KR101921553B1 - Eco-Friendly Polyurethane Resine Diluent And Washer Detergent - Google Patents

Abstract

The present invention relates to a diluent and a detergent for a polyurethane resin, comprising 10 to 30% by weight of 1,3-dioxolane; 5 to 30% by weight of 2-pyrrolidone; And 40 to 70% by weight of propylene glycol monomethyl ether acetic acid or glyme, and a cleaning agent for the polyurethane resin.

Description

[0001] The present invention relates to an eco-friendly polyurethane resin diluent and a detergent,

The present invention relates to environmentally friendly polyurethane diluents and cleaners, and more particularly to diluents and cleaners in which 1,3-dioxolane, 2-pyrrolidone, and propylene glycol monomethyl ether acetic acid or glyme are mixed .

Today, coatings using urethane resin are applied to various fields such as artificial leather, fabric, film, and plastic, and are applied to various coating methods such as screen printing, gravure, coma, and spray depending on the application.

Among them, the ink used for screen printing generally includes a resin which forms an ink film, a pigment, an organic solvent which can use the resin, a drying retarder for controlling the drying speed of the ink, a diluent for controlling the viscosity of the ink, It is composed of an auxiliary additive which improves printing workability and gives various functionalities. Natural resins, thermoplastic resins, thermosetting resins and the like are used as the resins for forming the coating of ink. The inks using the thermosetting resins are excellent in screen printability for preventing bleeding and bleeding during screen printing, Is known to be superior. As a typical thermosetting resin used as a film-forming component of the screen printing ink, there is a urethane resin. At this time, as a drying retarder, mainly ditoku oil or isophorone is used, and as a diluent, cyclohexanone, acetone, methyl ethyl ketone and the like are used.

However, Dongrock oil is a substance harmful to human body, such as causing strong odor and causing headache, vomiting, unconsciousness during inhalation, so care should be taken for handling. In addition, when a cloth is screen printed using an ink containing a dung oil, even if there is a trace amount of the dung oil on the fabric, a strong odor may give an uncomfortable feeling to the consumer. In addition, isophorone is a substance having a long odor and flammability, and since it has a high viscosity of itself, the viscosity of the ink is increased, so that a relatively large amount of diluent is required.

Accordingly, a diluent and a cleaning agent are indispensable for the use of the coating agent regardless of the coating method and the application field, and a strong solvent such as ananine, methyl ethyl ketone (MEK), or toluene has been used due to the characteristics of the urethane resin.

These solvents are regulated by the Industrial Safety and Health Act or the Chemical Substance Control Act specified in the Material Safety Data Sheet. Workers using the substance must regularly receive a special medical checkup and periodic measurements of the working environment. This is harmful to the worker, and the product made through it may also have harmful effects on the health of consumers using the product if the solvent is left in it.

Cyclohexanone, acetone, and methyl ethyl ketone (MEK), which are commonly used diluents, have a boiling point of less than 160 ° C., and thus merely control the viscosity of the ink. Rather, There is a problem that clogging of the screen plate is caused. In the case of clogging of the screen plate, the printing pattern becomes poor and a screen plate washing process is required to solve the problem.

It is an object of the present invention to provide a harmless substance to a human body as a diluent to be added for controlling the concentration of a coating agent using a polyurethane resin.

It is another object of the present invention to provide a thinner for adjusting the concentration of a coating agent using a polyurethane resin, and has a low odor intensity and low VOCs.

The object of the present invention is also to provide a cleaning agent for removing impurities after the operation.

In order to solve the above problems, the present invention provides a diluent and a detergent for a polyurethane resin, which comprises 10 to 30% by weight of 1,3-dioxolane; 5 to 30% by weight of 2-pyrrolidone; And 40 to 70% by weight of propylene glycol monomethyl ether acetic acid or glyme, and a detergent for the polyurethane resin.

The present invention also relates to a process for producing 2-pyrrolidone as described above, wherein the 2-pyrrolidone is N-methyl-2-pyrrolidinone (NMP, 2-pyrrolidinone). The present invention also provides a diluent and a cleaning agent for a polyurethane resin.

In another aspect, the present invention the articles reamer (glyme) is _{Monoglyme (CH 3 -O-CH 2} CH 2 -O-CH 3) (Ethylene glycol dimethyl ether), Ethyl glyme (CH 3 CH 2 -O-CH 2 CH 2 - _{O-CH 2 CH 3) (} Ethylene glycol diethyl ether), Diglyme (CH 3 -O- (CH 2 CH 2 -O) 2 -CH 3) (Diethylene glycol dimethyl ether), Proglyme (CH 3 -O- (CH _{2 CHCH 3 -O) 2 -CH 3} ) (Dipropylene glycol dimethyl ether), Ethyl diglyme (CH 3 CH 2 -O- (CH 2 CH 2 -O) 2 -CH 2 CH 3) (Diethylene glycol diethyl ether), _{Triglyme (CH 3 -O- (CH 2} CH 2 -O) 3 -CH 3) (Triethylene glycol dimethyl ether), Butyl diglyme (CH 3 CH 2 CH 2 CH 2 -O- (CH 2 CH 2 -O) 2 _{-CH 2 CH 2 CH 2 CH 3} ) (Diethylene glycol dibutyl ether), Tetraglyme (CH 3 -O- (CH 2 CH 2 -O) 4 -CH 3) (Tetraethylene glycol dimethyl ether), Polyglyme (CH 3 -O - (CH ₂ CH ₂ -O) n-CH ₃ ) (Poly (ethylene glycol) dimethyl ether).

The present invention also provides a diluent and a detergent for a polyurethane resin characterized in that 5 to 20% by weight of methyl sulfoxide can be added to the diluent and the cleansing agent of the polyurethane resin.

The present invention also provides a diluent and a detergent for a polyurethane resin characterized by being capable of adding 5 to 20% by weight of an organic acid to the diluent and the cleansing agent of the polyurethane resin.

The present invention also relates to the use of the organic acid as the organic acid in the present invention, wherein the organic acid is at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, 2-methylbutyric acid, 2,2-dimethylbutyric acid, But are not limited to, lactic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, methyl succinic acid, 2,2-dimethyl succinic acid, glutaric acid, adipic acid, pimelic acid, Is at least any one of adipic acid, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, lactic acid, gluconic acid, tartaric acid, malic acid, glycolic acid, citric acid, The present invention provides a diluent and a cleaning agent for a polyurethane resin having a characteristic.

The present invention is a diluent which is added to control the concentration of a coating agent using a polyurethane resin, and is harmless to the human body.

Further, the present invention is characterized by a low odor intensity and low VOCs when it is used as a diluent for adjusting the concentration of a coating agent using a polyurethane resin.

The present invention is also characterized in that it can be used as a cleaning agent for removing impurities after the operation.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted so as to avoid obscuring the subject matter of the present invention.

As used herein, the terms " about, " " substantially, " " etc. ", when used to refer to a manufacturing or material tolerance inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The present invention relates to a diluent and a detergent for a polyurethane resin, comprising 10 to 30% by weight of 1,3-dioxolane; 5 to 30% by weight of 2-pyrrolidone; And 40 to 70% by weight of propylene glycol monomethyl ether acetic acid or glyme.

First, polyurethane resins are used as raw materials for various coating materials and are used in various fields such as artificial leather, fabric, film, and plastic. Depending on the application, it can be used in various coating methods such as screen printing, gravure, coma, and spray, and forms a coating on the surface of the coating to uniformly fix the pigment.

The film-forming component is an important factor for determining the ink performance, and ink workability, gloss, adhesiveness, hardness, plasticity, water resistance, oil resistance, chemical resistance and weather resistance depend on the film forming component.

 More specifically, the polyurethane resin generally refers to a polymer compound having a main chain bonded with a urethane bond by reaction of a polyisocyanate and a compound containing a hydroxyl group (for example, a polyol).

Further, the polyurethane may further include a chain extender or a crosslinking agent as a monomer. Examples of the polyisocyanate compound which is one of the main monomers constituting the polyurethane include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3 Trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, Diisocyanate, diphenylmethane-4,4'-diisocyanate, (o, m or p) -xylene diisocyanate, diisobutylene diisocyanate, , Methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methyleneditholylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene Diisocyanate, norbornane diisocyanate, hydrogenated (1,3- or 1,4-) xylylene diisocyanate, etc. These may be used singly or in combination of two or more kinds . The polyol compound, which is one of the main monomers constituting the polyurethane, includes low molecular weight diols (e.g., ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4- Polyether diol, both terminal hydroxylated polybutadiene, polyester diol, dimer diol, tricyclodecanedimethanol, cyclohexanedimethanol, cyclohexanedimethanol, cyclohexanedimethanol, cyclohexanedimethanol, polycarbonate diol, Linear aliphatic diols, trimethylol ethane, trimethylol propane, glycerin, pentaerythritol, etc. These may be used alone or in combination of two or more. The present invention also includes modified polyurethanes in which the polyurethane resin is imparted with various functions by polysiloxane, silane, halogen, acryl, or the like.

Next, the composition of the diluent and the cleaning agent of the polyurethane resin of the present invention will be described in detail.

First, 1,3-dioxolane is used as a strong aprotic solvent and is one of the strongest solvents among the aprotic solvents used in diluents. The feature of 1,3-dioxolane is the ability to rapidly dissolve polar polymers such as polyesters, epoxides and urethanes.

1,3-Dioxolane has a pentagonal ring structure, which is smaller in volume than the chain structure, and thus has excellent polymer permeability to be diluted. The low boiling point has a relatively low drying temperature of 78 캜.

Also, 1,3-dioxolane is a colorless transparent liquid, and can be used as a polyacetal, a comonomer in the production of a polymer, a solvent in a chemical reaction, a stabilizer in a halogenated organic solvent, and a starting material or reagent in organic synthesis. It is toxic in the ingestion, inhalation, skin and intraperitoneal routes and is highly irritating to the skin and eyes. Exposure to heat or flame creates a fire hazard. Experimental results showed that toxicity was relatively low and inhibited the central nervous system. If exposed to snow, immediately wash with water. If ingested, do not induce vomiting. Rinse mouth with water, then dilute with water and administer activated carbon.

Next, 2-pyrrolidinone has a boiling point of 245 ° C and is a colorless-pale yellow liquid with a slight odor of amine. This product is a high aprotic polar solvent which is mixed with organic solvent such as synthetic resin, pesticide, polyhydric alcohol, printing ink and paint, iodine as well as water. (NMP, 1-methyl-2-pyrrolidinone), N-ethyl-2-pyrrolidinone (NEP, 1-ethyl- 2-pyrrolidinone), and the higher the molecular weight of the substituted alkyl group, the higher the boiling point of the pyrrolidone. The N-methyl-2-pyrrolidinone (NMP, 1-methyl-2-pyrrolidinone) Pyrrolidinone) is 212 < 0 > C.

Propylene Glycol Monomethyl Ether Acetate is an excellent industrial solvent with a boiling point of 146 ° C and low toxicity. It is also used as a solvent for printing ink as well as amino, methyl ester, ethyl ester, polyester, cellulose acetate, glycolic acid It has a high solubility for other polymers including resins, and is also suitable for a chryly acidic resin, an epoxy resin, nitrocellulose, an unsaturated polyester, a polyurethane, a klyric acid resin and an epoxy resin.

Next, the glyme (C _n H _{2n + 2} O _{n / 2} ) of BASF's product is used as aprotic polar solvent as a kind of glycol diethers and has a strong dissolving ability Stability can be maintained especially in acidic solutions. Most of the glimmer is also soluble in water, so it can be used in water-soluble polyurethane resin, and it has various melting range and boiling point depending on the kind of the glimmer. It has a mild odor compared to the usual ester alcohol in odor. Types _{include, Monoglyme (CH 3 -O-CH} 2 CH 2 -O-CH 3) (Ethylene glycol dimethyl ether) is _{84 ℃, Ethyl glyme (CH 3} CH 2 -O-CH 2 CH 2 -O-CH 2 _{CH 3) (Ethylene glycol diethyl ether} ) is _{121 ℃, Diglyme (CH 3 -O-} (CH 2 CH 2 -O) 2 -CH 3) (Diethylene glycol dimethyl ether) is 160 ℃, Proglyme (CH ₃ -O- (CH ₂ CHCH ₃ -O) ₂ -CH ₃ ) (Dipropylene glycol dimethyl ether) was heated at 175 ° C in Ethyl diglyme (CH ₃ CH ₂ -O- (CH ₂ CH ₂ -O) ₂ -CH ₂ CH ₃ ) glycol diethyl ether at 189 ° C and Triglyme (CH ₃ -O- (CH ₂ CH ₂ -O) ₃ -CH ₃ ) (Triethylene glycol dimethyl ether) at 216 ° C, Butyl diglyme (CH ₃ CH ₂ CH ₂ CH ₂ - _{O- (CH 2 CH 2 -O)} 2 -CH 2 CH 2 CH 2 CH 3) (Diethylene glycol dibutyl ether) is _{251 ℃, Tetraglyme (CH 3 -O-} (CH 2 CH 2 -O) 4 -CH 3 (Tetraethylene glycol dimethyl ether) at 277 ° C and Polyglyme (CH ₃ -O- (CH ₂ CH ₂ -O) n-CH ₃ ) (Poly (ethylene glycol) dimethyl ether) at 275 ° C.

Next, dimethylsulfoxide (DMSO) is a highly polar, colorless and transparent hygroscopic solvent. It has strong solubility for various organic and inorganic compounds, and is permeable to cell tissues and specific for reaction solvents. It has a boiling point of 189 ° C and easily mixes with water and has neutral properties. It is also soluble in acetone, ethanol, ether, benzene, and chloroform. The spinning solution of various fibers. Various solvents, organic synthesis raw materials, gas adsorbents. It is used as a stripping agent.

When the diluting agent is a mixed organic solvent having various boiling points as described above, the diluting agent may have various boiling points depending on the characteristics of the azeotrope, that is, depending on the content of the composition. Also, when the boiling point is controlled, The natural drying properties can also be controlled.

Second, organic acids have a fresh citrus-like aroma that can neutralize the unpleasant odors of other organic solvents in the diluent. It can also help the glimmer to maintain stability in acidic solutions. Specific examples of the organic acid itself include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, 2-methylbutyric acid, 2,2- , Ethylmalonic acid, dimethylmalonic acid, succinic acid, methyl succinic acid, 2,2-dimethyl succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, lactic acid, gluconic acid, tartaric acid, malic acid, glycolic acid, citric acid and benzoic acid.

Hereinafter, the present invention will be described in more detail with reference to examples. It is to be understood, however, that these examples are provided so as to understand the scope of the present invention, and are not to be construed as limiting the scope of the present invention.

Example  One

20% by weight of 1,3-dioxolane, 20% by weight of 1-ethyl-2-pyrrolidone and 60% by weight of propylene glycol monomethyl ether acetic acid are mixed to prepare a diluting solvent.

Example  2

20% by weight of 1,3-dioxolane, 20% by weight of 1-ethyl-2-pyrrolidone, 40% by weight of propylene glycol monomethyl ether acetic acid and 20% by weight of methyl sulfoxide are mixed to prepare a diluting solvent.

Example  3

20% by weight of 1,3-dioxolane, 20% by weight of 1-ethyl-2-pyrrolidone, 40% by weight of Progllyme and 20% by weight of methyl sulfoxide are mixed to prepare a diluting solvent.

Example  4

20% by weight of 1,3-dioxolane, 20% by weight of 1-ethyl-2-pyrrolidone, 40% by weight of propylene glycol monomethyl ether acetic acid, 10% by weight of methyl sulfoxide and 10% by weight of glutaric acid Make a solvent.

Comparative Example  One

The use of Annon (cyclohexanone) as a solvent and cleaning agent.

Comparative Example  2

Methyl ethyl ketone is used as a diluting solvent and a cleansing agent.

※ Odor judgment

With the solvents of Examples 1 to 4 and Comparative Examples 1 and 2, 20 wt% of a diluting solvent was added to the screen printing ink, and printing was performed to a thickness of 20 microns. The screen printing ink is composed of 10% by weight of methyl ethyl ketone, 10% by weight of anionine, 10% by weight of dimethylformamide, 20% by weight of propylene glycol monomethyl ether acetate, 25% by weight of pigment and 25% by weight of polyurethane resin . After printing and left at room temperature for 6 hours, specimens were collected and evaluated for odor.

In the odor evaluation method, the collected specimens are cut into a size of 10 cm * 10 cm, placed in a 4 L container, and then subjected to an oven treatment at 80 ° C. for 2 hours. The container is conditioned for 1 hour at room temperature, and then the lid is opened to measure the odor. The odor classification is divided into 1 ~ 6 grades. The evaluation criteria are as follows.

Rating Strength of odor division One No smell Odorless 2 I do not know what the smell is, but I feel the smell Odor detection 3 The smell is weakly wound and you can see what smell it is. Normal smell 4 Easily detectable strong odor A strong smell 5 A very strong smell An extreme odor 6 Strong odor that makes you feel difficulty breathing Unpleasant smell

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Odor rating 3 3 3 2 4 4

※ Evaluation of VOCs

The printing is completed and left at 80 DEG C for 6 hours. Make specimens with the same size as the odor evaluation 10 * 10 cm ² . Place the specimen in a plastic bag ^{(50 * 50 * 100cm 3)} . Insert the VOC tester into the entrance of the plastic bag. Check the detection amount of the VOC tester for 10 seconds.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 VOC (ppm) 80 67 31 25 107 180

As can be seen from Tables 1 and 2, Examples 1 to 4 show grades of 2,3 and lower than normal odor, and in Example 4 in which glutaric acid, an organic acid, is added, do. Also in the evaluation of VOCs, the example has a lower value than the comparative example.

On the other hand, the comparative organic solvents, such as the organic solvent, are classified as grade 4, which is easily perceivable.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be clear to those who are.

Claims (6)

In the diluent of the polyurethane resin,
10 to 30% by weight of 1,3-dioxolane; 5 to 30% by weight of 2-pyrrolidone; And 40 to 70% by weight of propylene glycol monomethyl ether acetic acid.
The method according to claim 1,
The 2-pyrrolidone is preferably selected from N-methyl-2-pyrrolidinone (NMP, 1-methyl-2-pyrrolidinone) Dinon) is a thinner of polyurethane resin.
delete The method according to claim 1,
Characterized in that 5 to 20% by weight of methyl sulfoxide is added to the diluent of the polyurethane resin.
The method according to claim 1 or 4,
Characterized in that 5 to 20% by weight of an organic acid is added to the diluent of the polyurethane resin.
6. The method of claim 5,
The organic acid may be selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, 2-methylbutyric acid, 2,2-dimethylbutyric acid, 2-dimethyl succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, gallic acid, 3-methyladipic acid, 1 Characterized by being at least one of 2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, lactic acid, gluconic acid, tartaric acid, malic acid, glycolic acid, citric acid and benzoic acid. Urethane resin diluent.