JP2008214365A - Solvent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a solvent composition that does not substantially contain an aromatic hydrocarbon, comprises a naphthene-based solvent having a high safety to the human body as a main component, has an excellent solubility and is preferably useful as a solvent for a coating material, an adhesive, a printing ink, a mold release agent, etc. <P>SOLUTION: The solvent composition comprises 50-90 vol.% of a cyclic aliphatic hydrocarbon and 10-50 vol.% of a polar solvent and has <10 vol.% chain aliphatic hydrocarbon content and <0.1 vol.% aromatic hydrocarbon content and a mixed aniline point of 30-50°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a solvent composition substantially free of aromatic hydrocarbons. Specifically, the present invention has the same solubility as an aromatic solvent even if it does not substantially contain an aromatic hydrocarbon, and is used as a solvent for paints, adhesives, printing inks, release agents, and the like. It is related with the solvent composition which can be used conveniently.

  Petroleum hydrocarbon solvents are mainly used as solvents used in paints, printing inks, adhesives, pressure-sensitive adhesives, cleaning agents, and the like. In general, the dissolving power of the hydrocarbon solvent decreases in the order of aromatic hydrocarbon, cycloaliphatic hydrocarbon, and chain aliphatic hydrocarbon. Aromatic hydrocarbon solvents such as toluene and xylene have been used in a wide range of fields because they have particularly excellent dissolving power. However, a solvent containing a large amount of aromatic content may leave an odor, significantly contaminate the work environment, and may adversely affect the health of workers. Of the aromatic components, benzene, toluene, and xylene are particularly concerned about the effects on the human body. Therefore, the Ministry of Labor's regulations on prevention of specific chemical substances, etc., prevent benzene from exceeding 1% by volume. Under the poisoning prevention regulations, those with a total amount of toluene and xylene exceeding 5% by weight are obliged to restrict use and indicate the presence of compounds. In addition, the amount used and discharged is managed by each local ordinance, and the reduction of the amount discharged to the environment is promoted.

  In addition, for naphthalene, which is a bicyclic aromatic hydrocarbon, according to the International Agency for Research on Cancer (IARC), the carcinogenicity rank may be classified as 2B carcinogenicity, and there are more restrictions on human risk. It became strict.

Thus, especially regarding the use of aromatic hydrocarbon solvents, organic solvent emission regulations have been strengthened from the viewpoint of safety.
Under such circumstances, in the field of hydrocarbon cleaners used in the fields of electric / electronic parts, automobile parts, precision equipment parts, etc., it is more safe from the aromatic solvents that have been conventionally used in general. It is being converted to non-aromatic solvents such as naphthenic solvents and paraffinic solvents, which are high cycloaliphatic hydrocarbons. Development of water-based and powder-type paints that do not use organic resins and resins for paints that are soluble in non-aromatic solvents is also progressing. Under such circumstances, naphthenic solvents such as alkylcyclohexane solvents (Patent Documents 1 and 2), paint solvents not containing aromatic hydrocarbons mainly composed of mineral spirits (Patent Document 3), aliphatic carbonization A paint made of hydrogen and a glycol derivative (Patent Document 4) has been proposed.

However, there are many technical problems in terms of coating film performance, drying properties, and work efficiency, and in particular, there is a drawback that the solubility is not sufficient.
JP 2003-313562 A JP 2006-96786 A JP 2003-55605 A JP 2006-22149 A

The present invention solves such problems, and is a solvent that does not substantially contain aromatic hydrocarbons such as benzene, toluene, xylene, and naphthalene, and has a high safety for human bodies. The main object is to provide a solvent composition that has excellent solubility and can be suitably used as a solvent for paints, adhesives, printing inks, release agents and the like.

  As a result of diligent research, the present inventor has found that a solvent composition containing a cycloaliphatic hydrocarbon having a specific property and a polar solvent does not substantially contain an aromatic hydrocarbon. The present inventors have found that the solubility is excellent and have completed the present invention.

  That is, the solvent composition of the present invention is a solvent composition containing 50 to 90% by volume of a cyclic aliphatic hydrocarbon and 10 to 50% by volume of a polar solvent, and the chain aliphatic hydrocarbon content is less than 10% by volume. The aromatic hydrocarbon content is less than 0.1% by volume, and the mixed aniline point is 30 to 50 ° C.

In such a solvent composition of the present invention, the cycloaliphatic hydrocarbon preferably has a boiling point of 100 to 255 ° C and an aniline point of 55 ° C or lower.
In the solvent composition of the present invention, the polar solvent is preferably one or more selected from the group consisting of esters, ketones and alcohols, and preferably has a Kauributanol value of 70 to 270.

  The solvent composition of the present invention is preferably a solvent for paints, adhesives, pressure-sensitive adhesives, inks or release agents.

  According to the present invention, the main component is a naphthenic solvent that is substantially free of aromatic hydrocarbons such as benzene, toluene, xylene, and naphthalene, and is highly safe to the human body, and has excellent solubility and drying properties. It is possible to provide a solvent composition that can be widely used in various fields such as paint applications, adhesives, pressure-sensitive adhesives, inks and cleaning agents.

Hereinafter, the present invention will be specifically described.
The solvent composition of the present invention contains a cyclic aliphatic hydrocarbon (naphthene hydrocarbon) and a polar solvent.

Cycloaliphatic hydrocarbon The cycloaliphatic hydrocarbon according to the present invention preferably has a boiling point of 100 to 255 ° C, more preferably 110 to 240 ° C. When the boiling point of the cycloaliphatic hydrocarbon is less than 100 ° C., the volatility is high, the flash point becomes low, and the risk of ignition increases. When the temperature exceeds 255 ° C., the viscosity may be increased or the evaporation rate may be slow.

Further, the aniline point (AP) of the cyclic aliphatic hydrocarbon is 55 ° C. or lower, preferably 52 ° C. or lower. Here, the aniline point is a measure of solubility, and is JIS K22.
65. When the aniline point of the cycloaliphatic hydrocarbon is too high, the solubility is lowered, and the mixing effect when mixed with a polar solvent is reduced. In order to maintain the solubility of the solvent composition containing a cyclic aliphatic hydrocarbon having a high aniline point, it is necessary to increase the content of the polar solvent, but this is not preferable in terms of increase in viscosity and production cost.

  In the present invention, the cycloaliphatic hydrocarbon is an aliphatic hydrocarbon in which a plurality of rings such as a single ring, a 2-membered ring, or a 3-membered ring are formed, and may have a substituted hydrocarbon group. These may be a single compound or a mixture of two or more.

  In the present invention, although not particularly limited, for example, a hydrogenated oil mainly composed of cyclic aliphatic hydrocarbons obtained by hydrogenating a petroleum fraction containing aromatic hydrocarbons, A solvent composition containing a cyclic aliphatic hydrocarbon derived therefrom can be prepared as it is or by using a fraction obtained by fractional distillation.

Specifically, the cycloaliphatic hydrocarbon used in the present invention is a petroleum distillate having a boiling point range of 110 to 280 ° C. containing aromatic hydrocarbon of 7 to 14 carbon atoms in an amount of 90% by volume or more, preferably 95% by volume. It can be obtained by performing nuclear hydrogenation (nuclear hydrogenation) of aromatic hydrocarbons by the method disclosed in Japanese Patent Application Laid-Open No. 2006-96786 using the components as raw materials. This raw oil fraction can be easily obtained by cutting the reformed fraction obtained by the naphtha catalytic reforming reaction within the above boiling range by precision distillation. The reaction conditions for nuclear hydrogenation (nuclear hydrogenation) of aromatic components include commonly used nuclear hydrogenation catalysts such as nickel, nickel oxide, nickel / diatomaceous earth, Raney nickel, nickel / copper, and platinum. In the presence of platinum oxide, platinum / activated carbon, platinum / rhodium, platinum / alumina, etc., the temperature is 100 to 300 ° C.
The hydrogen pressure may be appropriately selected from 1 to 10 MPa.

  The hydrogenated oil obtained from the nuclear hydrogenation reaction is a cyclic aliphatic hydrocarbon having 7 to 14 carbon atoms, specifically, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, diethylcyclohexane, methylpropylcyclohexane, methyl The main component is alkylcyclohexane such as isopropylcyclohexane and hexamethylcyclohexane, and alkyldecalin such as decalin, methyldecalin, dimethyldecalin, ethyldecalin and tetramethyldecalin. The cyclic aliphatic hydrocarbon obtained from the nuclear hydrogenation reaction may be used by fractional distillation to limit the boiling range, or may be used as a single compound by precision distillation.

  As cycloaliphatic hydrocarbons, for example, methylcyclohexane (MCH), a naphthenic solvent that is commercially available as an alternative to aromatic hydrocarbons of toluene and xylene, has insufficient solubility compared to toluene and xylene. Depending on the application, there is a drawback that the drying property is too fast. By combining a polar solvent with a naphthenic hydrocarbon having a boiling point range of 100 to 255 ° C., the solubility is improved and the drying property of toluene and xylene is improved. It can be equivalent and is particularly preferred as an alternative to toluene and xylene.

  In the solvent composition of the present invention, the cycloaliphatic hydrocarbon content is usually 50 to 90% by volume, preferably 60 to 90% by volume, more preferably 60 to 85% by volume, from the viewpoints of drying property and viscosity of the solvent. % Range.

Polar Solvent The polar solvent according to the present invention is not particularly limited as long as it is a solvent having a polar group, but one or more polar solvents selected from the group consisting of esters, ketones and alcohols are included. Preferably used.

As the polar solvent selected from the group of esters, ketones and alcohols, the following are preferable from the viewpoint of availability and price. Examples of the esters include ethyl acetate, n-butyl acetate, n-propyl acetate, n-amyl acetate, and 3-methyl-3-methoxybutylacetate. Among them, ethyl acetate and n-butyl acetate are preferably used. Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. Among them, methyl ethyl ketone and methyl isobutyl ketone are preferably used. Examples of alcohols include isopropyl alcohol, normal butanol, normal propyl alcohol, isobutanol, and 3-methyl-3-methoxybutanol. Of these, isopropyl alcohol and normal butanol can be preferably used. These polar solvents may be used alone or in combination of two or more.

  As the boiling point of the polar solvent used here, it is particularly preferable from the viewpoint of practical performance as a solvent to select a polar solvent close to the boiling point of the cyclic aliphatic hydrocarbon constituting the solvent composition. For this reason, although it does not specifically limit, The boiling point of a polar solvent becomes like this. Preferably it is the range of about 50-200 degreeC.

The polar solvent used in the present invention preferably has a Kauributanol number (KB), which is a measure of the dissolving power, in the range of 70 to 270. Even if a polar solvent having a Kauributanol value of less than 70 is used, the contribution to improving the solubility of the solvent composition is small. This Kauri-butanol value is measured by a method based on ASTM D1133. The solubility parameter (SP) is also known as another solubility index, but the polar solvent used in the present invention is preferably 8 to 13 (MPa) ^1/2 in SP.

  In the solvent composition of the present invention, the content of the polar solvent is 10 to 50% by volume, preferably 10 to 40% by volume, more preferably 15 to 40% by volume. If the amount is less than 10% by volume, the effect of enhancing the dissolving power due to the addition of the polar solvent cannot be exerted. If the amount exceeds 50% by weight, not only the viscosity of the solvent composition increases, but also the cost increases relatively. Is also not preferred.

Chain aliphatic hydrocarbon The solvent composition of the present invention may contain a chain aliphatic hydrocarbon together with a cyclic aliphatic hydrocarbon and a polar solvent. Examples of the chain aliphatic hydrocarbon that may be contained in the solvent composition of the present invention include those having a boiling point of about 100 to 255 ° C., preferably about 110 to 240 ° C., for the same reason as the cyclic aliphatic hydrocarbon. It is done.

  In the solvent composition of the present invention, the chain aliphatic hydrocarbon content is desirably less than 10% by volume, preferably less than 5% by volume, and particularly preferably less than 3% by volume from the viewpoint of dissolving power.

Solvent composition The solvent composition of the present invention comprises 50 to 90% by volume of cyclic aliphatic hydrocarbon, 10 to 50% by volume of polar solvent, the content of chain aliphatic hydrocarbon is less than 10% by volume, and aromatic carbonization. The hydrogen content is less than 0.1% by volume. In the solvent composition of the present invention, the aromatic hydrocarbon is preferably not contained from the viewpoint of safety to human bodies and various regulations, and the content is less than 0.1% by volume, particularly less than 0.05% by volume. . Here, the hydrocarbon composition (volume%) of the solvent composition or its preparation raw material can be determined by measuring in accordance with JIS K2536.

  The solvent composition of the present invention has a mixed aniline point (MAP) of 30 to 50 ° C, preferably 35 to 50 ° C. If the mixed aniline point of the solvent composition exceeds 50 ° C., it is not preferable because the dissolving power for paints and inks is insufficient. On the other hand, when the temperature is lower than 30 ° C., the content of the polar solvent increases, so that not only the viscosity of the solvent composition increases, but also the cost increases relatively, which is not preferable from the economical viewpoint. Here, the mixed aniline point is a measure of solubility and is measured according to JIS K2265.

  The solvent composition of the present invention has higher solubility than conventional naphthenic solvents, and can be used widely in solvents for paints, solvents such as inks, adhesives, and cleaning agents for metal parts and precision equipment. In particular, it can be suitably used as a solvent for paints, adhesives, pressure-sensitive adhesives, inks or release agents.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

Each component used in the following examples and comparative examples is as follows.
・ Aliphatic hydrocarbon solvents A and B
Aliphatic hydrocarbon solvents A and B were prepared as follows.

  A petroleum fraction (boiling point 111 to 161 ° C.) containing 98% by volume of aromatic hydrocarbon having 7 to 10 carbon atoms was reacted at a hydrogen pressure of 2 MPa and 240 ° C. under a nickel catalyst to obtain a reaction product. As a result of measuring the hydrocarbon composition in the reaction product in accordance with JIS K2536, 99.0 vol% cyclic aliphatic hydrocarbon, 0.95 vol% chain aliphatic hydrocarbon, 0.05 vol aromatic hydrocarbon %Met. This was fractionated by distillation, and the aliphatic hydrocarbon solvent A (carbon number 7-9, aniline point 48 ° C., boiling point 109-136 ° C.) was determined from the light component, and aliphatic hydrocarbon solvent B (carbon number) was determined from the heavy component. 9 to 10, aniline point 47 ° C., boiling point 143 to 161 ° C.).

Other aliphatic hydrocarbons As the aliphatic hydrocarbons other than the above aliphatic hydrocarbon solvents A and B, the following were used. 1) Decalin (reagent: manufactured by Tokyo Chemical Industry, aniline point 34 ° C, boiling point 190 ° C)
2) Methylcyclohexane (MCH) (reagent: manufactured by Tokyo Chemical Industry, aniline point 39 ° C., boiling point 101 ° C.)
3) n-decane (reagent: manufactured by Tokyo Chemical Industry, aniline point 77 ° C., boiling point 169 to 173 ° C.)
-Polar solvent The following were used as polar solvents.
1) Isopropanol (IPA) (reagent: manufactured by Tokyo Chemical Industry, KB: 233, boiling point 82 ° C.)
2) n-butanol (reagent: manufactured by Tokyo Chemical Industry, KB: 238, boiling point 118 ° C.)
3) Ethyl acetate (reagent: manufactured by Tokyo Chemical Industry, KB: 110, boiling point 77 ° C.)
4) n-butyl acetate (reagent: manufactured by Tokyo Chemical Industry, KB: 80, boiling point: 126 ° C.)
5) Methyl isobutyl ketone (MIBK) (reagent: manufactured by Tokyo Chemical Industry, KB: 75, boiling point 128 ° C.)
Other components 1) Toluene (Reagent: manufactured by Tokyo Chemical Industry, boiling point 110 ° C.)
2) Xylene (reagent: manufactured by Tokyo Chemical Industry, boiling point 134 ° C)
In the following examples and comparative examples, the methods for measuring or evaluating each property are as follows.

-Flash point: JIS K2265
・ Sulfur content: JIS K2541-6
・ Nitrogen content: JIS K2609
Distillation property (boiling point): JIS K2254
-Aniline point and mixed aniline point: JIS K2256
Kauributanol value: ASTM D1133
-Measurement of evaporation rate ratio: The evaporation rate ratio was measured by the test method of the following procedure.
(1) Collect 50 mL of solvent in a 100 mL beaker with a cross-sectional area of 20 cm ² .
(2) This was placed in a high-temperature bath (explosion-proof type) at 80 ° C. and allowed to stand for 1 hour, and the amount of solvent evaporated V _S per unit time and unit area was measured.
(3) The measured toluene: unit time toluene conducted at (reagent, product of Tokyo Kasei Co., Ltd.) to measure the amount of evaporation V _T of the solvent per unit area.
(4) From the V _S and V _T measured above, the evaporation rate ratio V _S / V _T of each solvent with respect to the evaporation rate of toluene was calculated.

・ Solubility test 1:
10 parts by weight of each of the solvents of Examples and Comparative Examples were added to 1 part by weight of the synthetic rubber resin adhesive base material, and the solubility of the resin and the like after being left in an ultrasonic bath for 10 minutes was evaluated. Evaluation was colorless and transparent (circle), cloudiness (triangle | delta), and partially insoluble x.

-Solubility test 2:
A paint raw material was prepared by removing 80% of the solvent content under reduced pressure from a paint composed of an alkyd resin, pigment, nitrocellulose and an organic solvent (47%) (brush lacquer, manufactured by Nippe Home Products). 2 parts by weight of each solvent of Examples and Comparative Examples was mixed with 3 parts by weight of the coating material, and the state immediately after mixing and the state after 24 hours of mixing were evaluated. In the evaluation, a uniform dispersion state was evaluated as “◯”, a partial precipitation was evaluated as “Δ”, and a case where the dispersion was not dispersed was evaluated as “×”.

[Example 1]
These components were mixed to prepare a solvent composition so that 90% by volume of decalin, which is a cyclic aliphatic hydrocarbon, and 10% by volume of ethyl acetate, which is a polar solvent, were mixed. About the obtained solvent composition, each property was measured or evaluated as mentioned above. The results are shown in Table 1 or Table 2.

[Examples 2 to 13, Reference Examples 1 and 2, Comparative Examples 1 to 12]
In Example 1, a solvent composition was prepared in the same manner as in Example 1 except that the mixing ratio of each component was changed to the ratio shown in Table 1 or Table 2, and the properties thereof were evaluated. The results are shown in Table 1.

  From the results regarding the solubility test 1, it can be seen that the solvent composition of the present invention exhibits high solubility in a synthetic rubber resin. In addition, the results regarding the solubility test 2 show that the solvent composition of the present invention is in a state in which the paint is uniformly dispersed both immediately after mixing and after 6 hours of mixing, and is excellent in dispersibility. It is shown to be suitable as a diluent for ink and the like.

In addition, from the measurement results of the mixed aniline point, the solvent composition of Examples 1 to 13 which is the solvent composition of the present invention is compared with the solvent of Comparative Example 1 which is only cycloaliphatic hydrocarbon methylcyclohexane, It can be seen that the mixed aniline point is low and the solubility is high. Further, from the measurement result of the evaporation rate ratio, the solvent composition of the present invention is equivalent to toluene and xylene, which are representative aromatic solvents, in terms of drying property, and is an excellent solvent that can be substituted for toluene and xylene. I know that there is.

  The solvent composition of the present invention can be widely used in solvents for paints, solvents for inks, adhesives, etc., and cleaning agents for metal parts, precision equipment, etc., and in particular, paints, adhesives, adhesives, inks. Or it can use suitably as a solvent of a mold release agent.

Claims (4)

A solvent composition containing 50 to 90% by volume of a cyclic aliphatic hydrocarbon and 10 to 50% by volume of a polar solvent,
The chain aliphatic hydrocarbon content is less than 10% by volume, the aromatic hydrocarbon content is less than 0.1% by volume, and
A solvent composition having a mixed aniline point of 30 to 50 ° C.   The solvent composition according to claim 1, wherein the cycloaliphatic hydrocarbon has a boiling point of 100 to 255 ° C. and an aniline point of 55 ° C. or less.   The solvent composition according to claim 1 or 2, wherein the polar solvent is one or more selected from the group consisting of esters, ketones, and alcohols, and has a Kauri-butanol value of 70 to 270. object.   The solvent composition according to any one of claims 1 to 3, which is a solvent for a paint, an adhesive, a pressure-sensitive adhesive, an ink, or a release agent.