JP2011111535A - Plastisol composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plastisol composition having no sticky feeling of the cover resin, causing no sheet crack, and having good surface smoothness. <P>SOLUTION: There is provided a plastisol composition comprising (A) 40-60 pts.wt. vinyl chloride-based resin having ≥1,000 average polymerization degree and containing no tetrahydrofuran-insoluble material, (B) 60-40 pts.wt. vinyl chloride-based resin containing tetrahydrofuran-insoluble materials, and (C) 40-60 pts.wt. plasticizer per 100 pts.wt. vinyl chloride-based resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to plastisol compositions.

  Vinyl chloride resin is very important as an insulating material compared to rubber, polyolefin and the like because it has excellent electrical insulation, arc resistance, tracking resistance and voltage resistance. However, vinyl chloride-based resins are deteriorated in their excellent properties due to thermal and oxidative deterioration, and are practically unusable.

  Therefore, in order to use the vinyl chloride resin composition for surface coating or the like, a plasticizer is blended to impart flexibility. However, blending a plasticizer has the disadvantage that the heat resistance of the vinyl chloride resin composition is reduced, and when a phthalic plasticizer such as general-purpose di-2-ethylhexyl phthalate is used, There are problems such as the stickiness of the resin, sheet cracking, and poor surface smoothness.

  For this reason, a vinyl chloride resin composition for electric wires formed by blending trimellitic acid ester of mixed decanol and clay has been proposed (Patent Document 1), and pyromellitic acid ester, stabilizer and lubricant of mixed decanol are used. A vinyl chloride resin composition for electric wires is proposed (Patent Document 2), and a vinyl chloride resin composition for electric wires containing a mixed decanol pyromellitic ester, a stabilizer and a lubricant is proposed. (Patent Document 3).

  However, these methods do not sufficiently solve problems such as the stickiness of the coating resin, sheet cracking, and poor surface smoothness.

  Separately, Patent Document 4 discloses that (A) a vinyl chloride resin having a particle size of 0.5 to 10 μm is 80% by weight or more and a tetrahydrofuran-insoluble content is 30 to 60% by weight of 60 to 95%. And (B) a vinyl chloride resin comprising 40 to 5 parts by weight of a vinyl chloride resin consisting essentially of a tetrahydrofuran-soluble component, wherein particles having a particle diameter of 0.1 to 0.4 μm are 80% by weight or more. A plastisol composition comprising 100 parts by weight of a resin and (C) 30 to 250 parts by weight of a plasticizer has been proposed.

  However, this plastisol composition relates to a vinyl chloride resin having a dull surface, that is, a matte surface, and solves problems such as a sticky feeling of the coating resin, sheet cracking, and poor surface smoothness. It is not a plastisol intended to do.

JP-A-7-102141 Japanese Patent Laid-Open No. 7-207093 Japanese Patent Application Laid-Open No. 7-2111153 JP-A-8-259761

  An object of the present invention is to provide a plastisol composition that does not cause the coating resin to be sticky, does not cause sheet cracking, and provides a vinyl chloride resin-coated sheet or electric wire with good surface smoothness.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that if a specific plastisol composition is used for a sheet or wire coating, there is no stickiness of the coating resin, and sheet cracking does not occur. The inventors have found that a surface-coated vinyl chloride resin with good surface smoothness can be obtained, and have completed the present invention. That is, the present invention includes (A) 40 to 60 parts by weight of a vinyl chloride resin having an average degree of polymerization of 1000 or more and containing no tetrahydrofuran insoluble matter, and (B) a vinyl chloride resin 60 to 60 containing a tetrahydrofuran insoluble matter. A plastisol composition comprising 40 to 60 parts by weight of a plasticizer with respect to 40 parts by weight and (C) 100 parts by weight of a vinyl chloride resin.

  Hereinafter, the present invention will be described in more detail.

  The plastisol composition of the present invention comprises (A) an average degree of polymerization of 1000 or more and 40 to 60 parts by weight of a vinyl chloride resin not containing tetrahydrofuran insolubles. When the amount of the vinyl chloride resin is less than 40 parts by weight, the surface coating is not preferable because a sticky feeling is produced. On the other hand, when it exceeds 60 parts by weight, sheet cracking occurs on the surface coating, which is not preferable. When the average degree of polymerization of the vinyl chloride resin is less than 1000, a problem of stickiness occurs.

  Here, as the vinyl chloride resin, for example, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinyl chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride- Propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylic Ronilittle copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-malein Acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylic acid Chlorine-containing resins such as nitrile copolymers, vinyl chloride-various vinyl ether copolymers, and their blends, or synthetic resins not containing chlorine and other chlorine-containing resins such as acrylonitrile-styrene copolymers , Ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blends with polyester, block copolymers, graft copolymers, and the like.

  Tetrahydrofuran insoluble matter that does not contain vinyl chloride resin refers to insoluble matter in tetrahydrofuran. For example, for thermoplastic resins, fluororesins such as polytetrafluoroethylene, polyvinylidene fluoride, perfluoroalkoxyalkane, thermosetting Examples of the resin include phenol resin of phenol formaldehyde, furfuryl alcohol, furfural / phenol cocondensate, furan resin such as furfural / ketone cocondensate, and xylene resin.

  As a method for producing the above (A) vinyl chloride resin having an average degree of polymerization of 1000 or more and containing no tetrahydrofuran insolubles, the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. may be used. Although there is no particular limitation, micro suspension polymerization and emulsion polymerization are suitable, and the polymerization temperature needs to be 60 ° C. or lower.

  The plastisol composition of the present invention comprises (B) 60 to 40 parts by weight of a vinyl chloride resin containing a tetrahydrofuran insoluble material. When the vinyl chloride resin exceeds 60 parts by weight, a problem of sheet cracking occurs. When the vinyl chloride resin is less than 40 parts by weight, a sticky feeling problem occurs.

  Here, the vinyl chloride resin is the same as described above.

  The tetrahydrofuran insolubles contained in the vinyl chloride resin are the same as those described above. The amount of the tetrahydrofuran-insoluble material to be contained is not particularly limited, but is preferably 50 to 95% by weight, and more preferably 70 to 90% by weight in order to reduce the stickiness.

  The method for producing the above (B) vinyl chloride-based resin containing insoluble tetrahydrofuran is not particularly limited to the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. It is necessary to polymerize using a polyfunctional monomer having 2 or more ethylenic double bonds in the molecule.

  The plastisol composition of the present invention comprises (C) 40 to 60 parts by weight of a plasticizer with respect to 100 parts by weight of the above-described vinyl chloride resin. If it is less than 40 parts by weight, sheet cracking is not preferable, and if it exceeds 60 parts by weight, a sticky feeling is not preferable.

  In the present invention, the type of plasticizer is not particularly limited, but various compounds such as phthalic acid diesters, aliphatic dibasic acid diesters, polyesters, phosphoric acid esters, and epoxy plasticizers are usually used. These plasticizers are used singly or in combination of two or more depending on the purpose. Among them, phthalic acid diesters, especially di-2-ethylhexyl phthalate, are used for plasticizing efficiency, thermal stability and cold resistance. These properties are in a suitable range and are often used.

  With the expansion and advancement of the use range of soft vinyl chloride resin molded products, there is an increasing demand for even better durability. Advancing, the coating layer is also thinner. For this reason, the coating layer is also required to have higher durability, that is, heat aging resistance, low volatility, and high volume resistivity so that even a thin coating layer can be sufficiently insulated.

  As such plasticizers with improved heat aging resistance, diisononyl phthalate (hereinafter referred to as “DiNP”) and diisodecyl phthalate (hereinafter referred to as “DiDP”), which are less volatile than DOP, are used. Moreover, as a plasticizer which improved the intensity | strength and cold resistance of the soft vinyl chloride-type resin sheet obtained, the diester of 2-propyl heptanol and phthalic acid is mention | raise | lifted (for example, refer Unexamined-Japanese-Patent No. 4-106146).

  In the present invention, in addition to (A) a vinyl chloride resin having an average degree of polymerization of 1000 or more and not containing tetrahydrofuran insolubles, (B) a vinyl chloride resin containing tetrahydrofuran insolubles, and (C) a plasticizer (D) A plastisol composition containing a diluent is preferred because the viscosity of the plastisol is low, and the processing speed during surface coating is increased.

  The type of diluent used in the present invention is not particularly limited, and any diluent that is generally used as a diluent for polyvinyl chloride sol, such as ethyl cellosolve, naphtha, and mineral spirit, may be used. Two or more kinds may be mixed and used. A blending amount of 10 parts by weight or more is preferable because the viscosity at the time of melting of plastisol becomes very small.

  In addition, (A) a vinyl chloride resin having an average degree of polymerization of 1000 or more and containing no tetrahydrofuran insolubles is a vinyl chloride-vinyl acetate copolymer, and the vinyl acetate content in the copolymer is If the plastisol composition is 2% by weight or more, if it is used for sheet or wire coating, there will be no more sticky feeling, sheet cracking will occur, and a vinyl chloride resin surface coating with good surface smoothness will be obtained. preferable.

  In addition, the plastisol composition of the present invention includes additives that are usually used in vinyl chloride resins as necessary, for example, crosslinking agents, antistatic agents, antifogging agents, plate-out preventing agents, surface treatment agents, lubricants. In addition, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, and the like can be blended.

  If a vinyl chloride resin-coated electric wire is produced using the plastisol composition of the present invention, the coating resin does not have a sticky feeling, the sheet cracks do not occur in the coating resin, and the surface smoothness of the coating resin is good. Sheet material and covered electric wire can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

  In the examples and comparative examples, the sol viscosity measurement of the plastisol composition and the sheet forming process were performed under the following conditions.

<Viscosity measurement>
The plastisol composition was measured with a B-type viscometer (B8H type) at a measurement temperature of 23 ° C., a rotor of # 5, and a rotation speed of 20 rpm.

<Sheet molding processing method>
A plastisol composition was applied on a base material (mylar film) and heated and melted at 180 ° C. for 5 seconds to produce a sheet molded product.

<Evaluation method>
The sticky feeling of the obtained sheet molded product was observed by tactile sensation, and was evaluated in three stages: ◯ (none), Δ (slightly), and x (very sticky).

  The cracks in the obtained sheet molded product were visually observed from a bending test with a finger and evaluated in three stages: ○ (none), Δ (slightly), and x (many).

  The surface state of the obtained sheet molded product was visually observed, and evaluated in three stages: ○ (smooth), Δ (slightly rough), and × (rough).

Synthesis example 1
Before starting polymerization in a 2.5 L autoclave, 500 g of deionized water, 800 g of vinyl chloride monomer, 110 g of seed particles containing 2% by weight of lauroyl peroxide, 70 g of seed particles obtained by emulsion polymerization, 0.0 g. 4 g of a 1% by weight aqueous ferrous sulfate solution and a surfactant were added, the temperature of the reaction mixture was raised to 58 ° C., and 130 g of a 0.1% by weight ascorbic acid aqueous solution was continuously added until the polymerization was completed. Further, the surfactant was continuously added from 1.5 hours to 7.5 hours after the start of polymerization. As the surfactant before and during the polymerization, sodium dodecylbenzenesulfonate was used. The polymerization was stopped when the polymerization temperature dropped from the saturated vapor pressure of vinyl chloride at 58 ° C. by 0.44 MPa, and after the completion of the polymerization, the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride polymer latex. Next, this latex was dried by a rotary disk spray dryer, and a vinyl chloride resin (A) for paste was obtained through a pulverizer.

Synthesis example 2
Before starting polymerization in a 2.5 L autoclave, 500 g of deionized water, 800 g of vinyl chloride monomer, 110 g of seed particles containing 2% by weight of lauroyl peroxide, 70 g of seed particles obtained by emulsion polymerization, surface activity The agent was charged and the temperature of the reaction mixture was raised to 64 ° C. to initiate polymerization. The surfactant was continuously added from 1.0 hour to 6.0 hours after the start of polymerization. As the surfactant before and during the polymerization, sodium dodecylbenzenesulfonate was used. The polymerization was stopped when the polymerization temperature dropped from the saturated vapor pressure of vinyl chloride at 64 ° C. by 0.5 MPa, and after the polymerization was completed, the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride polymer latex. Next, this latex was dried with a rotary disk spray dryer, and a vinyl chloride resin (B) for paste was obtained through a pulverizer.

Synthesis example 3
A seed obtained by emulsion polymerization of 110 g of seed particles containing 500 g of deionized water, 800 g of vinyl chloride monomer, 60 g of vinyl acetate monomer, and 2% by weight of lauroyl peroxide before starting polymerization in a 2.5 L autoclave. 70 g of particles, 4 g of 0.1 wt% ferrous sulfate aqueous solution and surfactant are added, the temperature of the reaction mixture is raised to 53 ° C., and 150 g of 0.1 wt% ascorbic acid aqueous solution is continuously added until the polymerization is completed. did. Further, the surfactant was continuously added from 1.5 hours to 7.5 hours after the start of polymerization. As the surfactant before and during the polymerization, sodium dodecylbenzenesulfonate was used. The polymerization was stopped when the polymerization temperature dropped from the saturated vapor pressure of vinyl chloride at 53 ° C. by 0.32 MPa, and after the polymerization was completed, the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride polymer latex. Next, this latex was dried by a rotary disk spray dryer, and a vinyl chloride resin (C) for paste was obtained through a pulverizer.

Synthesis example 4
A vinyl chloride resin for paste (D) was obtained in the same manner as in Synthesis Example 3 except that 20 g of vinyl acetate monomer was added.

Synthesis example 5
A vinyl chloride resin for paste (E) was obtained in the same manner as in Synthesis Example 3 except that 110 g of vinyl acetate monomer was added.

Synthesis Example 6
A vinyl chloride resin for paste (F) was obtained in the same manner as in Synthesis Example 3 except that 40 g of vinyl acetate monomer was added.

Synthesis example 7
110 g of seed particles containing 500 g of deionized water, 800 g of vinyl chloride monomer, 3.0 g of triallyl isocyanurate, and 2% by weight of lauroyl peroxide before starting polymerization in a 2.5 L autoclave were obtained by emulsion polymerization. 70 g of seed particles, 8 g of 0.1 wt% ferrous sulfate aqueous solution, and a surfactant were added, and the temperature of the reaction mixture was raised to 48 ° C., and 160 g of 0.1 wt% ascorbic acid aqueous solution was continuously added until the polymerization was completed. Added. Further, the surfactant was continuously added from 1.5 hours to 7.5 hours after the start of polymerization. As the surfactant before and during the polymerization, sodium dodecylbenzenesulfonate was used. The polymerization was stopped when the polymerization temperature dropped from the saturated vapor pressure of vinyl chloride at 48 ° C. by 0.29 MPa, and after the polymerization was completed, the unreacted vinyl chloride monomer was recovered to obtain a vinyl chloride polymer latex. Next, this latex was dried by a rotary disk spray dryer, and a vinyl chloride resin (G) for paste was obtained through a pulverizer.

Example 1
The vinyl chloride resin for paste (A) obtained in Synthesis Example 1 and the vinyl chloride resin for paste (G) obtained in Synthesis Example 7 were mixed at 40/60 (weight ratio) to obtain a vinyl chloride resin for paste. A resin was obtained. For 100 parts by weight of the vinyl chloride resin for paste, 40 parts by weight of dioctyl phthalate as a plasticizer, 10 parts by weight of a diluent (exxon mobile, trade name Exol D40), a heat stabilizer (manufactured by Asahi Denka Co., Ltd.) Product name SC34) A plastisol composition was prepared by mixing and stirring 3 parts by weight and degassing under reduced pressure at -700 mmHg to -760 mmHg for 15 minutes.

  Using the plastisol composition having the composition shown in Table 1, a vinyl chloride resin sheet molded article was produced, and the evaluation items were evaluated. The results are shown in Table 1.

表１から明らかなように、本発明の組成のプラスチゾル組成物を使用して塩化ビニル樹脂シート成形物や電線被覆などの被覆物を作製すれば、得られた塩化ビニル樹脂シート成形物や被覆物のベタツキ感がなく、シート割れが起こらず、また、表面平滑性が良好な塩化ビニル樹脂シート物や被覆物が得られた。

As is apparent from Table 1, when a coating such as a vinyl chloride resin sheet molding or a wire coating is produced using the plastisol composition having the composition of the present invention, the resulting vinyl chloride resin sheet molding or coating is obtained. Thus, a vinyl chloride resin sheet or coating with good surface smoothness was obtained.

Example 2 to Example 9
Except that the vinyl chloride resin for paste, plasticizer, and diluent were changed as shown in Table 1, a vinyl chloride resin sheet molded article was prepared in the same manner as in Example 1, and the evaluation items were evaluated. did. The results are shown in Table 1.

  As is apparent from Table 1, when a coating such as a vinyl chloride resin sheet or a wire coating is produced using the plastisol composition having the composition of the present invention, the resulting vinyl chloride resin sheet or a stickiness of the coating is obtained. There was no feeling, no sheet cracking occurred, and a vinyl chloride resin sheet or coating with good surface smoothness was obtained.

Comparative Example 1 to Comparative Example 9
Except for changing the vinyl chloride resin for paste, plasticizer, and diluent as shown in Table 2, a vinyl chloride resin sheet molded article was prepared in the same manner as in Example 1, and the evaluation items were evaluated. did. The results are shown in Table 2.

表２から明らかなように、本発明の組成以外のプラスチゾル組成物はベタツキ感、シート割れ、表面平滑性を満足するものは得られなかった。

As is clear from Table 2, no plastisol compositions other than the composition of the present invention satisfying the stickiness, sheet cracking, and surface smoothness were obtained.

Claims (3)

(A) 40 to 60 parts by weight of vinyl chloride resin having an average degree of polymerization of 1000 or more and not containing tetrahydrofuran insolubles, (B) 60 to 40 parts by weight of vinyl chloride resin containing tetrahydrofuran insolubles, and ( C) A plastisol composition comprising 40 to 60 parts by weight of a plasticizer with respect to 100 parts by weight of a vinyl chloride resin. (D) The plastisol composition according to claim 1, further comprising a diluent. The vinyl chloride resin (A) having an average degree of polymerization of 1000 or more according to claim 1 and containing no tetrahydrofuran insolubles is a vinyl chloride-vinyl acetate copolymer, and the vinyl acetate contained in the copolymer The plastisol composition according to claim 1 or 2, wherein the amount is 2% by weight or more.