JP2009132853A - Halogen-containing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a halogen-containing resin composition especially excellent in heat resistance and volatility resistance. <P>SOLUTION: The halogen-containing resin composition comprises, to 100 pts.wt. of a halogen-containing resin, at least, 1 to 200 pts.wt. of a dialkyl phthalate and/or a dialkyl adipate, 0.1 to 10 pts.wt. of a dialkyl fumarate in which the alkyl has 8 to 10 carbon atoms, 0.01 to 10 pts.wt. of a metal compound, and 0.01 to 50 pts.wt. of an epoxy compound, wherein the proportion of the dialkyl fumarate to the dialkyl phthalate and/or the dialkyl adipate is 0.05 to 30% by weight. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a halogen-containing resin composition, and particularly relates to a halogen-containing resin composition excellent in heat resistance and volatile resistance.

  Halogen-containing resins typified by vinyl chloride resins are used in various applications from the viewpoints of their excellent processability and transparency as well as low cost.

  In general, a halogenated resin is blended with a dialkyl phthalate and / or an adipic acid dialkyl ester as a plasticizer, and the proportion thereof is appropriately selected according to the degree of plasticization. 1 to 200 parts by weight per part. Moreover, when heat resistance and volatile resistance are requested | required, 0.01-10 weight part of metal compounds and 0.01-50 weight part of epoxy compounds are mix | blended with respect to 100 weight part of halogen-containing resin.

As a halogen-containing resin composition having improved heat resistance, 0.01 to 200 parts by weight of diisononyl fumarate, 0.01 to 10 parts by weight of zinc compound, 0.01 to 10 parts by weight of epoxy compound with respect to 100 parts by weight of halogen-containing resin A composition comprising 10 parts by weight has been proposed (Patent Document 1). And the compounding amount of diisononyl fumarate with respect to 100 weight part of vinyl chloride resin of the composition which the effect was confirmed concretely as an Example is 40 weight part.
WO2002 / 077099

  However, when a large amount of a dialkyl ester of fumaric acid having a higher vapor pressure than the dialkyl phthalate or adipic acid dialkyl ester that is widely used is used as described above, volatility resistance becomes a problem.

  Accordingly, an object of the present invention is to provide a halogen-containing resin composition that is particularly excellent in heat resistance and volatile resistance.

  As a result of intensive studies, the inventor unexpectedly achieved the above object by replacing a part of commonly used plasticizers (dialkyl phthalates and dialkyl esters of adipic acid) with a small amount of dialkyl esters of fumaric acid. The knowledge that it can be achieved was obtained, and the present invention was completed.

  That is, the gist of the present invention is that at least 1 to 200 parts by weight of dialkyl phthalate and / or adipic acid dialkyl ester and 8 to 10 alkyl carbon chains of alkyl dialkyl fumarate per 100 parts by weight of halogen-containing resin. 0.1-10 parts by weight, 0.01-10 parts by weight of a metal compound, 0.01-50 parts by weight of an epoxy compound, and a dialkyl ester of fumaric acid relative to a dialkyl phthalate and / or a dialkyl ester of adipic acid The halogen-containing resin composition is characterized by having a ratio of 0.05 to 30% by weight.

  According to the present invention, it is possible to provide a halogen-containing resin composition particularly excellent in heat resistance and volatility resistance.

  Hereinafter, the present invention will be described in detail. The halogen-containing resin in the present invention is typically polyvinyl chloride or polyvinylidene chloride. In addition, a copolymer of vinyl chloride and a monomer copolymerizable therewith can be mentioned. Here, examples of the monomer that can be copolymerized with vinyl chloride include olefins such as ethylene and propylene, vinyl acetate, vinyl laurate, acrylic acid ester, methacrylic acid methyl ester and other saturated carboxylic acid vinyl esters, and unsaturated carboxylic acids. Examples include acid alkyl esters, alkyl vinyl ethers such as lauryl vinyl ether, maleic acid, acrylonitrile, styrene, methylstyrene, vinylidene chloride, and vinylidene fluoride. Moreover, the graft polymer and block polymer of vinyl chloride are mentioned. 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 phthalic acid dialkyl ester is an ester compound of phthalic acid and one or more of monohydric alcohols. Examples of monohydric alcohols include 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-trimethyl-1-hexyl alcohol, decyl alcohol, isodecyl alcohol, 2-propylheptyl alcohol, undecyl alcohol, dodecyl Examples include alcohol and benzyl alcohol. The adipic acid dialkyl ester is an ester compound of adipic acid and one or more of monohydric alcohols as described above. These may be used in combination, but dialkyl phthalate is preferably used alone, and bis (2-ethylhexyl) phthalate, diisononyl phthalate, and diisodecyl phthalate are more preferable.

  The fumaric acid dialkyl ester in the present invention is an ester compound of fumaric acid and one or more of monohydric alcohols. You may contain acids other than a fumaric acid in the range which does not impair the effect of this invention. Examples of acids other than fumaric acid include maleic acid which is an impurity of industrial raw materials. In order to achieve a high effect by suppressing the blending amount to the halogen-containing resin, it is preferable that the acid other than fumaric acid is 30% by weight or less in the total carboxylic acid.

  It is essential that the carbon chain of the alkyl group in the dialkyl ester of fumaric acid, that is, the carbon chain of the monohydric alcohol used is 8-10. When the carbon chain is 7 or less, the resulting fumaric acid dialkyl ester is highly volatile, and when the carbon chain is 11 or more, the compatibility (kneading property) with the halogen-containing resin tends to be poor. There is. Specific examples of monohydric alcohols having 8 to 10 carbon chains include octyl alcohol, isooctyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, isononyl alcohol, 3,5,5-trimethyl-1-hexyl alcohol, decyl alcohol , Isodecyl alcohol, 2-propylheptyl alcohol and the like, and these may be used in combination. Of these monohydric alcohols, monohydric alcohols having a branched chain are preferred because the freezing point of the resulting dialkyl ester of fumaric acid is low and industrial availability, and particularly preferred monohydric alcohols are 2 -Ethylhexyl alcohol, isononyl alcohol, isodecyl alcohol.

  Alcohols other than those described above may be contained within the range not impairing the effects of the present invention, such as aliphatic alcohols such as butyl alcohol, hexyl alcohol, oleyl alcohol and stearyl alcohol, aromatic alcohols such as benzyl alcohol, and ethylene. Examples include alcohols having an ether bond such as glycol monomethyl ether and alcohols having a double bond such as ethylene glycol monoallyl ether. In order to achieve a high effect by suppressing the blending amount of the halogen-containing resin to a small amount, it is preferable to keep the alcohol other than the monohydric alcohol having 8 to 10 carbon chains at 30% by weight or less in the total alcohol.

  In the present invention, if the amount of unreacted alcohol in the dialkyl ester of fumarate, for example, bis (2-ethylhexyl) fumarate, is reacted with FID (hydrogen flame ionization detector), the amount of unreacted 2-ethylhexyl alcohol. The amount obtained from the area ratio of the gas chromatograph is preferably 0.5% or less. When the unreacted alcohol exceeds 0.5%, there may be a problem as a volatile component from the halogen-containing resin. The preferred amount of unreacted alcohol is preferably 0.1% or less. The lower limit of the unreacted alcohol is about 50 ppm from the viewpoint of easy industrial production. Unreacted alcohol in the dialkyl fumarate can be reduced by a known method. For example, after completion of the esterification reaction, water vapor or inert gas (nitrogen, helium, etc.) may be blown and removed at an appropriate temperature and pressure. The same treatment can be performed on a once extracted product or a commercially available product using an appropriate reactor.

  Examples of the metal of the metal compound in the present invention include lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminum, zinc, tin and the like. Examples of metal compounds include saturated fatty acids, unsaturated fatty acids, polyvalent carboxylic acids, phenolic compounds, compounds with substituents on these compounds, phenolic compounds, salt compounds with ligand compounds, metals Inorganic salts, coordinated compounds, and the like. Specific examples of these 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 Benzoate, 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, and barium stearate.

Examples of the epoxy compound in the present invention include 3,4-epoxy-6-methylcyclohexylcarboxylate, 3,4-epoxycyclohexanecarboxylic acid, methyl-3,4-epoxycyclohexanecarboxylate, 3- (2-xenoxy)- 1,2-epoxypropane-9,10-12,13-diepoxystearic acid, 3,4-epoxycyclohexylmethanol, 3,4-epoxycyclohexyl-9,10-epoxystearate, evichlorohydrin and bisphenol A Condensates of: tert-butylphenyl epoxy stearate, 2-ethylbutyl epoxy stearate, 2-ethylhexyl epoxy stearate, acetoxyethyl epoxy stearate, isooctyl epoxy stearate, isopropanol epoxy stearate Sil, cyclohexyl epoxy stearate, tetrahydrofuryl epoxy stearate, phenyl epoxy stearate, epoxy stearic acid, benzoyl epoxy stearate, methoxyethyl epoxy stearate, -2-ethylhexyl epoxidized tall oil, octyl epoxy tall oil, 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, epoxyhexahydrophthalic acid Isooctyl, epoxyhexahydrophthalate diisodecyl, epoxyhexahydrophthalate bis (9,10-epoxystearyl), epoxidized linseed oil, epoxidized linseed oil fatty acid butyl, epoxidized safflower oil, epoxidized diacetomonoolein, epoxidation Tall oil, epoxidized sunflower oil, epoxidized polybutadiene, epoxidized beef oil, epoxidized fish oil, epoxidized whale oil, epoxidized soybean oil, epoxidized soybean oil diacetate monoglyceride, 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.

  In the halogen-containing resin composition of the present invention, the amount of each component described above is as follows with respect to 100 parts by weight of the halogen-containing resin.

  The amount of dialkyl phthalate and / or dialkyl adipate is selected according to the degree of plasticization, and is 1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 1 to 100 parts by weight. . The compounding amount of the metal compound and the epoxy compound is determined from the viewpoint of dispersibility in addition to heat resistance and volatility, and the compounding amount of the metal compound is 0.01 to 10 parts by weight, preferably 0.05. -5 parts by weight, more preferably 0.1-3 parts by weight, and the compounding amount of the epoxy compound is 0.01-50 parts by weight, preferably 0.05-30 parts by weight, more preferably 0.1-0.1 parts by weight. 20 parts by weight.

  In the present invention, the amount of dialkyl fumarate is 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight, and more preferably 1 to 5 parts by weight. Further, the ratio of the dialkyl ester of fumaric acid to the dialkyl phthalate and / or adipic acid dialkyl is 0.05 to 30% by weight, preferably 0.1 to 20% by weight. When the blending amount of the fumaric acid dialkyl ester deviates from the above conditions and is too small, the effect of improving the heat resistance becomes small, and when it is too large, volatility becomes a problem.

  In the halogen-containing 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, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, succinic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, and citric acid. And plasticizers such as malic acid and phosphoric acid. 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 -Ester compounds of monohydric alcohols such as trimethyl-1-hexyl alcohol, decyl alcohol, isodecyl alcohol, 2-propylheptyl alcohol, undecyl alcohol, dodecyl alcohol and benzyl alcohol. In this esterification reaction, a monovalent carboxylic acid such as acetic acid may be used in combination as necessary. Polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol and monovalent carboxylic acids such as benzoic acid, acetic acid, lauric acid, stearic acid, and myristic acid An ester compound 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 further in detail, this invention is not limited by a following example, unless the summary is exceeded. Table 1 shows the types of monohydric alcohol and the content of unreacted alcohol in the used dialkyl ester of fumaric acid and dialkyl phthalate.

  The unreacted monohydric alcohol content of dialkyl fumarate and dialkyl phthalate in Table 1 was analyzed according to the following method.

  It measured by GC (gas chromatograph) method. “GC-14B” manufactured by Shimadzu Corporation was used as the instrument, and “Capillary CBP1-W25-500” manufactured by Shimadzu Corporation was used as the column. The column temperature was set to 50 ° C. (10 minutes holding) → temperature rising rate 10 ° C./min→250° C. (30 minutes holding). The temperature of the injector and the detector was 250 ° C., an FID (flame ionization detector) was used as the detector, and the content (ppm) of unreacted monohydric alcohol was determined from the peak area ratio. The hydrogen pressure, air pressure, and helium pressure were all 50 kPa.

  In Table 1, Table 2 shows monohydric alcohols used for the synthesis of fumaric acid dialkyl esters (1) to (4).

Examples 1-3 and Comparative Examples 1-5:
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, heat resistance, volatilization amount, and mechanical strength were evaluated by the method described later, and the results are shown in Table 3.

  Table 4 shows the types of raw materials used in Table 3.

  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”. Note that the compound sheet of Comparative Example 1 had already turned light black at the stage of sheet preparation, and no further evaluation was possible.

(2) Volatilization amount:
The compound sheet was cut out to about 30 × 30 mm and weighed, and then stored in an oven at 100 ° C. for 3 days. It was taken out and weighed again to determine the amount of volatilization.

(3) Mechanical strength:
The mechanical strength was measured with reference to JIS A73111995. The tensile test piece was measured according to JIS K7113 and the tear test piece was measured according to JIS K7311-3.

Claims (5)

  At least 1 to 200 parts by weight of dialkyl phthalate and / or adipic acid dialkyl ester, 0.1 to 10 parts by weight of dialkyl fumarate whose alkyl carbon chain is 8 to 10, relative to 100 parts by weight of halogen-containing resin, 0.01-10 parts by weight of a metal compound and 0.01-50 parts by weight of an epoxy compound are blended, and the ratio of the dialkyl ester of fumaric acid to the dialkyl phthalate and / or adipic acid dialkyl ester is 0.05-30. A halogen-containing resin composition, characterized in that the content is% by weight.   The halogen-containing resin composition according to claim 1, wherein the alkyl of the dialkyl fumarate is a branched chain.   The halogen-containing resin composition according to claim 1 or 2, wherein the amount of unreacted alcohol in the dialkyl fumarate is 0.5% or less in terms of a concentration determined from an area ratio of a gas chromatograph.   The halogen-containing resin composition according to any one of claims 1 to 3, wherein the metal compound is at least one selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, aluminum, zinc and tin.   The halogen-containing resin composition according to any one of claims 1 to 4, wherein the halogen-containing resin is polyvinyl chloride.