry out graft copolymerization of vinyl chloride.

In this case, the appropriate amount of the acrylic copolymer used is 1 to 30 parts by weight.

If the amount of the acrylic copolymer used is less than 1 part by weight, the impact resistance will not be sufficient, and if it exceeds 30 parts by weight, the impact resistance will improve, but the flexural modulus will decrease, which is not preferable.

Graft copolymerization methods include suspension polymerization, emulsion polymerization,
Examples include solution polymerization method, solventless polymerization method, etc., but in order to carry out the present invention advantageously, it is desirable to employ suspension polymerization method.

When carrying out the suspension polymerization method, the amount of water used is preferably 1 to 5 times, preferably 1 to 3 times the total amount of the acrylic copolymer and vinyl chloride hexamer.

To obtain a graft copolymer resin by a general suspension polymerization method, for example, pure water,
Add a suspension stabilizer such as hydroxypropyl methyl cellulose, a radical polymerization initiator, and if necessary a polymerization degree reducing agent, add the acrylic copolymer to this, suspend it, and then remove the air inside the can. Next, vinyl chloride is charged together with other vinyl compounds as required. Thereafter, the inside of the can is heated by a jacket, the acrylic copolymer is dissolved in vinyl chloride, and graft copolymerization is started. Graft copolymerization is an exothermic reaction, and the internal temperature is controlled by a jacket as necessary.

After the reaction is completed, unreacted vinyl chloride is removed from the can to obtain a slurry of graft copolymer resin. The slurry is dehydrated and dried according to a conventional method to obtain a graft copolymer resin. Furthermore, the charging method to the polymerization reactor is not limited, and among the charged raw materials such as pure water, suspension stabilizer, acrylic copolymer, and vinyl chloride, the acrylic copolymer is replaced with vinyl chloride. A method of melting and charging is also adopted.

In graft copolymerization, other monomers may be present in the coexistence within a range that does not reduce impact resistance, weather resistance, and physical properties.

In addition, it is advantageous to carry out the graft copolymerization by a radical polymerization method, and the radical polymerization initiators used for this purpose include lauroyl peroxide, tert-butyl peroxy pivalate, diisopropyl peroxy dicarbonate, and dioctyl peroxy. oil-soluble polymerization initiators for azo compounds such as peroxides such as dicarbonates, 2.2'-7zobisisoputyronitrile, and 2.2'-azobis-2,4-dimethylvaleronitrile;
and water-soluble polymerization initiators such as potassium persulfate and ammonium persulfate. The amount of these polymerization initiators used is 0.005 to 1.0 parts by weight of vinyl chloride IQQ. Of
It is preferable to use 1 part i.

Examples of dispersants include methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, polyvinyl alcohol and its partially saponified products, gelatin, polyvinylpyrrolidone, organic substances such as starch, and inorganic substances such as magnesium carbonate, calcium carbonate, and calcium phosphate. Used alone or in combination. The amount used is usually 0.01 to 1.0 parts by weight per 100 parts by weight of vinyl chloride.Furthermore, in this graft copolymerization, it is used in the conventional method of polymerizing vinyl monomers. A chain transfer agent may be added in an amount of 0, 00 to 10 parts by weight per 100 parts by weight of vinyl chloride.

The degree of polymerization of the graft copolymer is from 400 to 1,500, preferably from 700 to 1,350.

On the other hand, the α-methylstyrene resin used in the present invention is
- A copolymer resin containing 50% by weight or more of a methylstyrene component, with other copolymerizable monomers having 2 to 3 carbon atoms such as ethylene, propylene, l-butene, etc.
Styrenes such as α-olefins, styrene, and chlorinated styrene.

Vinyl esters such as vinyl acetate and vinyl propionate; alkyl ethers having 1 to 28 carbon atoms such as methyl vinyl ether and ethyl vinyl ether; unsaturated fatty acids such as acrylic acid, methacrylic acid, fumaric acid, and maleic acid; Examples include esters, unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl chloride, vinylidene chloride, fluorine-containing ethylene, butadiene, and isoprene. One or more of these are used and copolymerized with α-methylstyrene.

If the α-methylstyrene component in the α-styrene resin is less than 50% by weight, the effect of adding the α-methylstyrene resin will hardly be obtained.

If the amount of α-methylstyrene m-fat used is outside the above range, the excellent effects of the present invention cannot be obtained.

Used in the resin composition of the present invention. Examples of organic tin stabilizers include butyltin laurate, butyltin laurate, malate, butyltin carboxylate, butyltin maleate, butyltin maleate polymer, butyltin mercapto, and octyltin urate. , octyltin malate, laurate, octyltin malate, octyltin mercapto, and butyltin mercapto may be used alone or in combination of two or more. The amount of tin stabilizer used is 10% of the mixture of vinyl chloride resin and α-methylstyrene resin.
0.5 to 10 parts by weight is preferable (less than 0.5 parts by weight will result in insufficient thermal stability, and if it exceeds 10 parts by weight, the effect of thermal stability will not change, which is economically disadvantageous). be.

Furthermore, fillers, lubricants, other resins, plasticizers, ultraviolet absorbers, antistatic agents, antioxidants, flame retardants, pigments, etc. that are blended during processing of vinyl chloride resin are blended as necessary.

As the filler, calcium carbonate, talc, silica, clay, etc. can be used, but fillers with an average particle size of 1x or less, preferably 0.7 tons or less are suitably used.

Examples of lubricants include hydrocarbon lubricants such as natural paraffin, liquid paraffin, and polyethylene wax, fatty acid lubricants such as stearic acid, fatty acid amide lubricants such as stearamide, ester lubricants such as ethylene glycol monostearate, and ST7. Examples include higher alcohol-based lubricants such as lyl alcohol, and metal soap-based lubricants such as calcium laurate.

The effects of lubricants include adjusting the friction between the wall of the processing machine and the plastic material (external lubricity), adjusting gelation of the plastic (internal lubricity), enhancing the stabilizing effect of stabilizers, and adjusting processability. In order to achieve these effects, it is advantageous to combine two or more types of materials, one having external lubricity and one having internal lubricity.

The amount used for lubricating properties is 0.5 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight, and 0.5 to 100 parts by weight of the mixture of vinyl chloride resin and α-methylstyrene resin. If the amount is less than the weight part, a large amount of frictional heat is generated due to the lack of internal and external lubricity, and gelation occurs in the compression zone, resulting in an increase in viscosity and temperature, causing decomposition and discoloration of the resin.

Moreover, if it exceeds 3.0 parts by weight, the slipperiness is too strong, resulting in insufficient kneading and insufficient gelation, which is not preferable.

Pigments include barium sulfate, calcium chloride, zinc oxide, titanium oxide, iron oxide, chromium oxide, silica, mica, and talc.

Both inorganic pigments such as carbon black and organic pigments such as Diazoe 0-, Rehz FC, Phthalocyanine Blue or Green can be used, and other colorants such as dyes can also be used.

Other resins that can be added include ethylene/vinyl acetate,
Methyl acrylate/butyl acrylate, methyl methacrylate/ethyl acrylate, methyl acrylate/butyl methacrylate copolymer, ethylene/vinyl acetate/vinyl chloride ternary copolymer, chlorinated polyethylene, acrylonitrile/butadiene/styrene ternary copolymer, methyl methacrylate/butadiene/ PV such as ternary copolymers such as styrene/methyl methacrylate/butyl acrylate/ethyl acrylate, methyl methacrylate/ethyl acrylate/acrylonitrile, methyl methacrylate/styrene/butyl 7-acrylate, methyl methacrylate/butyl methacrylate/ethyl acrylate/ethyl methacrylate quaternary copolymer, etc.
Any resin may be added as long as it is compatible with C and does not impair the physical properties of the composition of the present invention.

Examples of the plasticizer include phthalate ester, trimellitate ester, adipate ester, phosphate plasticizer, epoxy plasticizer, and polyester plasticizer.

Examples of UV absorbers include benzophenone-based UV absorbers such as 2,4-dihydroxybenzonephenone, benzotriazole-based UV absorbers such as 2-(2°-hydroxy-5-methylphenyl)benzotriazole, and salicyl ugly ester UV absorbers such as phenyl salicylate. can be given.

Examples of the antistatic agent include anionic surfactants, cationic surfactants, and nonionic surfactants.

As an antioxidant, 2,2'-methylene-bis-(4
-methyl-6-tert-butylphenol), monophenol-based antioxidants such as 2,6-ditertiary-butylphenol, and hydroquinone-based antioxidants such as 2,5-ditertiary-butylhydroquinone.

Examples of flame retardants include known halides such as chlorinated paraffin, chlorinated polyethylene, perchloropentacyclodecane, hexabromobenzene, decabucomodiphenyl ether, and tetrabromobisphenol A, antimony trioxide, antimonates, and methacrylates. Examples include inorganic compounds such as mm barium, zinc borate, and aluminum hydroxide.

The vinyl chloride resin composition of the present invention is a vinyl chloride resin in which 98 to 70 parts by weight of vinyl chloride is graft copolymerized to 1 to 30 parts by weight of an acrylic copolymer, and a lead-based stabilizer and titanium white are mainly blended. A vinyl chloride resin obtained by copolymerizing 89 to 70 parts by weight of vinyl chloride with 1 to 30 parts by weight of an acrylic copolymer to match the melt viscosity of the vinyl chloride resin composition and 50% by weight of α-methylstyrene. The α-methylstyrene resin containing the above, a nucleated tin stabilizer, and a pigment are mainly blended.

The vinyl chloride resin composition of the present invention can be blended to a desired melt viscosity and uniformly mixed by a known method using a Henschel Mikiner, a ribbon blender, etc., to form a powder.

(Effects of the Invention) When using the vinyl chloride resin composition of the present invention, for example, powder or pellet, the vinyl chloride resin obtained by graft copolymerizing 88 to 70 parts by weight of vinyl chloride to 1 to 30 parts by weight of an acrylic copolymer can be used. Building materials such as window frames and decking materials can be molded using single-screw extruders, twin-screw extruders, and multi-screw extruders using the same mold as powder or pellets that are mainly formulated with lead-based stabilizers and titanium white. 6 The vinyl chloride resin composition of the present invention is
It has excellent weather resistance and impact resistance, and is particularly suitable for molding colored products.

(Example) Hereinafter, the present invention will be explained more specifically based on Examples.

Example 1 2 deionized water was added to a polymerization machine with a content of 7 m′ equipped with a stirrer.
, 7QOkg polyvinyl alcohol partially saponified product 2
．． 05kg, methylcellulose 2.05kg, 2.2°
-7 Zobisisobutyronitrile 0.075 kg, 2,
2゜-7zobis-2,4-dimethylvaleronitrile 0.
24 kg and n-butyl acrylate 97ffiff
i% and 1,3-butylene glycol dimethacrylate 3
After charging 800 kg of 15% acrylic copolymer latex with a composition of 15% by weight and removing the air inside, 1410 kg of vinyl chloride was charged and melted at 35°C for 1 hour.
Polymerization was carried out at 7°C, and 10 hours after the start of polymerization, the internal pressure of the polymerization machine decreased to f3.5 kg/ctn', so the unreacted monomer was collected and the slurry was dehydrated and dried.
kg of white powder resin was obtained. The degree of polymerization of this resin is 1030, and the content of components other than vinyl chloride is 7.0% by weight.
Met. α to 65 parts by weight of the obtained graft copolymer resin
- 35 parts by weight of α-methylstyrene resin with a composition of 65% by weight of methylstyrene, 25% by weight of acrylonitrile, 7% by weight of styrene, and 3% by weight of methyl methacrylate, and the tin-based stabilizer IRGASTAB T- manufactured by Ciba Geigy.
833 (product name) 3 parts by weight, Nippon Sekiro's lubricant Paraffin Works 7x 155 (product name) 0.4 parts by weight, Mitsui Petrochemical Co., Ltd. lubricant Hi-wax 450P (product name) 0.2
Parts by weight, processing aid PA-20 (trade name) manufactured by Kanekabuchi Chemical Co., Ltd.
1.0 parts by weight, ultraviolet absorber TI manufactured by Chipa Geigy
N (IWIN32G (trade name) 0.3 ffi quantity, Ciba Geigy's antioxidant IRGANOX1, Q, S (
Product name) 0.1 part by weight, Pigment Mr manufactured by Ciba Geigy
KROLI Hbrown 5RKP (product name) 0.7
Weight part MIKROLITHblue 4GKP (Product name) 0.0? Powders were prepared according to the formulation in parts by weight.

For mixing, the graft copolymer resin and compounding agents were placed in a Henschel mixer, heated to 120°C while stirring, and heated to 40°C.
After cooling to below C, it was discharged.

The melt viscosity of this powder was measured using a Brabender Plastograph (4.0 kg-m), and this powder was extruded using a φ30II+1 twin-screw extruder in different directions (Plastics Institute M).

The molding conditions and results are shown in Table 1.

Reference Example 1 Graft copolymer resin 10 obtained in the same manner as Example 1
0 parts by weight, 2 parts by weight of tribasic lead sulfate, 2 parts by weight of dibasic lead sulfite, 1 part by weight of pigment titanium white R-950 manufactured by Ishihara Sangyo Co., Ltd.
Product name) 3 parts by weight, 0.4 parts by weight of Ca stearate, 0.4 parts by weight of stearic acid, Loxi lubricant manufactured by Henkel
ol G-80 (trade name) 0.4 parts by weight, axial
A powder was prepared using a blending recipe of 0.4 parts by weight of G-30 (trade name), 1.0 parts by weight of PA-20, and 5 parts by weight of calcium carbonate Hakuyahana CCR (trade name) manufactured by Shiraishi Kogyo Co., Ltd.

Mixed in the same manner as in Example 1, the melt viscosity of this powder was measured using a Brabender Plastograph and found to be 4.0k.
It was g@-. In addition, extrusion molding was performed using this powder using a φ30 twin-screw extruder in different directions. Table 1 shows the molding conditions and results.

Comparative Example 1 In Example 1, 65 parts by weight of the graft copolymer resin was added to 1
00 parts by weight, α-methylstyrene resin 3 consisting of 65% by weight of α-methylstyrene, 25% by weight of acrylonitrile, 7% by weight of styrene, and 3% by weight of methyl acrylate.
A powder was prepared in the same manner as in Example 1, except that the addition of 5 parts by weight was discontinued, and the melt viscosity of this powder was measured using a Bengooplastograph, and it was 3.8.
He was wearing kge shoes. Also, using this powder, φ30m
Extrusion molding was performed using a 5-different-direction twin-screw extruder.

The molding conditions and results are shown in Table 1.

The conditions of Prabender Plastograph (Brabender Co., Ltd.) employed in each of the above Examples, Reference Examples, and Comparative Examples are as follows.

Neegoo 50cc Temperature 150°C Number of revolutions 5 Orpm Sample amount 65g Mixture Lead-based or tin-based weight 10kg Preheating 3 minutes As is clear from the results in Table 1, the composition of the present invention has the melt viscosity matched by Brabender Plastograph. can be extruded under the same mold conditions as compositions containing lead-based stabilizers and TiO2. The obtained product had good surface condition and shape.

Claims (1)

[Claims] 1. (a) 45 to 95% by weight of a vinyl chloride resin obtained by graft copolymerizing 99 to 70 parts by weight of vinyl chloride to 1 to 30 parts by weight of an acrylic copolymer and 50 parts by weight of an α-methylstyrene component. (b) 0.5 to 10.0 parts by weight of an organotin stabilizer to 100 parts by weight of a mixture containing 5 to 55% by weight of α-methylstyrene resin containing % or more. A vinyl chloride resin composition with excellent processability.