JP4845593B2 - Vinyl chloride paste resin composition and waterproof gloves using the same - Google Patents

Description

  The present invention relates to a vinyl chloride paste resin composition having a small amount of oil extracted after molding and having excellent processability and oil resistance, and a waterproof glove using the same.

  Conventionally, a vinyl chloride paste resin composition contains a plasticizer such as di-2-ethylhexyl phthalate (DOP), di-2-ethylhexyl adipate (DOA) or butylbenzyl phthalate (BBP) in a vinyl chloride paste resin. It is used for flooring, wall materials, flexible containers, gloves, etc. In particular, waterproof gloves in which the surface of PVC resin gloves and fiber gloves are coated with vinyl chloride resin are used in various fields such as household use, food processing, medical use, and precision industrial use. In addition to soft vinyl chloride resins, gloves are made of acrylic resin, polyurethane resin, natural or synthetic rubber, etc., but they are soft and have good usability, are inexpensive and have high workability. Therefore, a soft vinyl chloride resin is often used.

  As described above, the soft vinyl chloride resin contains a plasticizer, and phthalate ester, adipate ester, citrate ester plasticizer, benzoate ester plasticizer, and acrylic copolymer are known. (For example, Patent Documents 1, 2, and 3).

  Among these, phthalate esters have balanced physical properties and are suitable for dip molding and shower molding. However, some phthalate esters, such as DOP, have restrictions on the use of ultra-thin gloves for cooking. As an industry trend, this is an excellent alternative to phthalate plasticizers such as DOP. Development of plasticizers with high performance is desired.

  For this reason, for example, citrate ester plasticizers, adipic acid esters, benzoate ester plasticizers, and acrylic copolymers are used as alternative plasticizers in some applications. It was a problem because it was insufficient in terms of volatility and weather resistance.

  Polyester plasticizers (for example, Patent Documents 4 and 5) have excellent performance in applications that require non-migration, oil resistance, non-volatility, and weather resistance. When a polyester plasticizer is used in the resin composition, since the viscosity is higher than that of aromatic dicarboxylic acid esters such as DOP, the product thickness tends to be non-uniform and it is difficult to obtain a molded product equivalent to the conventional one. There is a problem.

  In order to reduce the viscosity, diisononyl adipate (DINA) or the like is used to lower the viscosity. However, depending on the application, the compatibility, migration and oil resistance of DINA tend to be problematic.

Further, even when a cyclohexane dicarboxylic acid diester is used for the purpose of lowering the viscosity (Patent Document 6), the oil resistance is insufficient.
Therefore, the vinyl chloride paste resin composition using the polyester plasticizer has a high viscosity, so that there is a problem that gloves mainly using the polyester plasticizer have not been put into practical use.
JP-A-9-291118 JP 2002-194159 A JP 2005-126860 A JP-A-4-185634 JP2004-161801 JP 2003-277561 A

  The object of the present invention is to solve such problems, and to provide a vinyl chloride paste resin composition having excellent processability, soft molded products and excellent oil resistance, and the aforementioned vinyl chloride paste resin. It is providing the waterproof glove formed by shape | molding a composition.

  As a result of diligent research, the present inventor has formulated an adipic acid polyester, an aromatic solvent having a boiling point of 150 to 220 ° C., and a defoaming agent in a vinyl chloride paste resin. It has been found that the above object is achieved.

  Furthermore, this inventor discovered that the unsupport glove excellent in waterproofness is obtained by immersing a hand type | mold in the said composition, pulling up, and heat-processing. Moreover, it discovered that the support glove excellent in waterproofness was obtained by apply | coating and heat-processing the said composition to the fiber gloves original hand.

  That is, the vinyl chloride paste resin composition according to claim 1 of the present invention is an aromatic solvent having a vinyl chloride paste resin of 100 parts by weight, an adipic acid polyester of 80 to 150 parts by weight, and a boiling point of 150 to 220 ° C. It consists of 7 to 55 parts by mass and a defoamer 0.01 to 0.2 parts by mass.

The waterproof glove according to claim 2 is obtained by immersing a hand mold in a bathtub of the vinyl chloride paste resin composition according to claim 1, pulling up, and heat-treating.
The waterproof glove according to claim 3 is obtained by applying and heat-treating the vinyl chloride paste resin composition according to claim 1 to a fiber glove.

  As described above, the vinyl chloride paste resin composition of the present invention prepared by blending has high processability and oil resistance, and is molded using this vinyl chloride paste resin composition. It is possible to provide an unsupported glove having oil resistance by immersing it in a bathtub of the composition, pulling it up and heating it.

  Moreover, the durable waterproof glove which has oil resistance can be provided by making it apply | coat and heat-treat to a fibrous knitted glove using the said vinyl chloride-type paste resin composition.

Embodiments of the present invention will be described below.
The present invention comprises 100 parts by weight of a vinyl chloride paste resin, 80 to 150 parts by weight of an adipic acid polyester, 7 to 55 parts by weight of an aromatic solvent (boiling point 150 to 220 ° C.), and a defoaming agent 0.01 to 0.2. It is a vinyl chloride paste resin composition consisting of parts by mass.

  Adipic acid-based polyester is used as a plasticizer, and is excellent in that it increases the oil resistance of the molded product and lowers the oil extractables of the molded product. Moreover, the usage-amount is mix | blended 80-150 mass parts in order to give a soft feel to a molded article. If the content of the plasticizer is less than 80 parts by mass, the obtained molded product becomes hard, which is not preferable. If the content of the adipic acid polyester plasticizer exceeds 150 parts by mass, the composition does not gel and cannot be molded. Furthermore, it is preferably 90 to 140 parts by mass, and more preferably 95 to 130 parts by mass.

  The higher the molecular weight of the adipic acid-based polyester, the higher the viscosity, but the lower the solubility in oil, the harder it is to extract. The average molecular weight is preferably 1000 to 6000, more preferably 1500 to 5000, and still more preferably 2000 to 4000.

  The plasticizer of the adipic acid polyester is adipic acid, which is a dicarboxylic acid, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-butyl-2-ethyl-1,3-diol as a diol component. Propanediol, 1,4-butanediol, neopentylglycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, etc. are obtained by polycondensation with the molecular weight adjusting component, and are commercially available. As a product, Dai Nippon Ink Chemical Co., Ltd. Polycizer W-2610 (Polycizer is a registered trademark), Asahi Denka Kogyo Co., Ltd. Adeka Sizer PN-7650 (Adeka Sizer is a registered trademark), LANXESS Ultramol IV manufactured by Co., Ltd. (however, Ultramol is registered) Target), and the like.

  As diluents for vinyl chloride paste resin compositions for glove applications, paraffinic, isoparaffinic and naphthenic solvents are known. However, since adipic acid-based polyester has higher viscosity and lower solubility than phthalic acid-based plasticizers, phase separation occurs in paraffinic, isoparaffinic and naphthenic solvents. Therefore, a plasticizer other than the adipic acid-based polyester must also be blended, which tends to result in poor oil resistance. A small amount of naphthenic solvent can be mixed, but it is difficult to reduce the viscosity to a workable viscosity, and even when the viscosity reaches a workable viscosity, a large amount of addition is often required. Tend to generate bubbles. As a result of intensive studies, it was found that aromatic solvents can be easily mixed with adipic acid-based polyesters and can easily reduce the viscosity. Furthermore, it has been found that aromatic solvents tend to evaporate more slowly than naphthenic solvents, and that bubbles tend not to be generated even at the same boiling point as naphthenic solvents.

  Therefore, the aromatic solvent is added in an amount of 7 to 55 parts by mass in order to reduce the viscosity of the blend. If it is less than 7 mass parts, the viscosity of a compounding agent does not fall, but there exists a tendency for workability to be bad. The solvent volatilizes gently during processing, but if it exceeds 55 parts by mass, the volatilization amount increases and bubbles tend to be generated in the molded product, which is not preferable. The blending amount of the aromatic solvent is preferably 10 to 50 parts by mass, and more preferably 15 to 45 parts by mass.

  The boiling point of the aromatic solvent is preferably 150 to 220 ° C. because the ultimate temperature of the workpiece is 160 to 170 ° C. When the boiling point is less than 150 ° C., the volatilization rate during processing is high, and there is a tendency that bubbles due to volatilization are formed in the molded product. Although a diluent having a boiling point of 220 ° C. or higher can be used, it may remain in the molded product even after molding, causing a bleed phenomenon, and tends to be extracted into oil. Therefore, the boiling point of the aromatic solvent is more preferably 155 to 210 ° C, and further preferably 160 to 200 ° C.

  As the commercially available aromatic solvent, Ipsol 100 (manufactured by Idemitsu Kosan Co., Ltd., except that Ipsol is a registered trademark, boiling point 159 to 172 ° C.), SOLVESSO 100 (manufactured by Exxon Chemical Co., Ltd., but SOLVESSO is a registered trademark, boiling point 164 to 176) ℃) etc., and these can be used.

  Further, the defoaming agent is blended in an amount of 0.01 to 0.2 parts by mass in order to prevent air bubbles in the vinyl chloride paste resin composition. If it is less than 0.01 parts by mass, it tends to be difficult to prevent the entrapment of bubbles. If it exceeds 0.2 parts by mass, the paste sol will repel and there is a tendency that it is difficult to form a uniform film. Therefore, Preferably it is 0.02-0.15 mass part, More preferably, it is 0.03-0.1 mass part.

  As such a defoaming agent, commercially available products such as BYK-3105 (Made by Big Chemie Japan Co., Ltd., methylalkylpolysiloxane, BYK is a registered trademark), KS-66 (made by Shin-Etsu Chemical Co., Ltd., dimethylpolysiloxane), etc. These can be used.

  A viscosity modifier can be blended in the vinyl chloride paste resin composition. The amount used is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the vinyl chloride paste resin. When it exceeds 30 mass parts, there exists a tendency for oil resistance to be inferior. As the viscosity modifier, 2,2,4-trimethyl 1,3-pentanediol diisobutyrate is preferable. In addition to its function as a viscosity modifier, it is highly compatible with both polyester plasticizers and diluents, and has the effect of allowing the diluent to be easily mixed into the polyester plasticizer. Kyowanol D (manufactured by Kyowa Hakko Kogyo Co., Ltd., but Kyowanol is a registered trademark) is commercially available as such a viscosity modifier.

  Various additives such as secondary plasticizers, stabilizers, thickeners, and pigments are added to the vinyl chloride paste resin composition according to the present invention as required, so long as the processability and oil resistance are not lowered. Needless to say, a desired amount is contained.

  The vinyl chloride paste resin composition obtained as described above has high processability and can produce a molded article made of vinyl chloride resin having oil resistance. The molding can be performed as follows.

  For example, a cotton thread knitted glove that has been subjected to water / oil repellent treatment is put on a hand mold, and a vinyl chloride paste resin composition is applied to the hand mold by a shower process, and then in a furnace at 200 to 240 ° C. for 1 to 3 minutes. The gloves can be obtained by heat treatment and curing by heat treatment for 5 to 30 minutes in a furnace at 170 to 220 ° C. In addition, after 1 to 3 minutes of heat treatment, a step of spraying non-slip particles may be provided, or a step of strengthening fingertips, palms, or the like may be provided. And after processing, it removes from a hand type | mold and provides a support glove. As described above, the vinyl chloride paste resin composition is suitable for providing a support glove having oil resistance.

  In addition to the above, for example, after a hand mold is dipped in a vinyl chloride paste resin composition and pulled up, it is heat treated for 1 to 3 minutes in a furnace at 200 to 240 ° C., and 5 to 30 minutes in a furnace at 170 to 220 ° C. A glove can be obtained by curing by the heat treatment. In addition, after the heat treatment for 1 to 3 minutes, a step of applying and drying the lubricant particle liquid may be provided, or a step of applying an adhesive and performing antistatic flocking processing may be provided. And after a process, it removes from a hand type | mold and provides an unsupport glove. Thus, the vinyl chloride paste resin composition is suitable for providing an unsupported glove having oil resistance.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not restrict | limited at all by these.
In addition, about each sample glove obtained in the following Examples and Comparative Examples, processability, evaporation residue after n-heptane extraction (200 ml of n-heptane was used on one side 100 cm ² and extracted at 25 ° C. for 1 hour) After concentration by an evaporator, evaluation of evaporation to dryness at 105 ° C. for about 2 hours was performed, and the obtained results are shown in Table 1.
Example 1

  100 parts by mass of a vinyl chloride paste resin (manufactured by Shin-Daiichi PVC Co., Ltd., ZEST P21, where ZEST is a registered trademark), 100 parts by mass of adipic acid polyester (Asahi Denka Kogyo Co., Ltd., PN-7550), aromatic 40 parts by mass of a solvent (Ipsol 100, boiling point 159 to 172 ° C.), 0.05 part of defoaming agent (BYK-3105), and 3 parts by mass of a stabilizer (SC-72, manufactured by Asahi Denka Kogyo Co., Ltd.) were blended.

Immerse the hand mold in the bath of the compound, pull it out, heat at 230 ° C. for 2 minutes, then at 180 ° C. for 10 minutes, cool to room temperature, reverse mold from the hand mold, and remove the gloves. A sample was obtained. Said evaluation was performed about the obtained sample. As a result of evaluation, processability is good (excellent defoaming property of the composition, good moldability of the glove, no air bubbles in the glove), and the evaporation residue of the extract by n-heptane is very small as 120 ppm. It was a thing.
Example 2

  Example 1 is the same as Example 1 except that 100 parts by mass of the vinyl chloride paste resin (ZEST P21) in Example 1 is changed to 100 parts by mass of the vinyl chloride paste resin (ZEST EA).

Evaluation similar to Example 1 was performed about the obtained sample. As a result of evaluation, processability is good (excellent defoaming property of the composition, good moldability of the glove, no bubbles in the glove), and evaporation residue of the extract by n-heptane is very low as 98 ppm. It was a thing.
Comparative Example 1

100 parts by mass of vinyl chloride paste resin (ZEST P21) was mixed with 100 parts by mass of di-2-ethylhexyl phthalate (manufactured by J. Plus Co., Ltd., DOP) and 3 parts by mass of stabilizer (SC-72). Glove sample preparation and evaluation are the same as in Example 1. As a result of the evaluation, the processability was good (excellent defoaming property of the composition, the moldability of the glove was good, and there were no bubbles in the glove), but the evaporation residue of the extract by n-heptane was very high at 7210 ppm. It was a lot.
Comparative Example 2

Comparative Example 1 except that 100 parts by mass of di-2-ethylhexyl phthalate (DOP) in Comparative Example 1 was changed to 70 parts by mass of di-2-ethylhexyl phthalate (DOP) and 30 parts by mass of adipic acid-based polyester (PN-7550). The same. Glove sample preparation and evaluation are the same as in Example 1. As a result of the evaluation, the processability was good (excellent defoaming property of the composition, the moldability of the glove was good, and there were no bubbles in the glove), but the evaporation residue of the extract by n-heptane was very 1580 ppm. It was a lot.
Comparative Example 3

Example 1 is the same as Example 1 except that the amount of the aromatic solvent (Ipsol 100) used in Example 1 is 5 parts by mass.
As a result of carrying out the same evaluation as Example 1 about the obtained sample, it was excellent in the defoaming property of a composition, but there was no generation | occurrence | production of the bubble in a glove, but the problem that the thickness was nonuniform about the moldability of a glove. there were. The evaporation residue of the extract with n-heptane was very low at 122 ppm.
Comparative Example 4

Example 1 is the same as Example 1 except that the amount of the aromatic solvent (Ipsol 100) used in Example 1 is 60 parts by mass.
As a result of carrying out the same evaluation as Example 1 about the obtained sample, it was excellent in the defoaming property of a composition and the moldability of a glove, but the bubble generate | occur | produced in the glove.
Comparative Example 5

  It is the same as Example 1 except that instead of the aromatic solvent (Ipsol 100) used in Example 1, 40 parts by mass of xylene (boiling point 138 to 144 ° C.) manufactured by Idemitsu Kosan Co., Ltd. was used.

As a result of evaluating the obtained sample in the same manner as in Example 1, the composition was excellent in the defoaming property of the composition and the moldability of the glove, but bubbles were generated in the glove.
Comparative Example 6

  The same as Example 1 except that Exol Chemical Co., Ltd., and SOLVESSO 200 (boiling point 231 to 278 ° C.) were used in an amount of 40 parts by mass instead of the aromatic solvent (Ipsol 100) used in Example 1.

As a result of carrying out the same evaluation as Example 1 about the obtained sample, workability was good (it was excellent in the defoaming property of a composition, the moldability of a glove, and there was no bubble in a glove), but n- A large amount of evaporation residue of heptane extract was generated at 257 ppm.
Comparative Example 7

  Example 1 except that 40 parts by mass of IP solvent 1620 (boiling point 166 to 202 ° C.) manufactured by Idemitsu Kosan Co., Ltd., which is a paraffinic solvent, was used instead of the aromatic solvent (Ipsol 100) used in Example 1. The same.

The compatibility between the solvent and the plasticizer was poor, and phase separation occurred, making it impossible to make gloves.
Comparative Example 8

  40 parts by mass of EXXSOL D-40 (boiling point 153 to 196 ° C., EXXSOL is a registered trademark) manufactured by Exxon Chemical Co., Ltd., which is a naphthenic solvent, instead of the aromatic solvent (Ipsol 100) used in Example 1 Except for the above, this is the same as Example 1.

As a result of evaluating the obtained sample in the same manner as in Example 1, the compatibility between the solvent and the plasticizer was poor, and it took a long time to form a uniform paste sol, and the glove had poor moldability. Bubbles are generated inside.
Comparative Example 9

The same as Example 1 except that the amount of the defoaming agent (BYK-3105) used in Example 1 was 0.005 parts by mass.
As a result of performing the same evaluation as Example 1 about the obtained sample, although the moldability of a glove was good, the defoaming property of a composition was bad and the bubble generate | occur | produced in the glove. The evaporation residue of the extract with n-heptane was very low at 120 ppm.
Comparative Example 10

The same as Example 1 except that the amount of the defoaming agent (BYK-3105) used was 0.25 parts by mass.
When paste sol was applied to the hand mold, repellency occurred and gloves could not be formed.

Claims (3)

It consists of 100 parts by weight of a vinyl chloride paste resin, 80 to 150 parts by weight of an adipic acid polyester, 7 to 55 parts by weight of an aromatic solvent having a boiling point of 150 to 220 ° C., and 0.01 to 0.2 parts by weight of a defoaming agent. A vinyl chloride paste resin composition characterized by that. A waterproof glove obtained by immersing a hand mold in a bath of the vinyl chloride paste resin composition according to claim 1, pulling up and heat-treating. A waterproof glove obtained by applying and heat-treating the vinyl chloride paste resin composition according to claim 1 to a fiber glove.