Plasticizer for resins containing ester groups

Abstract

The object of the present invention is to provide a plasticizer for resins having ester groups that provides an excellent effect of lowering the glass transition temperature (Tg) of resins having ester groups, such as polycarbonate resins. [Solution] A plasticizer containing a polyester (A) composed of an alcohol component (X) and a carboxylic acid component (Y), wherein the carboxylic acid component (Y) contains a linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms, and the polyester (A) has an ester group having a number average molecular weight (Mn) of 500 to 25,000.

Description

Technical Field

[0001] The present invention relates to a plasticizer for a resin having an ester group.

Background Art

[0002] Generally, polycarbonate resin is a resin excellent in mechanical properties and thermal properties. However, it has a high glass transition point (Tg) and has problems in flexibility and processability. Regarding this problem, Patent Document 1 proposes a resin composition containing polyethylene glycol, a phosphorus stabilizer, and an aromatic polycarbonate.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Disclosure of the Invention

Problems to be Solved by the Invention

[0004] However, even in Patent Document 1, the reduction of the glass transition point (Tg) was not sufficient. An object of the present invention is to provide a plasticizer for a resin having an ester group, which gives an excellent effect of reducing the glass transition point (Tg) to a resin having an ester group such as a polycarbonate resin.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention is a plasticizer containing a polyester (A) having an alcohol component (X) and a carboxylic acid component (Y) as constituent monomers, wherein the carboxylic acid component (Y) contains a linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms, and the plasticizer (α) for a resin (E) having an ester group, in which the number average molecular weight (Mn) of the polyester (A) is 500 to 25,000.

Effects of the Invention

[0006] The plasticizer (α) for resins having an ester group of the present invention provides the following effects. (1) Provides an excellent effect in lowering the glass transition temperature (Tg). As a result, it has excellent flexibility and processability. [Modes for carrying out the invention]

[0007] <Alcohol content (X)> Examples of the alcohol component (X) in the present invention include a diol component (x1), a trivalent or higher alcohol component (x2), and a monoalcohol component (x3).

[0008] The diol component (x1) includes linear aliphatic diols (containing 2 to 20 carbon atoms, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, 18-octadecanediol and 1,20-eicosanediol, etc.), branched aliphatic diols (including those with 3 to 18 carbon atoms, for example propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol and 1,2-octadecanediol, etc.), alkylenes with 4 to 36 carbon atoms Examples include polyethylene glycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols having 4 to 36 carbon atoms (e.g., 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), alkylene oxide adducts of the above alicyclic diols (hereinafter, "alkylene oxide" will be abbreviated as AO) [e.g., ethylene oxide (hereinafter, "ethylene oxide" will be abbreviated as EO), propylene oxide (hereinafter, "propylene oxide" will be abbreviated as PO), butylene oxide (hereinafter, "butylene oxide" will be abbreviated as BO), etc.] (preferably with an average number of added moles of 1 to 30); AO (EO, PO, BO, etc.) adducts of bisphenols (e.g., bisphenol A, bisphenol F, bisphenol S, etc.) (preferably with an average number of added moles of 2 to 30); polylactone diols (e.g., polyε-caprolactone diol); and polybutadiene diol. Two or more of these may be used in combination.

[0009] Among these diols, linear aliphatic diols are preferred, more preferably linear aliphatic diols having 2 to 18 carbon atoms, even more preferably linear aliphatic diols having 2 to 16 carbon atoms, and particularly preferred are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol.

[0010] The linear aliphatic diol content is preferably 80% by weight or more, and more preferably 90% by weight or more, based on the weight of the diol component (x1).

[0011] Similarly, preferably the alcohol component (X) contains a diol component (x1), and the content of the diol component (x1) is preferably 80% by weight or more, and more preferably 90% by weight or more, based on the weight of the alcohol component (X).

[0012] Examples of trivalent or higher alcohol components (x2) include polyhydric aliphatic alcohols with 3 to 36 carbon atoms and a valency of trivalent or higher [alkane polyols and their intramolecular or intermolecular dehydrated products (e.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin)], sugars and their derivatives (e.g., sucrose and methyl glucoside), AO adducts of trisphenols (trisphenol PA, etc.) (preferably with 2 to 30 moles added), AO adducts of novolac resins (phenol novolac and cresol novolac, etc.) (preferably with 2 to 30 moles added), and acrylic polyols [e.g., copolymers of hydroxyethyl (meth)acrylate and other vinyl monomers]. One trivalent or higher alcohol component (x2) may be used, or two or more may be used in combination. Of these, preferred are AO adducts of polyhydric aliphatic alcohols with a valency of 3 or higher and novolac resins, and more preferred are AO adducts of novolac resins.

[0013] The content of trivalent or higher alcohol components (x2) is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the weight of alcohol component (X).

[0014] The monoalcohol component (x3) includes monoalcohols with 1 or more carbon atoms, for example, primary alcohols {methanol, ethanol, linear saturated aliphatic monoalcohols (n-propan-1-ol, n-butan-1-ol, n-pentan-1-ol, n-hexane-1-ol, n-heptan-1-ol, n-octan-1-ol, n-nonan-1-ol, n-decane-1-ol, n-undecane-1-ol, n-dodecane-1-ol, n-tridecane-1-ol, n-tetradecane-1-ol, n- Pentadecane-1-ol, n-hexadecane-1-ol, n-heptadecane-1-ol, n-octadecane-1-ol, n-nonadecane-1-ol, n-icosane-1-ol, n-heneicosane-1-ol, n-docosane-1-ol, n-tricosane-1-ol, n-tetracosane-1-ol, n-pentacosane-1-ol, n-hexacosane-1-ol, n-heptacosane-1-ol, n-octacosane-1-ol, n-nonacosane-1-ol and n-triacontan-1-ol and the These include mixtures (policosanol, etc.), branched saturated aliphatic monoalcohols (2-methylpropan-1-ol, 2-methylbutan-1-ol and 3-methylbutan-1-ol, etc.), secondary alcohols (propan-2-ol, butan-2-ol, pentan-2-ol, hexane-2-ol, heptan-2-ol and cyclohexanol, etc.), and tertiary alcohols (2-methylpropan-2-ol, 2-methylbutan-2-ol, 2-methylpentan-2-ol, 2-methylhexane-2-ol, 2-methyl Examples include heptan-2-ol, 3-methylpentan-3-ol, and 3-methyloctan-3-ol. Furthermore, commercially available higher monoalcohols (primary alcohols at one end of a straight-chain saturated hydrocarbon) with 23 or more carbon atoms include Unilin 350 (26 carbon atoms), Unilin 425 (33 carbon atoms), Unilin 550 (39 carbon atoms), and Unilin 700 (50 carbon atoms) (all manufactured by Baker Petrolite). The other monoalcohol components (x3) may be used individually or in combination of two or more.

[0015] (x3) is preferably a primary alcohol (including commercially available higher monoalcohols with 23 or more carbon atoms), more preferably a primary alcohol with 16 or more carbon atoms (particularly preferably a linear saturated aliphatic monoalcohol, including commercially available higher monoalcohols with 23 or more carbon atoms), and even more preferably n-octadecane-1-ol, n-docosane-1-ol, uniline 350, and uniline 425.

[0016] The content of the monoalcohol component (x3) is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the weight of the alcohol component (X), which is a constituent monomer of polyester (A).

[0017] <Carboxylic acid component (Y)> The carboxylic acid component (Y) in this invention contains a linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms. Based on the weight of the carboxylic acid component (Y), the weight of (y1) is preferably 90% by weight or more.

[0018] <Linear aliphatic dicarboxylic acids with 2 to 12 carbon atoms (y1)> Examples of linear aliphatic dicarboxylic acids (y1) having 2 to 12 carbon atoms (including the carbon atoms of the carbonyl group) include linear saturated aliphatic dicarboxylic acids having 2 to 12 carbon atoms {oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, and dodecanediic acid, etc.} and linear unsaturated aliphatic dicarboxylic acids having 4 to 12 carbon atoms {maleic acid and fumaric acid, etc.}. One type of dicarboxylic acid (y1) may be used, or two or more types may be used in combination.

[0019] (y1) is preferably a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms, more preferably succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanediic acid, and even more preferably azelaic acid, sebacic acid, and dodecanediic acid. One type of (y1) may be used, or two or more types may be used in combination.

[0020] <Polyester (A)> The polyester (A) in the present invention uses the alcohol component (X) and the carboxylic acid component (Y) as constituent monomers. The number average molecular weight (Mn) of the polyester (A) is 500 to 25,000, preferably 800 to 21,000, and more preferably 1,000 to 18,000.

[0021] The number average molecular weight (Mn) and weight average molecular weight (Mw) in the present invention are measured under the following conditions. · Apparatus (example): HLC-8120 manufactured by Tosoh Corporation · Column: 2 pieces of TSKgel (registered trademark) GMH6 [manufactured by Tosoh Corporation] · Mobile phase: THF · Measurement temperature: 40 °C · Sample solution: 0.25 wt% THF solution · Solution injection volume: 100 μL · Flow rate: 1 ml / min · Detection device: Differential refractive index detector · Standard substance: 12 points of standard polystyrene (TSKstandard POLYSTYRENE) manufactured by Tosoh Corporation (molecular weights: 500, 1050, 2800, 5970, 9100, 18100, 37900, 96400, 190000, 355000, 1090000, 2890000)

[0022] The polyester (A) can be produced by subjecting the alcohol component (X) and the carboxylic acid component (Y) to an esterification reaction by a known method. Also, the number average molecular weight (Mn) of the polyester (A) can be appropriately adjusted according to the types and weights of the respective monomers of the alcohol component (X), the types and weights of the respective monomers of the carboxylic acid component (Y), and the progress of the esterification reaction.

[0023] <Plasticizer (α) for resin (E) having an ester group> The plasticizer (α) for resins (E) having ester groups according to the present invention contains the polyester (A). The plasticizer (α) has a plasticizing effect (glass transition temperature reduction effect) on various resins, but it can be used particularly suitably as a plasticizer for resins (E) having ester groups as described below.

[0024] The weight of (A) in the plasticizer (α) is preferably 90-100% by weight, more preferably 95-100% by weight, and particularly preferably 98-100% by weight, based on the weight of the plasticizer (α). The plasticizer (α) may optionally contain substances other than (A), such as resin additive (F) [antioxidant: 2,6-di-t-butyl-p-cresol, etc.], as long as it does not impair the effects of the present invention.

[0025] <Resin containing an ester group (E)> The resin (E) having an ester group in the present invention may be any resin other than (A) as described above, for example, at least one selected from the group consisting of polycarbonate resin (E1), polyester resin (E2), and polyacrylic resin (E3). Resin (E) may be used alone or in combination of two or more types. When (E) is polyester resin (E2), it can be distinguished by its number average molecular weight (Mn) or by the presence or absence of (y1) which constitutes (A). Of the above (E), (E1) and (E2) are preferred, and (E2) is even more preferred.

[0026] Examples of polycarbonate resins (E1) include condensates of bisphenol A and phosgene, condensates obtained by transesterification of bisphenol A and carbonate esters, and polycarbonate / ABS alloy resins (PC / ABS).

[0027] Examples of polyester resins (E2) include crystalline polyethylene terephthalate (PET), amorphous polyethylene terephthalate (A-PET), glycol-modified polyethylene terephthalate (PET-G), polybutylene terephthalate (PBT), polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate, and polylactic acid. Of the above (E2), crystalline polyethylene terephthalate (PET) is preferred.

[0028] Examples of polyacrylic resins (E3) include polymethyl methacrylate (PMMA), styrene / methyl methacrylate copolymer (MS), methyl methacrylate / butadiene / styrene copolymer (MBS), and polymethyl methacrylate / (acrylonitrile / butadiene / styrene copolymer) alloy resin (PMMA / ABS).

[0029] <Resin composition (β)> The resin composition (β) of the present invention contains a plasticizer (α) for resins (E) having ester groups and a resin (E) having ester groups. The weight ratio of plasticizer (α) to resin (E) [(α) / (E)] is preferably 0.5 / 99.5 to 10 / 90, and more preferably 1 / 99 to 5 / 95.

[0030] The resin composition (β) can be obtained by melt-mixing a plasticizer (α), a resin (E), and optionally a resin additive (F). Generally, a method of melt-mixing can be applied in which each component, in pellet or powder form, is mixed in a suitable mixer (such as a Henschel mixer), and then melt-mixed in an extruder to form pellets.

[0031] <Molded product (γ)> The molded article (γ) of the present invention is obtained by molding the resin composition (β) of the present invention. Examples of molding methods include injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, and film molding (casting method, tenter method, and inflation method, etc.). Depending on the purpose, the article can be molded using any method that incorporates means such as single-layer molding, multi-layer molding, or foam molding. [Examples]

[0032] The present invention will be further explained below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0033] <Example 1> In a reaction vessel equipped with a condenser, heating and cooling device, thermometer, stirrer, and nitrogen inlet tube, 400 parts by weight of 1,6-hexanediol (x1-1), 20 parts by weight of n-docosane-1-ol (x3-1), 700 parts by weight of sebaciac acid (y1-1), and 1.5 parts by weight of tetrabutoxytitanate as a condensation catalyst were added, and the mixture was reacted at 170°C under a nitrogen stream for 8 hours while distilling off the water produced. Next, the reaction was carried out for 4 hours under a nitrogen stream while gradually increasing the temperature to 210°C and distilling off the generated water. The reaction was further carried out under reduced pressure of 0.5 to 2.5 kPa, and the mixture was removed when the acid value reached 1.5 mg KOH / g. After the removed resin was cooled to room temperature, it was pulverized to form particles, and a plasticizer (α-1) containing polyester (A-1) was obtained. The manganese content of (A-1) was 13,000.

[0034] <Example 2> In a reaction vessel equipped with a condenser, heating and cooling device, thermometer, stirrer, and nitrogen inlet tube, 350 parts by weight of 1,6-hexanediol (x1-1), 650 parts by weight of dodecanediol (y1-2), and 1.5 parts by weight of tetrabutoxytitanate as a condensation catalyst were placed, and the reaction was carried out at 170°C under a nitrogen stream for 8 hours while distilling off the water produced. Next, the reaction was carried out for 4 hours under a nitrogen stream while gradually increasing the temperature to 210°C and distilling off the generated water. The reaction was further carried out under reduced pressure of 0.5 to 2.5 kPa, and the mixture was removed when the acid value reached 10.0 mg KOH / g. After the removed resin was cooled to room temperature, it was pulverized to form particles, and a plasticizer (α-2) containing polyester (A-2) was obtained. The manganese content of (A-2) was 6,000.

[0035] <Example 3> In a reaction vessel equipped with a condenser, heating and cooling device, thermometer, stirrer, and nitrogen inlet tube, 370 parts by weight of 1,6-hexanediol (x1-1), 630 parts by weight of sebaciac acid (y1-1), and 1.5 parts by weight of tetrabutoxytitanate as a condensation catalyst were placed, and the reaction was carried out at 170°C under a nitrogen stream for 8 hours while distilling off the water produced. Next, the reaction was carried out for 4 hours under a nitrogen stream while gradually increasing the temperature to 210°C and distilling off the generated water. The reaction was further carried out under reduced pressure of 0.5 to 2.5 kPa, and the mixture was removed when the acid value reached 20.0 mg KOH / g. After the removed resin was cooled to room temperature, it was pulverized to form particles, and a plasticizer (α-3) containing polyester (A-3) was obtained. The manganese content of (A-3) was 4,000.

[0036] <Example 4> In a reaction vessel equipped with a condenser, heating and cooling device, thermometer, stirrer, and nitrogen inlet tube, 296 parts by weight of ethylene glycol (x1-2), 855 parts by weight of sebaciac acid (y1-1), and 1.5 parts by weight of tetrabutoxytitanate as a condensation catalyst were added, and the reaction was carried out at 170°C under a nitrogen stream for 8 hours while distilling off the water produced. Next, the reaction was carried out for 4 hours under a nitrogen stream while gradually increasing the temperature to 210°C and distilling off the generated water. The reaction was further carried out under reduced pressure of 0.5 to 2.5 kPa, and the mixture was removed when the acid value reached 2.0 mg KOH / g. After the removed resin was cooled to room temperature, it was pulverized to form particles, and a plasticizer (α-4) containing polyester (A-4) was obtained. The manganese content of (A-4) was 2,000.

[0037] <Example 5> In a reaction vessel equipped with a condenser, heating and cooling device, thermometer, stirrer, and nitrogen inlet tube, 499 parts by weight of ethylene glycol (x1-2), 782 parts by weight of succinic acid (y1-3), and 1.5 parts by weight of tetrabutoxytitanate as a condensation catalyst were added, and the reaction was carried out at 170°C under a nitrogen stream for 8 hours while distilling off the water produced. Next, the reaction was carried out for 1 hour under a nitrogen stream while gradually increasing the temperature to 210°C and distilling off the generated water. The reaction was further carried out under reduced pressure of 0.5 to 2.5 kPa, and the mixture was removed when the acid value reached 35.0 mg KOH / g. After the removed resin was cooled to room temperature, it was pulverized to form particles, and a plasticizer (α-5) containing polyester (A-5) was obtained. The manganese content of (A-5) was 1,000.

[0038] <Comparative Example 1> Commercially available polyethylene glycol [Mn:600] was used as a plasticizer (ratio α-1) for comparison.

[0039] <Example 11> Using a mixing test apparatus (Laboplastmill 2D20C, manufactured by Toyo Seiki Seisakusho Co., Ltd.), 49 parts by weight of polyester resin (E-1) [product name "NES-2040", PET, manufactured by Unitika Ltd., Mn approximately 30,000] and 1 part by weight of plasticizer (α-1) were mixed at 270°C for 5 minutes to obtain resin composition (β-1). The obtained resin composition (β-1) was then used to produce molded products [100mm (length) x 100mm (width) x 2mm (thickness)] using an injection molding machine "PS40E5ASE" [manufactured by Nissei Plastic Industrial Co., Ltd.] at a cylinder temperature of 270°C and a mold temperature of 80°C, and evaluated by the performance tests described below. The results are shown in Table 1.

[0040] <Examples 12-15, Comparative Example 11> In Example 11, each resin composition (β) was obtained and each molded article was prepared in the same manner as in Example 11, except that the resin composition (parts by weight) was as shown in Table 1.

[0041] <Performance Test> (1) Glass transition temperature (Tg) (unit: °C) A sample was taken from the molded product and heated from 30°C to 280°C at a rate of 10°C / min using DSC (Differential Scanning Calorimetry) (first heating process). Next, it was left at 280°C for 10 minutes and then cooled to 0°C at a rate of 10°C / min (first cooling process). Next, it was left at 0°C for 10 minutes and then heated to 280°C at a rate of 10°C / min (second heating process). The glass transition point observed during this second heating process was used as the measured value.

[0042] (2) Decrease in glass transition temperature (Tg) (unit: °C) The glass transition temperature (Tg) of resin (E) without each plasticizer (α) was measured using the procedure described in (1) above. This was defined as (Tg2). The glass transition temperature (Tg) measured in (1) above was designated as (Tg1). From (Tg2) and (Tg1), the decrease in Tg was calculated using the following formula. Tg decrease (°C) = (Tg1) - (Tg2)

[0043] The glass transition temperature (Tg) of resin (E-1) was 81°C.

[0044] [Table 1]

[0045] The results in Table 1 show that the plasticizer (α) for resins having an ester group of the present invention provides a superior glass transition temperature (Tg) reduction effect to the resin (E) having an ester group compared to the comparative example. [Industrial applicability]

[0046] The plasticizer (α) for resins having an ester group according to the present invention facilitates the plasticization of resins having an ester group and can effectively reduce the glass transition temperature. As a result, it becomes possible to set a lower processing temperature for resin molded products, which can lead to reduced energy costs, shorter processing times, and increased efficiency in the manufacturing process.

Claims

1. A plasticizer containing a polyester (A) composed of an alcohol component (X) and a carboxylic acid component (Y), wherein the carboxylic acid component (Y) contains a linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms, and the polyester (A) has an ester group having a number average molecular weight (Mn) of 500 to 25,000.

2. The plasticizer (α) for resins (E) having an ester group according to claim 1, wherein the alcohol component (X) contains a diol component (x1), and the content of the diol component (x1) is 80% by weight or more based on the weight of the alcohol component (X).

3. A resin composition (β) comprising the plasticizer (α) for resins (E) having ester groups according to claim 1 or 2 and the resin (E) having ester groups.

4. A molded article (γ) obtained by molding the resin composition (β) described in claim 3.

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