WO2007110978A1 - Terpenic alcohol compound, terpenic (meth)acrylate compound, and process for producing them - Google Patents

Abstract

A terpenic alcohol compound is obtained with high yield at relatively low cost through simple means in consideration of any impact on environment by hydroformylating a terpenic compound having a double bond into a terpenic aldehyde compound and thereafter carrying out a catalytic hydrogen reduction thereof. Further, through reaction of the terpenic alcohol compound with a (meth)acrylic acid compound, there can be obtained a novel terpenic (meth)acrylate compound capable of enhancing the performance of curing shrinkage, heat resistance, water absorption, etc. in the use as a photosensitive material such as resist, an ink, a coating material such as paint, a raw material for sticky adhesive, a building material, etc.

Description

 Specification

 Terpene-based alcohol compound, terpene-based (meth) atalylate complex, and method for producing them

 Technical field

 [0001] The present invention relates to terpene-based monoalcohols synthesized by hydroformylation, terpene-based alcohol compounds such as terpene-based dialcohols, and terpene-based (meth) allylates which are derivatives of the terpene-based alcohol compound. The present invention relates to a compound and a method of manufacturing the same.

 Background art

 Terpene-based monoalcohols are used in solvents for solder flux, solvents for glass and metal paste, and electronic materials such as intermediates for resist materials, while terpene-based dialcohols are used in polycarbonate resin, epoxy resin, etc. It can be used as a raw material for electronic components, especially as a raw material for resins such as polyester and polyurethane resin, and as a precursor for reactive monomers such as atalylate, vinyl ether and glycidyl ether. It can be used over a wide range, including reaction solvents, adhesives, and resin modifiers.

 On the other hand, the terpene-based (meth) atalylate complex is used as a photosensitive reactive monomer, for example, a sealant for a resist or a semiconductor, a UV curable ink 'toner, a UV curable adhesive, a monomer for photofabrication, It can be used in the fields related to optics and electronics, such as polymer materials for optical fiber applications, and further, paints, coating materials, adhesive materials, building materials, polymer materials, developers, surfactants, plasticizers, insecticides It can also be used in various technical fields, such as raw materials such as germicides, pharmaceuticals, and chemicals for rubber.

 Further, since these terpene-based alcohol compounds and terpene-based (meth) atarylate compounds are compounds derived from biomass, they are also considered as environmentally-friendly materials from the viewpoint of carbon-eutral.

As a conventional method for producing a terpene-based alcohol compound, for example, 3 (hydroxymethyl) γ, 4 dimethyl-cyclohexanepropanol (the following formula) is dipentene ( Alternatively, there has been a method of synthesizing via methylation reaction after methylolization using d-limonene), formaldehyde or the like (Non-patent Document 1). In addition, a similar reaction is described in Non-Patent Document 2 as well.

[Chem. 1]

 However, in the method described in Non-patent Document 1, both the yield and selectivity are low, while in the method described in Non-patent Document 2, it is necessary to use theoretical amounts of alkylaluminums and anionic zeolites. In order to carry out industrially, problems such as cost remain. Furthermore, it is not desirable to use chemicals such as formaldehyde because of recent environmental problems.

 [0006] In addition, with respect to various olefins of hydroformylic acid, many patents have been filed, and many of them use even more specialized and expensive catalysts without using terpenes. There are many cases (Patent Documents 1, 2 and 3).

[0007] Also, conventionally, regarding radiation curable compositions using methyl methacrylate, methacrylamide, glycidyl methacrylate, bisphenol A diglycidyl methacrylate, and the like as raw materials,

Has already been patented as a fast-curing, highly productive material for applications such as coating agents and paints (Patent Document 4).

 However, these photosensitive compositions do not have sufficient performance in terms of cure shrinkage, heat resistance, water absorption and the like.

Non-patent literature l: Watanabe, Yuichi, "Reaction of dipentene with formale hyde. II. Synthesis of 1, 3-dioxane and its reduction", Nippon kaga ku Zassiku vol. 80, 1959, pl063-1066 Non-Patent Document 2: Atsushi Oonaka, Rui, Yoichi Masui "A New Development in Solid Acid and Base Catalysis Research", Organic Synthesis, vol. 63, No. 5, 2005, p492-502

 Patent Document 1: Japanese Patent Publication No. 2000-504001

 Patent Document 2: Japanese Patent Application Laid-Open No. 2003-342210

 Patent Document 3: Japanese Patent Application Laid-Open No. 2002-241329

 Patent Document 4: Japanese Patent Application Laid-Open No. 4-11609

 Disclosure of the invention

 Problem that invention tries to solve

 The present invention provides a terpene-based alcohol compound, a resist, a sealant, a UV curable ink, and a terpene-based alcohol compound which can be relatively inexpensive and high yield by a simple method in consideration of environmental impact. New terpene-based (meth) atalylate elates that improve the properties such as curing shrinkage, heat resistance, and water absorption as photosensitive materials such as adhesive and adhesive compositions, paints, coating materials, building materials, etc. The purpose is to provide a composite.

 Means to solve the problem

 The present invention relates to a terpene-based alcohol compound obtained by hydroformylation of a terpene-based compound having a double bond to form a terpene-based aldehyde compound, followed by hydrogen reduction.

 Here, as the terpene compound having a double bond, d-limonene, p-menthene, j8-pinene, camphene, γ-terbinene and the like are preferable from the viewpoints of cost, availability, usage and the like.

 Next, the present invention relates to a terpene type (meth) atalylate complex obtained by reacting the above-mentioned terpene type alcohol compound with a (meth) acrylic acid complex.

 Here, when expressed as a chemical structural formula, as the terpene alcohol complex, the following formulas (1) to (4), and as the terpene (meth) atalylate complex, the following formula (5) to The one represented by (8) is preferred.

In addition, when d-limonene is used, the terpene-based alcohol compound is represented by the formula (2), the formula (4), and the terpene-based (meth) atalylate complex compound is represented by (6), It becomes something like 8).

(ε) ...

(Τ)

ίΖ9Ι / 900 // 13ά V 8.60ΪΪ / .00ΪΪ OAV

 ... Equation (6)

[Wherein, in the formula (6), R = H or CH] [Formula 8]

 'Equation (7)

 [Wherein, in the formula (7), R = H or CH]

 twenty three

 [Formula 9]

 ... Equation (8)

 [Wherein, in the formula (8), R = H or CH]

 twenty three

 When p-menthene is used as a terpene compound having a double bond, a terpen alcohol compound is represented by the following formula (9), and a terpene compound having a double bond When y terpinene is used, the terpene alcohol compound is as represented by the following formula (10).

 [Formula 10]

'Expression (9) [Formula 11]

 ... expression (1 0)

 Effect of the invention

 The terpene-based alcohol compound of the present invention can be produced relatively inexpensively by a simple method without the need for complicated chemical treatment that increases the cost. Further, the terpene-based alcohol compound obtained in the present invention has very special performance as a polymer raw material and a solvent, and is a compound which is extremely useful industrially.

 In addition, the curable composition using the terpene-based (meth) atarylate complex of the present invention can improve the performance such as curing shrinkage, heat resistance and water absorption.

 Brief description of the drawings

FIG. 1 is an IR chart of the product obtained in Example 1.

 FIG. 2 is an EI-MS chart of the product obtained in Example 1.

FIG. 3 is a ¹ H-NMR chart of the product obtained in Example 1.

FIG. 4 is a ¹³ C-NMR chart of the product obtained in Example 1.

 FIG. 5 is an IR chart of the product obtained in Example 2.

 FIG. 6 is an EI-MS chart of the product obtained in Example 2.

FIG. 7 is a ¹ H—NMR chart of the product obtained in Example 2.

FIG. 8 is a ¹³ C-NMR chart of the product obtained in Example 2.

 FIG. 9 is an IR chart of the product obtained in Example 3.

 FIG. 10 is an EI-MS chart of the product obtained in Example 3.

FIG. 11 is a ¹ H-NMR chart of the product obtained in Example 3.

FIG. 12 is a ¹³ C-NMR chart of the product obtained in Example 3. FIG. 13 is an IR chart of the product obtained in Example 4.

 FIG. 14 is an EI-MS chart of the product obtained in Example 4.

FIG. 15 is a ¹ H-NMR chart of the product obtained in Example 4.

FIG. 16 is a ¹³ C-NMR chart of the product obtained in Example 4.

 BEST MODE FOR CARRYING OUT THE INVENTION

The terpene alcohol compound of the present invention will be described.

 First, terpene compounds having a double bond will be described.

 Terpene compounds are compounds generally contained in plant essential oils such as plant leaves, leaves, roots and the like.

 Here, terpene is generally a polymer of isoprene (C 2 H 5), and is a monoterpene (C

 5 8 10

H;), sesquiterpenes (C 6 H 5), diterpenes (C 6 H 6), and the like.

 18 15 24 20 32

 The terpene compounds having a double bond of the present invention are compounds having these as a basic skeleton. Among these, monoterpene force is preferably used in the present invention. The terpene compound having a double bond of the present invention may be a chain-like terpene compound. Specific examples of the terpene compounds having a double bond of the present invention include, for example, the following.

As monotenolepen, at binene, 13 binene, dipentene, d-limonene, p-menthene, p-menthene, camphene, minolecene, arosiocene, oscimene, a-phenlandene, a-tenolepinene, γ-tervinene, terpinorene, a-terpineol 13-terbineol, γ-terbineol, sabinene, paramentagens, karenes and the like. Among these compounds, d limonene [the following formula (Α)], γ terpinene [the following formula (B)], a-binene, j8-pinene, dipentene and α-terpinene are particularly preferably used. [Formula 12]

[Chem. 13]

 (B)

 A terpene compound having a double bond may be a raw material of the method for producing a terpene alcohol compound of the present invention, but from the viewpoint of supply and cost, in (C H),

 Compounds from monoterpenes to triterpenes of 5 8 η η = 2 to 6 are preferably used.

Next, the hydroformylation of the present invention will be described.

 In general, hydroformylation is also referred to as oxo synthesis, and is a method of synthesizing a saturated aldehyde having one more carbon atom than that of raw alphane by the catalytic reaction of olefin, carbon dioxide with hydrogen and hydrogen. The same applies to the hydroformylation of The main reaction is represented as follows: two isomers are formed simultaneously.

[0030] [Formula 14]

RCH = CH ₂ + CO + H ₂ ► RC I-1 ₂ CH ₂ CH 0

, RCHCH ₃ [Wherein, R is a general organic chemical structure such as alkane, cycloalkane, aryl, ether, ester, etc.]

 The reaction for producing a terpene-based aldehyde complex with the hydroformyl bond of the present invention can be carried out, for example, by adding a catalyst to a terpene-based compound having a double bond and a solvent, and then subjecting it to pressure and temperature. Good.

 The total feed ratio of hydrogen and carbon monoxide to the terpene compound having a double bond is usually 1 to 2 moles. Further, the feed ratio of hydrogen to carbon monoxide is about 0.9: 1 to 1.5: 1 in volume ratio.

 In addition, the terpene type compound which does not have a double bond can also be used as a solvent. Further, in the reaction, the method of feeding the raw material, the raw material gas, the solvent and the catalyst is not limited to the above-mentioned method.

 Here, as the catalyst used for the hydroformylation of the present invention, cobalt-based catalysts such as cobalt hydrocarbyl, rhodium chloride (ΠΙ), rhodium nitrate (ΠΙ), rhodium (III) acetate, acetyl acetate, etc. Rhodium chalcogenide such as acetonato rhodium (ΠΙ), rhodium sulfate (ΠΙ), ammonium rhodium (II I) chloride, oxygen oxide such as rhodium oxide (ΠΙ) or rhodium sulfide (ΠΙ), salt of rhodium rhodium, tetrarhodium Dodecacarbonyl or Hexarhodium Hexarhodium Force Rhodium-based catalysts such as rhodium carbonyl compounds such as rubonyl are not limited to these. The amount of the catalyst used is preferably 0.05 to 3% by weight, more preferably 0.05 to 1% by weight, based on 100% by weight of the terpene compound having a double bond. If it is less than 0.03% by weight, the reaction does not proceed sufficiently, while if it exceeds 3% by weight, it is not preferable because the catalyst is wasted or the control of the reaction becomes difficult.

In the hydroformylation reaction, it is preferable to add a tertiary organic phosphorus compound from the viewpoint of the stability of the rhodium-catalyzed active species involved in the reaction. Examples of tertiary organophosphorus compounds include triphenyl phosphite, tris (2-methylphenyl) phosphite, tris (2-ethylphenyl) phosphite, tris (2-isopropylphenyl) phosphate, tris 2-phenylphenyl) phosphite, tris (2-tert-butylphenyl) phosphate, tris (2-tert-butyl-5-methylphenyl) phosphite, bis (2-methyl phenyl) (2-t) —Butyl phenyl) phosphite, bis (2-t-butyl phenyl) (2-methyl) Phenyl) phosphite, phosphite compound such as tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphine, tri-tolyl phosphine, tri-cyclohexyl phosphite, tri-n-butyl phosphine And phosphine compounds such as tris-octyl phosphine; 1,2 bis (diphenylphosphino) aetane; 1,3 bis (diphenyl phosphite) propane; diphosphine compounds such as 1,4 bis (diphenylphosphino) butane; Can be mentioned. Among these, triphenyl phosphine, triphenyl phosphite and tris (2,4-di tert-butylphenyl) phosphite are preferable. The tertiary organic phosphorus compound may be used alone or in combination of two or more.

The amount of the tertiary organophosphorus compound to be used is not particularly limited, but if the tertiary organophosphorus compound is present in a large excess relative to the rhodium-catalyzed active species which causes the hydroformylation reaction to proceed. Since the reaction activity is lowered, it is usually in the range of 2 to 150 times mol, preferably 10 to 50 times mol based on the rhodium atom in the rhodium compound.

 In the reaction, the reaction solvent is not particularly used, but there is no limitation as long as it is a non-reactive solvent such as an alicyclic or aliphatic saturated hydrocarbon compound, and it has no double bond. And terpene compounds can be used as a solvent as they are.

 Also, aromatic solvents such as toluene and xylene can be used under special conditions.

 The reaction temperature of the hydroformylation of the present invention is usually 30 to 160 ° C., preferably 70 to 150 ° C. If the reaction temperature is less than 30 ° C., the reaction rate is slow, while if it exceeds 160 ° C., side reactions such as isomerization and disproportionation preferentially proceed, which is not preferable because the yield is lowered.

 [0037] The reaction time of the hydroformyl ide of the present invention is usually 0.5 to 20 hours, preferably 2 to 8 hours. If the reaction time is less than 0.5 hours, the conversion rate is low, and if it exceeds 20 hours, the production efficiency is unfavorably reduced. After reacting for a predetermined time, the reaction solution obtained by the above reaction is subjected to decatalysis according to the catalyst used, and the terpene-based aldehyde complex and terpene-based alcohol complex of the present invention are obtained. A mixture can be obtained. The removal of the catalyst may be carried out, for example, by washing the reaction solution with water. Also, the catalyst may be removed by filtration.

[0038] The reaction pressure of the hydroformylation of the present invention is usually 0.1 to 20 MPa, preferably 0.5 to 5 It is 15 MPa. If the reaction pressure is less than 0.1 MPa, the reaction rate will be slow, while if it exceeds 20 MPa, it is not preferable in terms of difficulty in controlling the reaction, cost and other aspects.

The reaction liquid after the decatalysis may be subjected to distillation to distill a terpene aldehyde compound to obtain a purified product, but the purification method is not limited to this method. Purification by column separation or purification may be carried out as the product is recovered by crystallization. In addition, the reaction solution may be used as it is for the next reaction without purification.

 In the reaction, the method of feeding the raw material, the raw material gas, the solvent and the catalyst is not limited to the above-mentioned method.

 Next, a hydrogen reduction reaction of a terpene aldehyde compound for producing a terpene alcohol compound will be described. The hydrogen reduction reaction of a terpene-based aldehyde compound for producing a terpene-based alcohol compound is carried out using a reducing agent or a hydrogen-reducing agent in the presence of a metal catalyst for hydrogen reduction.

 The hydrogenation reduction reaction is carried out, for example, by charging a terpene-based aldehyde compound, a solvent, and a hydrogen reduction catalyst, and performing hydrogen reduction at a predetermined temperature under a predetermined pressure of hydrogen until it absorbs a theoretical amount of hydrogen. It is good.

 Examples of metal catalysts used for the hydrogen reduction reaction include Raney Ni, stabilized Ni powder, Pt / Al 2 O, PtZC, Ru / C, Ru / Al 2 O, Pd / C, Pd / Al 2 O, Re / Al 2 O, etc. general

2 3 2 3 2 3 2 3

 It is possible to use metal catalysts used for hydrogen reduction, but it is not limited thereto.

 The amount of the metal catalyst used is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, particularly preferably 1 to 20% by weight, based on 100% by weight of the reaction mixture after removal of the terpene aldehyde compound or terpene compound. : L 0% by weight. If the amount is less than 0.01% by weight, the hydrogen reduction does not proceed sufficiently, while if it exceeds 30%, the cost is not preferable.

A solvent may not be used, but if it is used, a solvent which dissolves a terpene aldehyde compound and can be stable under hydrogen reduction reaction conditions can be used, for example, propyl alcohol, isopropyl alcohol Alcohol solvents such as butanol or heptanol and the like, and saturated hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane and menthanes. In addition, aromatic solvents such as toluene and xylene can also be used under special conditions.

 The hydrogen reduction temperature is usually 0 to 300 ° C., preferably 50 to 250 ° C., and more preferably 80 to 180 ° C. If this temperature is less than 0 ° C., the hydrogen reduction reaction rate will be slow, and if it exceeds 300 ° C., side reactions will proceed preferentially and the yield will decrease, which is not preferable.

 The hydrogen reduction time is usually 1 to 40 hours, preferably 2 to 20 hours, and more preferably 4 to 15 hours. If this time is less than 1 hour, the conversion rate is low, and if it exceeds 40 hours, production efficiency decreases, which is preferable.

 The hydrogen pressure at the time of hydrogen reduction is usually atmospheric pressure to 20 MPa, preferably 0.1 to 10 MPa, and more preferably 0.5 to 5 MPa. If the hydrogen pressure is lower than normal pressure, the reaction rate will be slow, and if it exceeds 20 MPa, viewpoints such as the degree of difficulty and cost of reaction control are not preferable.

 After the hydrogen reduction reaction is performed for a predetermined time, the obtained reaction liquid is subjected to decatalysis according to the metal catalyst used. The decatalystation may be carried out by filtering out the metal catalyst or by letting the reaction solution flow out of the system.

 In addition, in the case of performing hydrogen reduction using a reducing agent, the reducing agent is added dropwise to one obtained by diluting the terpene aldehyde compound with a solvent such as toluene, methanol, or tetrahydrofuran, or the reducing agent is dissolved. The reduction reaction may be allowed to proceed by dropping the terpene aldehyde compound into the reaction solution.

 Examples of the reducing agent include lithium aluminum hydride and sodium borohydride.

 The amount of the reducing agent used is preferably 0.5 to 3 molar equivalents, more preferably 0.9 to 3 molar equivalents to the terpene aldehyde compound or the aldehyde group contained in the reaction solution after decatalysis. Equal amounts, particularly preferably 1 to 2 molar equivalents. If the amount is less than 0.5 molar equivalent, sufficient hydrogen reduction does not proceed, while if it exceeds 3 molar equivalents, side reactions preferentially take place, or productivity decreases, which is not preferable! .

A solvent may not be used, but when it is used, a solvent similar to the method using the above metal catalyst can be used.

Aromatic solvents such as toluene and xylene can also be used under special conditions such as hydrogen pressurization. When hydrogen is reduced by a reducing agent, the temperature is usually 40 to 100 ° C., preferably 20 to 80 ° C., and more preferably −10 to 40 ° C. If this temperature is less than -40 ° C, the hydrogen reduction rate will be slow, while if it exceeds 100 ° C, side reactions will proceed preferentially and the yield will decrease, which is not preferable.

 The hydrogen reduction time is usually 1 to 40 hours, preferably 3 to 20 hours, and more preferably 5 to 10 hours. If this time is less than 1 hour, the conversion rate is low, but if it exceeds 40 hours, the production efficiency is reduced, which is not preferable.

 After the hydrogen reduction reaction is performed for a predetermined time, a dereducing agent corresponding to the used reducing agent is applied to the obtained reaction solution. For example, after a deactivating agent such as alcohol or water is added, the reducing agent may be sufficiently stirred to deactivate the reducing agent.

 The terpene-based alcohol compound thus obtained can be usually purified by distillation and distilled to obtain a purified product. However, the purification method is not limited to this method. Purification by column separation or purification may be performed to recover the product by crystallization.

 Terpene Compounds Having a Double Bond In the case of d limonene or γ-terpinene, the main component of the resulting terpene alcohol complex is the formula (2) for d limonene as described above. In equation (4), y Terpinene is as equation (10).

 [Formula 15]

'Expression (2) [Formula 16]

 ... expression (1 0)

 [0056] In order to form a monoalcohol compound such as the above formula (4) using d-limonene, the reaction temperature is 100 ° C. or less and the reaction pressure is 4 MPa or less in the hydroformylation reaction. It is necessary to

[0057] terpene alcohol compounds of the present invention, the infrared absorption spectrum, O-H due to the extension contraction 3, 300 cm ^_1 vicinity of broad peaks, 3 due to C-H stretching, 000 to 2, 800 cm ^_1 , C-H 1 due to deformation, 500~1, 350cm ^_1, can be confirmed by a peak in the vicinity of 1, 050cm ^_1 due to C-O stretching.

 In addition, it can be confirmed by an NMR chart that a signal of 0.84-1. 90 ppm derived from a terpenes-derived hydrocarbon and a signal of 3. 50-3. 80 ppm derived from a methylene group adjacent to a hydroxyl group.

Furthermore, it is confirmed by the ¹³ C-NMR and the DEPT chart that the signal from the terpenes-derived hydrocarbon is 16.2 to 46.5 ppm, and the signal from the methylene group adjacent to the hydroxyl group is 61.0 to 66. Oppm. be able to. Next, the reaction of the terpene alcohol compound with the (meth) acrylic acid compound, which is the terpene (meth) atalylate compound of the present invention, will be described.

 In this reaction, a method of esterifying terpene-based alcohol compound and (meth) acrylic acid, a method of reacting terpene-based alcohol compound and (meth) acrylic acid or rhogenic acid, terpene-based method Method of reacting alcohol compound and (meth) acrylic anhydride, and method of transesterification reaction of the terpene type alcohol compound and acrylic ester such as methyl (meth) acrylate or ethyl (meth) acrylate and so on. However, the reactions used in the present invention are not limited to these.

 Examples of the (meth) acrylic acid compound include (meth) acrylic acid, anhydrous (meth) acrylic acid, (meth) acrylic acid chloride, methyl (meth) acrylate and ethyl (meth) acrylate. , (Meth) aryl, aryl (meth) acrylate, isopropyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylate 2 — Hexyl hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid hexyl and the like, (meth) acrylic acid, (meth) acrylic acid chloride, methyl (meth) acrylic acid, (meth) acrylic acid Acid ethyl is preferably used.

 Among the above reactions, the preparation ratio of (meth) acrylic acid in the esterification reaction using (meth) acrylic acid is 0.1 to 20 moles relative to 1 mole of the terpene alcohol compound as the raw material. , Preferably 1 to 10 moles. If the amount of (meth) acrylic acid is less than 0.1 mol per 1 mol of the terpene alcohol compound, the ester reaction may not proceed sufficiently, while if it exceeds 20 mol, it is unreacted. Preferred because (meth) acrylic acid may remain and cost may increase!

 [0061] Also, as the solvent, an aromatic compound such as benzene, toluene, or xylene, or a hydrocarbon compound such as hexane or cyclohexane is generally used as a solvent that forms an azeotrope with water. You do not have to use it because acids etc. also serve as a solvent.

 When a solvent is used, the amount of the solvent used is 0.3 to 10 times by weight, preferably 0.5 to 7 times by weight that of the raw material terpene alcohol compound.

[0062] Examples of the catalyst include sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, ion exchange resins, activated clay, heteropolyacids such as phosphotungstic acid, etc. It can be used.

 The amount of the catalyst used is not particularly limited, but it is 0.0001 to 0.1 mole, preferably 0.001 to 0.01 mole relative to 1 mole of the raw material terpene based alcohol compound.

At the time of this ester ring reaction, it is preferable to add a polymerization inhibitor. The polymerization inhibitor is not particularly limited as long as it is a compound capable of capturing radicals generated in the reaction system, and examples thereof include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, phenothiazine, t-butyl hydroquinone and the like. it can. The addition amount of the polymerization inhibitor is usually 5 to: LO, OOO ppm, preferably 20 to 5, OOO ppm, and more preferably 50 to: L, OOO ppm relative to the charged (meth) acrylic acid.

The reaction temperature of esterification is 30 to 200 ° C., preferably 60 to 150 ° C. If the reaction temperature is less than 30 ° C., the reaction rate may be extremely slow, while if it exceeds 200 ° C., side reactions such as polymerization become significant, which is not preferable. The esterification reaction is usually carried out under normal pressure, but can also be carried out under reduced pressure or under pressure depending on the boiling point of the solvent used.

A method of reacting the above-mentioned terpene alcohol compound and (meth) acrylic acid halide, a method of reacting the terpene alcohol complex and (meth) acrylic anhydride, a terpen alcohol compound and (meth As a method of transesterification reaction of acrylic acid esters such as methyl acrylate and ethyl (meth) acrylate, terpene alcohol compounds and (meth) acrylic acid halides or (meth) acrylic acid anhydrides may be A method of reacting at 0 to 70 ° C. in a basic solvent such as pyridine, in the presence of a catalyst used for general transesterification such as p-toluenesulfonic acid, titanium (IV) tetraisopropyl, dioctyltin, dibutyltin, lithium hydroxide and the like , Terpene alcohol compounds and methyl acrylate, or acrylic acid A method such as reacting with ruethyl acetate at 20 to 150 ° C. may, for example, be mentioned.

C Of申縮【こ起因する 1, 300〜1, 180cm^{_ 1}のピーク【こより確認する ことができる。 また、 — NMRチャートにより、テルペン類由来炭化水素に起因する 0. 79-1. 86ppmのシグナノレ、エステノレ【こ隨接するメチレン基【こ起因する 4. 02〜4. 36ppm のシグナル、アタリレートに起因する 5. 80〜6. 42ppmのシグナルにより確認するこ とがでさる。 According to the infrared absorption spectrum of the terpene-based (meth) atalylate complex of the present invention, C 縮 [attributable to 3, 000 to 2, 800 cm ^_1 , C = Of 縮 attributable] , C = Cf constriction [attributable to 1, 640 ~ 1, 620 cm ^_1 , CH deformation [attributable to 1, 500 ~ 1,

C Of Consensus [peaks of 1, 300 to 1, 180 cm ^{_ 1} caused by this] can be confirmed from this. In addition, according to the NMR chart, 0.79-1. 86 ppm signole, estenore, and methylene group derived from terpenes-derived hydrocarbon, 4. 02-4. 36 ppm signal, attributed to atalylate. Yes 5. Confirm with a signal of 80 to 6. 42 ppm.

Furthermore, according to ¹³ C-NMR and DEPT charts, 15. 0 to 45.5 ppm of the signal derived from terpenes-derived hydrocarbon, 60.0 to 68. O ppm of the signal due to the methylene group adjacent to the ester, It can be confirmed by the signals of 128.6 to 130.7 ppm and 166.5 to 166.5 ppm due to

Example

 Hereinafter, the present invention will be more specifically described by way of examples.

 Synthesis Example 1 (Synthesis of terpene-based aldehyde complex with hydroformyl)

 d-limonene (Yasuhara Chemical Co., Ltd. d-limonene N (purity 99%)) 136g, Otacha boll Bicobalt catalyst (Wako Pure Chemical Industries, Ltd. 136 mg, triphenylphosphine (Wako Pure Chemical Co., Ltd.) Five grams were injected into a 500 ml autoclave.

 The mixture was stirred at 120 ° C. for 15 minutes, reacted with a mixed gas of monobasic carbon Z hydrogen = 1Z1 for 15 hours while maintaining a pressure of 7 Mpa, and after reaction, the catalyst was removed to obtain a reaction oil . The reaction oil was distilled under reduced pressure and purified to obtain lOlg as product A.

The reaction oil was analyzed by Agilent Technologies' 6890N gas chromatography and GC- MS (Hewlett Packard 6890, ionization mode: EI), and the product (p-menthane dicarbaldehyde, main component) The following formula (11) was 60.3%, p-menthene monocarbaldehyde was 25.2%, and p-menthanedimethanol was 4.5%

[Formula 18]

Synthesis Example 2 (Synthesis of Terpene-Based Aldehyde Compound by Hydroformylation)

 d-limonene (Yasuhara Chemical Co., Ltd. d-limonene Ν (purity 99%)) 136g, Otacha bollunicobalt catalyst (Wako Pure Chemical Industries, Ltd. 136 mg, triphenylphosphine (Wako Pure Chemical Co., Ltd.) Five grams were injected into a 500 ml autoclave.

 The mixture is stirred at 80 ° C. for 30 minutes, using a mixed gas of monobasic carbon Z hydrogen = 1Z1

After reacting for 6 hours while maintaining a pressure of 4 Mpa, after reaction, the catalyst was removed to obtain a reaction oil. The reaction oil was distilled under reduced pressure and purified to obtain 157 g of product A.

 The reaction oil was analyzed by Agilent Technologies' 6890N gas chromatography and GC-MS (Hewlett Packard 6890), and as a result, the product (p-menthane monocarbaldehyde, the main component was the following formula ( 12) 95. 2%, p-menthene dicarbaldehyde S 3.2%, p-menthane dimethanol was 4.5%.

[Chem. 19]

実施例 1 (テルペン系アルコール化合物の合成 1)

Example 1 (Synthesis of Terpene-Based Alcohol Compound 1)

150 g of the terpene series aldehyde compound obtained in Synthesis Example 1, 400 ml of isopropanol, and a stabilized nickel catalyst in the form of powder 5. Charge Og, then seal it and Was replaced with nitrogen gas, and then introduced while applying a pressure of hydrogen gas IMPa. When heated to 140 ° C. while stirring, the pressure of hydrogen was set to 2 MPa, and the reaction was carried out for 4 hours while maintaining the pressure at 2 MPa by supplementing the absorbed hydrogen. After the reaction, filter the catalyst! d

 By removing the oil, and distilling and purifying the reaction oil to obtain the terpene-based alcohol compound of the present invention

 o o

 A (the main component was the formula (2 o)), 120.5 g was obtained.

 To

[0072] The o t obtained in Example 1

 The analysis results of the Oo terpene-based alcohol compound A are shown in FIGS. 1 to 4 and Tables 1 to 2. In addition, the symbol which shows attribution of Table 1 and 2 shows the position shown to Formula (13).

 'result of analysis

： C— H変角、 1, 052cm^_1 :C— O伸縮、 1, 008cm"¹: C H面内変角 1) FIG. 1: IR chart 3, 308 cm ^_1 : O—H stretch, 2, 918 to 2, 856 cm ^_1 : C—H stretch, 1, 454, 1,

: C-H deformation, 1, 052 cm ^_1 : C-O expansion and contraction, 1, 008 cm " ¹ : CH in-plane deformation

 2) Figure 2: EI-MS chart mZz = 200 [M] + and mZz = 182 [M-H 0] + observed

 2

 It was done.

 3) Figure S ^ H-NMR chart

4) Figure 4: ¹³ C—NMR chart

[Chemical Formula 20] d

 h c, no c

 ,

 b e f OH formula (1 3)

[Table 1] 1 H-NMR

 δ (ppm) Number of protons Cleavage state Assignment

 3 m d

 3 d e

 0, 96–1, 77 12 m a, b, c, f, g

4 mh [Table 2]

 Example 2 (Synthesis of Terpene-Based Alcohol Compound 2)

 150 g of the terpene series aldehyde compound obtained in Synthesis Example 2, 400 ml of isopropanol, and a stabilized nickel catalyst in powder form 5. Og are charged, and then sealed, and the atmosphere is replaced with nitrogen gas; It was introduced while applying pressure. Then, when heated to 140 ° C. while stirring, the pressure of hydrogen was set to 2 MPa, and the reaction was carried out for 4 hours while maintaining the pressure at 2 MPa by supplementing the absorbed hydrogen. After completion of the reaction, the catalyst was removed by filtration, and the reaction oil was purified by distillation to obtain the terpene alcohol compound B of the present invention [the main component is the formula (4)], 131. Og.

 The analysis results of the terpene-based alcohol compound B obtained in Example 2 are shown in FIGS. 5 to 8 and Tables 3 to 4. In addition, the symbol which shows attribution of Table 3 and 4 shows the position shown to Formula (14).

 'result of analysis

： C— H変角、 1, 054cm^_1 :C— O伸縮、 1, 002cm"¹: C H面内変角 1) FIG. 5: IR chart 3, 319 cm ^_1 : 0—H stretching, 2, 918 to 2, 852 cm ^_1 : C—H stretching, 1, 448, 1,

: C-H deformation, 1, 054 cm ^_1 : C-O stretchability, 1, 002 cm " ¹ : CH in-plane deformation

 2) Fig. 6: EI-MS chart mZz = 152 [M-H 0] +, m / z = 124 [M-H O-

 twenty two

C H] +, mZ z = 97 [M-H O-C H] + were observed.

 2 4 2 4 8

 3) Figure Y ^ H-NMR chart

4) Figure 8: ¹³ C—NMR chart [Formula 21]

ez f OH ■ Formula (1 4)

[0079] [Table 3]

 [Table 4]

 Example 3 (Synthesis of Terpene-Based (Meth) Atalylate Compound)

Next, 20 g (0.1 mol) of the terpene-based alcohol compound obtained in Example 1 and 100 g of toluene were added to a 300 ml four loft flask equipped with a Dean-Stark tube, a cooling tube, a thermometer, and a stirring rod. 30 g (0.417 mol), 2.5 mg of hydroquinone monomethyl ether, and ion-exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) 2. Og were charged. The mixture was refluxed under reduced pressure at 100 ° C. for 12 hours, and the resulting mixture was filtered to separate the catalyst. Subsequently, toluene was distilled off at 80 ° C. under reduced pressure to obtain 21.56 g (yield 70%, purity 98.7%) of a terpene type (meth) atalylate compound A. The analysis results of the resulting terpene-based (meth) atalylate complex A are shown in FIG. 9 12 and Table 56. In addition, the symbol which shows attribution of Table 5 and 6 shows the position shown to Formula (15).

 'Analysis 分析 results

： C— H変 角、 1, 296 1, 271 1, 184 1058cm^_1:C— O伸縮、 984 966cm^_1:C— H面 外変角 1) Fig. 9: IR chart 2, 923 2, 857 cm ^_1 : C-H stretch, 1, 721 cm ^_1 : C = 0 stretch, 1, 637 1, 621 cm ^_1 : C = C stretch, 1, 458 1, 408 1,

: C—H variation, 1, 296 1, 271 1, 184 1058 cm ^_1 : C—O stretching, 984 966 cm ^_1 : C— H plane out-of-plane variation

 2) FIG. 10: EI-MS chart mZz = 308 [M] + mZz = 164 [M-ataryloyl group X 2] + etc. were observed.

 3) Figure l ^ H-NMR chart

4) Figure 12: ¹³ C—NMR chart

[Formula 22]

 'Expression (1 5)

 [Table 5]

¹ H-NM R

 δ (ppm) Number of protons Cleavage state Assignment

 6 m e, e '

 11 m a, f, d, g, c

 1.72-1.79 1 m b

 4.16-4.21 4 m h, h '

 5.82 2 dd i

 6.12 2 ddd k

6.40 2 dd i [Table 6]

 Example 4 (Synthesis of Terpene-Based (Meth) Atalylate Compound 2)

 In a 300 ml four-necked flask equipped with a Dean-Stark tube, a cooling tube, a thermometer, and a stirring rod, 17.6 g (、 18, 0.104 mol) of the terpene alcohol compound obtained in Example 2 and 100 g of toruen 12.7 g of an acid (0.176 monole), 2.5 mg of noidoquinone quinone monomethyoleate, and ion-exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) 2. Og was charged. The mixture was refluxed under reduced pressure at 100 ° C. for 12 hours, and the resulting mixture was filtered to separate the catalyst. Next, 0.5 g of phenothiazine was added, toluene was distilled off at 80 ° C. under reduced pressure, and toluene was distilled off at 80 ° C. under terpene (meth) atarylate mixture B 18.82 to give a terpene system. There were obtained 19.5 g (yield 84. 1%, purity 97.5%) of (meth) atalylate mixture B.

 [0087] The analysis results of the resulting terpene-based (meth) atalylate complex B are shown in Figs. 13-16 and Tables 7-8. In addition, the symbol which shows attribution of Table 7 and 8 shows the position shown to Formula (16).

： C— H変 角、 1, 296、 1, 272、 1, 185、 1061cm^_1:C— O伸縮、 985、 965cm^_1:C— H面 外変角 1) Fig. 13: IR shear relief 2, 920 to 2, 852 cm ^_1 : C-H stretch, 1, 725 cm ^_1 : C = 0 stretch, 1, 638, 1, 621 cm ^_1 : C = C stretch, 1, 457, 1, 408, 1,

: C—H deformation, 1, 296, 1, 272, 1, 185, 1061 cm ^_1 : C—O stretching, 985, 965 cm ^_1 : C— H plane out-of-plane angle

 2) FIG. 14: EI-MS chart mZz = 224 [M] +, mZz = 152 [M-ataryloyl group] + and the like were observed.

 3) Fig. 15: !! NMR chart

4) Figure 16: ¹³ C—NMR chart [Formula 23]

 Formula ... (1 6)

[Table 7]

 [Table 8]

 Test Example 1 (Application to Photosensitive Composition)

The terpene-based (meth) atarylate compound A obtained in Example 3 was added to Ciba 'Specialty Chemicals Inc. (purity 100%) IRGACURE 184 (1-hydroxy-cyclohexyl-phenyl-ketone) 3 parts by weight was mixed to prepare a photocurable resin composition. Test Example 2

 The same procedure as in Test Example 1 was carried out except that the terpene (meth) atarilate compound B obtained in Example 4 was used instead of the terpene (meth) atalylate compound A. A photocurable resin composition was prepared.

Comparative Test Example 1

 A photocurable resin composition was prepared in the same manner as in Test Example 1 except that butyl atalylate was used in place of terpene (meth) atalylate complex A.

Comparative Test Example 2

 A photocurable resin composition was prepared in the same manner as in Test Example 1 except that 1, 6 hexanediol ditalylate was used instead of the terpene (meth) atalylate compound A.

 Test Example 1 to Test Example 2 and Comparative Test Example 1 to Comparative Test Example 2 The cure shrinkage, the water absorption rate, and the glass transition temperature of Comparative Test Example 2 were evaluated by the following methods. The results are shown in Table 9

(Set cure shrinkage rate)

The specific gravity (D 2) at 23 ° C. of the photocurable resin composition was measured using a pycnometer. Next, the photocurable resin composition was irradiated with ultraviolet light at 1400 mj Z cm ² to obtain a cured product. The specific gravity (D 2) at 23 ° C. of the resulting cured product was measured using an electronic densitometer.

 2

 From the difference in specific gravity before and after curing, the cure shrinkage was determined by the following formula.

 Curing shrinkage (%) = ((D-D) / D) x 100

 2 1 2

 (Water absorption)

 The cured product obtained when the cure shrinkage rate was determined was immersed in water at 23 ° C. for 192 hours, and the ratio of weight change after immersion and before immersion was determined.

 Water absorption rate (%) = [(weight after immersion weight before immersion) weight before immersion Z] x 100

(Glass transition temperature)

The glass transition temperature was determined by measuring the DSC of the cured product. [0099] [Table 9]

産業上の利用可能性

Industrial applicability

 [0100] The terpene-based alcohol compound of the present invention is a compound having a special performance having a terpene group, and thus can be produced inexpensively and in large quantities, so that polymer raw materials, various solvents, and perfumes can be obtained. It can be used in a wide range of fields, and can show unique characteristics in each field. In addition, the terpene-based (meth) atarylate complex of the present invention can be used in various technical fields such as photosensitive materials such as resists, inks, coating materials such as paints, adhesive materials, and the like.

Claims

The scope of the claims  A terpene-based alcohol compound obtained by hydroformylation of a terpene-based compound having a double bond to form a terpene-based aldehyde compound, and then hydrogen reduction.  The terpene-based alcohol compound according to claim 1, wherein the chemical structural formula is represented by the formula (1). [Formula 1]

 ... Equation (1)  The terpene-based alcohol compound according to claim 1 or 2, wherein the terpene-based compound having a double bond is d-limonene and is represented by the terpene-based alcohol compound power formula (2). [Formula 2]

 ... Equation (2)  The terpene-based alcohol compound according to claim 1, wherein the chemical structural formula is represented by the formula (3). [Chemical 3]

The terpene-based alcohol compound according to claim 1 or 4, wherein the terpene-based compound having a double bond is d-limonene, and the terpene-based alcohol compound is represented by the formula (4).  [Formula 4]

 'Equation (4) [6] A terpene type (meth) atalylate compound obtained by reacting the terpene type alcohol compound according to any one of claims 1 to 5 with a (meth) acrylic acid compound.  [7] The terpene type (meth) atarylate complex according to claim 6, wherein the chemical structural formula is represented by the formula (5).  [Chem. 5]

 ... expression (5)  [Wherein, in the formula (5), R = H or CH]  13 [8] The terpene (meth) ataletote compound according to claim 6 or 7, wherein the chemical structural formula is represented by the formula (6). [Chemical 6]

 ... Equation (6)  [Wherein, in the formula (6), R = H or CH]  13  [9] The terpene type (meth) atarylate complex according to claim 6, wherein the chemical structural formula is represented by the formula (7).  Formula  [Chem. 7]  8

 ... expression (7)  [Wherein, in the formula (7), R = H or CH]  twenty three  [10] The terne based (meth) atalylate compound according to claim 6 or 9, wherein the terpene based (meth) atalylate compound is represented by the formula (8).  [Formula 8]

[Wherein, in the formula (8), R = H or CH] A method for producing a terpene alcohol compound, which is subjected to hydrogen reduction after hydroformylation of a terpene compound having a double bond to form a terpene aldehyde compound.  The manufacturing method of the terpene type (meth) atarylate compound which makes the terpene type alcohol compound of Claim 11 and (meth) acrylic acid complex react.