KR101679654B1 - Plasticizers for resin compositions and resin compositions including the same - Google Patents

Abstract

The present invention relates to a resin composition comprising as a plasticizer at least one compound selected from glyceryl carbonate and derivatives thereof, such as glyceryl carbonate esters and glyceryl carbonate ethers.

Concretely, it is a resin composition obtained by adding the plasticizer to at least one resin selected from aliphatic or aromatic polycarbonate resin, urethane resin, polyvinyl chloride resin and epoxy resin to lower the glass transition temperature (Tg) To a resin composition for imparting flexibility to a product. In addition, the plasticizer has an excellent plasticizing efficiency, which results in a low glass transition temperature even with a small plasticizer content and an excellent flexibility at low temperatures, thereby improving physical properties such as tensile strength.

Glyceryl carbonate ester, glyceryl carbonate ether, polycarbonate, polyurethane, epoxy, polyvinyl chloride, plasticizer, esterification reaction

Description

[0001] Plasticizers for resin compositions and resin compositions containing the same [0002]

The present invention uses at least one selected from glyceryl carbonate, glyceryl carbonate ester and glyceryl carbonate ether as a plasticizer of a resin composition, and plastic containing the plasticizer, especially polyvinyl chloride (PVC) resin, epoxy An epoxy resin, a polyurethane resin, and an aliphatic or aromatic polycarbonate resin.

The polyvinyl chloride resin is a homopolymer of vinyl chloride or an interpolymer containing 50% or more of vinyl chloride and is a general-purpose resin that can be used by a process such as extrusion molding, injection molding, calendering, and sol casting. Through its processability, it is widely used as a material for various products ranging from pipes, wires, electromechanical products, toys, films, sheets, artificial leather, tarpaulins, tapes, food packaging materials and medical supplies.

Polyurethane can be produced by thermoplastic polyurethane which can be injection-molded or extruded, and post-polymerization of isocyanate with an oligomer of a polyurethane or polyhydric alcohol on the sol, which is used for artificial leather, coating, coating, There are polyurethanes in which polymers are formed by post curing. These polyurethanes have been used extensively in various films, gloves, artificial leather, as well as in electrical and electronic protective coatings, coatings and architectural interiors.

Epoxy resin is widely used for building interior material or battery electronic material filling material. One-pack type or two-pack type post curing product is generally used. Especially, when it is used as interior material for building, plasticity is used.

Polycarbonates are generally aromatic polycarbonates using Bis-phenol A, but the use of aliphatic polycarbonates to improve aromatic properties is increasing. Particularly, aliphatic polycarbonates that are attracting attention as eco-friendly polycarbonates generally include polypropylene carbonate, ethylene oxide (EO), and carbon dioxide produced by copolymerization of propylene oxide (PO) and carbon dioxide There is a polyethylene carbonate which is produced through a similar reaction pathway by copolymerization. In order to improve the mechanical properties of these, there are used cyclohexen oxide, glycidyl ethers, silicidyl esters other than PO / EO And terpolymers in which glycidyl esters and the like are additionally used have been developed and applied.

The polyvinyl chloride resin, the polyurethane resin, the epoxy resin or the polycarbonate resin may be added with various additives such as plasticizers, stabilizers, viscosity regulators, internal mold release agents, pigments, etc., The plasticizer is an essential additive added to the above resins to impart various physical properties and functions such as processability, flexibility and tackiness. The plasticizer should be very low in volatility and is very important in terms of maintaining the physical properties by continuously performing the performance during the actual use of the molded product as well as the molding process of the plastic composition using the resins. In addition, the plasticizers provided for applications in food, beverage and medical applications should be harmless to health, and the emission of volatile organic compounds should be delayed in the case of building materials.

Examples of plasticizers used for this purpose include dialkyl phthalates, and in particular polycarbonates, dibasic esters such as citric acid ester compounds and dioctyl adipate (dibasic esters) ) Can be used. However, the use of dialkyl phthalates is expected to decline significantly due to the controversy over regeneration toxicity under legislation regulating toxic substances associated with human stability, particularly polypropylene carbonate or polyethylene carbonate, and glycidyl ethers In the case of a copolymer of glycidyl ether or glycidyl ester, a plasticizer such as a dialkyl phthalate or a dibasic esters is insufficient in plasticity, and the plasticizer content is as low as 10% or less It is difficult to lower the glass transition temperature sufficiently. Therefore, in order to secure sufficient flexibility, the use amount must be high. In this case, there is a problem that surface stickiness after processing of the resin composition becomes high.

In order to solve the above problems, the inventors of the present invention have found that, as a plasticizer of a resin composition containing at least one selected from a polyvinyl chloride resin, a polyurethane resin, an epoxy resin and a polycarbonate resin,

At least one compound selected from glyceryl carbonate, glyceryl carbonate esters and glyceryl carbonate ethers is predicted to have compatibility with the resin, a sample is prepared, and a plasticizer The inventors of the present invention have completed the present invention based on experimental results that the above compound is excellent as a plasticizer.

Accordingly, an object of the present invention is to provide a plasticizer for a resin composition, which is capable of replacing a conventional dialkyl phthalate or dibasic ester plasticizer with a compound selected from glyceryl carbonate, glyceryl carbonate ester and glyceryl carbonate ether having excellent physical properties And a resin composition comprising at least one of the above plasticizers and at least one resin selected from a polyvinyl chloride resin, an epoxy resin, a polyurethane resin and a polycarbonate resin.

In order to accomplish the above object, there is provided a plasticizer for a resin composition according to the first aspect of the present invention, which comprises glyceryl carbonate represented by Chemical Formula 1 and derivatives thereof.

[Chemical Formula 1]

Wherein R is selected from a hydrogen atom, a straight-chain (C1-C18) alkyl group, and a carbonyl group substituted with a straight chain (C1-C18) alkyl group, a (C6-C18) alkylcyclohexyl group or a .

In order to achieve still another object of the present invention, there is provided a resin composition comprising at least one resin selected from a polyvinyl chloride resin, a polyurethane resin, an epoxy resin and a polycarbonate resin according to the second aspect of the present invention, A resin composition comprising a plasticizer is provided.

Hereinafter, the present invention will be described in detail.

The present invention provides, as a plasticizer for a resin composition, glyceryl carbonate represented by the following general formula (1) and derivative compounds thereof.

[Chemical Formula 1]

Wherein R is selected from a hydrogen atom, a straight-chain (C1-C18) alkyl group, and a carbonyl group substituted with a straight chain (C1-C18) alkyl group, (C6-C18) alkylcyclohexyl group or (C7- do.

 Preferably, R is selected from a hydrogen atom, an octanoyl group, a decanoyl group, a dodecanoyl group, a tetradecanoyl group, an octyl group, a decyl group, a dodecyl group and a tetradecyl group.

The glyceryl carbonate ester or glyceryl carbonate ether of the formula 1 according to the present invention may be prepared by reacting glycerol carbonate with glycerol and dimethyl carbonate, , And the obtained glyceryl carbonate can be subjected to esterification or etherification to obtain a glyceryl carbonate ester or a glyceryl carbonate ether.

According to the present invention, the at least one plasticizer represented by Formula 1 may be added to at least one resin selected from a polyvinyl chloride resin, a polyurethane resin, an epoxy resin and a polycarbonate resin to prepare a resin composition. The amount of the plasticizer to be charged into the resin is not limited, but may be at least one selected from a polyvinyl chloride resin, a polyurethane resin, an epoxy resin, and a polycarbonate resin, And 5 to 150 parts by weight of one or more plasticizers. The plasticizer-containing resin composition can suitably increase or decrease the plasticizer according to the use of the resin composition. However, when the plasticizer is added in an amount of less than 5 parts by weight, flexibility and processability that can be exhibited by the plasticizer can not be achieved. When it is added in an amount exceeding the amount by weight, it is difficult to ensure proper mechanical properties and the viscosity may be lowered too much.

The present invention relates to at least one resin selected from a polyvinyl chloride resin, a polyurethane resin, an epoxy resin and a polycarbonate resin, and specific examples thereof include chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate Vinyl chloride copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-various vinyl ether copolymer Containing resins and chlorine-containing resins, such as acrylonitrile-styrene copolymers, acrylonitrile-styrene-butadiene terpolymer A blend with an ethylene-vinyl acetate copolymer, a polyester, etc., a block copolymer, a graft copolymer It can be applied to a resin selected from copolymers and the like.

The present invention is a polyvinyl chloride resin composition comprising the above plasticizer, and the production method thereof is not limited and can be produced by a method well known in the art. For example, a resin having a sufficiently high molecular weight through crosslinking or curing Can be added or added to the precursor in oligomer form to proceed the curing reaction.

The present invention is not limited to the epoxy resin composition containing the above plasticizer, and can be produced by a method well known in the art, and it is most preferable to add the plasticizer before the curing reaction by the curing agent occurs Do.

The present invention is a polycarbonate resin composition containing the above plasticizer, and the production method thereof is not limited, and can be produced by a method well known in the art. Preferably, the polycarbonate resin is prepared by using a polypropylene carbonate having a weight average molecular weight of 2,000 to 3,000,000 g / mol or a copolymer having a weight average molecular weight of 2,000 to 3,000,000 g / mol as a polycarbonate copolymerized with an alkylene oxide good. Specific examples of the alkylene oxide may include cyclohexene oxide, glycidyl ester, glycidyl ether, and butylene oxide. Or bisphenol A (Bis-phenol A) having a weight average molecular weight of 2,000 to 3,000,000 g / mol or polycarbonate derived from hydrogenated bisphenol A, or a copolymer thereof, as the polycarbonate.

The present invention is a polyurethane resin composition containing the above plasticizer, and its production method is not limited, and can be produced by a method known in the art.

As described above, the resin composition according to the present invention has excellent physical properties as compared with the resin composition to which the conventional plasticizer is added. In particular, in the physical properties of hardness, tensile strength, elongation, elastic modulus, bleeding and glass transition temperature, the resin composition of the present invention has a hardness of 30 to 90 A (Shore A), a tensile strength of 100 to 230 Kgf / Strength, an elongation of 200 to 500%, an elongation of 30 to 90 Kgf / cm < 2 >, and a glass transition temperature (Tg) lower than that of a resin composition containing a conventional plasticizer, and no bleeding occurred at all. As described above, the resin composition containing the plasticizer of the present invention exhibits excellent physical properties due to its excellent plasticizing efficiency, and thus it is possible to produce a product having superior physical properties in a conventional resin composition or a product using the resin composition in various fields .

The present invention relates to a resin composition comprising the plasticizer and the plasticizer. The plasticizer is excellent in tensile strength, low in glass transition temperature, and excellent in molding into a film, It has the advantage of being able to be processed into the same flexible product. The plasticizer of the present invention is excellent in compatibility with the four resins and low in extractability by an organic solvent or water, thereby extending the service life of films, sheets and the like using the resin composition.

In addition, the resin composition of the present invention comprising, as a plasticizer, at least one compound selected from glyceryl carbonate and derivatives thereof, such as glyceryl carbonate ester or glyceryl carbonate ether,

Building materials such as wall cladding, flooring, window frames, and wallpaper;

Wire covering material;

Automotive interior and exterior materials;

Agricultural materials such as houses and tunnels;

Packaging materials for foods such as fish, such as wraps and trays;

Film forming agents such as underbody sealants, plastisols, paints and inks;

Articles of synthetic leather, coated fabrics, hoses, pipes, sheets, infant toys, gloves and the like; And the like, but this is merely one example, and is not limited thereto.

The present invention relates to a process for producing 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms selected from a polyvinyl chloride resin, a polyurethane resin, an epoxy resin and a polycarbonate using at least one compound selected from glyceryl carbonate and glyceryl carbonate carbonate When a resin composition of the above kind or more is produced, an excellent product in terms of plasticization efficiency can be obtained, and the physical properties such as tensile strength and transparency at the time of production of a transparent film can be improved.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are illustrative of the present invention but are not limited thereto.

[ Manufacturing example  One] Glyceryl Carbonate  Preparation of plasticizers

In a first step, 1 mol of glycerol and 2 mol of diethyl carbonate were added to a 2 L round flask equipped with a stirrer and a condenser, 3 mol% of sodium methoxide was added as a catalyst to glycerol, The reaction was carried out for a period of time.

After the reaction, unreacted dimethyl carbonate was decompressed to 90 ° C at a pressure of 5 mmHg by a vacuum pump, removed with an adsorbent, and filtered to obtain a final glyceryl carbonate.

[ Example  1] Preparation of Resin Composition

To evaluate the performance of the glycerol carbonate plasticizer of Preparation Example 1, a polyvinyl chloride resin composition was prepared by mixing 100 parts by weight of a polyvinyl chloride resin (LG Chem, product name LS-100) , 1 phr of KFDA LFX-1100 as a stabilizer, and preheated at 185 ° C for 1 min, pressurized for 1.5 min and cooled for 2 min to prepare 2 mm sheets, and various dumbbell specimens . The polyurethane resin composition was prepared by mixing a polyol having a molecular weight of 3000 g / mol and 4,4'-dihexyl methane diisocyanate (H12MDI) in an equivalent ratio of 3: 1, adjusting the plasticizer to 10% The mixture was mixed well, coated on release paper, and cured at 150 DEG C for 1 minute to obtain a sheet. The epoxy sheet was prepared by mixing 30 parts by weight (phr) of a 4,4-diaminodiphenylmethane (DDM) in Epxosy resin (Diglycidyl Ether Bisphenol A; DGEBA, YD-128) And then coated on release paper and cured at room temperature for 1 day. The polycarbonate sheet was prepared by mixing a polypropylene carbonate resin having a molecular weight of 300,000 g / mol and a plasticizer, mixing them using a 3-roll mill, and extruding them.

The above test was carried out with the plasticizer and the specimen, and the results are summarized in Table 1 below.

[ Manufacturing example  2] Glyceryl Carbonate  Octanoate [ Glyceryl carbonate  Octanoate] Preparation of Plasticizer

An acylation reaction was carried out by using sodium carbonate as a base catalyst in an amount of 10 mol% based on glyceryl carbonate so that the equivalent ratio of glyceryl carbonate and octanoyl chloride prepared in Preparation Example 1 was 2: do. Unreacted glyceryl carbonate is extracted with water and ether.

[ Example  2] Preparation of Resin Composition

Each resin composition was prepared in the same manner as in Example 1 except that glyceryl carbonate octanoate of Preparation Example 2 was used instead of glyceryl carbonate as a plasticizer. The results of the experiment are shown in Table 1 below.

[ Manufacturing example  3] Glyceryl Carbonate  Laureate [ Glyceryl carbonate  laurylate] Preparation of plasticizer

The acylation reaction was carried out using the base catalyst sodium carbonate in an amount of 10 mol% based on glyceryl carbonate so that the equivalent ratio of the glyceryl carbonate and lauroyl chloride prepared in Example 1 was 2: 1. Unreacted glyceryl carbonate is extracted with water and ether.

[ Example  3] Production of Resin Composition

Each resin composition was prepared in the same manner as in Example 1 except that glyceryl carbonate laurelate of Preparation Example 3 was used instead of glyceryl carbonate as a plasticizer. The results of the experiment are shown in Table 1 below.

[ Manufacturing example  4] Glyceryl Carbonate Octyl  ether[ Glyceryl carbonate octyl  ether]

The glyceryl carbonate and octyl bromide prepared in Example 1 were used in an equivalent ratio of 2: 1, and the sodium hydroxide was etherified using the same amount of sodium hydride as the glyceryl carbonate. Unreacted glyceryl carbonate is extracted with water and ether.

[ Example  4] Production of Resin Composition

The resin compositions were prepared in the same manner as in Example 1 except that the glyceryl carbonate oligomer of Preparation Example 4 was used instead of glyceryl carbonate as a plasticizer. The results of the experiment are shown in Table 1 below.

[ Manufacturing example  5] Glyceryl Carbonate Lauryl  ether[ Glyceryl carbonate  lauryl ether ]

The glyceryl carbonate and lauryl bromide prepared in Example 1 were mixed in an equivalent ratio of 2: 1, and sodium hydroxide was etherified using the same amount of sodium hydride as that of glyceryl carbonate . Unreacted glyceryl carbonate is extracted with water and ether.

[ Example  5] Production of Resin Composition

Resin compositions were prepared in the same manner as in Example 1 except that glyceryl carbonate lauryl ether of Preparation Example 5 was used instead of glyceryl carbonate as a plasticizer. The results of the tests are shown in Table 1 below.

[Comparative Example 1]

Specimens were prepared in the same manner as in Example 1 using the most widely used di-2-ethylhexyl phthalate as a plasticizer. The test specimens were tested in the same manner as in Example 1, and the results are summarized in Table 1 below.

[Comparative Example 2]

Specimens were prepared in the same manner as in Example 1 except that no plasticizer was added. The test specimens were tested in the same manner as in Example 1, and the results are summarized in Table 1 below. However, PVC is excluded because it is not processed without plasticizer.

[Table 1]

From the results shown in Table 1, Examples 1 to 5, which are plasticizers of the present invention, are superior in plasticization efficiency as compared with Comparative Example 1, which is the most common plasticizer, and have excellent physical properties such as tensile strength and glass transition temperature Is also excellent. From the results of the comparative example, it can be seen that bleeding does not occur compared with the conventional general plasticizer. Therefore, the novel plasticizer of the present invention is excellent in the plasticizing efficiency and is more suitable for various molding according to various uses and can be used for various purposes.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, The present invention may be modified in various ways. Therefore, the present invention is not limited to the above embodiments.

Claims (9)

A plasticizer composition for molding represented by the following formula (1). [Chemical Formula 1]

(Wherein R is selected from a linear or branched (C6-C18) alkyl group, a (C6-C18) alkylcyclohexyl group and a (C6-C18) alkylbenzoyl group substituted carbonyl group. The method according to claim 1, Wherein the resin is at least one resin selected from a polyvinyl chloride resin, a polyurethane resin, a polycarbonate resin and an epoxy resin. At least one resin selected from a polyvinyl chloride resin, a polyurethane resin, a polycarbonate resin and an epoxy resin, and at least one plasticizer represented by the following formula (1). [Chemical Formula 1]

(Wherein R is selected from a linear or branched (C6-C18) alkyl group, a (C6-C18) alkylcyclohexyl group and a (C6-C18) alkylbenzoyl group substituted carbonyl group. The method of claim 3, Wherein the resin composition comprises 5 to 150 parts by weight of at least one plasticizer represented by the formula (1) based on 100 parts by weight of the resin. The method of claim 3, Wherein the epoxy resin is added with a plasticizer before the curing reaction by the curing agent. The method of claim 3, Wherein the polycarbonate is a polypropylene carbonate having a weight average molecular weight of 2,000 to 3,000,000 g / mol. The method of claim 3, Wherein the polycarbonate is a copolymer having a weight average molecular weight of 2,000 to 3,000,000 g / mol copolymerized with an alkylene oxide. 8. The method of claim 7, Wherein the alkylene oxide is selected from cyclohexene oxide, glycidyl ester, glycidyl ether, and butylene oxide. The method of claim 3, Wherein the polycarbonate is a polycarbonate derived from bisphenol A or hydrogenated bisphenol A having a weight average molecular weight of 2,000 to 3,000,000 g / mol, or a copolymer thereof.