Monohydric alcohol-based solvent mixture

Abstract

Provided is a monohydric alcohol-based solvent which has high handling safety and excellent use characteristics as a solvent. A monohydric alcohol solvent mixture which is characterized by containing 96.0 mass% or more of a C7-9 alicyclic monohydric alcohol having a monocyclic alicyclic skeleton, and in that 75.0 mass% or more of the alicyclic monohydric alcohol is composed of a monocyclic alicyclic monohydric alcohol having 8 carbon atoms and a monocyclic alicyclic monohydric alcohol having 9 carbon atoms, when the sum of the content of the alicyclic monoalcohol having 8 carbon atoms and the content of the alicyclic monoalcohol having 9 carbon atoms is 100.0 mass%, the content of the alicyclic monoalcohol having 9 carbon atoms is 0.4-4.0 mass%, and the chromaticity represented by Hassen unit chromaticity (APHA) is 30 or less.

Description

Technical Field

[0001] The present invention relates to a monohydric alcohol solvent having excellent convenience and use thereof. Background Art

[0002] Among monoalcohol solvents, aliphatic and alicyclic monoalcohol solvents are less harmful to the working environment and the natural environment than aromatic hydrocarbon solvents such as toluene and xylene, and are in increasing demand as safe solvents. Among them, alicyclic monoalcohol solvents have a cyclic structure, so they have better solubility of cyclic compounds than chain aliphatic monoalcohol solvents with the same carbon number, and are solvents with a wider range of applications.

[0003] On the other hand, in order to use stably in indoor and outdoor painting operations, when used at high temperatures, the flash point is preferably 50°C or above. In addition, solvents with a flash point of 50°C or above are equivalent to Class 4, Type 2 petroleum, a dangerous substance in the Fire Protection Act of Japan, and are easy to handle in terms of the amount that can be transported and stored, and the demand is rising. In addition, solvents are widely used in coatings, inks, and adhesives, and are also required to be colorless and transparent from the perspective of appearance and the degree of freedom in matching.

[0004] As a technology of alicyclic monohydric alcohol-based solvents suitable for such needs, ink solvents containing alicyclic monohydric alcohols and hydrocarbons and using silver nanoparticles are disclosed in Patent Documents 1 and 2. Specifically, Patent Document 1 discloses 3,3,5-trimethylcyclohexanol (flash point 74°C), d,l-menthol (flash point 95°C), cyclohexane methanol (flash point 71°C), and cyclohexane ethanol (flash point 72°C). In addition, Patent Document 2 discloses 3,5-dimethylcyclohexanol (flash point 73°C), 2-ethylcyclohexanol (flash point 68°C), and 1-methylcyclohexanol (flash point 68°C) in addition to the above. In Patent Documents 1 and 2, these solvents are mixed with n-hexadecane (flash point 136°C) or n-pentadecane (flash point 120°C) and used.

[0005] However, the solvents proposed in Patent Documents 1 and 2 are obtained by mixing different types of compounds with very different structures. In this case, when the mixture is made, there are sometimes problems in terms of usability due to the very different volatility. For example, when a solvent composed of multiple components is used in a coating, due to the volatilization of the solvent components, the composition ratio of the solvent changes, the solubility (solubility parameter) and viscosity change greatly, and sometimes the initially dissolved material components unexpectedly precipitate or condense. In the inventions described in Patent Documents 1 and 2, no considerations related to such usability are made.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2019-099756

[0009] Patent Document 2: Japanese Patent Application Publication No. 2019-102376 Summary of the invention

[0010] Problems to be solved by the invention

[0011] In view of the above-mentioned actual situation, the present invention aims to provide a monohydric alcohol solvent which has high safety in handling and excellent properties as a solvent.

[0012] Means for solving problems

[0013] The present inventors have conducted intensive studies to achieve the above-mentioned objects and, as a result, have found that a mixture of the constituent components of the alicyclic monohydric alcohol-based solvent within a specific range can achieve the above-mentioned objects, thereby completing the present invention.

[0014] That is, the first present invention relates to a monohydric alcohol-based solvent mixture, which contains 96.0% by mass or more of an alicyclic monohydric alcohol having 7 to 9 carbon atoms and a monocyclic alicyclic skeleton, 75.0% by mass or more of the above-mentioned alicyclic monohydric alcohol having 7 to 9 carbon atoms is composed of a monocyclic alicyclic monohydric alcohol having 8 carbon atoms and a monocyclic alicyclic monohydric alcohol having 9 carbon atoms, and when the sum of the content of the above-mentioned alicyclic monohydric alcohol having 8 carbon atoms and the content of the above-mentioned alicyclic monohydric alcohol having 9 carbon atoms is set to 100.0% by mass, the content of the alicyclic monohydric alcohol having 9 carbon atoms is 0.4 to 4.0% by mass, and the Hazen unit chromaticity (APHA) is 30 or less.

[0015] The second present invention relates to the above-mentioned monoalcohol solvent mixture, wherein the content of the monocyclic carbon number 7 alicyclic monoalcohol is 0.5 to 25.0% by mass, when the sum of the content of the monocyclic carbon number 8 alicyclic monoalcohol and the content of the monocyclic carbon number 9 alicyclic monoalcohol is 100.0% by mass.

[0016] According to the present invention, the following effects are obtained.

[0017] Effects of the Invention

[0018] According to the present invention, a monohydric alcohol solvent mixture that can be stably used at most outdoor environmental temperatures above ground is provided. The monohydric alcohol solvent mixture of the present invention is a monohydric alcohol solvent having a stable solubility parameter for volatilization operation and excellent solvent properties, and has excellent transparency, and can be particularly suitable for use as a solvent for coatings, ink solvents, and adhesives for design purposes, and as a solvent with low flammability, can be used as a solvent for applications used at high temperatures.

[0019] The monohydric alcohol solvent mixture of the present invention has the excellent effect of being able to be used well as a solvent for coatings, a solvent for adhesives, a solvent for pressure-sensitive adhesives (adhesives), and a solvent for inks. Specifically, by using the monohydric alcohol solvent of the present invention, a coating that forms a coating film with good adhesion, a pressure-sensitive adhesive with high pressure-sensitive adhesiveness, and an oil-based ink with excellent dispersibility can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a diagram showing the classification of peeling conditions of the coating film. DETAILED DESCRIPTION

[0021] The monoalcohol solvent mixture of the present invention (hereinafter also referred to as "solvent") comprises or consists of a monoalcohol mixture containing specific components at specific ratios. The monoalcohol solvent of the present invention has excellent properties when used as a solvent compared to a single monoalcohol.

[0022] In the present invention, the alicyclic monohydric alcohol having a monocyclic alicyclic skeleton refers to a compound having one unfused saturated or unsaturated carbon ring, which has no aromaticity and one hydroxyl group bonded to any carbon atom constituting the saturated or unsaturated carbon ring, and preferably a compound having one unfused saturated carbon ring and one hydroxyl group bonded to a saturated hydrocarbon skeleton. Examples of the monocyclic alicyclic skeleton, the unfused saturated carbon ring, are cyclopentane ring, cyclohexane ring, and cycloheptane ring, and the cyclohexane ring is more preferred for reasons such as stability of the compound and low-cost availability.

[0023] In the alicyclic monohydric alcohol of the present invention, one or more aliphatic branches may be substituted on the monocyclic alicyclic skeleton. For example, in the present invention, the so-called "monocyclic carbon number 8 alicyclic monohydric alcohol" means an alicyclic monohydric alcohol having the above-mentioned monocyclic alicyclic skeleton, and the number of carbon atoms constituting the alicyclic monohydric alcohol is 8 including branches.

[0024] Hereinafter, the monocyclic alicyclic monohydric alcohol having 7, 8 or 9 carbon atoms contained in the monohydric alcohol-based solvent may be referred to as a C7 component, a C8 component or a C9 component, respectively.

[0025] The monoalcohol solvent of the present invention contains 96.0% by mass or more of an alicyclic monoalcohol having a monocyclic alicyclic skeleton and having 7 to 9 carbon atoms. The content of the alicyclic monoalcohol having a monocyclic alicyclic skeleton relative to the entire monoalcohol solvent can be obtained as the sum of the alicyclic monoalcohol contents detected in gas chromatography. For example, for each peak appearing in gas chromatography, the structure is identified by estimating the composition of raw materials, etc., and based on the results, it can be determined by using an internal standard substance for quantitative analysis.

[0026] In the present invention, when the total content of the alicyclic monool component having 7 to 9 carbon atoms is 100.0 mass %, 75.0 mass % or more of the alicyclic monool is composed of monocyclic alicyclic monool having 8 carbon atoms and monocyclic alicyclic monool having 9 carbon atoms.

[0027] Furthermore, when the sum of the content of the alicyclic monohydric alcohol having 8 carbon atoms and the content of the alicyclic monohydric alcohol having 9 carbon atoms is 100.0 mass %, the content of the alicyclic monohydric alcohol having 9 carbon atoms is 0.4 to 4.0 mass %.

[0028] In the monoalcohol-based solvent mixture of the present invention, the content of the alicyclic monoalcohol having a monocyclic alicyclic skeleton and the contents of the C8 component and the C9 component of the alicyclic monoalcohol are important.

[0029] The monohydric alcohol solvent mixture of the present invention is characterized in that the chromaticity represented by Hazen unit chromaticity (APHA) is 30 or less.

[0030] As for the component ratio of the alicyclic monohydric alcohol solvent mixture in the present invention, it is obtained by gas chromatography. As a gas chromatography method, a method of separating the peaks of each component of the alicyclic monohydric alcohol well and quantifying by an internal standard method is adopted. Specifically, it is possible to adopt a method in which a nonpolar column, a polar column and an FID detector are used to raise the column temperature from 40°C to 220°C. As a nonpolar column, TC-1 (manufactured by Hurlett Packard Co., Ltd.), SH-I-1MS (manufactured by Shimadzu Corporation), and DB-1 (manufactured by Agilent Technologies Corporation) can be exemplified. In addition, as a polar column, DB-WAXetr (manufactured by Shimadzu Corporation) and DB-WAX (manufactured by Agilent Technologies Corporation) can be exemplified.

[0031] The content of the alicyclic monohydric alcohol is 96.0% by mass or more, preferably 97.0% by mass or more, and more preferably 98.0% by mass or more, relative to the entire monohydric alcohol solvent mixture. When the content of the alicyclic monohydric alcohol is within this range, when the monohydric alcohol solvent of the present invention is volatilized, the difference in solubility parameter and viscosity associated with the change in the component composition can be ensured to be relatively small.

[0032] In the alicyclic monoalcohol having a monocyclic alicyclic skeleton constituting the monoalcohol-based solvent mixture of the present invention, 75.0% by mass or more, preferably 77.0% by mass or more, is composed of a monocyclic alicyclic monoalcohol having 8 carbon atoms and a monocyclic alicyclic monoalcohol having 9 carbon atoms. The sum of the contents of the monocyclic alicyclic monoalcohol having 8 carbon atoms and the monocyclic alicyclic monoalcohol having 9 carbon atoms relative to the alicyclic monoalcohol having a monocyclic alicyclic skeleton can be determined by, for example, identifying the structure of each peak in gas chromatography by GC-MS and estimating the composition of raw materials, quantifying the contents of the monocyclic alicyclic monoalcohol having 8 carbon atoms and the contents of the monocyclic alicyclic monoalcohol having 9 carbon atoms using an internal standard substance, and comparing the sum of the two with the content of the alicyclic monoalcohol. The content of the monocyclic alicyclic monoalcohol having 7 carbon atoms described later can also be determined by the same method.

[0033] In the present invention, the content of the alicyclic monohydric alcohol having 9 carbon atoms is 0.4 to 4.0% by mass, when the sum of the content of the alicyclic monohydric alcohol having 8 carbon atoms and the content of the alicyclic monohydric alcohol having 9 carbon atoms is 100.0% by mass. The ratio of the alicyclic monohydric alcohol having 9 carbon atoms to the sum of the alicyclic monohydric alcohol having 8 carbon atoms and the alicyclic monohydric alcohol having 9 carbon atoms can be determined by the above-mentioned method in gas chromatography.

[0034] As for the C9 component, it contains 0.4 to 4.0 mass % relative to the sum of the C8 component content and the C9 component content. The C9 component has a high boiling point and a small amount of residue remains when the monohydric alcohol solvent evaporates, which helps to improve the adhesion with the adherend when used as an adhesive solvent. If the content of the C9 component is less than 0.4 mass %, the above-mentioned adhesion effect is insufficient. If it exceeds 4.0 mass %, the high boiling point component becomes too much, which impairs the volatility as a monohydric alcohol solvent, so it is not preferred. As for the C9 component, it is more preferred that the lower limit of the alicyclic monohydric alcohol is 0.36 mass % and the upper limit is 4.0 mass %.

[0035] Specifically, the C9 component is preferably a secondary alcohol, more preferably trimethylcyclohexanol, and more preferably 2,3,6-trimethylcyclohexanol, 3,4,5-trimethylcyclohexanol, 3,4,6-trimethylcyclohexanol, or 4-ethyl-2-methylcyclohexanol, which is a positional isomer thereof.

[0036] The C8 component is the main component of the monohydric alcohol solvent of the present invention, and has a high flash point and excellent solvent properties. As for the C8 component, it contains 96.0 to 99.6% by mass relative to the sum of the C8 component content and the C9 component content. When the content of the C8 component is less than 96.0% by mass relative to the sum of the C8 component content and the C9 component content or exceeds 99.6% by mass, it becomes difficult to have the above characteristics. The C8 component is preferably a secondary alcohol, more preferably dimethylcyclohexanol or ethylcyclohexanol, and more preferably 3,5-dimethylcyclohexanol, 3,4-dimethylcyclohexanol, 2,3-dimethylcyclohexanol, 2,4-dimethylcyclohexanol 2,5-dimethylcyclohexanol, or 3-ethylcyclohexanol, 4-ethylcyclohexanol, etc., which are positional isomers thereof.

[0037] In addition, it is preferred that 58.0% by mass or more of the C8 component is dimethylcyclohexanol. The content of dimethylcyclohexanol in the C8 component is more preferably 70.0% by mass or more, and even more preferably 73.0% by mass or more.

[0038] The monohydric alcohol solvent of the present invention is a mixture consisting of a specific composition, so that the difference in solubility parameter and viscosity accompanying the change in the component composition can be relatively small, and the flash point measured by the Tag Closed Method of JIS K 2265-1 can be set to a temperature of 50° C. or higher, preferably 55° C. or higher.

[0039] It should be noted that the flash point using the Tiger closed method of JIS K 2265-1, the rapid equilibrium closed method of JIS K 2265-2 (rapid equilibrium closed method), etc. can be measured using a commercially available Tiger closed flash point tester. Specifically, based on the following method: in a sample cup sealed with a 50mL±0.5mL sample, when the expected flash point exceeds 50°C, slowly heat from 50°C at a temperature increase rate of 3°C in 60±6 seconds, expose an ignition source to (close to) the sample cup at every 1.0°C temperature interval, and find the lowest temperature at which the vapor of the sample ignites.

[0040] A preferred embodiment of the present invention is further a monohydric alcohol solvent, wherein the content of the monocyclic carbon number 7 alicyclic monohydric alcohol is 0.5 to 25.0% by mass relative to the sum of the content of the monocyclic carbon number 8 alicyclic monohydric alcohol and the content of the monocyclic carbon number 9 alicyclic monohydric alcohol. By including a certain amount of C7 component, better volatility and better coating film properties can be imparted. Specifically, the C7 component is preferably a secondary alcohol, more preferably methylcyclohexanol, and particularly preferably 3-methylcyclohexanol and 4-methylcyclohexanol as positional isomers thereof. The upper limit of the preferred content of the C7 component is 21% by mass.

[0041] If the content of C7 component is lower than the above range, the above improvement effect is difficult to show. For example, when used in a solvent of a coating, the adhesion of the coated object as a coating tends to decrease. On the other hand, C7 component is equivalent to a low flash point component, so if the content is higher than the above range, the flash point as a monohydric alcohol solvent tends to become lower. If the content of C7 component is higher than the above range, the solvent evaporates all at once, and the surface of the coating tends to be prone to the phenomenon of unevenness like orange peel (also called "orange peel" or "grapefruit peel").

[0042] In addition, the present invention is characterized in that the solvent has high transparency. Specifically, in the Hazen unit chromaticity measurement specified in JIS K0071-1, the Hazen unit chromaticity (APHA) of the solvent mixture of the present invention is 30 or less, preferably 25 or less, and more preferably 20 or less. Solvents with a Hazen unit chromaticity (APHA) of 30 or less have excellent transparency, high degree of freedom in the combination of dyes and pigments, and are particularly suitable for use in solvents for coatings, ink solvents, and adhesives for design purposes.

[0043] The Hazen unit chromaticity is a color scale in which the color of a solution containing 1 mg of platinum in the form of hexachloroplatinum ions and 2 mg of cobalt (II) chloride hexahydrate in 1 L is set to 1, and is obtained by equivalently measuring (when measuring) the sample with the tristimulus values ​​X, Y, and Z. As a measuring method, for example, a method of using a calibration curve made of the tristimulus values ​​X, Y, and Z of a platinum-cobalt color standard solution to obtain the corresponding chromaticity from the tristimulus values ​​X, Y, and Z of a sample measured using the same colorimeter can be cited. As a colorimeter, a spectrophotometer, a photoelectric colorimeter, or a spectrophotometer is used.

[0044] In addition, the monohydric alcohol solvent mixture of the present invention preferably has a solubility parameter at 25°C of 18.0 to 20.0 MPa. 0.5 , preferably 18.5~19.5MPa 0.5 The alicyclic monohydric alcohol solvent within this range can dissolve a wide range of materials such as rubbers such as styrene-butadiene rubber, natural rubber, butyl rubber, nitrile rubber, acrylic rubber, chloroprene rubber, ethylene-vinyl acetate rubber, polystyrene, petroleum resin, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride and other resins. The solubility parameters can be calculated by known methods. As specific examples, the estimated values ​​of Hansen solubility parameters at 25°C using SMILES using computer software Hansen Solubility Parameters in Practice (HSPiP) ver5.2.06 and DIY (a function to estimate Hansen solubility parameters from the molecular structure of the solvent) can be cited.

[0045] As for the monohydric alcohol solvent of the present invention, the desired effect is exerted by the above-mentioned alicyclic monohydric alcohol in a specific composition range, and in particular, it is more preferably composed of compounds with similar structures and similar solubility parameters. Specifically, it is preferred that 94.0% by mass or more, preferably 95.0% by mass or more, of the alicyclic monohydric alcohol with a monocyclic alicyclic skeleton and a carbon number of 7 to 9 is occupied by more than 3 selected from methylcyclohexanol, dimethylcyclohexanol, ethylcyclohexanol and trimethylcyclohexanol, and it is most preferred that 95.0% by mass or more, preferably 96.0% by mass or more of the monohydric alcohol solvent is occupied by the above 4. For alicyclic monohydric alcohols with a carbon number of 6, such as cyclohexanol, it is preferred that the content is small from the viewpoint of flash point reduction. In addition, for alicyclic monohydric alcohols with a carbon number of 10 or more, since the synthesis reaction and the hydrogenation reaction from the corresponding phenol are difficult, it is not preferred from the viewpoint of availability, so it is preferred that the content is small.

[0046] The preferred method for producing the monohydric alcohol solvent of the present invention is exemplified below.

[0047] The monohydric alcohol solvent of the present invention can be produced by an aromatic ring hydrogenation reaction (also referred to as "nuclear hydrogenation reaction" or "nuclear hydrogenation reaction") of an alkylphenol mixture. When the alkylphenol mixture is a mixture of cresol, xylenol, ethylphenol, and trimethylphenol, a monohydric alcohol solvent mainly containing a mixture of methylcyclohexanol as the C7 component, dimethylcyclohexanol, ethylcyclohexanol as the C8 component, and triethylcyclohexanol as the C9 component or consisting of the same can be obtained. In the present invention, the alkylphenol corresponding to each alicyclic monohydric alcohol is referred to as a precursor.

[0048] The aromatic ring hydrogenation reaction can adopt the nuclear hydrogenation (nuclear hydrogenation) reaction conditions of phenols. That is, it can be carried out under the conditions appropriately selected from the temperature of 100 to 300 ° C and the hydrogen pressure of 1 to 10 MPa in the presence of a nuclear hydrogenation catalyst. The amount of catalyst, reaction time, etc. are determined by considering the above-mentioned reaction temperature, hydrogen pressure, etc. so that the residual aromatic component becomes less than 1.0 mass%. The reaction mode can be carried out in an intermittent manner or a flow-through manner. For the nuclear hydrogenation catalyst, for example, nickel, nickel oxide, nickel / diatomaceous earth, Raney nickel, nickel / copper, platinum, platinum oxide, platinum / activated carbon, or platinum / rhodium can be used. In the case of considering the manufacturing cost, platinum / aluminum oxide and nickel-based catalysts are preferably used.

[0049] The ratio of the C7 component, C8 component, and C9 component constituting the monohydric alcohol solvent of the present invention reflects the ratio of the components of its precursors. Therefore, it is important to control the mixture of these precursors (hereinafter referred to as the "precursor mixture") to an appropriate ratio of components. As for the precursor mixture, for example, a tar fraction in a specific boiling point range can be subjected to acid treatment, alkali treatment, etc. to produce a mixture mainly composed of phenols that have been separated into components, and phenol and cresol are distilled off from the phenol mixture to obtain the precursor mixture of the monohydric alcohol solvent of the present invention. Among them, by optimizing the distillation conditions of phenol and cresol (distillation temperature, pressure, theoretical plate number of the distillation tower, etc.), the precursor mixture of the monohydric alcohol solvent of the present invention can be obtained.

[0050] Specifically, when phenol is completely removed from the phenol mixture, it is preferred that cresol is not completely removed but 0.5 to 20.0% by mass is allowed to remain. In addition, the precursor mixture contains 95.0% by mass or more of monocyclic phenols, and 75.0% by mass or more of the phenols are composed of precursors of C8 components and precursors of C9 components, and when the sum of the precursors of the C8 components and the precursors of the C9 components is 100.0% by mass, the precursor of the C9 component is allowed to remain in the precursor mixture in a manner of 0.4 to 4.0% by mass. In addition, since the sulfur content in the precursor mixture becomes a catalyst poison for the hydrogenation reaction, the sulfur content is preferably 50 ppm or less, more preferably 30 ppm or less, and further preferably 20 ppm or less.

[0051] As a method for obtaining the highly transparent alicyclic monohydric alcohol solvent mixture of the present invention, the following method can be cited: using a tar component as a raw material, when distilling it, fractionating the components such as amines as coloring components by rectification, thereby obtaining an alkylphenol mixture mainly composed of C8 phenol with high transparency, and hydrogenating it. In addition, it can also be obtained by obtaining highly transparent alkylphenols separately by synthesis, etc., using the mixed product of these as a raw material, and hydrogenating it. In addition, it can also be obtained by preparing highly transparent alicyclic monohydric alcohol solvent components corresponding to the present invention separately by synthesis, distillation, etc., and mixing them.

[0052] The monohydric alcohol solvent of the present invention can be suitably used as a solvent for coating materials, a solvent for adhesives, a solvent for pressure-sensitive adhesives, and a solvent for inks.

[0053] As a coating solvent, it is used as a solvent blended in an oil-based coating containing a resin exemplified in acrylic resin coatings, ester resin coatings such as alkyd resin coatings, urethane resin coatings, epoxy resin coatings, etc. For example, in the case of alkyd resin coatings, the alkyd resin as the main component is dissolved in a coating solvent containing the monohydric alcohol solvent of the present invention. Among the solvents containing the monohydric alcohol solvent of the present invention, it is preferred to use it in ester resin coatings and urethane resin coatings because of its high resin solubility. For example, the coating solvent is blended in 1 to 99% by mass of the entire coating.

[0054] To the paint solvent, additives for the paint such as a desiccant, a dispersant, an anti-settling agent, a defoaming agent, a mildew preventer, a rust preventer, an anti-color separation agent, and an ultraviolet absorber may be further added.

[0055] Generally, coatings are composed of pigments, resins, solvents, and additives. Therefore, as for the solvent, the dispersion of the pigment and the dissolution of the resin are required. Therefore, in order to meet the above requirements, among the coating solvents, a coating solvent other than the monohydric alcohol solvent of the present invention can be used in combination. That is, the coating solvent can contain a coating solvent other than the monohydric alcohol solvent of the present invention in an amount of less than 40% by mass of the total solvent, more preferably less than 20% by mass, further preferably less than 10% by mass, and further preferably less than 5% by mass.

[0056] As an adhesive solvent, it is used as a solvent compounded in a resin adhesive containing the resin exemplified in the polar group-modified rubber adhesive, chloroprene rubber adhesive, etc. as the main material. As for the polar group-modified rubber system, for example, polar group-modified butadiene having polar groups such as hydroxyl groups and (meth)acryloyl groups given to the ends can be cited. The chloroprene rubber adhesive has the same composition as the above-mentioned polar group-modified rubber adhesive except that the main material is chloroprene rubber. The polar group-modified rubber adhesive is formed by dissolving the polar group-modified rubber as the main component in an adhesive solvent containing the monohydric alcohol solvent of the present invention. For example, the adhesive solvent is compounded in 1 to 99% by mass of the entire adhesive.

[0057] To the adhesive solvent, additives for the adhesive such as a tackifier such as a terpene resin, a curing agent, a plasticizer, and a filler may be further added.

[0058] The adhesive solvent may contain 40% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and further preferably 5% by mass or less of an adhesive solvent other than the monohydric alcohol solvent of the present invention, based on the entire solvent.

[0059] As a solvent for pressure-sensitive adhesives, it is used as a solvent blended in a resin-based pressure-sensitive adhesive containing a resin exemplified in polar group-modified rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, etc. as a main material. As for polar group-modified rubber-based pressure-sensitive adhesives, for example, polar group-modified butadiene having polar groups such as hydroxyl groups and (meth)acryloyl groups given to the ends can be cited. The acrylic pressure-sensitive adhesive has the same composition as the above-mentioned polar group-modified rubber-based pressure-sensitive adhesive except that the main material is a (meth)acrylic polymer. For example, the polar group-modified rubber-based pressure-sensitive adhesive is formed by dissolving the polar group-modified rubber as the main component in a pressure-sensitive adhesive solvent. For example, the pressure-sensitive adhesive solvent is blended in 1 to 99% by mass of the entire pressure-sensitive adhesive.

[0060] To the pressure-sensitive adhesive, additives for the pressure-sensitive adhesive, such as a tackifier such as a terpene resin, a filler, a cross-linking agent, and an antioxidant, may be further added.

[0061] The pressure-sensitive adhesive solvent may contain 40% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and further preferably 5% by mass or less of the pressure-sensitive adhesive solvent other than the monohydric alcohol solvent of the present invention, based on the total solvent.

[0062] As the ink solvent, it is used as a solvent blended in an oily ink containing a resin exemplified in acrylic materials, silicon materials, etc. as a main material. Among them, as an ink solvent using an acrylic material, it is preferred from the viewpoint of high resin solubility. For example, acrylic ink is obtained by dissolving an acrylic resin as a main component in an ink solvent. In particular, an ink solvent that does not contain silver particles is preferred.

[0063] Alkylcyclohexanols have extremely weak metal oxidizing properties depending on the type of metal. When the ink contains silver particles, silver discolors more seriously than other metals due to oxidation. Therefore, when used in ink containing silver particles, more care should be taken than when using ink using other metal particles.

[0064] When the monohydric alcohol solvent of the present invention is used as the ink solvent, it is blended in an amount of 1 to 99% by mass of the total ink. Known additives such as a desiccant, a dispersant, an anti-settling agent, an antifoaming agent, an anti-mold agent, an anti-rust agent, an anti-color separation agent, and an ultraviolet absorber may be further added.

[0065] Generally, ink is composed of a pigment, a dye, a resin, a solvent, a carrier composed of oil, and various auxiliary agents such as a regulator. Therefore, as far as the solvent is concerned, the dispersion of the pigment and the dissolution of the dye and the resin are required. Therefore, in order to meet the above requirements, a known solvent other than the monohydric alcohol solvent of the present invention can be used in combination. That is, the ink solvent can contain an ink solvent other than the monohydric alcohol solvent of the present invention of less than 40% by mass of the whole solvent, more preferably less than 20% by mass, further preferably less than 10% by mass, and further preferably less than 5% by mass.

[0066] In the monohydric alcohol solvent of the present invention, when a plurality of substances need to be dissolved simultaneously, different types of solvents may be mixed and used. However, in order to maintain the physicochemical properties, the mixed solvents preferably have similar chemical structures.

[0067] The monohydric alcohol solvent of the present invention can be used in combination with a known solvent in accordance with the application and the object to be dissolved, and can be optimized. Specific examples of the solvent to be combined include water, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters, ether esters, alcohols, glycols, ether alcohols, phenolic compounds, etc.

[0068] Example

[0069] Hereinafter, the present invention will be described in detail by way of examples.

[0070] As for the components of the precursor and the hydride, the peaks were identified by GC mass spectrometry. Next, the reagents of the precursor and the component of the present invention, the high-concentration components such as the fractions obtained by distilling and fractionating the precursor and the component of the present invention, and the products of hydrogenating the high-concentration components of the precursor were used as samples, and n-propylbenzene was used as an internal standard substance. The internal standard method was used to quantify the following gas chromatography analysis conditions. Using these quantitative results, the precursor and the solvent components described in the examples and comparative examples were quantified.

[0071] In addition, the boiling points of isomers were supplemented by confirmation using standard samples, estimation from boiling point sequences in databases, and the like.

[0072] For gas chromatography analysis, the sample was diluted with ethanol to 10% by weight, n-propylbenzene was used as an internal standard substance, and the internal standard method was adopted, with the chromatogram obtained by gas chromatography analysis under the following conditions as the composition. In the gas chromatography analysis, column A was used for the main analysis, and the analysis results of column B were used to supplement the separation and confirmation of peaks that were difficult to separate due to their close boiling points. The above gas chromatography analysis conditions were implemented under the following conditions.

[0073] GC device: 7890A GC System (manufactured by Agilent Technologies)

[0074] Column A: TC-1 (manufactured by DIESEL SYSTEMS, non-polar) φ0.25 mm×60 m, film thickness 0.25 μm

[0075] Column B: DB-WAX (manufactured by Agilent Technologies, polar) φ0.25 mm×30 m, film thickness 0.25 μm

[0076] Split ratio: 100

[0077] Injection temperature: 250°C

[0078] Gas linear velocity in column: 20cm / s

[0079] Detection method: FID (Flame Ionization Detector)

[0080] Detection temperature: 250℃

[0081] Oven temperature: Keep at 40℃ for 10 minutes, then increase the temperature by 4℃ per minute to 220℃. Once reached, keep at 220℃ for 5 minutes.

[0082] Hazen Unit Chromaticity (APHA) Evaluation

[0083] A colorimeter (TC-8600A, Tokyo Denshoku Co., Ltd.) was used to determine the chromaticity using the colorimeter method of JIS K 0071-1. A calibration curve was made using the tristimulus values ​​X, Y, and Z of the platinum-cobalt standard solution prepared at each stage. The corresponding chromaticity was determined from the tristimulus values ​​X, Y, and Z of the sample measured using the same colorimeter.

[0084] Example 1

[0085] Phenol and cresol are removed from a mixture of phenol and alkylphenols that has undergone a desulfurization and denitrification process from a tar distillation component mainly containing phenols, thereby obtaining a precursor mixture A that is mainly composed of xylenol and ethylphenol and contains cresol and trimethylphenol and is colored brown. Furthermore, the precursor mixture A is fractionated to obtain a colorless and transparent precursor mixture B having substantially the same composition as the precursor mixture A.

[0086] 600 g of the precursor mixture B and 6.0 g of a Ni-based catalyst (SN-300L manufactured by Sakai Chemical Industry Co., Ltd.) were placed in a 1-liter autoclave, and a hydrogenation reaction was carried out for 40 hours at a temperature of 200° C., a pressure of 8 MPa, and a stirring blade speed of 600 rpm. The hydrogen absorption amount according to the pressure change of the hydrogen bottle was 99.0% by mass of the theoretical amount. Gas chromatography analysis was used to track the composition change of the precursor mixture during hydrogenation, and it was confirmed that the aromatic compounds in the precursor mixture were converted into alicyclic monohydric alcohols such as cyclohexanols by hydrogenation.

[0087] After the hydrogenation reaction is completed, a monohydric alcohol solvent having the composition and the Hazen unit chromaticity (APHA) shown in Table 2 is obtained. In Table 2, C7-C9 alicyclic monohydric alcohol, aromatic monohydric alcohol, C7 alicyclic monohydric alcohol (4), C8 alicyclic monohydric alcohol (1), dimethyl cyclohexanol (2), ethyl cyclohexanol, and C9 alicyclic monohydric alcohol (3) are all mass % relative to the entire solvent mixture. Furthermore, based on this, the total amount (mass %) of C8 alicyclic monohydric alcohol (1) and C9 alicyclic monohydric alcohol (3) and the ratio (mass %) of C9 alicyclic monohydric alcohol (3) and the ratio (mass %) of C7 alicyclic monohydric alcohol (4) when the total amount is set to 100 mass % are calculated and shown. In the obtained monohydric alcohol solvent, the content of the residual aromatic component is less than 1.0 mass %.

[0088] According to GC mass spectrometry analysis, the C7 component was methylcyclohexanol, the C8 component was dimethylcyclohexanol and ethylcyclohexanol, and the C9 component was trimethylcyclohexanol and ethylmethylcyclohexanol (the C7, C8 and C9 components were all mixtures of positional isomers).

[0089] The monohydric alcohol solvent was used to perform various solvent property evaluations shown below. The results are shown in Table 2.

[0090] Coating evaluation

[0091] 100 g of the obtained monohydric alcohol solvent, 70 g of butyl acetate, 200 g of alkyd resin and 20 g of pigment were mixed to prepare an alkyd paint, which was applied to a flat plate made of SUS304 and dried at about 20°C for 18 hours to form a coating film.

[0092] The coating film was evaluated for surface smoothness by (1) visually observing the surface condition, with smooth surfaces being marked as ○ and surfaces with irregularities being marked as ×. In addition, (2) the peeling condition of the coating film was evaluated by the cross-cut method described in JIS K 5600-5-6. Figure 1 The adhesion of the coating film is evaluated by classification from 0 to 5. In the above classification, the smaller the value, the more difficult it is to peel off, and the better the adhesion of the coating film.

[0093] Pressure-sensitive adhesive evaluation

[0094] 100 parts by weight of urethane-bound polybutadiene (TE-2000 manufactured by Nippon Soda Co., Ltd.) with a methacryloyl group introduced at the end was dissolved in 720 parts by weight of the obtained monohydric alcohol solvent, and then a polyisocyanate curing agent (Colonet L manufactured by Tosoh Co., Ltd.) was added to obtain an acrylic solvent-based pressure-sensitive adhesive. It was applied to a test plate with an applicator, dried at 100°C for one night, and then stabilized at room temperature for one day to prepare a 100mm long and 0.30μm thick pressure-sensitive adhesive test plate. A pressure-sensitive adhesive evaluation tester (ball adhesion tester No. 183-BT manufactured by Yasuda Seiki Co., Ltd.) was used to evaluate the pressure-sensitive adhesiveness using the JIS Z 0237 inclined ball adhesion. The largest ball No. that stopped the ball for more than 5 seconds at an inclined angle of 30° was used for evaluation. The larger the ball No., the more balls with a larger nominal diameter can be stopped, and the higher the pressure-sensitive adhesiveness.

[0095] Ink dilution evaluation

[0096] The dispersion state of the oily ink using acrylic material was visually evaluated when it was diluted 2 times with the monohydric alcohol solvent obtained above and when the same oily ink was diluted 2 times with a commercially available diluent (Toyo Petrochemical Co., Ltd., ink diluent) as a control example. The dispersion state of the oily ink after the diluted oily ink was stored at -5 degrees for 24 hours, that is, the presence or absence of separation and precipitation, was visually compared and evaluated. In these two comparative evaluations, the case where no separation or precipitation was found was evaluated as ink dilution ○, and the case where separation or precipitation was found was evaluated as ink dilution ×.

[0097] When the monoalcohol solvent of Example 1 is used in the coating, a coating film having a smooth surface and being difficult to peel off is obtained. When the monoalcohol solvent of Example 1 is used in the pressure-sensitive adhesive of a pressure-sensitive adhesive sheet, a pressure-sensitive adhesive sheet having high pressure-sensitive adhesive properties is obtained. When the monoalcohol solvent of Example 1 is used in the diluent of an oil-based ink, a diluted oil-based ink having excellent ink dispersibility is obtained.

[0098] Example 2

[0099] An alicyclic monohydric alcohol solvent having the composition shown in Table 2 was obtained by the same method as in Example 1 except that the precursor mixture obtained by changing the distillation conditions of phenol and cresol was used.

[0100] The content of the residual aromatic components of the obtained monohydric alcohol solvent was less than 1.0% by mass. According to GC mass spectrometry, the C7 component was methylcyclohexanol, the C8 component was dimethylcyclohexanol and ethylcyclohexanol, and the C9 component was trimethylcyclohexanol and ethylmethylcyclohexanol (the C7, C8 and C9 components were all positional isomer mixtures). In addition, the Hazen unit chromaticity (APHA) was 10.

[0101] The same solvent property evaluation as in Example 1 was carried out using this monohydric alcohol solvent.

[0102] The results are shown in Table 2. Using the monohydric alcohol solvent of Example 2, a good coating film, a good pressure-sensitive adhesive sheet, and a good diluted oil-based ink were obtained.

[0103] Example 3

[0104] The alicyclic monohydric alcohol solvent having the composition described in Table 2 was obtained by using a precursor mixture obtained by changing the distillation conditions of phenol and cresol.

[0105] The content of the residual aromatic components of the obtained alicyclic monohydric alcohol solvent was less than 1.0% by mass. According to GC mass spectrometry, the C7 component was methylcyclohexanol, the C8 component was dimethylcyclohexanol and ethylcyclohexanol, and the C9 component was trimethylcyclohexanol and ethylmethylcyclohexanol (the C7, C8 and C9 components were all positional isomer mixtures). In addition, the Hazen unit chromaticity (APHA) was 10.

[0106] The same solvent property evaluation as in Example 1 was carried out using this monohydric alcohol solvent.

[0107] The results are shown in Table 2. Using the monohydric alcohol solvent of Example 3, a good coating film, a good pressure-sensitive adhesive sheet, and a good diluted oil-based ink were obtained.

[0108] Example 4

[0109] An alicyclic monoalcohol solvent having the composition shown in Table 2 was obtained by the same method as in Example 1 except that the monoalcohol solvent obtained in Example 1 was mixed with commercially available methylcyclohexanol.

[0110] The content of the residual aromatic components of the obtained monohydric alcohol solvent was less than 1.0% by mass. According to GC mass spectrometry, the C7 component was methylcyclohexanol, the C8 component was dimethylcyclohexanol and ethylcyclohexanol, and the C9 component was trimethylcyclohexanol and ethylmethylcyclohexanol (the C7, C8 and C9 components were all positional isomer mixtures). In addition, the Hazen unit chromaticity (APHA) was 10.

[0111] The same solvent property evaluation as in Example 1 was carried out using this monohydric alcohol solvent.

[0112] The results are shown in Table 2. Using the monohydric alcohol solvent of Example 4, a good coating film and a good diluted oil-based ink were obtained.

[0113] Comparative Example 1

[0114] An alicyclic monohydric alcohol solvent having the composition shown in Table 2 was obtained by the same method as in Example 1 except that the precursor mixture and methylcyclohexanol were mixed in the same manner as in Example 4 using the precursor mixture obtained by changing the distillation conditions of phenol and cresol.

[0115] The content of residual aromatic components in the obtained monoalcohol-based solvent was less than 1.0% by mass, the total content of the alicyclic monool (1) of the C8 component and the alicyclic monool (3) of the C9 component was 69.1% by mass, and the content of the alicyclic monool of the C9 monocyclic monool was 0.3% by mass when the sum of the content of the alicyclic monool of the C8 monocyclic monocyclic alcohol and the content of the alicyclic monool of the C9 monocyclic monocyclic alcohol was 100.0% by mass. According to GC mass spectrometry, the C7 component was methylcyclohexanol, the C8 component was dimethylcyclohexanol and ethylcyclohexanol, and the C9 component was trimethylcyclohexanol and ethylmethylcyclohexanol (the C7, C8 and C9 components were all positional isomer mixtures).

[0116] The same solvent property evaluation as in Example 1 was carried out using this monohydric alcohol solvent.

[0117] The results are shown in Table 2. When the monohydric alcohol solvent of Comparative Example 1 was used, a good coating film and a good pressure-sensitive adhesive sheet could not be obtained.

[0118] Comparative Example 2

[0119] An alicyclic monohydric alcohol solvent having the composition shown in Table 2 was obtained in the same manner as in Example 1 except that the precursor mixture obtained by changing the distillation conditions of phenol and cresol was used.

[0120] The content of residual aromatic components in the obtained monoalcohol-based solvent was less than 1.0% by mass, and the content of the monocyclic alicyclic monoalcohol with a carbon number of 8 and the content of the monocyclic alicyclic monoalcohol with a carbon number of 9 was 5.0% by mass when the sum of the content of the monocyclic alicyclic monoalcohol with a carbon number of 8 and the content of the monocyclic alicyclic monoalcohol with a carbon number of 9 was 100.0% by mass. According to GC mass spectrometry, the C7 component was methylcyclohexanol, the C8 component was dimethylcyclohexanol and ethylcyclohexanol, and the C9 component was trimethylcyclohexanol and ethylmethylcyclohexanol (the C7, C8 and C9 components were all positional isomer mixtures).

[0121] The same solvent property evaluation as in Example 1 was carried out using this monohydric alcohol solvent.

[0122] The results are shown in Table 2. When the monohydric alcohol solvent of Comparative Example 2 was used, a good coating film could not be obtained.

[0123] Comparative Example 3

[0124] An alicyclic monohydric alcohol solvent was obtained in the same manner as in Example 1 except that the colored precursor mixture A obtained in Example 1 was used and the hydrogenation reaction was carried out under the hydrogenation conditions described in Example 1 without fractionation.

[0125] The content of residual aromatic components in the obtained monool-based solvent was less than 1.0% by mass, and the total content of the alicyclic monool (1) as the C8 component and the alicyclic monool (3) as the C9 component was 97.6% by mass. When the sum of the content of the monocyclic alicyclic monool having 8 carbon atoms and the content of the above-mentioned monocyclic alicyclic monool having 9 carbon atoms was set to 100.0% by mass, the content of the monocyclic alicyclic monool having 9 carbon atoms was 1.4% by mass.

[0126] According to GC mass spectrometry, the C7 component is methylcyclohexanol, the C8 component is dimethylcyclohexanol and ethylcyclohexanol, and the C9 component is trimethylcyclohexanol and ethylmethylcyclohexanol (the C7, C8 and C9 components are all positional isomer mixtures). The Hazen unit chromaticity (APHA) exceeds 100.

[0127] The obtained monoalcohol solvent was light brown and was colored in the coating film evaluation and the ink dilution property evaluation. It was not suitable as a solvent for coating films or inks, which requires transparency of the solvent.

[0128]

Table 2

[0129] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 C7-C9 alicyclic monohydric alcohol (mass %) 99.0 99.0 99.0 99.0 99.0 99.0 99.0 Aromatic monohydric alcohol (mass %) <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 C7 alicyclic monohydric alcohol (4) (mass %) 1.1 0.5 15.7 18.8 29.7 0.3 1.4 C8 alicyclic monohydric alcohol (1) (mass %) 96.7 95.0 82.0 79.2 69.1 93.7 97.2 Dimethylcyclohexanol (2) (mass %) 75.4 79.0 64.0 62.9 54.0 77.5 76.0 Ethyl cyclohexanol (mass %) 21.3 16.0 18.0 16.3 15.1 16.2 21.2 C9 alicyclic monohydric alcohol (3) (mass %) 1.2 3.5 1.3 1.0 0.2 5.0 1.4 Total of C8+C9 (1)+(3) (mass %) 97.9 98.5 83.3 80.2 69.3 98.7 97.6 Ratio of (3) when (1) + (3) is 100 (mass %) 1.2 4.0 1.6 1.2 0.3 5.1 1.4 Ratio (mass %) of (4) when (1) + (3) is 100 1.1 0.5 18.9 23.5 42.9 0.3 1.4 Hazen Unit Chromaticity (APHA) 10 10 10 10 10 10 >100 Coating evaluation (1) Surface smoothness ○ ○ ○ ○ × × × Coating evaluation (2) Coating adhesion 2 2 3 3 4 2 2 Evaluation of pressure-sensitive adhesiveness (ball No.) 13 14 11 10 8 15 13 Ink dilution ○ ○ ○ ○ ○ ○ ×

[0130] Industrial Applicability

[0131] The monohydric alcohol solvent of the present invention can be used as a low-flammability solvent usable at high temperatures, and can be used as an excellent industrial solvent particularly for use as a coating solvent, an adhesive solvent, a pressure-sensitive adhesive solvent, and an ink solvent.

Claims

1. A monohydric alcohol solvent mixture, characterized in that: Contains 96.0% by mass or more of an alicyclic monohydric alcohol having 7 to 9 carbon atoms and having a monocyclic alicyclic skeleton, 75.0% by mass or more of the alicyclic monohydric alcohol having 7 to 9 carbon atoms is composed of a monocyclic alicyclic monohydric alcohol having 8 carbon atoms and a monocyclic alicyclic monohydric alcohol having 9 carbon atoms, When the sum of the content of the alicyclic monohydric alcohol having 8 carbon atoms and the content of the alicyclic monohydric alcohol having 9 carbon atoms is 100.0 mass %, the content of the alicyclic monohydric alcohol having 9 carbon atoms is 0.4 to 4.0 mass %, and The chromaticity expressed in Hazen unit chromaticity is 30 or less.

2. The monohydric alcohol solvent mixture according to claim 1, wherein When the sum of the content of the monocyclic alicyclic monohydric alcohol having 8 carbon atoms and the content of the monocyclic alicyclic monohydric alcohol having 9 carbon atoms is taken as 100.0 mass %, the content of the monocyclic alicyclic monohydric alcohol having 7 carbon atoms is 0.5 to 25.0 mass %.

3. The monohydric alcohol solvent mixture according to claim 1, wherein The alicyclic monohydric alcohol having 7 to 9 carbon atoms is an alkylated cyclohexanol.

4. The monohydric alcohol solvent mixture according to claim 1, wherein 58.0% by mass or more of the alicyclic monohydric alcohol having 8 carbon atoms is dimethylcyclohexanol.

5. Use of the monohydric alcohol solvent mixture according to any one of claims 1 to 4 as a coating solvent. 6 . Use of the monohydric alcohol solvent mixture according to claim 1 as a solvent for an adhesive. 7 . Use of the monohydric alcohol solvent mixture according to claim 1 as a solvent for a pressure-sensitive adhesive. 8 . Use of the monohydric alcohol solvent mixture according to claim 1 as an ink solvent. 9 . Use of the monohydric alcohol solvent mixture according to claim 1 in an ink containing no silver particles.

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