KR20030077970A - Vinyl chloride resin paste for slush molding and molded article formed from the same - Google Patents

Abstract

The present invention does not impair the viscosity characteristics of the slush molding vinyl chloride-based resin paste sol or the obtained molded product even when the excess amount of the vinyl chloride-based resin paste for slush molding heated in the slush molding process is repeatedly used. It provides a vinyl chloride resin paste for slush molding. The present invention also provides a molded product obtained by using the vinyl chloride resin paste. The slush molding vinyl chloride resin paste contains a cyclohexene carboxylic acid ester as the vinyl chloride resin for the paste and a plasticizer. The molded product is obtained by molding the vinyl chloride resin paste according to the slush molding method.

Description

VINYL CHLORIDE RESIN PASTE FOR SLUSH MOLDING AND MOLDED ARTICLE FORMED FROM THE SAME}

The present invention relates to a vinyl chloride resin paste for slush molding and a molded article obtained using the same.

More specifically, the present invention is acrylonitrile butadiene styrene resin which is excellent in thermal stability at the time of slush molding, the sol viscosity of the vinyl chloride resin paste for slush molding is low enough for practical use, and is required for moldings such as toys. The present invention relates to a vinyl chloride resin paste that is excellent in non-performance and has a high bleed resistance to ABS resins, polystyrene resins, and the like, and molded articles obtained by using the same.

The vinyl chloride resin paste for slush molding in the present invention is generally referred to as "paste sol" among those skilled in the art.

Conventionally, vinyl chloride-based resin pastes are used by blending and producing aromatic carboxylic acid esters as plasticizers in vinyl chloride-based resins for pastes. Among these aromatic carboxylic acid esters, phthalic ester plasticizers, in particular, bis (2-ethylhexyl) phthalate (hereinafter referred to as DOP), have relatively balanced physical properties, and are formed in dip molding, coating molding, rotational molding, and slush molding. It is suitable for molding method such as mold, etc., and it can be used for a wide range of applications such as housing, such as toys, gloves, wallpaper or flooring, automobile related undercoat or sealant, steel sheet coating or canvas coating. It is used.

However, some of the above-mentioned phthalic ester plasticizers may be a substance (so-called environmental hormone) that disturbs the endocrine action and affects reproduction and development of wild animals or humans. It is necessary to develop a plasticizer having excellent performance instead of the system plasticizer.

As such an alternative plasticizer, for example, acetyl citrate tributyl (ATBC), which is a citric acid ester-based plasticizer, is used in some applications, but this plasticizer does not have good thermal decomposition resistance of itself, and the acid value of the plasticizer increases under high temperature conditions. There is.

In particular, in the slush molding method, which is a molding method that is widely used in toys, etc., the vinyl chloride resin paste for slush molding is injected into a mold and heated, and the excess vinyl chloride resin paste for slush molding, which is not gelled, is discharged and reused. In this case, however, the temperature of the discharged slush molding vinyl chloride-based resin paste is generally raised to 40 to 100 ° C., so that thermal stability that can withstand repeated use is required.

However, any conventional plasticizer has insufficient thermal stability to withstand such repeated use. As one of the causes, it is considered that the alkyl group moiety in the plasticizer molecule is oxidatively decomposed by heating, thereby increasing the acid value of the plasticizer.

The acid value of the plasticizer greatly influences the viscosity characteristics of the vinyl chloride resin paste for slush molding, and is required to have excellent stability in terms of processability (flow during melting, thickness variation, etc.).

To this end, a technique using adipic acid diisononyl (DINA), which is an adipic acid ester-based plasticizer, has been proposed, but according to this technique, the initial viscosity of the vinyl chloride resin paste can be lowered, but thermally decomposable, There is a problem that the non-compliance (such as polystyrene-based resin), bleed resistance and the like are insufficient.

Accordingly, various methods for solving the above problems have been proposed.

As such a method, a technique using cyclohexane-based carboxylic acid ester as a plasticizer has been proposed (see, for example, Japanese Patent Application Laid-Open No. 2001-207002, p2: paragraphs "0005" to p3: paragraph "0011"). However, this technique has good bleeding resistance of the paste, non-compliance (to ABS resin, polystyrene resin, etc.), but the thermal decomposition resistance is insufficient, so that slush molding during molding is caused by an increase in acid value due to the thermal history of the plasticizer. There was a problem in thermal stability (sol viscosity, thixotropy, etc.) of the vinyl chloride resin paste.

The object of the present invention is not to impair the sol viscosity characteristics of the slush molding vinyl chloride resin paste, the properties of the molded product obtained, etc., even when the excess amount of the vinyl chloride resin paste for slush molding heated in the slush molding process is repeatedly used. It is to provide a vinyl chloride resin paste for slush molding, and a molded article obtained using the same.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, as a result, using cyclohexene carboxylic acid ester as an essential component as a plasticizer for vinyl chloride type resin for pastes, the excess ungelled chloride for slush molding in a slush molding process Even if the vinyl resin paste is used repeatedly, it has been found that the problem of deterioration of the sol viscosity characteristic due to the acid value increase of the plasticizer according to the thermal history does not occur, and the thermal decomposition resistance can be improved, thereby completing the present invention.

That is, the present invention provides a vinyl chloride resin paste for slush molding, which contains a vinyl chloride resin for paste and a cyclohexene carboxylic acid ester as a plasticizer.

The present invention also provides a molding obtained by molding a vinyl chloride resin for paste and a vinyl chloride resin paste containing a cyclohexene carboxylic acid ester as a plasticizer according to the slush molding method.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The vinyl chloride resin paste for slush molding of the present invention contains a vinyl chloride resin for a paste and a cyclohexene carboxylic acid ester as a plasticizer, and is present in a state in which the vinyl chloride resin for a paste is dispersed in a plasticizer.

The vinyl chloride resin for pastes used in the present invention is a vinyl chloride resin that can be used for a resin paste that can be used in the slush molding method. As such a vinyl chloride resin for pastes, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl stearate copolymer resin, vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene copolymer resin, vinyl chloride-iso Polyvinyl chloride copolymer resins of known monomers and vinyl chloride, such as butylene copolymer resin, vinyl chloride-methacrylic acid ester copolymer resin, vinyl chloride-isobutyl vinyl ether copolymer resin, and polyvinyl chloride resin or polyvinyl chloride system The chlorinated polyvinyl chloride resin etc. which substituted the hydrogen atom in the copolymer resin with the chlorine atom can be illustrated, and the thing of spherical form is mentioned. These may be used as one kind or a mixture of two or more kinds.

As used herein, the term "slush molding" refers to a kind of processing method for molding a hollow molded article using a resin paste, which will be described later.

It is preferable that the average particle diameter of the vinyl chloride type resin for pastes used for this invention is several micrometers or less, More preferably, it exists in the range of 0.02-2 micrometers.

Such a vinyl chloride-based resin for paste can be produced by drying an emulsion obtained by emulsion polymerization of a monomer mixture such as vinyl chloride or a suspension obtained by microsuspension polymerization.

The emulsion polymerization is usually carried out using monomer mixtures such as chlorine-containing vinyl monomers such as vinyl chloride, emulsifiers such as sodium lauryl sulfate and sodium dioctylsulfosuccinate, which are anionic surfactants, and water-soluble catalysts such as ammonium persulfate and potassium persulfate. Can be carried out in a water medium. It is also possible to introduce a hydrophilic group into the monomer and to perform a soap-free emulsion polymerization without using an emulsifier.

The microsuspension polymerization is usually carried out with monomer mixtures such as chlorine-containing vinyl monomers such as vinyl chloride, emulsifiers such as sodium lauryl sulfate and sodium dioctylsulfosuccinate as anionic surfactants, dispersing aids and lauroyl peroxide, di-2- Oil-soluble catalysts such as ethylhexyl peroxide can be used and dispersed in oil droplets by mechanical shearing using a homogenizer or the like in a water medium.

Spray drying etc. are mentioned as a drying method of the said emulsion, suspension, etc.

The cyclohexene carboxylic acid ester is used as the plasticizer in the vinyl chloride resin paste for slush molding of the present invention, but plasticizers other than the cyclohexene carboxylic acid ester may be used in combination.

In this case, the content of the cyclohexene carboxylic acid ester in all the plasticizers used is preferably in the range of 50 to 100% by weight, particularly preferably in the range of 70 to 100% by weight, and the cyclohexene carboxylic acid ester is 100% by weight. Is most preferred. When the content of the cyclohexene carboxylic acid ester is in the range of 50 to 100% by weight, it is excellent in pyrolysis resistance of the plasticizer, and also excellent in balance of sol viscosity, sol viscosity stability, bleed resistance, non-migration, and non-volatility.

Examples of the cyclohexene carboxylic acid ester used in the present invention include cyclohexene monocarboxylic acid esters, cyclohexene dicarboxylic acid diesters, cyclohexericarboxylic acid triesters, and cyclohexene tetracarboxylic acid tetraesters.

Of these, cyclohexenedicarboxylic acid diesters and cyclohexericarboxylic acid triesters are preferable in terms of compatibility with the vinyl chloride resin for pastes and nonvolatile properties.

Examples of the cyclohexene dicarboxylic acid diester include 4-cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl) ester, 4-cyclohexene-1,2-dicarboxylic acid diisononyl ester, and 4-cyclohexene- 1,2-dicarboxylic acid diisodecyl ester, 2-cyclohexene-1,4-dicarboxylic acid diisononyl ester, etc. can be illustrated.

In addition, as the cyclohexerilic carboxylic acid triester, 4-cyclohexene-1,2,3-tricarboxylic acid tri (2-ethylhexyl) ester and 5-cyclohexene-1,2,4-tricarboxylic acid triisononyl ester Etc. can be illustrated.

The acid value of the cyclohexene carboxylic acid ester used in the present invention is preferably 0.2 or less for bleed resistance.

The acid value here means the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the sample.

The cyclohexene carboxylic acid ester used in the present invention can be produced, for example, by condensation reaction of a cyclohexene carboxylic acid and a monohydric alcohol according to a known conventional method. For example, while stirring a predetermined raw material in a nitrogen stream, a reflux condenser is attached to reflux the excess monohydric alcohol and the heating is continued at preferably 130 to 250 ° C. until the acid value of the sample is 0.5 or less. While the water produced is continuously removed, the unreacted alcohol component is then removed under reduced pressure, preferably at 180 to 230 ° C and 10 hPa or less, more preferably 4 hPa or less, and then neutralized if necessary. Next, it can be filtered to obtain a plasticizer having a predetermined property.

Examples of the cyclohexene carboxylic acid that can be used in the present invention include cyclohexene monocarboxylic acid, cyclohexene dicarboxylic acid, cyclohexericarboxylic acid, cyclohexene tetracarboxylic acid, and the like. Of these cyclohexene carboxylic acids, cyclohexenedicarboxylic acid and cyclohexeric carboxylic acid are preferable for compatibility and non-volatileness of the esterified product and the vinyl chloride resin for paste.

Examples of the cyclohexene dicarboxylic acid include 1-cyclohexene-1,2-dicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, and 4-cyclohexene-1. , 2-dicarboxylic acid, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid, 1-cyclohexene-1,3-dicarboxylic acid, 3-cyclohexene-1,3-dicarboxylic acid, 4-cyclohexene -1,3-dicarboxylic acid, 1-cyclohexene-1,4-dicarboxylic acid, 2-cyclohexene-1,4-dicarboxylic acid, etc. can be illustrated.

Examples of the cyclohexene tricarboxylic acid include 1-cyclohexene-1,2,3-tricarboxylic acid, 3-cyclohexene-1,2,3-tricarboxylic acid, 4-cyclohexene-1,2,3-tricarboxylic acid, 1-cyclohexene-1,2,4-tricarboxylic acid, 2-cyclohexene-1,2,4-tricarboxylic acid, 3-cyclohexene-1,2,4-tricarboxylic acid, 4-cyclohexene-1,2 Examples of, 4-tricarboxylic acid, 5-cyclohexene-1,2,4-tricarboxylic acid, 6-cyclohexene-1,2,4-tricarboxylic acid, 1-cyclohexene-1,3,5-tricarboxylic acid and the like can do.

In addition to the cyclohexene carboxylic acids as described above, ester-forming derivatives such as their acid anhydrides and their acid chlorides can be used in place of the cyclohexene carboxylic acids. Moreover, the alkyl ester compound of these cyclohexene carboxylic acids can also be used. Among these alkyl ester compounds, lower alkyl ester compounds are preferred in that the de-alcohol reaction step can be performed under relaxed conditions, and methyl ester compounds are particularly preferred.

These may be used individually or may mix and use 2 or more types.

As monohydric alcohol which can be used for manufacturing cyclohexene carboxylic acid ester used for this invention, butanol, isobutanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, 2-ethyl Hexanol, nonanol, isononanol, 2-methyloctanol, decanol, isodecanol, undecanol, dodecanol, tridecanol, and the like.

These may be used alone or in combination of two or more thereof.

The alcohol constitutes an alcohol unit in the cyclohexene carboxylic acid ester obtained by condensation reaction with the cyclohexene carboxylic acid described above.

The alcohol is preferably a monohydric alcohol having an alkyl group having 6 to 11 carbon atoms. When the alkyl group carbon number of the said monohydric alcohol is in the range of 6-11, the cyclohexene carboxylic acid ester obtained is excellent in nonvolatileness and excellent compatibility with the vinyl chloride type resin for pastes.

Examples of the monohydric alcohol having an alkyl group having 6 to 11 carbon atoms include hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, 2-ethylhexanol, nonanol and isononanol. , 2-methyloctanol, decanol, isodecanol, undecanol and the like can be exemplified.

Moreover, in the monohydric alcohol which has an alkyl group whose carbon number of the said alkyl group is the range of 6-11, it is especially preferable that it is a monohydric alcohol whose hydroxyl value is the range of 370-420. Examples of the monohydric alcohol having an alkyl group having 6 to 11 carbon atoms and a hydroxyl value of 370 to 420 include nonanol, isononanol and 2-methyloctanol in the monohydric alcohol. Cyclohexene carboxylic acid esters obtained using monohydric alcohols satisfying both the carbon number and hydroxyl value range of such alkyl groups have better compatibility with nonvolatile and vinyl chloride resins for pastes.

The term "hydroxyl value" as used in the present invention refers to the number of milligrams of potassium hydroxide required to neutralize the acetic acid produced when a sample 1 g is reacted at a prescribed temperature and a specified time using an acetylating agent based on a prescribed method.

In the condensation reaction for synthesizing the cyclohexene carboxylic acid ester used in the present invention, it is preferable to use a catalyst to promote the condensation reaction. Examples of such a catalyst include acid catalysts such as paratoluenesulfonic acid and phosphoric acid, metal catalysts such as tetraisopropyl titanate, tetrabutyl titanate, dibutyl tin oxide, dioctyl tin oxide, and zinc chloride.

Moreover, it is preferable that it is 100-250 degreeC, and, as for the temperature at the time of the said condensation reaction, it is more preferable that it is 130-250 degreeC.

In addition to the cyclohexene carboxylic acid ester, a known plasticizer can be used for the vinyl chloride resin paste for slush molding of the present invention. Examples of other plasticizers that can be used include phthalic acid esters, adipic acid esters, sebacic acid esters, trimellitic acid esters, pyromellitic acid esters, epoxy esters such as epoxidized soybean oil, chlorinated paraffins, and phosphoric acid. Ester, polyester, cyclohexane type carboxylic acid ester, etc. are mentioned.

The amount of plasticizer used in the slush molding vinyl chloride resin paste of the present invention is preferably 10 to 300 parts by weight, and particularly preferably 20 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin for paste. When the amount of the plasticizer used in the vinyl chloride resin paste for slush molding of the present invention is in a preferred range, the processing viscosity is easily adjusted in the slush molding step, and bleeding does not occur.

In the case of slush molding the vinyl chloride-based resin paste of the present invention, the vinyl chloride-based resin paste for slush molding is usually used in combination with a heat stabilizer in order to suppress the dechlorination reaction of the vinyl chloride-based resin for the paste by heating. .

As said thermal stabilizer, various thermal stabilizers, such as lead type, tin type, Ba-Zn type, Ca-Zn type, Zn-K type, Zn-Na type, are mentioned, for example. It is preferable that the compounding quantity of such a heat stabilizer is 0.1-10 weight part with respect to 100 weight part of vinyl chloride resins for pastes.

The vinyl chloride resin paste for slush molding of the present invention may further contain various additives within a range not impairing the object of the present invention. Examples of such additives include antioxidants, ultraviolet absorbers, fillers, diluents, foaming agents, stabilizers, and the like.

Examples of the antioxidant include phenolic antioxidants such as 2,6-di-t-butyl-p-cresol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) prop Hindered phenolic antioxidants, such as a cionate, thioether antioxidants, such as dilauryl thiodipropionate, phosphoric acid antioxidants, such as trisnonyl phenol phosphite, etc. are mentioned. It is preferable that the compounding quantity of this antioxidant is the range of 0.1-10 weight part with respect to 100 weight part of vinyl chloride resins for pastes.

Examples of the ultraviolet absorber include salicylate compounds such as phenyl salicylate, benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone, and 2- (2'-hydroxy-5'-t. Benzotriazole compounds such as -butylphenyl) benzotriazole, cyanoacrylate compounds such as 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, bis (2,2,6, Hindered amine compounds, such as 6-tetramethyl-4- piperidyl) sebacate, etc. are mentioned. It is preferable that the compounding quantity of such an ultraviolet absorber is 0.1-10 weight part with respect to 100 weight part of vinyl chloride resins for pastes.

Examples of the filler include calcium carbonate, clay, talc, silica, aluminum hydroxide, magnesium oxide, magnesium carbonate, magnesium silicate, calcium silicate and the like. It is preferable that the compounding quantity of such a filler is 1-120 weight part with respect to 100 weight part of vinyl chloride resins for pastes.

Examples of the diluent include 2,2,4-trimethyl-1,3-pentanediol diisobutylate, n-paraffin, and the like. It is preferable that the compounding quantity of this diluent is 1-50 weight part with respect to 100 weight part of vinyl chloride resins for pastes.

Examples of the blowing agent include azodicarbonamide, an organic foaming agent typified by p, p'-oxybisbenzenesulfonyl hydrazide, and an inorganic foaming agent typified by sodium bicarbonate. It is preferable that the compounding quantity of such a blowing agent is 0.1-30 weight part with respect to 100 weight part of vinyl chloride resins for pastes.

Moreover, when the said stabilizing adjuvant is illustrated, epoxy compounds, such as epoxidized soybean oil, epoxidized linseed oil, and butyl epoxy stearate, etc. are mentioned.

It is preferable that the compounding quantity of the said stabilizing adjuvant is 0.5-50 weight part with respect to 100 weight part of vinyl chloride resins for pastes.

The vinyl chloride resin for paste and the plasticizer thus obtained are mixed with cyclohexene carboxylic acid ester and various additives and stirred, and the vinyl chloride resin for paste and various additives used as necessary are dispersed in the plasticizer. A vinyl chloride-based resin paste for slush molding of the present invention, which is composed of the plasticizer and a vinyl chloride-based resin for paste dispersed in the plasticizer, can be prepared.

Examples of devices that can be used for mixing, stirring and dispersing the components constituting the vinyl chloride resin paste for slush molding include kneaders, butterfly mixers, planetary mixers, Henschel mixers, and choppers ( chopper).

Slush molding is a shaping | molding method which shape | molds using the fluidity | liquidity of the vinyl chloride type resin paste for slush molding which disperse | distributed the vinyl chloride type resin for paste uniformly in a plasticizer, and gel-melts by heating, and obtains a molded object.

Although the particle diameter of general-purpose vinyl chloride resin is about 100 [mu] m, the vinyl chloride resin for paste used in slush molding is fine spherical particles having a particle diameter of several [mu] m or less. Maintains a stable solid-liquid dispersion form, and a homogeneous molding can be obtained with only thermal energy.

The molded article of the present invention is obtained by slush molding the vinyl chloride resin paste for slush molding thus obtained.

Since the vinyl chloride resin paste for slush molding of the present invention contains a cyclohexene carboxylic acid ester as a plasticizer, there is little acid value increase due to thermal decomposition of the plasticizer due to thermal history during repeated heating, and in particular, it is excellent in thermal decomposition resistance. It is effectively used for molding.

The term "slush molding" as used in the present invention refers to a molding method in which a molded product is usually obtained sequentially through the following steps (1) to (4).

Step (1); A slush molding vinyl chloride-based resin paste is injected into a mold from a paste tank to heat the mold, and the slush molding vinyl chloride-based resin paste in contact with the inner wall surface of the mold is gelled to form a gelling layer.

Step (2); The heating is stopped, and an excess amount of the ungelled slush molding vinyl chloride resin paste other than the gelling layer is discharged and collected in a paste tank.

Step (3); The mold is heated again and the gelled layer is melted to fully advance the gelation reaction.

Step (4); The mold is cooled to take out the molded product.

By passing through each said process sequentially, the target molded object can be obtained.

In addition, the metal mold | die used at the said process is a curved shape which has an uneven part etc. which have a desired design on an inner wall surface.

The method of heating the mold in the step (1) is not particularly limited as long as it can heat the mold, and examples thereof include a method using an oil bath, a method using an air heating furnace, and the like. . In addition, the heating temperature should just be the temperature which can normally gelatinize the vinyl chloride type resin paste for slush molding, Preferably it is the range of 120-200 degreeC.

In addition, in the step (1), since the gelling layer becomes thick with time, the thickness of the molding layer can be adjusted by appropriately setting the heating stop timing according to the type of molding.

The ungelled vinyl chloride-based resin paste for slush molding recovered in the paste tank in the step (2) is used again in the slush molding step (1), and the vinyl chloride-based resin paste for slush molding for reuse is not paste tank. It collect | recovers to and is used repeatedly, repeating a subsequent process several times.

The mold cooling method in the step (4) is not particularly limited, but for example, water cooling is performed to perform cooling.

Since the molding of the present invention uses a vinyl chloride resin paste for slush molding using a plasticizer containing the cyclohexene carboxylic acid ester of the present invention as an essential component, the vinyl chloride resin paste for slush molding is repeatedly used. Even in this case, there is little increase in the plasticizer acid value due to thermal decomposition due to thermal history, and a molded article having excellent balance of various characteristics such as non-bleeding (compatibility of plasticizer), non-migration, and non-volatileness is always obtained.

Examples of the molded article of the present invention include toys, gloves, automobile members, and the like.

As the molded article of the present invention, a toy is particularly preferable in that the high designability is required among the molded articles.

If the toy obtained by this invention is illustrated, the soft vinyl toy doll, a character goods, playing house goods, a figure model, etc. are mentioned.

Usually, since these toys are used in contact with or in combination with ABS resins, polystyrene resins, etc. in terms of their product structure, plasticizers in slush-molding vinyl chloride-based resin pastes do not transfer to these resins used in contact or in combination (i.e., , Non-compliance) is required, and the toy that is the molded article of the present invention is also excellent in this respect.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples. In addition, all "parts" in this specification shall be a basis of weight.

<< Examples 1-4 >> and << Comparative Examples 1-5 >>

With the compounding compositions shown in Table 1 and Table 2, a vinyl chloride-based resin paste for slush molding containing a vinyl chloride resin for a paste, a plasticizer and an additive was prepared, and a sheet was prepared using the paste. The results obtained by evaluating the thermal decomposition resistance, the sol viscosity, the bleed resistance, the non-performance, and the non-volatility of the vinyl chloride resin paste plasticizer and the molded article for slush molding are shown in Tables 1 and 2.

The manufacturing and evaluation method of the said vinyl chloride type resin paste for slush molding is as follows.

[Production of vinyl chloride resin paste for slush molding]

The mixing shown in Table 1 and Table 2 was carried out using a mixing stirrer (manufactured by Tokyo Chemical Co., Ltd., chemistor B-100) for 4 minutes at a stirring speed of 1100 rpm, followed by 30 minutes under reduced pressure. The stationary defoaming was performed and the vinyl chloride type resin paste for slush molding which the vinyl chloride type resin for paste was disperse | distributed was manufactured.

[Sheet firing conditions]

Using a vinyl chloride-based resin paste for slush molding obtained in Examples and Comparative Examples as a test piece, coating it on a glass plate with a thickness of 1 mm using a Womamatis oven (manufactured by Womamatis AG, LTF-ST), and then at 190 ° C. The sheet was prepared by baking for 10 minutes.

[Measurement Methods and Evaluation Criteria for Pyrolytic Resistance of Plasticizers]

100 g of the plasticizer used in Examples and Comparative Examples was placed in a 250 mm 3 sample bottle, and the lid was opened and heated in a dryer at 100 ° C. for 14 days. After completion of the test, the acid value of the plasticizer was measured, compared with the initial acid value, and evaluated according to the following evaluation criteria.

○: less than 2

×: acid value 2 or more

[Method and Evaluation Criteria for Sol Viscosity Stability]

Measurement of Initial Sol Viscosity

The vinyl chloride type resin paste for slush molding obtained in the examples and the comparative examples was measured at 6 rpm and a measurement temperature of 25 ° C. with a rotor No. 3 using a BM type viscometer.

<Measurement of Sol Viscosity Stability>

The vinyl chloride resin paste for slush molding was stored at 25 ° C. for 7 days, and the sol viscosity was measured using a BM viscometer under the same conditions as the initial sol viscosity.

The value of sol viscosity (sol viscosity after 7 days / initial sol viscosity after 7 days) with respect to initial sol viscosity was computed, and it evaluated according to the following evaluation criteria.

○: less than 1.5 times

×: 1.5 times or more

[Measurement Methods and Evaluation Criteria for Bleed Tolerance]

The sheet obtained above was cut into a size of 5 cm × 5 cm as a test piece, and left for 10 days, 20 days, 30 days, and 40 days under conditions of 70 ° C. and 95% relative humidity, and then the sheet state was visually observed. It observed and evaluated according to the following evaluation criteria.

○: no bleed.

(Triangle | delta): Although it is not bleeding, the adhesiveness on the surface is increasing.

X: There is bleed.

Curing: Although not bleeding, the plasticizer is volatilized and the test piece is cured.

[Measurement Methods and Evaluation Criteria]

The sheet obtained above was cut into 2.5 mm x 2.5 mm in size and used as a test piece. Manufacture, AGI02], sandwiching the test piece between the two resin plates, respectively, and holding it at 40 ° C for 24 hours under a load of 10 g / cm 2, then transferring the plasticizer to the ABS resin plate and the HIPS resin plate. The erosion state according to the naked eye was observed, and evaluated according to the following evaluation criteria.

(Circle): Resin plate erosion by migration of a plasticizer is not observed.

(Triangle | delta): Although there is no resin plate erosion by migration of a plasticizer, a trace is recognized slightly.

X: Resin plate erosion by migration of a plasticizer is recognized.

Xx: Resin plate erosion by the migration of a plasticizer is remarkably recognized.

[Non-Volatile Measurement Method]

The sheet obtained above was cut into 5 cm × 5 cm size using the test piece, the weight (a) was measured beforehand, put into a drier and dried at 100 ° C. for 120 hours. Subsequently, after taking out a sheet, the weight (b) was measured again and the weight loss rate (%) was calculated | required according to the following formula.

Weight loss (%) = (a-b) / a × 10O

TABLE 1

TABLE 2

In Example 4 and Comparative Example 5, evaluation items described in Table 2 were carried out using a plasticizer 14 days after the start of the pyrolysis resistance test.

[Description and Notes of Plasticizer in Tables 1 and 2]

Cyclohexene Type A: 4-cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl) ester prepared from 4-cyclohexene-1,2-carboxylic acid and 2-ethylhexanol (hydroxyl group 432). Viscosity 37 mPa * s (25 degreeC).

Cyclohexene B: 4-cyclohexene-1,2- produced from 4-cyclohexene-1,2-dicarboxylic acid and isononanol (manufactured by Co., Ltd., trade name; oxocol 900, hydroxyl group 390) Dicarboxylic acid diisononyl ester. Viscosity 48 mPa * s (25 degreeC).

Cyclohexene C: 4-cyclohexene-1,2-dicarboxylic acid diisodecyl ester prepared from 4-cyclohexene-1,2-dicarboxylic acid and isodecanol (hydroxyl group 355). Viscosity 67 mPa * s (25 degreeC).

DOP: Bis phthalate (2-ethylhexyl).

DINA: Adipic acid diisononyl.

ATBC: Tributyl acetylcitrate.

Cyclohexane system: Cyclohexane- 1, 2- dicarboxylic-acid diisononyl ester which condensed cyclohexane- 1, 2- dicarboxylic acid and isononanol (manufactured by Co., Ltd., brand name; oxocol 900). Viscosity 42 mPa · s (25 ° C).

* 1) Polyvinyl chloride resin for paste (polymerization degree 1650)

* 2) Stabilization aid, Dainihon Inki Kagaku Kogyo Co., Ltd., W-100-EL

* 3) Thermal stabilizer, Dainihon Inki Kagaku Kogyo Co., Ltd., Gurekku ML-610A

From the results of Table 1 and Table 2, the vinyl chloride resin paste for slush molding of the present invention is equivalent to DOP in terms of sol viscosity, bleed resistance, non-migration, non-volatility, and the like. Since the cyclohexene carboxylic acid ester is contained as a plasticizer in the inside, it turns out that it is excellent in heat stability and viscosity stability of a sol.

Especially, Example 2 whose hydroxyl value of the alcohol unit which comprises cyclohexene type carboxylic acid ester is 390 is a very good balance of sol viscosity, bleed tolerance, non-migration, and non-volatile.

Since the vinyl chloride resin paste for slush molding of the present invention contains a cyclohexene carboxylic acid ester as an essential component as a plasticizer, the vinyl chloride resin paste for slush molding is also used in repetitive heating in the slush molding process as compared with conventionally known vinyl chloride resin paste for slush molding. Pyrolysis of the alkyl group portion of the plasticizer due to the thermal history is difficult to occur, excellent pyrolysis resistance, excellent viscosity stability, non-migration, bleed resistance, non-volatile, so it is very suitable for slush molding. The vinyl chloride-based resin paste for slush molding of the present invention can be widely used as a hollow molded article such as a toy in which molding is mainly performed by the slush molding method.

Claims (5)

A vinyl chloride resin paste for slush molding, comprising a cyclohexene carboxylic acid ester as a vinyl chloride resin for a paste and a plasticizer. The method of claim 1, The vinyl chloride type resin paste for slush molding, wherein the alcohol unit constituting the cyclohexene carboxylic acid ester is derived from a monohydric alcohol having an alkyl group having 6 to 11 carbon atoms. The method according to claim 1 or 2, The alcohol unit constituting the cyclohexene carboxylic acid ester is a vinyl chloride resin paste for slush molding, wherein the hydroxyl value is derived from a monohydric alcohol having a range of 370 to 420. A molded article obtained by molding a vinyl chloride resin paste containing a cyclohexene carboxylic acid ester as a vinyl chloride resin for a paste and a plasticizer according to the slush molding method. The method of claim 4, wherein A molding wherein the molding is a toy.