JPH1180306A - Urethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a urethane composition improved in performances such as heat resistance, adhesiveness, hydrolytic resistance, etc., of a cured reaction product, by including a phenol-based compound containing a cyclic terpene skeleton in the molecule as a hydroxyl component. SOLUTION: This composition comprises a mono- and/or a polyoxyalkylenemonool of a phenol-based compound [a reaction product of a cyclic terpene compound and a phenol compound such as an adduct of one molecule of a cyclic terpene/one molecule/two molecules of a phenol obtained by addition of one molecule of a cyclic terpene compound of formula I (X1 to X4 are each H, a 1-5C alkyl or OH) or formula II and two molecules of a phenol compound substituted with a 1-5C alkyl group or a hydroxyl group, etc.] or a mono- and/or a polyoxyalkylenepolyol of a phenolic compound containing a cyclic terpene skeleton in the molecule as a hydroxyl component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a urethane resin composition. More specifically, the present invention relates to a urethane resin composition excellent in heat resistance, adhesiveness, hydrolysis resistance, and the like of urethane foam, urethane-based elastomer, polyurethane molded product, urethane-based paint, urethane-based adhesive, sealing material, binder, and the like.

[0002]

2. Description of the Related Art Conventionally, a urethane resin is a polymer material composed of a raw material having a high activity and a high reactivity, and a wide range of properties such as hardness, softness and rigidity can be relatively easily obtained by changing the composition of the raw material. Therefore, it is used for a wide range of applications such as foams, elastomers, molded products, paints, adhesives, sealing materials and binders. In particular, in recent years, environmental issues such as solvent regulations and energy saving have been highlighted, and the use of (poly) urethane as a polymer for useless agents and energy saving has been increasing.

[0003] Urethane is a urethane group-containing compound obtained by reacting an isocyanate compound with an active hydrogen-containing compound. Examples of the isocyanate compound used for the urethane resin include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate (TODI),
1,6-hexamethylene diisocyanate (HDI),
Diisocyanates such as isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI) and hydrogenated MDI are generally used.

Examples of the compound containing an active hydrogen compound include glycols such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol, poly (ethylene adipate) and poly (1,4-butylene adipate). Polyester polyols such as poly (1,6-hexane adipate), poly (propylene adipate), poly (neopenthylene adipate), polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene oxide / polypropylene oxide copolymer, etc. And polyether polyols.

[0005] However, urethane resin compositions obtained from these compounds are not suitable for use in paints, adhesives, sealing materials, binders and the like.
Performances such as adhesion and hydrolysis resistance were not always satisfactory. Among them, reactive hot-melt adhesives and moisture-curable one-part urethane resin compositions have recently attracted particular attention.However, cured products with excellent heat durability and excellent adhesive strength or hydrolysis resistance have been developed. Nothing has been satisfactory enough. In other words, a urethane-based adhesive or sealing agent utilizing a curing reaction originally gives a high-strength cured product, but if the environment in which it is used is exposed to a high temperature, the cured product softens or degrades due to decomposition or the like. At present, there is no composition which can sufficiently satisfy the durability. Also,
When used as an adhesive or a sealing material, there are cases where the adhesive strength of the cured product is not sufficient. This is due to an insufficient moisture curing reaction or an essential defect of the urethane resin composition. Further, when the use environment is under a high humidity condition, the cured product undergoes a reduction in strength due to hydrolysis, but at present, there is no composition that sufficiently satisfies the hydrolysis resistance.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art. In a urethane resin composition, the properties of a cured reaction product such as heat resistance, adhesion and hydrolysis resistance are improved. The purpose is to improve.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above objects can be achieved, and have reached the present invention. That is, the present invention provides a urethane resin composition characterized in that a phenolic compound having a cyclic terpene skeleton in the molecule is used as a hydroxy component.

In addition, the present invention relates to a mono- and / or polyoxyalkylene monool of a phenolic compound having a cyclic terpene skeleton in the molecule and / or a mono- and / or polyoxyalkylene monool of a phenolic compound having a cyclic terpene skeleton in the molecule. Another object of the present invention is to provide a urethane resin composition comprising a polyoxyalkylene polyol as a hydroxy component.

The phenolic compound having a cyclic terpene skeleton in the molecule used in the present invention includes an addition product of one molecule of a cyclic terpene compound and two molecules of a phenol, and addition of one molecule of a cyclic terpene compound and one molecule of a phenol. Reactant, polycyclic terpene / phenol condensate obtained by condensation reaction between one molecule of cyclic terpene compound and two molecules of phenol and aldehyde or ketone, one molecule of cyclic terpene compound and one molecule of phenol And a polycyclic terpene / phenol condensate obtained by a condensation reaction of an addition reaction product with an aldehyde or a ketone, or a copolymer of a cyclic terpene compound and a phenol.

The phenolic compound having a cyclic terpene skeleton in the molecule used in the present invention is a reaction product of a cyclic terpene compound and a phenolic compound, for example, a cyclic terpene represented by the following general formulas (1) and (2). A cyclic terpene / phenol 1 molecule / 2 molecule adduct to which 1 molecule of compound and 2 molecules of phenol or a phenol compound substituted with an alkyl group and / or hydroxyl group having 1 to 5 carbon atoms (hereinafter referred to as phenols) are added. it can.

In addition, for example, the following general formulas (3) to (4)
A cyclic terpene compound represented by the following formula and a phenol or a phenol compound having 1 to 5 carbon atoms substituted with an alkyl group and / or a hydroxyl group (hereinafter referred to as phenols) are added to a cyclic terpene / phenol 1 molecule / 1 molecule Adducts can be mentioned. However, the phenolic compound containing a cyclic terpene skeleton in the molecule used in the present invention is not limited to these compounds.

[0012]

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中 In the general formula (1), X1, X2, X3, X
4 are the same or different and each represents a hydrogen atom or a carbon number of 1
5 represents an alkyl group or a hydroxyl group. ｝

[0014]

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In the general formula (2), X1, X2, X3, X
4 is the same or different and is a hydrogen atom or 1 carbon atom;
And represents an alkyl group of 5 to 5 or a hydroxyl group. ｝

[0016]

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In the general formula (3), A represents a paramenthanyl group (-C10H19) or a paramentenyl group (-C10H19).
H17), and X5 and X6 are the same or different and represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group. ｝

[0018]

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In the general formula (4), X7 and X8 are the same or different and represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group. ｝

The phenolic compound mono- and / or polyoxyalkylene monool containing a cyclic terpene skeleton in the molecule and / or the phenolic compound mono- and phenolic compound containing a cyclic terpene skeleton in the molecule used in the present invention. The polyoxyalkylene polyol is obtained by reacting an alkylene oxide or an alkylene halohydrin with the phenolic compound having a cyclic terpene skeleton in the molecule.

The starting cyclic terpene compound for producing the phenolic compound having a cyclic terpene skeleton in the molecule used in the present invention may be a monocyclic terpene compound or a bicyclic terpene compound. It may be.
Specific examples thereof include the following, but are not limited thereto.

Α-pinene, β-pinene, dipentene, limonene, α-pherandrene, β-pherandrene, α
-Terpinene, β-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1,4-cineole,
α-terpineol, β-terpineol, γ-terpineol, 4-terpineol, sabinene, camphene, tricyclene, paramentene-1, paramenten-
2, paramenten-3, paramenten-8, paramentadienes, Δ2-carene, Δ3-carene and the like.

Among the above terpene compounds, α-pinene,
β-pinene, dipentene, limonene, paramenthen-1, camphene are preferably used. These cyclic terpene compounds can be used alone or
A mixture of more than one species may be used.

The phenols which are the other raw materials for producing the phenolic compound having a cyclic terpene skeleton in the molecule used in the present invention include phenol or an alkyl group having 1 to 5 carbon atoms and / or a hydroxyl group. Substituted phenol compounds are mentioned.

Examples of the phenol compound to which an alkyl group having 1 to 5 carbon atoms is added include o-cresol, p-cresol, m-cresol, 2,6-xylenol, 2,4
Xylenol, propylphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol,
o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,6-xylenol, p
-Compounds such as phenylphenol, but are not limited to these compounds.

Examples of the phenol compound having a substituted hydroxyl group include compounds such as catechol, resorcin, hydroquinone and pyrogallol, but are not limited to these compounds.

In addition to the above phenols, compounds such as p-methoxyphenol, m-methoxyphenol, bisphenol A, bisphenol F, and naphthol can also be used. These phenols can be used alone or in combination of two or more.

The method for producing a phenolic compound having a cyclic terpene skeleton in the molecule used in the present invention is characterized in that the phenolic compound having a cyclic terpene skeleton in the molecule is obtained by adding one molecule to two molecules of cyclic terpene / phenols. When the phenol is used, for example, the phenol is used in an amount of 0.5 to 20 mol, preferably 2 to 12 mol, per 1 mol of the cyclic terpene compound. It is performed by reacting for a time.

When the phenolic compound having a cyclic terpene skeleton in the molecule is a cyclic terpene / phenol 1 molecule / 1 molecule adduct, for example, 0.1 to 0.1 mol of phenol per 1 mol of cyclic terpene compound. 6 moles, preferably 0.5 to 4 moles, and 2 moles in the presence of an acidic catalyst
The reaction is carried out at a temperature of 0 to 150 ° C. for 1 to 10 hours.

Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boron trifluoride or a complex thereof, a cation exchange resin, a heteropoly acid, and activated clay. At this time, a reaction solvent may not be used, but a solvent such as an aromatic hydrocarbon, an alcohol, or an ether may be used.

A phenolic compound having a cyclic terpene skeleton in the molecule is a polycyclic terpene / phenol obtained by a condensation reaction between an addition product of one molecule of a cyclic terpene compound and two molecules of phenols and an aldehyde or ketone. When it is a polycondensate or a polycyclic terpene / phenol condensate obtained by a condensation reaction of one molecule of a cyclic terpene compound and one molecule of a phenol with an aldehyde or ketone, for example, a cyclic terpene skeleton The aldehydes and ketones are in an amount of 0.1 to 2.0 moles, preferably 0.2 to 1.
The reaction is carried out at a temperature of 40 to 200 ° C. for 1 to 12 hours in the presence of an acidic catalyst. Too much aldehydes or ketones are not preferred because the polycyclic terpene / phenol condensate has a high molecular weight. The weight average molecular weight of the polycyclic terpene / phenol condensate in terms of polystyrene measured by GPC is usually 250.
~ 5,000.

In the condensation reaction of one molecule of the cyclic terpene compound and two molecules of the phenol, aldehydes and ketones used as a condensing agent include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, hydroxybenzaldehyde and phenyl. Examples include acetaldehyde, furfural, acetone, and cyclohexanone.

In the condensation reaction, an addition product of one molecule of a cyclic terpene compound and two molecules of a phenol or an addition product of one molecule of a cyclic terpene compound and one molecule of a phenol are reacted with another phenol in combination. In this case, an addition product of one molecule of the cyclic terpene compound and two molecules of the phenol compound or the cyclic terpene compound 1
The ratio of the addition reaction product of a molecule and one molecule of a phenol is as follows:
It is at least 20% by weight, preferably 40% by weight or more, based on the total amount with other phenols. If the proportion of the cyclic terpene / phenol addition product is small, a satisfactory polycyclic terpene / phenol condensate cannot be obtained.

Examples of the acidic catalyst for the condensation reaction include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, formic acid, acetic acid, oxalic acid, and the like.
Organic acids such as toluenesulfonic acid can be used. The amount of the acidic catalyst used is 0.1 to 0.1 part by weight based on 100 parts by weight of an addition reaction product of one molecule of the cyclic terpene compound and two molecules of the phenol or an addition reaction product of one molecule of the cyclic terpene compound and one molecule of the phenol compound. 5 parts by weight. In the condensation reaction, inert solvents such as aromatic hydrocarbons, alcohols and ethers can be used.

When the phenolic compound having a cyclic terpene skeleton in the molecule is a copolymer of a cyclic terpene compound and a phenol, for example, 0.3 to 12 mol of the phenol per 1 mol of the terpene compound, The reaction is preferably carried out at a temperature of 0 to 120 ° C. for 1 to 10 hours in the presence of a Friedel-Crafts type catalyst in an amount of 0.5 to 6 mol. Examples of the Friedel-Crafts type catalyst include aluminum chloride, boron trifluoride, and complexes thereof. At that time, a reaction solvent such as an aromatic hydrocarbon is generally used. At this time, if the amount of the phenol is less than 0.3 mol, the curing performance of the urethane resin composition is inferior, which is not preferable, and if the amount exceeds 12 mol, no change is observed in the product. The weight average molecular weight of the obtained terpene phenol copolymer is preferably 300 to 2
000.

The mono- and / or polyoxyalkylene monool of a phenolic compound having a cyclic terpene skeleton in the molecule and / or the mono- and phenolic compound of a phenolic compound having a cyclic terpene skeleton in the molecule used in the present invention. The method for producing a polyoxyalkylene polyol is generally carried out by adding an alkylene oxide to a phenolic compound having a cyclic terpene skeleton in the molecule obtained by the above method while adding an alkylene oxide in the presence of an alkali catalyst.
It is carried out by carrying out an addition reaction at a temperature of ~ 200 ° C. Examples of the alkali catalyst include sodium hydroxide and potassium hydroxide. Examples of the alkylene oxide include, but are not limited to, ethylene oxide, propylene oxide, and butylene oxide. The addition mole number of the alkylene oxide is 1 to 15 equivalents, preferably 2 to 10 equivalents, based on the phenolic hydroxyl group of the phenolic compound having a cyclic terpene skeleton in the molecule. At that time, a reaction solvent may not be used, but a solvent such as an aromatic hydrocarbon may be used.

As a method for producing a monooxyalkylene monool or a mono- and / or polyoxyalkylene polyol of a phenolic compound containing a cyclic terpene skeleton in the molecule, for example, the above-mentioned compound containing a cyclic terpene skeleton in the molecule is used. The reaction can also be carried out by converting a phenolic compound into an alkali salt and reacting the alkylene halohydrin at a temperature of 20 to 150 ° C. Examples of the alkylene halohydrin include ethylene chlorohydrin, propylene chlorohydrin, butylene chlorohydrin, ethylene bromhydrin, propylene bromhydrin and the like.

The phenolic compound containing a cyclic terpene skeleton in the molecule or the phenolic compound containing a cyclic terpene skeleton in the molecule, mono- and / or polyoxyalkylene monool, and / or
Alternatively, a mono- and / or polyoxyalkylene polyol of a phenolic compound having a cyclic terpene skeleton in the molecule is constituted as the hydroxy component of the urethane resin composition of the present invention, but can be used alone or 2
More than one species can be used in combination.

As the isocyanate compound as the other main component of the present invention, a diisocyanate compound or a polyisocyanate compound is usually used. Examples of the diisocyanate compound include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate (TODI),
1,6-hexamethylene diisocyanate (HDI),
Isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated MDI, hydrogenated XD
I, lysine diisocyanate, polymeric MDI, but is not limited thereto.

Representative examples of the polyisocyanate compound include triphenylmethane triisocyanate and tris (isocyanatephenyl) thiophosphate.

In addition, tetramethyl xylene diisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, lysine ester triisocyanate,
Compounds such as 1,3,6-hexamethylene triisocyanate and bicycloheptane triisocyanate are exemplified.

In the present invention, an isocyanate derivative can be used as the isocyanate compound. For example, urethane-modified polyisocyanate modified with polyether polyols or polyester polyols, allophanate modified, buret modified,
Modifications of isocyanurate, carbodiimide and the like are given, but not limited thereto.

In the present invention, these isocyanate compounds can be used alone or in combination of two or more.

In the urethane resin composition of the present invention, a hydroxy component other than the hydroxy component used in the present invention can be used in combination. For example, ethylene glycol, 1,
Glycols such as 4-butanediol and 1,6-hexanediol, poly (ethylene adipate), poly (1,
Polyester polyols such as 4-butylene adipate), poly (1,6-hexane adipate), poly (propylene adipate), poly (neopenthylene adipate) and polycarbonate polyol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene oxide / Polypropylene oxide copolymers, polyether polyols such as amine-modified polyols, and other acrylic polyols, polybutadiene polyols, phenolic polyols,
Examples include, but are not limited to, epoxy polyols and flame retardant polyols. These hydroxy components can be used alone or in combination of two or more.

The amount of the hydroxy component used in the present invention other than the hydroxy component is generally 0 to 95% by weight, preferably 0 to 95% by weight, based on the total amount of the hydroxy component used in the present invention.
90% by weight. If it exceeds 95% by weight, performances such as heat resistance, adhesion and hydrolysis resistance are not sufficiently exhibited, which is not preferable.

The urethane resin composition of the present invention comprises the above isocyanate compound and a compound having a hydroxy component. The form includes a one-pack type and a two-pack type.

In the case of the one-pack type, a urethane prepolymer having an isocyanate group at the terminal is usually used in the present invention, in which a hydroxy component and an excess amount of an isocyanate compound are reacted in advance with respect to the hydroxyl group in the hydroxy component. Can be used as a component of the urethane composition.

When producing this urethane prepolymer,
The amount of the isocyanate compound used may be a mono- and / or polyoxyalkylene monol of a phenolic compound having a cyclic terpene skeleton in the molecule or a phenolic compound having a cyclic terpene skeleton in the molecule, and / or a cyclic terpene skeleton in the molecule. The isocyanate group is 1.5 to 1.5 to the hydroxyl group of the mono- and / or polyoxyalkylene polyol of the phenolic compound having a terpene skeleton.
The ratio is 5.0 equivalent times, preferably 1.8 to 3.0 equivalent times. If the ratio of the isocyanate group is less than 1.5 equivalent times, the urethane prepolymer is multiplied and the viscosity increases. On the other hand, if the ratio of the isocyanate group exceeds 5.0 equivalent times, the amount of free isocyanate groups increases, which not only causes air bubbles to enter during moisture curing, but also deteriorates heat resistance and adhesive performance, which is not preferable.

In the case of the two-pack type, it usually comprises two packs of a composition comprising an isocyanate compound and a composition comprising a hydroxy compound, and these two liquids are mixed and used at the time of use.

At this time, the amount of the isocyanate compound used may be a mono- and / or polyoxyalkylene monool of a phenolic compound having a cyclic terpene skeleton in the molecule or a phenolic compound having a cyclic terpene skeleton in the molecule. And / or 0.2 to the hydroxyl group of the mono- and / or polyoxyalkylene polyol of the phenolic compound having a cyclic terpene skeleton in the molecule.
To 10.0 equivalent times, preferably 0.5 to 5.0 equivalent times. If the ratio of the isocyanate group is less than 0.2 equivalent times, the curing reaction becomes insufficient, and the heat resistance and the adhesive strength are not sufficiently exhibited. On the other hand, when the ratio of the isocyanate group exceeds 10.0 times, the molecular weight of the formed polymer becomes too large and the adhesive strength is not obtained, which is not preferable.

A tertiary amine catalyst or an organometallic catalyst can be used in the urethane resin composition of the present invention, if necessary, to accelerate the reaction. Examples of the tertiary amine catalyst include triethylenediamine, pentamethylenediethylenetriamine, triethylamine, N, N-
Examples include, but are not limited to, dimethylethanolamine and ethylmorpholine. Examples of the organometallic catalyst include, but are not limited to, stannasoctoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, and sodium bicarbonate.

The urethane resin composition of the present invention may contain a crosslinking agent, a flame retardant, an antioxidant, an ultraviolet absorber, a deterrent, and a hydrolysis inhibitor, if necessary.

When the urethane resin composition of the present invention is used, a coloring agent for a pigment or a dye, an inorganic filler, a leveling agent, a surfactant, an antifoaming agent, an adhesion promoter, Components such as a plasticizer, a solvent, a storage stabilizer, and water can be added.

The urethane resin composition of the present invention comprises a mono- and / or polyoxyalkylene monool of a phenolic compound having a cyclic terpene skeleton in the molecule or a phenolic compound having a cyclic terpene skeleton in the molecule. By reacting a mono- and / or polyoxyalkylene polyol of a phenolic compound having a cyclic terpene skeleton in the molecule as a hydroxy component with an isocyanate compound as the other main component, heat-resistant adhesion or hydrolysis resistance is obtained. Provides a cured product with excellent decomposability and the like.

This is considered to be due to the introduction of the cyclic terpene skeleton into the cured urethane resin. That is,
It is considered that a cyclic terpene skeleton such as a menthane skeleton, a pinane skeleton, and a bornan skeleton composed of carbon atoms and hydrogen atoms imparts heat resistance, adhesiveness, or hydrolysis resistance of the urethane cured product.

The phenolic compound containing a cyclic terpene skeleton in the molecule or the phenolic compound containing a cyclic terpene skeleton in the molecule used in the present invention is a mono- and / or polyoxyalkylene monool, and / or
Alternatively, a mono- and / or polyoxyalkylene polyol of a phenolic compound having a cyclic terpene skeleton in the molecule can be used as a hydroxy component of the polyester in addition to the urethane resin composition.

Examples of the polyester include a saturated polyester, an unsaturated polyester, and an aromatic polyester. As in the case of the urethane resin composition of the present invention, the properties such as heat resistance, adhesiveness, and hydrolysis resistance are improved. .

[0058]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below.
The present invention is not limited to these Examples. In the examples, parts and percentages are by weight unless otherwise specified.

An example of the synthesis of a phenolic compound having a cyclic terpene skeleton is shown below. Synthesis Example 1 Phenolic Compound Containing Cyclic Terpene Skeleton (a) 6 mol of phenol, strongly acidic cation exchange resin in a 1-liter internal four-necked flask equipped with a thermometer, stirrer, dropping funnel and condenser After charging 34g, 80
While maintaining the temperature at ° C., 1 mol of α-pinene was added dropwise over 4 hours, followed by stirring for 2 hours to cause a reaction. Then
The cation exchange resin is removed from the mixture by filtration,
After washing the obtained reaction solution twice with distilled water,
The unreacted substances and by-products were distilled off by distillation at a temperature of 250 ° C. for 30 minutes under reduced pressure of g to obtain a pale yellow resinous substance. This pale yellow resinous material was purified by crystallization using a recrystallization method using toluene to obtain 98 g of a white powder. As a result of analyzing the white powder by gas chromatography, it was found that the compound corresponding to the general formula (1) and the compound corresponding to the general formula (2) were contained in 63% by weight and 31% by weight, respectively. Further, the nuclear magnetic resonance spectrum (NM
R) and mass spectrometry (MS) to give the compound of general formula (1) as 1,3-bis (4-hydroxy-benzene) -p
-Menthane, the compound of the general formula (2) is 2,8-bis (4
-Hydroxy-benzene) -p-menthane.

Synthesis Examples 2 and 3 The phenolic compounds containing a cyclic terpene skeleton (b) and (c) were prepared in the same manner as in (a) except that the starting phenol was changed to o-cresol and 2,6-xylenol. Similarly manufactured,
124 g of terpene di-cresol (b) and 135 g of terpene di 2,6-xylenol (c) were obtained. The identification results were as follows. Product (b): compound of general formula (1) = 54% by weight, compound of general formula (2) =
39% by weight, product (c): compound of general formula (1) = 5
1% by weight, compound of general formula (2) = 43% by weight.

Synthesis Example 4 Phenolic Compound Containing Cyclic Terpene Skeleton (d) Phenol was added to a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser.
2.8 g (1.2 mol) of strong acid cation exchange resin
After charging 0 g, 138 g (1 mol) of paramenthen 1 was added dropwise over 3 hours while maintaining the temperature at 80 ° C., and the mixture was stirred and reacted for 3 hours. Next, the cation exchange resin was removed from the mixed solution by filtration, 300 g of toluene was added to the obtained reaction solution to dissolve the mixture, and the mixture was washed twice with distilled water, and distilled under reduced pressure of 5 mmHg to give a boiling point of 138. 195 g of a fraction at a temperature between 148C and 148C were obtained. The obtained fraction was a crystal having a melting point of 88 ° C., and was analyzed by gas chromatography. As a result, it was found that the fraction contained 93% of paramenthanylphenol represented by the general formula (3).

Synthesis Example 5 Phenolic Compound Containing Cyclic Terpene Skeleton (e) Phenol Compound Containing Cyclic Terpene Skeleton Obtained in Synthesis Example 1 in a Glass-Lined Autoclave Equipped with a Stirrer and Thermometer (a) Was charged, 5 g of 37% aqueous formalin solution, 0.25 g of oxalic acid, and 15 g of ion-exchanged water were stirred and reacted at 120 ° C. for 4 hours in a sealed state. Next, the mixture was cooled to 70 ° C., 60 g of toluene was charged to dissolve the reaction oil, and the mixture was washed three times with ion-exchanged water.
Toluene was removed from the obtained washing oil by distillation to obtain 51 g of a polycyclic terpene / phenol condensate.

Synthesis Example 6 Phenol Compound Containing Cyclic Terpene Skeleton (f) Phenol was added to a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser.
2.8 g (1.2 mol) of strong acid cation exchange resin
After charging 0 g, 136 g (1 mol) of camphene was added dropwise over 3 hours while maintaining the temperature at 80 ° C., and the mixture was stirred and reacted for 3 hours. Next, the cation-exchange resin was removed from the mixture by filtration, 300 g of toluene was added to the obtained reaction solution to dissolve it, and the mixture was washed twice with distilled water, and distilled under reduced pressure of 5 mmHg to give a boiling point of 1 mm.
Fraction at 40 ° C to 150 ° C (isobornylphenol) 1
68 g were obtained. Next, 156 g of the obtained isobornylphenol and a 37% formalin aqueous solution 46 were placed in a glass-lined autoclave equipped with a stirrer and a thermometer.
g and 0.5 g of oxalic acid at 100 ° C. for 6 hours, 200 g of toluene was added, and the mixture was washed three times with ion-exchanged water. Toluene and unreacted substances were distilled off to obtain a yellow resinous polycyclic terpene. / 150 g of phenol condensate was obtained.

Synthesis Example 7 Phenolic Compound Containing Cyclic Terpene Skeleton (g) In a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a condenser, 94 g of phenol and 230 of toluene were added.
g, 6 g of boron trifluoride etherate, 30 ° C.
136 g of limonene was added dropwise over 2 hours while stirring at, and the reaction was carried out after 2 hours. The obtained reaction oil was washed three times with ion-exchanged water, toluene was distilled off by distillation, and unreacted substances and low-polymerized substances were further distilled off at 250 ° C./5 mmHg to obtain a cyclic terpene phenol copolymer. 205 g were obtained.

Examples of the synthesis of mono- or polyoxyalkylene mono- or polyols of phenolic compounds having a cyclic terpene skeleton are shown below. Synthesis Example 8 Monooxyalkylene diol (h) 50 g of the phenolic compound (a) containing a cyclic terpene skeleton obtained in Synthesis Example 1 in a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a condenser. And 292 g of a 9.3% aqueous sodium hydroxide solution were charged and dissolved. To this, 31 g of toluene and 40 g of methanol were added, and while stirring, 54.6 g of ethylene chlorohydrin was added at 30 ° C for 30 minutes.
Dropped over minutes. Thereafter, the reaction was carried out at 70 ° C. for 2 hours. 100 g of toluene was added to the reaction oil, the mixture was neutralized with a 5% hydrochloric acid aqueous solution, and the oil layer was washed with water. The toluene was distilled off from the water-washed oil, and further distilled under the condition of 200 ° C./10 mmHg to obtain a yellow-brown solid target having a melting point of 56 ° C. by a DSC method as a residue.

Synthesis Example 9 Polyoxyalkylenediol (i) 35.2 g of the terpene di-cresol obtained in Synthesis Example 2 and 0.0162 g of sodium hydroxide powder were charged into a glass-lined autoclave, and heated and stirred at 160 ° C. Then, the pressure inside the reaction vessel was reduced to 10 mmHg, and
7.6 g of ethylene oxide was injected while controlling the inflow under a nitrogen pressure of 3 atm to carry out the reaction. 100 g of toluene was added to the reaction product, the reaction oil was washed with water, and distilled under reduced pressure to distill off toluene and unreacted substances, thereby obtaining 50.8 g of a yellow viscous liquid as a residue in a kettle residue. As a result of analysis by liquid chromatography, the purity of the target hydroxypolyoxyethylene was 95%.

Synthesis Example 10 Monooxyalkylene monool (j) A glass-lined autoclave was charged with 23.2 g of the paramenthanylphenol obtained in Synthesis Example 4 and 0.01 g of sodium hydroxide powder, and heated to 160 ° C. Stir,
Then, the pressure inside the reaction vessel was reduced to 10 mmHg, and the pressure was 4.4 g.
Of ethylene oxide was injected under a nitrogen pressure of 3 atm while controlling the inflow to carry out a reaction. Toluene in the reaction
After addition of 00 g, the reaction oil was washed with water and distilled under reduced pressure to distill off toluene, unreacted substances, and then the target substance to obtain 26.4 g of monooxyethylene hydroxy ether of paramenthanyl phenol. As a result of analysis by liquid chromatography, the purity of the target hydroxymonooxyethylene was 93%.

Synthesis Example 11 Polyoxyalkylene polyol (k) A glass-lined autoclave was charged with 33.6 g of the polycyclic terpene / phenol condensate obtained in Synthesis Example 5 and 0.0162 g of sodium hydroxide powder,
The mixture was heated and stirred at a temperature of 10 ° C., and then the pressure in the reaction vessel was reduced to 10 mmHg, and 17.6 g of ethylene oxide was injected while adjusting the inflow under a nitrogen pressure of 3 atm to carry out the reaction. 100 g of toluene was added to the reaction product, the reaction oil was washed with water, and distilled under reduced pressure to distill off toluene and unreacted substances, thereby obtaining 50.8 g of a yellow viscous liquid as a residue in a kettle residue. As a result of analysis by liquid chromatography, the purity of the target hydroxypolyoxyethylene was 92%.

Synthesis Example 12 Polyoxyalkylene polyol (l) A glass-lined autoclave was charged with 24.6 g of the polycyclic terpene / phenol condensate obtained in Synthesis Example 6 and 0.0162 g of powdered sodium hydroxide, and heated at 160 ° C.
Then, the pressure inside the reaction vessel was reduced to 10 mmHg, and 11.6 g of propylene oxide was injected while controlling the inflow under a nitrogen pressure of 3 atm to carry out the reaction. 100 g of toluene was added to the reaction product, the reaction oil was washed with water, and distilled under reduced pressure to distill off toluene and unreacted substances, thereby obtaining 35.4 g of a yellow viscous liquid as a residue in a still residue. As a result of analysis by liquid chromatography, the purity of the target hydroxypolyoxypropylene was 96%.

Example 1 30 parts of the phenolic compound (a) having a cyclic terpene skeleton obtained in Synthesis Example 1 was mixed with a poly (ethylene adipate) -based polyester polyol 70 having a molecular weight of 3,000.
Of purified diphenylmethane diisocyanate in a mixture of isocyanate groups / hydroxyl groups ([NCO] /
[OH] ratio) was mixed at 90 ° C. and reacted under a nitrogen stream for 2 hours to obtain a one-part urethane resin composition comprising a urethane prepolymer. The obtained composition was measured and evaluated for heat resistance and adhesive strength according to the methods described below. Table 1 shows the results.

[Heat resistance] A coating was applied between the SUS316 plate and the aluminum plate so as to have a thickness of 120 μm.
After leaving at 24 ° C. × 60 RH% for 24 hours, the temperature was raised to measure creep peeling, and the temperature at the time of peeling was measured.

[Adhesive Strength] A coating was applied between the SUS316 plate and the aluminum plate so that the thickness became 120 μm.
After leaving at 5 ° C. × 60 RH% for 6 hours and 24 hours,
Tensile shear strength was measured according to ASTM D1002.

[Hydrolysis resistance] A coating was applied to a thickness of 120 μm between a SUS316 plate and an aluminum plate, left at 25 ° C. × 60 RH% for 24 hours, and then heated to 80 ° C.
For 14 days. After that, the test piece is ASTM
The tensile shear strength was measured according to D1002.

Examples 2 to 12 The hydroxy compounds and polyols of Synthesis Examples 2 to 12 are shown in Table 1.
A one-part urethane resin composition comprising a urethane prepolymer was obtained in the same manner as in Example 1 using the compounding amounts shown in (2) and (2). The obtained composition was measured and evaluated for heat resistance and adhesive strength in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Comparative Examples 1 to 3 One-part urethane resin compositions comprising a urethane prepolymer were obtained in the same manner as in Example 1 except that the polyol shown in Table 3 was used as the hydroxy component. The obtained composition was measured and evaluated for heat resistance and adhesive strength in the same manner as in Example 1. Table 3 shows the results.

In the table, PESTPOL1 has a molecular weight of 3,000.
0 represents a poly (ethylene adipate) -based polyester polyol, PETPOL2 represents a polyethylene glycol-based polyether polyol having a molecular weight of 2,500,
PETPOL3 represents a polypropylene glycol-based polyether polyol having a molecular weight of 2,000. In the table, catalyst DBL represents dibutyltin dilaurate.

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[Table 1]

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[Table 2]

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[Table 3]

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[Effect] The urethane resin composition of the present invention is used for applications such as paints, adhesives, sealing agents and binders to improve the performance of the cured product such as heat resistance, adhesion and hydrolysis resistance. It is suitable for.

Continuation of the front page (72) Inventor Shinobu Mineyama 1080 Yasharake Mical Co., Ltd., Fuchu City, Hiroshima Pref. (72) Inventor Tatsuhiro Kuno 1080 Sakagakicho Fuchu City, Hiroshima Pref.

Claims (11)

[Claims] 1. A urethane resin composition comprising a phenolic compound having a cyclic terpene skeleton in a molecule as a hydroxy component. 2. Mono- and / or polyoxyalkylene monools of a phenolic compound having a cyclic terpene skeleton in the molecule and / or mono- and / or polyoxy of a phenolic compound having a cyclic terpene skeleton in the molecule. A urethane resin composition comprising an alkylene polyol as a hydroxy component. 3. The urethane resin composition according to claim 1, wherein the phenolic compound having a cyclic terpene skeleton in the molecule is an addition product of one molecule of the cyclic terpene compound and two molecules of phenols. 4. The urethane resin composition according to claim 1, wherein the phenolic compound having a cyclic terpene skeleton in the molecule is an addition product of one molecule of the cyclic terpene compound and one molecule of phenols. 5. A polycyclic terpene obtained by a condensation reaction of an addition product of one molecule of a cyclic terpene compound and two molecules of a phenol with an aldehyde or ketone, wherein the phenolic compound having a cyclic terpene skeleton in the molecule is obtained. 3. The urethane resin composition according to claim 1, which is a phenol condensate. 6. A polycyclic terpene obtained by a condensation reaction of an addition reaction product of one molecule of a cyclic terpene compound, one molecule of a phenol, and an aldehyde or ketone with a phenolic compound having a cyclic terpene skeleton in the molecule. 3. The urethane resin composition according to claim 1, which is a phenol condensate. 7. The urethane resin composition according to claim 1, wherein the phenolic compound having a cyclic terpene skeleton in the molecule is a copolymer of a cyclic terpene compound and a phenol. 8. The urethane resin composition according to claim 3, wherein the cyclic terpene compound is limonene or pinene, and the phenol is phenol or cresol. 9. The method according to claim 1, wherein the cyclic terpene compound is paramenthen-1.
5. The urethane resin composition according to claim 4, wherein the urethane resin composition is camphene, and the phenol is phenol. 10. The urethane resin composition according to claim 5, wherein the cyclic terpene compound is limonene or pinene, the phenol is phenol or cresol, and the aldehyde or ketone is formaldehyde or P-formaldehyde. 11. The urethane resin composition according to claim 6, wherein the cyclic terpene compound is 1-P-menthen or camphene, the phenol is phenol or cresol, and the aldehyde or ketone is formaldehyde or P-formaldehyde.