JP3285966B2 - Vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition containing a specific acrylic-modified polyorganosiloxane. Since this resin composition has remarkably improved fluidity, it is suitable for molding a hard or semi-hard vinyl chloride resin.

[0002]

2. Description of the Related Art Conventionally, when molding a vinyl chloride resin, an acrylic resin, particularly a polymethyl methacrylate resin, has been frequently used in order to improve the fluidity of the resin and promote gelation. In the molding of hard or semi-rigid vinyl chloride resin having a small amount, internal heat generation is large due to poor fluidity at the time of kneading and / or molding, so that uniform temperature control is difficult, and the resin compound is partially formed. Exposure to a high temperature causes deterioration of physical properties and an increase in discharge pressure, resulting in a decrease in extrusion rate.

[0003]

SUMMARY OF THE INVENTION The present invention is to provide a vinyl chloride resin composition which has the above-mentioned problems and is effective in improving fluidity during molding and suppressing abnormal internal heat generation. It was done as.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that the object can be attained by blending a specific acrylic-modified polyorganosiloxane, and reached the present invention. did.

That is, the present invention has solved the above-mentioned problems, and comprises (A) 100 parts by weight of a polyvinyl chloride resin , (B) 30 parts by weight or less of a plasticizer (not including 0), (C ) ) General formula 1

Embedded image [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 a 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 represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. Or a radical-reactive group or an organic group having a -SH group.), 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 general formula 2 CH ₂ ＣC (R
⁷ ) COOR ⁸ (wherein R ⁷ represents a hydrogen atom or a methyl group, R ⁸ is an alkyl group, an alkoxy-substituted alkyl group,
Represents a cycloalkyl group or an aryl group. ) Represented by (meth) acrylic acid ester or a this (meth) acrylic acid esters 70% by weight or more, which a monomer copolymerizable with
5:95 to 95: 5 by weight with a mixture of not more than 30% by weight
Formulated with acrylic-modified polyorganosiloxane 0.1-4 parts by weight obtained by graft-copolymerized in a proportion of the flow during molding
The present invention provides a vinyl chloride resin composition for extrusion molding having excellent dynamic properties .

Hereinafter, the present invention will be described in detail. There are no particular restrictions on the type of the polyvinyl chloride resin used as the component (A) in the present invention, and conventionally known ones, for example, vinyl chloride homopolymer, post-chlorinated vinyl chloride polymer, partially cross-linked 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. When the vinyl chloride-based resin is contained in an amount exceeding 50% by weight, a blend or an alloy of another resin such as chlorinated polyethylene, an olefin-based resin, NBR or the like can be used.

The monomers copolymerizable with vinyl chloride include, for example, fatty acid vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate, methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate. A) alkyl (meth) acrylate 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 such as (meth) acrylic acid and maleic anhydride or anhydrides thereof; vinylidene chloride; Examples include vinyl chloride and various urethanes, and these may be used alone or in combination of two or more. Particularly preferred among such copolymers with monomers are vinyl chloride-ethylene copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene-vinyl acetate copolymers,
Examples include a vinyl chloride-acrylic acid copolymer and a vinyl chloride-urethane copolymer.

[0008] The polyvinyl chloride resin described above is composed of 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 in the range of 600 to 1,500, from the viewpoint of the physical properties of the molded article, but the present invention is also suitable for resins in this range. . Of course, those having different average polymerization degrees can be appropriately blended and used. If the average degree of polymerization is less than 400, sufficient strength cannot be obtained, and if it exceeds 2,000, processability tends to decrease.

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

Examples of such a plasticizer include aromatic resins such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, trioctyl trimellitate, triisooctyl trimellitate, and tetraoctyl pyromellitate. Alkyl esters of polybasic acids, dibutyl adipate, dioctyl adipate, diisononyl adipate,
Dibutyl azelate, dioctyl azelate, alkyl esters of aliphatic polybasic acids such as diisononyl azelate, phosphate esters such as tricresyl phosphate, adipic acid, azelaic acid, sebacic acid, and polycarboxylic acids such as phthalic acid. The end of a polycondensate having a molecular weight of about 600 to 8,000 with polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol, Polyester plasticizers such as those blocked with monohydric alcohols or monocarboxylic acids, epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil fatty acid-2-epoxy plasticizers such as 2-ethylhexyl, chlorinated paraffin, etc. No. Each of these plasticizers may be used alone,
Two or more kinds may be used in combination.

The amount of the plasticizer is 30 parts by weight or less based on 100 parts by weight of the polyvinyl chloride resin. If the amount exceeds 30 parts by weight, a conventionally used processing aid for an acrylic resin can be sufficiently practically used for production.

In the production of the acrylic modified polyorganosiloxane of the component (C) 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, and aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group. Or 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,
Represents an allyl group, a radical reactive group exemplified by a γ-methacryloxypropyl group, or an —SH group-containing organic group exemplified by a γ-mercaptopropyl group. Z ¹ and Z ^{2 each} independently represent a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a compound represented by the formula —SiR ⁴ R ⁵ R ⁶ (R
⁴ and R ⁵ are each independently ¹ to 20 carbon atoms exemplified for 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 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent hydrocarbon group having 1 to 20 carbon atoms. 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 of Y may be the same or different.

[0013] Such a polyorganosiloxane can be produced by a known method. For example, it can be produced by using a chain or cyclic low-molecular-weight polyorganosiloxane having the above-mentioned group or an alkoxysilane and combining means of hydrolysis, polymerization and equilibration. Hydrolysis, polymerization, and equilibration can be performed in a state of being emulsified and dispersed in water by a known technique. 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) acrylate monomer. It may be adjusted by a known method such as mixing of raw materials. The siloxane chain may have some branches.

Further, as another raw material (meth) acrylate represented by the general formula 2, 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, Alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate; cyclohexyl Examples thereof include cycloalkyl (meth) acrylates such as (meth) acrylate, and aryl (meth) acrylates such as phenyl (meth) acrylate.
These can be used alone or in combination of two or more.

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

The polyfunctional ethylenically unsaturated monomers include:
Unsaturated amides such as (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxymethyl (meth) acrylamide; Unsaturated monomers containing oxirane groups such as alkoxyalkylated products, glycidyl (meth) acrylate, and glycidyl allyl ether; unsaturated monomers containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Carboxyl-group-containing unsaturated monomers such as (meth) acrylic acid, maleic anhydride, crotonic acid, itaconic acid,
Amino group-containing unsaturated monomers such as N-dimethylaminoethyl (meth) acrylate and N-diethylaminoethyl (meth) acrylate; polyalkylene oxide group-containing unsaturated monomers 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) 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, monofunctional ethylenically unsaturated monomers include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride,
Examples thereof include vinyl acetate and vinyl propionate.

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

The graft copolymerization can be performed by a known technique. For example, graft copolymerization occurs when a polyorganosiloxane and a (meth) acrylic acid ester or a mixture of this and another monomer are emulsified and dispersed in water and polymerized in the presence of a radical polymerization initiator. Emulsifiers and radical polymerization initiators used in this method may be those known for emulsion polymerization. After completion of the polymerization, an acrylic-modified polyorganosiloxane as 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 resulting polyorganosiloxane emulsion can be used as a raw material for graft copolymerization. .

This acrylic-modified polyorganosiloxane has both a gel-promoting effect by the acrylic component and a fluidity effect considered to be caused by the polyorganosiloxane component.
0.1 to 4 parts by weight based on 100 parts by weight. If less than 0.1 part by weight, the gelling property and fluidity during kneading and molding are insufficient, and if it exceeds 4 parts by weight, it is effective in dividing the amount. It is uneconomical because no improvement is observed. If necessary, an acrylic resin processing aid can be used in combination.

In the composition of the present invention, in addition to the above-mentioned components, stabilizers, fillers, lubricants, coloring agents, impact strengthening agents, flame retardants, elasticity-imparting agents, foaming agents which are generally used in polyvinyl chloride resins are used. And modifiers such as antibacterial agents, antistatic agents, surfactants, antifogging agents, and conductivity-imparting agents. The type and amount of these can be appropriately selected depending on the use, required characteristics, workability, cost, and the like.

The method of molding using the composition of the present invention is not particularly limited, and may be a conventionally known method, for example, the above-mentioned components (A), (B) and (C) and various additives used as desired. Are used at predetermined ratios, and the components are uniformly mixed by a compounding machine such as a ribbon blender, a Henschel mixer, a high-speed mixer, and the composition is further mixed with a single or twin screw extruder, a Banbury mixer, a pressure kneader, a co-kneader. What has been homogeneously kneaded and dispersed using a kneader such as this can be appropriately molded into a desired form using a conventional extruder. The molding conditions are not particularly problematic as the same conditions as in the case of the composition formulated without blending the component (C).

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described based on embodiments.
All parts in the examples are parts by weight, and% represents% by weight. (Production of polyorganosiloxane emulsion) 1500 parts of octamethylcyclotetrasiloxane, 1.2 parts of methacryloxypropylmethylsiloxane and 1500 parts of pure water were mixed, and 15 parts of sodium lauryl sulfate and 10 parts of dodecylbenzenesulfonic acid were added thereto. The mixture was then emulsified by stirring with a homomixer, and then passed twice through a homogenizer at a pressure of 3000 psi to form a stable emulsion. Then,
After heating at 70 ° C for 12 hours, cooling to 25 ° C and aging for 24 hours, the pH of this emulsion was adjusted using sodium carbonate.
Was adjusted to 7, and nitrogen gas was blown in for 4 hours, followed by steam distillation to distill off volatile siloxanes. Then, pure water was added to adjust the nonvolatile content to 45%. An emulsion of the contained polyorganosiloxane (hereinafter abbreviated as E-1) was obtained.

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

(Production of Acrylic-Modified Polyorganosiloxane) In a reaction vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet, 793 parts of the polyorganosiloxane emulsion E-1 obtained above (polyorganosiloxane content: 357 parts). Parts) and 1370 parts of pure water, and the inside of the vessel was adjusted to 30 ° C. under a stream of nitrogen gas. Then, 1.0 part of t-butyl hydroperoxide, 0.5 part of L-ascorbic acid, and ferrous sulfate heptahydrate 0.002 parts Then, 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 while maintaining the inside temperature at 30 ° C., and the addition was completed. Thereafter, stirring was further continued for 1 hour to complete the reaction. The obtained copolymer emulsion had a solid content of 30%.
Then, 1000 parts of this emulsion was charged into a container equipped with a stirrer and heated to 60 ° C., and 92 parts of sodium sulfate was added to pure water.
Add the solution dissolved in 563 parts to precipitate the acrylic-modified polyorganosiloxane, and repeat filtration and washing with water.
After drying at 60 ° C., an acrylic-modified polyorganosiloxane (this was abbreviated as P-1) was obtained.

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 Acrylic-modified polyorganopolymer was prepared in the same manner as in P-1 except that 214.5 parts of methyl methacrylate was dropped instead of a mixture of 348 parts of methacrylate, 7 parts of 2-hydroxyethyl methacrylate and 2 parts of 1,4-butanediol diacrylate. The siloxane P-2 was obtained.

Further, 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 is dropped, and P-1 except that the temperature was changed from 30 ° C to 10 ° C
In the same manner as in the above case, acrylic-modified polyorganosiloxane P-3 was obtained.

Example 1 Polyvinyl chloride resin (TK-1000, manufactured by Shin-Etsu Chemical Co., Ltd.)
Product name) Plasticizer dioctyl phthalate 3 parts, heavy calcium carbonate 10 parts, lead-based composite stabilizer per 100 parts
2.5 parts and acrylic-modified polyorganosiloxane P-1
After uniformly dispersing one part in a ribbon blender, it is fed to a different direction rotary twin screw extruder with a screw diameter of 45 mm, formed into a plate under the following extrusion conditions, and the resin temperature, resin pressure and extrusion of the cylinder head The amount was measured, and the molded product surface was visually observed. Table 1 shows the results. [Extrusion conditions] Cylinder temperature: C ₁ = 140 ° C, C ₂ = 170 ° C, C ₃
= 180 ° C, Head temperature: H = 170 ° C, Die temperature: D = 183 ° C, Screw rotation speed: 25rpm

Examples 2 to 4 Extrusion molding was carried out in the same manner as in Example 1 except that various acrylic-modified polyorganosiloxanes shown in Table 1 were blended in accordance with the blending amounts shown in the same table. 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 Kaneguchi Chemical Co., Ltd.) was used in place of the acrylic-modified polyorganosiloxane P-1. The resin was extruded, and 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 can be mixed or dispersed by a mixer such as a single-screw or twin-screw extruder or extruded.
Excellent fluidity during molding by molding machine , suppresses internal heat generation,
The discharge resin pressure can be reduced and the extrusion amount can be improved.
Its practicality is extremely large.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 27/06 C08L 51/08

Claims (1)

(57) [Claims] 1. (A) 100 parts by weight of a polyvinyl chloride resin , (B) 30 parts by weight or less of a plasticizer (not including 0), (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 a 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 represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or Represents a radical reactive group or an organic group having an -SH group.), 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 general formula 2
CH ₂ ＣC (R ⁷ ) COOR ⁸ (wherein R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an alkyl group, an alkoxy-substituted alkyl group, a cycloalkyl group or an aryl group) ( meth) acrylic acid ester or a (meth) acrylic acid esters 70% by weight or more and which
To no weight five ninety-five a mixture of copolymerizable monomers than 30% by weight 95: acryl-modified polyorganosiloxane 0.1-4 parts by weight obtained by graft-copolymerized in a ratio of 5 was blended, molded Vinyl chloride resin composition for extrusion molding with excellent fluidity at the time .