JP2009185199A - Polyvinyl chloride resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyvinyl chloride resin composition having excellent safety and hygiene for the environment and living bodies, and excellent transparency and heat resistance. <P>SOLUTION: The polyvinyl chloride resin composition is produced by compounding 100 pts.wt. of polyvinyl chloride resin comprising 0.01-10 pts.wt. of a polyester plasticizer, 0.01-50 pts.wt. of an epoxy-based compound, and 0.01-10 pts.wt. of a metal compound. The polyester plasticizer is prepared by reacting phthalic acid and/or terephthalic acid with at least one or more kinds selected from among the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, and glycerol, and the polyester plasticizer is an esterification reaction product having 200-600 mg KOH/g hydroxy value and ≤5 mg KOH/g acid value. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyvinyl chloride resin composition. Specifically, by adding a specific polyester plasticizer to the polyvinyl chloride resin, yellowing and blackening due to thermal deterioration of the resin during molding processing are prevented, and heat resistance The present invention relates to a polyvinyl chloride resin composition having improved properties.

  Polyvinyl chloride resin is inexpensive, excellent in stability and processability, and can easily control the hardness of the resin by adding a plasticizer such as dioctyl phthalate (hereinafter referred to as DOP). in use.

  On the other hand, although polyvinyl chloride resin is excellent in stability, higher heat resistance is required when it is molded at a high temperature. The same applies to applications in which resin products are used for a long time at high temperatures. Therefore, a method of adding a trace amount of a heat resistance improver such as a lead-based or tin-based compound for improving heat resistance is known. However, these heat resistance improvers have problems in safety and hygiene to the environment and living body even if they are in a very small amount. As a substitute, various metal compounds such as zinc, calcium, and barium are used. Has been. However, these metal compounds are inferior to lead-based and tin-based compounds in heat resistance. Therefore, for the purpose of further improving heat resistance, for example, a compound having a hydroxyl group in a molecule such as polyvinyl alcohol is used in combination (Patent Document 1).

  However, in general, polyvinyl alcohol has a low compatibility with polyvinyl chloride resin, although depending on the degree of polymerization and the degree of saponification, the amount added to 100 parts by weight of polyvinyl chloride resin is about 0.1 to 0.2 parts by weight. However, there is a drawback that turbidity is generated in the polyvinyl chloride resin if it is added more than that. Needless to say, the heat resistance is not sufficiently improved with the added amount.

  In addition, an esterification reaction product in which about 50% of the hydroxyl groups of pentaerythritol are esterified with an aliphatic carboxylic acid such as stearic acid or lauric acid has been proposed as an additive having improved compatibility with the polyvinyl chloride resin. (Patent Document 2). However, even this esterification reaction product has a limit of addition of about 0.5 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin, and is insufficient for improving the heat resistance.

  Furthermore, an esterification reaction product (so-called polyester plasticizer) obtained by reacting a polycarboxylic acid with a polyhydric alcohol and, if necessary, a monoalcohol is also known (Patent Document 3). This polyester plasticizer has a structure in which a monohydric alcohol is always used in order to improve compatibility with a polyvinyl chloride resin, and a terminal functional group is capped with an alkyl group. Thereby, even if a polyester plasticizer is added in a large amount, turbidity of the polyvinyl chloride resin can be prevented, but the effect of improving the heat resistance is insufficient.

Japanese Patent Laid-Open No. 6-286012 Japanese Unexamined Patent Publication No. 7-97495 Japanese Patent Laid-Open No. 9-241456

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyvinyl chloride resin composition that is excellent in safety and hygiene for the environment and living body, and that is excellent in transparency and heat resistance. There is.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by blending a polyester plasticizer having specific structural characteristics with a polyvinyl chloride resin together with an epoxy compound and a metal compound. The headline, the present invention has been reached.

  That is, the gist of the present invention is at least 0.01 to 10 parts by weight of a polyester plasticizer, 0.01 to 50 parts by weight of an epoxy compound, and 0.01 to 10 parts by weight of a metal compound with respect to 100 parts by weight of the polyvinyl chloride resin. The polyester plasticizer is obtained by reacting phthalic acid and / or terephthalic acid with at least one or more selected from the group of ethylene glycol, diethylene glycol, triethylene glycol and glycerin. And a polyvinyl chloride resin composition characterized by being an esterification reaction product having a hydroxyl value of 200 to 600 mgKOH / g and an acid value of 5 mgKOH / g or less.

  ADVANTAGE OF THE INVENTION According to this invention, the polyvinyl chloride resin composition excellent in the safety | security and hygiene to an environment and a biological body, and excellent in transparency and heat resistance is provided.

  Hereinafter, the present invention will be described in detail. The polyvinyl chloride resin used in the present invention includes, in addition to polyvinyl chloride, a copolymer with a monomer that can be copolymerized with vinyl chloride. Examples of monomers that can be copolymerized with vinyl chloride include olefins such as ethylene and propylene; saturated carboxylic acid vinyl esters such as vinyl acetate, vinyl laurate, acrylic acid ester, and methacrylic acid methyl ester; Alkyl vinyl ethers such as carboxylic acid alkyl ester and lauryl vinyl ether; other examples include maleic acid, acrylonitrile, styrene, methylstyrene, vinylidene chloride, vinylidene fluoride, and the like. In addition, polymer blends of polyvinyl chloride and terpolymers (eg, acrylonitrile-butadiene-styrene, methacrylic acid methyl ester-butadiene-styrene), chlorinated polyethylene, ethylene-vinyl acetate copolymer, etc., polyvinyl chloride alcohol And the like, and post-treated products such as post-chlorinated products.

  The polyester plasticizer used in the present invention is an ester compound obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol.

  As the polyvalent carboxylic acid, phthalic acid and / or terephthalic acid is used, but the total amount of the polyvalent carboxylic acid is preferably phthalic acid. In addition, phthalic acid may use an anhydride (phthalic anhydride),

  As the polyhydric alcohol, at least one or two or more selected from the group of ethylene glycol, diethylene glycol, triethylene glycol and glycerin is used, and the total amount of the polyhydric alcohol is preferably diethylene glycol. However, when the hydroxyl value described later is 400 mgKOH / g or more, it is preferable to use glycerin together. Depending on the conditions of the esterification reaction, a slight amount of the carboxylic acid group may remain as a terminal group.

  A general polyester plasticizer production apparatus and reaction method can be applied to the production of the polyester plasticizer. The end point of the reaction is usually determined by the amount of unreacted carboxylic acid groups of the polyvalent carboxylic acid used. From the viewpoint of improving the hydrolysis resistance of the polyester plasticizer, the amount of unreacted carboxylic acid, that is, the acid value is preferably as low as possible. Therefore, the acid value of the polyester plasticizer used in the present invention is usually 5 mgKOH / g or less, preferably 3 mgKOH / g or less, more preferably 1 mgKOH / g or less. The lower limit of the acid value is not particularly limited, but is usually 0.1 mgKOH / g based on the reaction conditions and reaction time.

  Usually, an esterification catalyst is used in the production of the polyester plasticizer. In general, an acid catalyst is used. As the Lewis acid, for example, orthotitanate such as tetraisopropyl titanate and tetra-n-butyl titanate, tin compounds such as diethyltin oxide and dibutyltin oxide, and metal compounds such as zinc oxide are used. In addition to Lewis acid, Bronsted acid such as sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid and the like may be used. Of these, orthotitanate is preferred.

  The amount of the esterification catalyst used is usually 0.1% by weight or less, preferably 0.07% by weight or less, more preferably 0.05% by weight as a ratio with respect to the total of the polyvalent carboxylic acid and polyhydric alcohol used in the raw material. % Or less. In some cases, the reaction may be carried out without using an esterification catalyst. If necessary, the esterification catalyst may be removed by a general method such as deactivation treatment, filtration, and purification.

  The hydroxyl value of the polyester plasticizer used in the present invention is 200 to 600 mgKOH / g, preferably 250 to 550 mgKOH / g, more preferably 300 to 500 mgKOH / g. When the hydroxyl value is less than 200 mgKOH / g, the effect of improving the heat resistance when added to the polyvinyl chloride resin is reduced. On the other hand, when it is larger than 600 mgKOH / g, the molecular weight distribution with a large amount of unreacted alcohol is obtained, and the compatibility with the polyvinyl chloride resin is lowered, so that the resin becomes turbid.

  The amount of the polyester plasticizer added to the polyvinyl chloride resin is 0.01 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. When the addition amount is less than 0.01 parts by weight, the effect of addition is not recognized. Conversely, when the addition amount exceeds 10 parts by weight, the resin may become turbid or, in some cases, the resin strength may be reduced.

  Examples of the epoxy compound used in the present invention include 3,4-epoxy-6-methylcyclohexylcarboxylate, 3,4-epoxycyclohexanecarboxylic acid, methyl-3,4-epoxycyclohexanecarboxylate, and 3- (2-xenoxy). ) -1,2-epoxypropane-9,10-12,13-diepoxystearic acid, 3,4-epoxycyclohexylmethanol, 3,4-epoxycyclohexyl-9,10-epoxystearate, shrimp chlorohydrin Condensate of bisphenol A, tert-butylphenyl epoxy stearate, 2-ethylbutyl epoxy stearate, 2-ethylhexyl epoxy stearate, acetoxyethyl epoxy stearate, isooctyl epoxy stearate, epoxy stearate Decyl, Epoxy stearate cyclohexyl, Epoxy stearate tetrahydrofuryl, Epoxy stearate phenyl, Epoxy stearate, Epoxy stearate benzoyl, Epoxy stearate methoxyethyl, Epoxidized tall oilate 2-ethylhexyl, Epoxy stearate octyl epoxy, Epoxy Isooctyl sulfonated tall oil, butyl epoxidized tall oil, glyceride epoxytriacetomonoricinoleate, butyldecyl epoxyhexahydrophthalate, bis (2-ethylhexyl) hexahexahydrophthalate, dioctyl epoxyhexahydrophthalate, epoxyhexahydrophthalate Didecyl acid, dibutyl epoxyhexahydrophthalate, dihexyl epoxyhexahydrophthalate, epoxyhexahydrophthalate Diisooctyl, diisodecyl epoxyhexahydrophthalate, bis (9,10-epoxystearyl) epoxyhexahydrophthalate, epoxidized linseed oil, epoxidized linseed oil fatty acid butyl, epoxidized safflower oil, epoxidized diacetomonoolein, epoxidized Tall oil, epoxidized sunflower oil, epoxidized polybutadiene, epoxidized beef oil, epoxidized fish oil, epoxidized whale oil, epoxidized soybean oil, diatomized monoglyceride of epoxidized soybean oil, epoxidized lard oil, epoxidized cottonseed oil, bis ( 3,4-epoxy-6-methylcyclohexylmethyl) adipate, benzoic acid epoxy stearyl ester and the like. Preferred epoxy compounds are epoxidized linseed oil and epoxidized soybean oil. The addition amount of the epoxy compound with respect to the polyvinyl chloride resin is 0.01 to 50 parts by weight, preferably 0.5 to 30 parts by weight as a ratio with respect to 100 parts by weight of the polyvinyl chloride resin.

  Examples of the metal of the metal compound used in the present invention include lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminum, zinc, and tin. Examples of the metal compound include a saturated fatty acid, an unsaturated fatty acid, a polyvalent carboxylic acid, a compound with a phenolic compound (which may be substituted), a salt with a compound serving as a ligand, and an inorganic metal salt Etc.

  Specific examples of the above compounds include zinc octylate, zinc stearate, zinc dibutyldithiophosphite, potassium didecylphosphite, zinc di (octylphosphite), zinc oxide, zinc sulfide, zinc chloride, hydroxide Zinc, zinc phosphite, zinc carbonate, zinc borate, calcium octoate, calcium stearate, calcium hydroxystearate, calcium behenate, calcium benzoate, calcium myristate, barium octoate, barium stearate, barium hydroxystearate Rate, barium behenate, barium benzoate, barium myristate, barium nonyl phenate, magnesium octoate, magnesium stearate, magnesium hydroxystearate, magnesium behenate, magnesium Nzoate, magnesium myristate, lithium octoate, lithium stearate, lithium hydroxystearate, lithium behenate, lithium benzoate, lithium myristate, barium sulfate, dehydrocalcium acetate, calcium sulfate, dehydroacetic acid barium dibutyltin dilaurate, dioctyltin dilaurate Etc. Preferred metal compounds are lithium, sodium, potassium, magnesium, calcium, barium, aluminum, zinc and tin compounds. From the viewpoint of safety and hygiene, more preferred metal compounds are calcium, barium and zinc compounds. Specific examples include zinc octylate, zinc stearate, calcium octoate, calcium stearate, barium octoate, barium stearate and the like. The addition amount of the metal compound with respect to the polyvinyl chloride resin is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight as a ratio with respect to 100 parts by weight of the polyvinyl chloride resin.

  In the polyvinyl chloride resin composition of the present invention, various plasticizers and auxiliaries other than the above can be blended within a range that does not adversely affect the effects of the present invention. Plasticizers include benzoic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, adipic acid, succinic acid, sebacic acid, azelaic acid, maleic acid , Fumaric acid-based, citric acid-based, malic acid-based and phosphoric acid-based plasticizers. These are carboxylic acid and propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, hexyl alcohol, cyclohexyl alcohol, octyl alcohol, isooctyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, isononyl alcohol, 3, 5, 5 -An ester compound with a monohydric alcohol such as trimethyl-1-hexyl alcohol, decyl alcohol, isodecyl alcohol, 2-propylheptyl alcohol, undecyl alcohol, dodecyl alcohol or benzyl alcohol. In this esterification reaction, a monovalent carboxylic acid such as acetic acid may be used in combination as necessary. In addition, polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and monovalents such as benzoic acid, acetic acid, lauric acid, stearic acid, and myristic acid. An ester compound with a carboxylic acid may be used.

  As auxiliary agents, phosphate ester, phosphite ester, antioxidant, antifogging agent, antistatic agent, lubricant, filler, processing aid, flame retardant, diluent, stabilizer, surfactant, thinning agent Agents, pigments and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.

Table 1 shows the raw material composition of the polyester plasticizer used and the analysis results of the acid value and hydroxyl value. The polyester plasticizer was synthesized by a known method, and the acid value and the hydroxyl value were analyzed in accordance with JIS K1557 ₁₉₇₀ .

  Table 2 shows the polyvalent carboxylic acids and polyhydric alcohols used for the polyester plasticizer synthesis.

Examples 1-4 and Comparative Examples 1-4:
A compound sheet of polyvinyl chloride resin was prepared according to the formulation in Table 3. In addition, the compounding part number of a raw material points out a weight part, respectively. Moreover, uniformity, transparency, heat resistance, and bleed-out resistance were evaluated by the methods described later, and the results are shown in Table 3.

  Table 4 shows the types of raw materials used for preparing the polyvinyl chloride resin compound sheet.

  The compound sheet was created under the following conditions.

(1) Compound creation conditions:
Using two rolls for kneading manufactured by Inoue Seisakusho, the conditions were 160 ° C./5 minutes.

(2) Press molding conditions:
Using a 50 ton hydraulic molding machine manufactured by Maruhichi Iron Works, it was performed under the conditions of 175 ° C./(60 kg / cm ² ) / 5 minutes. The mold dimensions were 220 × 220 × 1 mm.

  In Table 3, each evaluation was performed by the following method.

(1) Heat resistance:
The compound sheet was cut out to about 30 × 30 mm, placed in an oven at 160 ° C., and the blackening of the sheet was observed over time. That is, the sheet is observed every 30 minutes from the 90th minute after being put in the oven. If there is no blackening, “◯”, if less than about 50% of the sheet is black, “△”, about 50 of the sheet. If more than% was black, it was rated as “x”. In addition, the compound sheet of Comparative Example 2 already turned lightly black at the stage of sheet preparation and could not be evaluated further.

(2) Uniformity and transparency:
The uniformity and transparency of the compound sheet were evaluated visually. In the case of uniform and transparent, “◯”, and in the case of non-uniformity or a decrease in transparency, “X”.

(3) Bleed-out resistance:
Cut out the compound sheet to about 30 x 30 mm, hold it in an oven at 100 ° C for 3 days, and judge by palpation. If there is no stickiness, "○", if there is some stickiness, "△", if there is stickiness It was set as “x”.

  From Table 3, the following is apparent. That is, in the case of the examples in which the specific polyester plasticizer used in the present invention is combined with the metal compound and the epoxy compound, the heat resistance is greatly improved, and the uniformity and transparency are maintained. I can say that. On the other hand, in a comparative example using a polyester plasticizer and not using a metal compound and an epoxy compound, it can be said that the heat resistance is remarkably deteriorated. On the other hand, in the comparative example using polyvinyl alcohol, although heat resistance is excellent, uniformity and transparency are getting worse. It can be said that the bleed-out resistance in the examples is not inferior to that of the comparative examples and maintains a good state.

Claims (2)

  A polyester plasticizer is blended with at least 0.01 to 10 parts by weight of a polyester plasticizer, 0.01 to 50 parts by weight of an epoxy compound, and 0.01 to 10 parts by weight of a metal compound with respect to 100 parts by weight of a polyvinyl chloride resin. The plasticizer is obtained by reacting phthalic acid and / or terephthalic acid with at least one selected from the group of ethylene glycol, diethylene glycol, triethylene glycol and glycerin, and has a hydroxyl value of 200 to 200 A polyvinyl chloride resin composition, which is an esterification reaction product having an acid value of 600 mgKOH / g and an acid value of 5 mgKOH / g or less.   The polyvinyl chloride resin composition according to claim 1, wherein the metal compound is at least one selected from the group consisting of a zinc compound, a calcium compound, and a barium compound.