JPH06122800A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To prevent an unusually high heat build-up of a vinyl chloride resin compsn. during molding by compounding a polyvinyl chloride resin with a specific acryl-modified polyorganosiloxane to thereby improve the flowability. CONSTITUTION:The resin compsn. is prepd. by compounding 100 pts.wt. polyvinyl chloride resin, 0-30 pts.wt. plasticizer, and 0.1-4 pts.wt. acryl-modified polyorganosiloxane which is obtd. by the graft copolymn. of a (meth)acrylic ester of formula II (wherein R<7> is H or methyl; and R<8> is alkyl, cycloalkyl, etc.) or a mixture thereof with up to 30wt.% copolymerizable monomer onto a polyorganosiloxane of formula I (wherein R<1>, R<2>, and R<3> are each independently a 1-20C hydrocarbon group or a halogenated hydroarbon group; Y is an org. group having a radical-reactive group or an SH group; Z and Z<2> are each independently H, lower alkyl, etc.; (m) is a positive integer of 10,000 or lower; and n is an integer of 1 or higher) in a wt. ratio of the (meth)acrylic ester or the mixture thereof to the polyorganosiloxane of (5:95)-(95:5).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a vinyl chloride resin composition containing a specific acrylic modified polyorganosiloxane. Since the resin composition has remarkably improved fluidity, it is suitable for molding a rigid or semi-rigid vinyl chloride resin.

[0002]

2. Description of the Related Art Conventionally, an acrylic resin, particularly a polymethylmethacrylate resin has been widely used in order to improve the fluidity and accelerate the gelation of a vinyl chloride resin when it is molded. When molding a rigid or semi-rigid vinyl chloride resin with a small amount, internal heat generation is large due to poor fluidity during kneading and / or molding, and therefore uniform temperature control is difficult and the resin composition is partially Since it is exposed to a high temperature, the physical properties are deteriorated, the discharge pressure is increased, and the extrusion rate is reduced.

[0003]

DISCLOSURE OF THE INVENTION The present invention intends to provide a vinyl chloride resin composition which is improved in the above-mentioned problems and has an effect of improving fluidity during molding and suppressing abnormal internal heat generation. It was made as.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the object can be achieved by blending a specific acrylic modified polyorganosiloxane, and arrived at the present invention. did.

That is, the present invention has solved the above-mentioned problems. This is because (A) 100 parts by weight of polyvinyl chloride resin (B) 0 to 30 parts by weight of plasticizer (C) General formula 1

[Chemical 2] [Wherein R ¹ , R ² and R ³ independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, Y represents a radical reactive group or an organic group having a —SH group, Z ¹ and Z ²
Are independently a hydrogen atom, a lower alkyl group or the formula --SiR ⁴
R ⁵ R ⁶ (R ⁴ and R ⁵ independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and R ⁶ has 1 carbon atom.
To 20 hydrocarbon groups or halogenated hydrocarbon groups, radical-reactive groups or organic groups having --SH groups. ), A m is a positive integer of 10,000 or less, and n is an integer of 1 or more. And a polyorganosiloxane represented by the formula 2 CH ₂ ═C (R ⁷ ) COOR ⁸ (wherein R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an alkyl group, an alkoxy-substituted alkyl group, or a cycloalkyl group). Or (representing an aryl group) or a mixture of 70% by weight or more of this (meth) acrylic acid ester and 30% by weight or less of a copolymerizable monomer. To 0.1 to 4 parts by weight of acrylic modified polyorganosiloxane obtained by graft copolymerization at a ratio of 95 to 5: 5, a vinyl chloride resin composition,
Is the gist.

The present invention will be described in detail below. The type of the polyvinyl chloride resin as the component (A) used in the present invention is not particularly limited, and conventionally known ones such as vinyl chloride homopolymer, post-chlorinated vinyl chloride polymer and partially crosslinked vinyl chloride polymer. , And a copolymer of vinyl chloride and a copolymerizable monomer and the like, and the present invention can be applied to any of them. Further, when the vinyl chloride resin is contained in an amount of more than 50% by weight, it may be used as a blend or alloy with other resin such as chlorinated polyethylene, olefin resin, NBR and the like.

Examples of the monomer copolymerizable with the above vinyl chloride include, for example, vinyl acetate, vinyl propionate, vinyl laurate, and other fatty acid vinyl esters, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth). ) Alkyl (meth) acrylates such as acrylate, vinyl cyanide such as (meth) acrylonitrile,
Alkyl vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, α-olefins such as ethylene, propylene and styrene, unsaturated carboxylic acids or their anhydrides such as (meth) acrylic acid and maleic anhydride, vinylidene chloride, odor Examples thereof include vinyl chloride and various urethanes. These may be used alone or in combination of two or more. Particularly preferable among the copolymers with such monomers are vinyl chloride-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate copolymer,
Examples thereof include vinyl chloride-acrylic acid copolymers and vinyl chloride-urethane copolymers.

The polyvinyl chloride resin described above is 1
Only one kind may be used, or two or more kinds may be used in combination. The average degree of polymerization is preferably in the range of 400 to 2,000, more preferably 600 to 1,500 in view of the physical properties of the molded product, and the present invention is also suitable for resins in this range. . Of course, those having different average degrees of polymerization can be appropriately blended and used. If this average degree of polymerization is less than 400, sufficient strength cannot be obtained, and if it exceeds 2,000, the workability tends to deteriorate.

The plasticizer used as the component (B) in the present invention is not particularly limited and can be arbitrarily selected from those conventionally used for polyvinyl chloride resins.

Examples of such plasticizers include aromatic compounds such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, trioctyl trimellitate, triisooctyl trimellitate and tetraoctyl pyromellitic acid. Alkyl ester of polybasic acid, dibutyl adipate, dioctyl adipate, diisononyl adipate,
Alkyl ester of aliphatic polybasic acid such as dibutyl azelate, dioctyl azelate, diisononyl azelate, phosphoric acid ester such as tricresyl phosphate, polyvalent carboxylic acid such as adipic acid, azelaic acid, sebacic acid and phthalic acid The end of the polycondensate having a molecular weight of about 600 to 8,000 with a polyhydric alcohol such as ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol and 1,4-butylene glycol is used. Polyester plasticizers such as those blocked with monohydric alcohols or monocarboxylic acids, epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil fatty acid-2-ethylhexyl and other epoxy plasticizers, chlorinated paraffin, etc. Can be mentioned. These plasticizers may be used alone,
You may use it in combination of 2 or more type.

The blending amount of the plasticizer is 30 parts by weight or less with respect to 100 parts by weight of the polyvinyl chloride resin. With respect to the amount exceeding 30 parts by weight, the processing aid of the acrylic resin which has been used conventionally can be sufficiently practically used for production.

In the production of the (C) component acrylic-modified polyorganosiloxane used in the present invention, the polyorganosiloxane represented by the general formula 1 is used as a raw material.
R ¹ , R ² and R ³ in the general formula 1 are independently exemplified by alkyl groups such as methyl group, ethyl group, propyl group and butyl group, aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group. A monovalent hydrocarbon group having 1 to 20 carbon atoms, or at least one hydrogen atom bonded to a carbon atom of these groups.
Represents a group in which one is substituted with a halogen atom. Y is a vinyl group,
It represents a radical reactive group exemplified by an allyl group or γ-methacryloxypropyl group, or an —SH group-containing organic group exemplified by a γ-mercaptopropyl group. Z ¹ and Z ² are independently a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, or a group of the formula —SiR ⁴ R ⁵ R ⁶ (R
⁴ , R ⁵ are independently C 1-20 exemplified by R ^{1 to} R ^3.
Represents a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Halogenated hydrocarbon group of, or a radical-reactive group exemplified by Y or -S
Represents an organic group having an H group. ) Represents a triorganosilyl group. m represents a positive integer of 10,000 or less, and n represents an integer of 1 or more. In one molecule, R ^{1 to} R ⁶ ,
Each Y may be the same or different.

Such polyorganosiloxane can be produced by a known method. For example, a chain or cyclic low molecular weight polyorganosiloxane having the above group or an alkoxysilane can be used in combination with the means of hydrolysis, polymerization and equilibration. Hydrolysis, polymerization and equilibration can be carried out by a known technique even in a state of being emulsified and dispersed in water. m and n are as described above, but in the range of 500 <m <8,000 and 1 <n <500 in view of the characteristics of the polyorganosiloxane or the graft copolymer of the polyorganosiloxane and the (meth) acrylic acid ester monomer. It is preferable that it be adjusted by a known method such as blending raw materials. Note that the siloxane chain may have some branching.

Further, as the (meth) acrylic acid ester represented by the general formula 2 which is another raw material, methyl (meth)
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and other alkyl (meth) acrylates, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate and other alkoxyalkyl (meth) acrylates, cyclohexyl Examples are cycloalkyl (meth) acrylates such as (meth) acrylate, aryl (meth) acrylates such as phenyl (meth) acrylate,
Only one of these can be used, or two or more can be used in combination.

This (meth) acrylic acid ester can be used as a mixture with one or more other monomers copolymerizable therewith. However, in view of characteristics, it is preferable that the (meth) acrylic acid ester is 70% by weight or more and the other monomer copolymerizable therewith is 30% by weight or less. Other copolymerizable monomers include polyfunctional or monofunctional ethylenically unsaturated monomers.

As the polyfunctional ethylenically unsaturated monomer,
Alkylol of unsaturated amides and unsaturated amides such as (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide or Unsaturated monomer containing oxirane group such as alkoxyalkylated product, glycidyl (meth) acrylate, glycidyl allyl ether, and unsaturated monomer containing hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Body, (meth) acrylic acid, maleic anhydride, crotonic acid, itaconic acid and other carboxyl group-containing unsaturated monomers,
Amino group-containing unsaturated monomers such as N-dimethylaminoethyl (meth) acrylate and N-diethylaminoethyl (meth) acrylate, Polyalkylene oxide group-containing unsaturation such as ethylene oxide and propylene oxide adducts of (meth) acrylic acid Monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) A complete ester of polyhydric alcohol such as acrylate and (meth) acrylic acid,
Further, allyl (meth) acrylate, divinylbenzene and the like are exemplified.

On the other hand, as the monofunctional ethylenically unsaturated monomer, styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride,
Examples include vinyl acetate and vinyl propionate.

The above polyorganosiloxane and (meth)
When an acrylic modified polyorganosiloxane is produced by graft copolymerization using an acrylic acid ester or (meth) acrylic acid ester and a mixture of other monomers copolymerizable therewith, polyorganosiloxane:
The weight ratio of the total amount of monomers such as (meth) acrylic acid ester
5:95 to 95: 5. If the amount of polyorganosiloxane is too large, the compatibility with the polyvinyl chloride resin will be deteriorated and the effect of promoting gelation will be deteriorated, and if it is too small, the fluidity will be decreased.

The graft copolymerization can be carried out by a known technique. For example, when a polyorganosiloxane and a (meth) acrylic acid ester or a mixture thereof with another monomer is emulsified and dispersed in water and polymerized in the presence of a radical polymerization initiator, graft copolymerization occurs. The emulsifier and radical polymerization initiator used in this method may be those known for emulsion polymerization. After completion of the polymerization, an acryl-modified polyorganosiloxane which is a graft copolymer is obtained by a method such as salting out, filtration, washing with water, and drying. In this emulsion graft copolymerization method, if the polyorganosiloxane is produced in a state of being emulsified and dispersed in water as described above, the obtained polyorganosiloxane emulsion can be directly used as a graft copolymerization raw material. .

This acrylic-modified polyorganosiloxane has both a gelation-promoting effect due to the acrylic component and a fluidizing effect that is considered to be due to the polyorganosiloxane component, and the blending amount thereof is a polyvinyl chloride resin.
The amount is 0.1 to 4 parts by weight with respect to 100 parts by weight, but if it is less than 0.1 parts by weight, the gelling property and fluidity at the time of kneading or molding are insufficient, and if it exceeds 4 parts by weight, it is effective for the amount. It is uneconomical because the improvement of In addition, it is possible to use a processing aid of acrylic resin in combination, if necessary.

In the composition of the present invention, in addition to the above-mentioned components, stabilizers, fillers, lubricants, colorants, impact toughening agents, flame retardants, elasticity imparting agents, foaming agents usually used for polyvinyl chloride resins. A modifier such as an antibacterial agent, an antistatic agent, a surfactant, an antifogging agent, or a conductivity-imparting agent can be added. The type and amount of these can be appropriately selected depending on the application, required characteristics, workability, cost and the like.

The method of molding using the composition of the present invention is not particularly limited, and any conventionally known method such as the above-mentioned components (A), (B) and (C) and various additive components used as desired may be used. In a predetermined proportion, the blending ingredients are uniformly mixed by a blending machine such as a ribbon blender, a Henschel mixer, a high-speed mixer, and the composition is further fed into a single-screw or twin-screw extruder, a Banbury mixer, a pressure kneader, and a cokneader. A homogeneously kneaded and dispersed product using a kneading machine such as the above can be appropriately molded into a desired form using a conventional extrusion molding machine, injection molding machine, calender molding machine, or the like. The molding conditions are the same as in the case of the composition formulated without adding the component (C), and there is no particular problem.

[0023]

EXAMPLES The present invention will be specifically described based on examples.
All parts in the examples are parts by weight, and% is% by weight. (Production of polyorganosiloxane emulsion) 1500 parts of octamethylcyclotetrasiloxane, 1.2 parts of methacryloxypropylmethylsiloxane and 1500 parts of pure water are mixed, and 15 parts of sodium lauryl sulfate and 10 parts of dodecylbenzenesulfonic acid are added thereto. The mixture was stirred with a homomixer to emulsify, and then passed through a homogenizer having a pressure of 3000 psi twice to form a stable emulsion. Then, this
After heating at 70 ℃ for 12 hours, cooling to 25 ℃ and aging for 24 hours, the pH of this emulsion is adjusted with sodium carbonate.
Is adjusted to 7 and nitrogen gas is blown for 4 hours, and then steam distillation is performed to distill off the volatile siloxane, and then pure water is added to adjust the nonvolatile content to 45%, and 0.03 mol% of the methacrylic group is added. An emulsion of the polyorganosiloxane contained therein (hereinafter abbreviated as E-1) was obtained.

A polyorganosiloxane emulsion E-2 was obtained in the same manner as in the case of E-1, except that 98.4 parts of mercaptopropylmethylsiloxane was used instead of 1.2 parts of methacryloxypropylmethylsiloxane.

(Production of Acrylic Modified Polyorganosiloxane) 793 parts (polyorganosiloxane component 357) of the polyorganosiloxane emulsion E-1 obtained above was placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet. Part) and 1370 parts of pure water, and the inside of the vessel was adjusted to 30 ° C. under a nitrogen gas stream, then t-butyl hydroperoxide 1.0 part, L-ascorbic acid 0.5 part, ferrous sulfate heptahydrate 0.002 Then, while maintaining the temperature inside the vessel at 30 ° C., a mixture of 348 parts of methyl methacrylate, 7 parts of 2-hydroxyethyl methacrylate and 2 parts of 1,4-butanediol diacrylate was added dropwise over 3 hours, and the addition was completed. After that, stirring was continued for another hour to complete the reaction. The obtained copolymer emulsion had a solid content concentration of 30%.
Next, add 1000 parts of this emulsion to a container equipped with a stirrer and heat to 60 ° C, and add 92 parts of sodium sulfate to this with pure water.
Add the solution dissolved in 563 parts to precipitate the acrylic modified polyorganosiloxane and repeat filtration and washing with water.
It was dried at 60 ° C. to obtain an acrylic-modified polyorganosiloxane (hereinafter referred to as P-1).

Also, instead of 793 parts of polyorganosiloxane emulsion E-1 and 1370 parts of pure water, 1110 parts of polyorganosiloxane emulsion E-1 (500 parts of polyorganosiloxane) and 1053 parts of pure water were charged, and methyl was added. Acrylic-modified polyorgano was prepared in the same manner as in P-1, except that 214.5 parts of methyl methacrylate was added dropwise instead of the mixture of 348 parts of methacrylate, 7 parts of 2-hydroxyethyl methacrylate and 2 parts of 1,4-butanediol diacrylate. Siloxane P-2 was obtained.

Furthermore, instead of 793 parts of polyorganosiloxane emulsion E-1 and 1370 parts of pure water, 477 parts of polyorganosiloxane emulsion E-2 (214.5 parts of polyorganosiloxane) and 1400 parts of pure water were charged, and methyl was added. Instead of a mixture of 348 parts of methacrylate, 7 parts of 2-hydroxyethyl methacrylate and 2 parts of 1,4-butanediol diacrylate, a mixture of 150 parts of ethyl acrylate, 345 parts of methyl methacrylate and 5 parts of methacrylic acid was added dropwise to the inside of the container. P-1 except that the temperature was changed from 30 ℃ to 10 ℃
Acrylic modified polyorganosiloxane P-3 was obtained in the same manner as in the above.

Example 1 Polyvinyl chloride resin (TK-1000, manufactured by Shin-Etsu Chemical Co., Ltd.,
Brand name) 3 parts plasticizer dioctyl phthalate, 10 parts heavy calcium carbonate, 100 parts lead-based composite stabilizer per 100 parts
2.5 parts and acrylic modified polyorganosiloxane P-1
1 part of the mixture was evenly dispersed with a ribbon blender, and then fed to a counter-rotating twin-screw extruder with a screw diameter of 45 mm, molded into a plate under the following extrusion conditions, and the resin temperature, resin pressure and extrusion of the cylinder head part The amount was measured, and the surface of the molded product was visually observed. The results are shown in Table 1. [Extrusion conditions] Cylinder temperature: C ₁ = 140 ℃, C ₂ = 170 ℃, C ₃
= 180 ℃, Head temperature: H = 170 ℃, Die temperature: D = 183 ℃, Screw speed: 25rpm

Examples 2 to 4 Extrusion was carried out in the same manner as in Example 1 except that various acrylic modified polyorganosiloxanes shown in Table 1 were blended according to the blending amounts shown in the same table, and the resin temperature, resin pressure, The extrusion amount was measured and the surface of the molded product was observed, and the results are shown in Table 1.

Comparative Example The procedure of Example 1 was repeated except that 1 part of an acrylic resin processing aid Kaneace PA-20 (trade name, manufactured by Kanegafuchi Chemical Co., Ltd.) was used in place of the acrylic modified polyorganosiloxane P-1. After extrusion molding, the resin temperature, resin pressure, and extrusion amount at that time were measured, and the surface of the molded product was observed. The results are shown in Table 1.

[0031]

[Table 1]

[0032]

The vinyl chloride resin composition of the present invention is excellent in fluidity during mixing and dispersion by a mixer such as a single-screw or twin-screw extruder and during molding by an extrusion molding machine, an injection molding machine, etc.
The internal heat generation can be suppressed, the discharge resin pressure can be reduced, and the extrusion amount can be improved, and its practicality is extremely large.

Claims (1)

[Claims] 1. (A) 100 parts by weight of a polyvinyl chloride resin (B) 0 to 30 parts by weight of a plasticizer (C) General formula 1 [Wherein R ¹ , R ² and R ³ independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, Y represents a radical reactive group or an organic group having a —SH group, Z ¹ and Z ²
Are independently a hydrogen atom, a lower alkyl group or the formula --SiR ⁴
R ⁵ R ⁶ (R ⁴ and R ⁵ independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and R ⁶ has 1 carbon atom.
To 20 hydrocarbon groups or halogenated hydrocarbon groups, radical-reactive groups or organic groups having --SH groups. ), A m is a positive integer of 10,000 or less, and n is an integer of 1 or more. And a polyorganosiloxane represented by the formula 2 CH ₂ ═C (R ⁷ ) COOR ⁸ (wherein R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an alkyl group, an alkoxy-substituted alkyl group, or a cycloalkyl group). Or (representing an aryl group)) or a mixture of 70% by weight or more of this (meth) acrylic acid ester and 30% by weight or less of a copolymerizable monomer. A vinyl chloride resin composition comprising 0.1 to 4 parts by weight of an acrylic-modified polyorganosiloxane obtained by graft copolymerization at a ratio of 95: 5 to 95: 5.