JP2008115348A - Urethane resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a urethane resin composition which gives a cured product improved in adhesive property and hydrolytic resistance without degrading its weather resistance. <P>SOLUTION: The urethane resin composition is obtained by reacting (D) an isocyanate compound with a polyester polyol which is obtained by reacting three components consisting of (A) a polyol, (B) a dicarboxylic acid, and (C) a nucleus-hydrogenated terpene phenol resin and/or two components consisting of (B) the dicarboxylic acid and (C) the nucleus-hydrogenated terpene phenol resin as indispensable components. In order to obtain a moisture-curable urethane resin composition, the reaction ratio of (D) the isocyanate compound to the polyester polyol obtained by reacting three components consisting of (A) the polyol, (B) the dicarboxylic acid, and (C) the nucleus-hydrogenated terpene phenol resin and/or two components consisting of (B) the dicarboxylic acid and (C) the nucleus-hydrogenated terpene phenol resin as indispensable components, is preferably such that the amount of the isocyanate group is 1.1-5.0 moles per mol of the hydroxyl group of the polyol. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a urethane resin composition. Specifically, the present invention relates to a urethane resin composition excellent in adhesiveness, hydrolysis resistance, and weather resistance.

  Conventionally, a urethane resin is made of a highly active and highly reactive raw material. By changing the raw material composition, the urethane resin is a polymer material capable of producing a wide range of properties such as hard, soft and rigid. It is used in a wide range of applications such as elastomers, moldings, paints, inks, coating materials, adhesives, sealants and binders. In particular, in recent years, as the required performance for each material has increased, the use of polyurethane having a wide molecular design selectivity is increasing due to the wide variety of polyols and isocyanate compounds including polyester polyols.

  Disadvantages of the urethane resin composition include, when a urethane bond or polyester polyol is used, a decrease in strength of the urethane product due to a decrease in molecular weight due to hydrolysis of the ester bond, and a decrease in adhesive strength such as a urethane-based adhesive. In order to prevent this hydrolysis, there is a method of introducing an aromatic ring into a polyol or an isocyanate compound. However, in this case, there is a problem that weather resistance and heat discoloration are greatly lowered.

In addition, adhesives such as urethane adhesives using urethane resin compositions, adhesives, paints, inks, coatings, binders, etc., have poor adhesion to various adherends, especially adherends with low surface energy such as polyolefins. It is enough. In order to improve this adhesion, a method of adding a tackifying resin is known, but in this case, since it is compatible only with a highly polar tackifying resin, rosin phenol resin, terpene can be added. Limited to phenolic resins, alkylphenolic resins, and the like. However, they all have a pale yellow color and may be discolored depending on the usage environment, and are therefore unsuitable for applications where hue is important. (Patent Document 1)
Japanese Patent Laid-Open No. 11-45158

  The present invention has been made against the background of the problems of the prior art, and an object of the present invention is to improve the adhesion and hydrolysis resistance of a cured reaction product without reducing the weather resistance in a urethane resin composition.

As a result of intensive studies to solve the above problems, the present inventors have achieved the above object by using a urethane resin composition characterized by including (C) a nuclear hydrogenated terpene phenol resin in the structure. The inventors have found that the present invention can be achieved and have reached the present invention.
That is, (A) polyol, (B) dicarboxylic acid, (C) three components of nuclear hydrogenated terpene phenol resin and / or (B) dicarboxylic acid, (C) two components of nuclear hydrogenated terpene phenol resin as essential components This is a urethane resin composition obtained by reacting a polyester polyol obtained by reaction with an isocyanate compound (D).
Here, in order to obtain a moisture curable urethane resin composition, (A) polyol, (B) dicarboxylic acid, (C) three components of hydrogenated terpene phenol resin and / or (B) dicarboxylic acid, ( It is preferable that the reaction ratio of the polyester polyol obtained by reacting two components of C) nuclear hydrogenated terpene phenol resin as an essential component and the (D) isocyanate compound is 1.1 to 5.0 times mol.

  The urethane resin composition of the present invention is suitable as a urethane-based adhesive because it has high weather resistance and adhesiveness, and also has good hydrolysis resistance. In addition to adhesives, paints, inks, coating materials, sealing materials, binders, and the like can be used by taking advantage of performances such as adhesion, hydrolysis resistance, and weather resistance.

Now, the present invention will be described in detail.
The (C) nuclear hydrogenated terpene phenol resin of the present invention will be described.
The (C) nuclear hydrogenated terpene phenol resin used in the present invention is generally obtained by reacting a terpene phenol resin with hydrogen in the presence of a catalyst.

  The (C) nuclear hydrogenated terpene phenolic resin of the present invention was hydrogenated with all terpenes and phenol-derived double bonds in consideration of weather resistance and reactivity with carboxylic acid, carboxylic acid ester and isocyanate group. Nuclear hydrogenated terpene phenol resin is the most suitable, but when weather resistance is not important, only the reactivity with carboxylic acid, carboxylic acid ester, and isocyanate compound is considered, and some phenol groups in the resin are nucleated. A hydrogenated resin may be used.

  The terpene phenol resin is obtained by reacting a cyclic terpene monomer and phenols in the presence of a Friedel-Craft catalyst.

  The terpene monomer as the raw material of the terpene phenol resin may be a monocyclic terpene monomer or a bicyclic terpene monomer. Specific examples of the cyclic terpene monomer as a raw material include limonene, dipentene (an optical isomer of limonene), terpinolene, α-pinene, β-pinene, terpinene, and mentadiene.

  Specific examples of the phenols used as the raw material for the terpene phenol resin include phenol, cresol, xylenol, propylphenol, hydroquinone, resorcin, methoxyphenol, bromophenol, bisphenol A, bisphenol F, and the like.

  The terpene phenol resin is prepared by, for example, subjecting 1 mol of a terpene monomer and 0.1 to 50 mol of a phenol to a cationic polymerization reaction at a temperature of −10 to 120 ° C. for 0.5 to 20 hours under a Friedel-Craft catalyst. Can be manufactured.

  The reaction solvent may not be used, but usually a solvent such as aromatic hydrocarbons, alcohols, ethers may be used.

  Examples of the terpene phenol resin produced in this way include YS Polyster S145 manufactured by Yasuhara Chemical Co., Ltd.

(C) The hydrogenated terpene phenol resin is obtained by hydrogenating the terpene phenol resin.
The hydrogenation method is not particularly limited, and for example, a noble metal such as palladium, ruthenium, rhodium or the like supported on a carrier such as activated carbon, activated alumina, or diatomaceous earth is used as a catalyst. The method of performing is mentioned.
At this time, it is possible to use a batch system in which the reaction is performed while suspending and stirring the powdered catalyst, or a continuous system using a reaction tower packed with the molded catalyst, and there are no particular restrictions on the reaction format. Absent.

  When the reaction is a batch system, the amount of the catalyst used is 0.1 to 50% by weight, preferably 0.2 to 20% by weight, based on the terpene phenol resin as a raw material. If the amount of catalyst is less than 0.1% by weight, the hydrogenation reaction rate becomes slow. On the other hand, if it exceeds 50% by weight, it is not economically suitable.

  In the hydrogenation, a reaction solvent may not be used, but alcohols, ethers, esters, and saturated hydrocarbons may be usually used.

  The reaction temperature at the time of hydrogenation is usually 20 to 300 ° C, preferably 50 to 250 ° C. When the reaction temperature is less than 20 ° C., the hydrogenation rate is slow. On the other hand, when the reaction temperature exceeds 300 ° C., decomposition of the hydrogenated product increases, resulting in a decrease in molecular weight and a decrease in the recovery rate.

  The hydrogen pressure during hydrogenation is usually 5 to 300 kg / cm 2 (0.49 to 29.40 MPa). Preferably, it is 50-250 kg / cm2. More preferably, it is 80-240 kg / cm <2>. If it is less than 5 kg / cm 2, the hydrogenation rate becomes slow. On the other hand, if it exceeds 300 kg / cm 2, decomposition of the hydrogenated product increases, which is not preferable.

  The hydroxyl value of the (C) nuclear hydrogenated terpene phenol resin of the present invention is preferably 10 to 350 mgKOH / g. A hydroxyl value of less than 10 mg KOH / g is not preferred because there are few reactive sites with isocyanate and heat resistance is lowered, and performance is deteriorated due to bleed-out over time. On the other hand, in a resin exceeding 350 mgKOH / g, the number of hydroxyl groups in the nuclear hydrogenated terpene phenol resin increases, and when reacted with dicarboxylic acid, dicarboxylic acid ester, or isocyanate, it reacts three-dimensionally. It is not preferable because it causes solidification and solidification and a decrease in handling.

The polyester polyol used in the present invention comprises (A) polyol, (B) dicarboxylic acid, (C) three components of nuclear hydrogenated terpene phenol resin and / or (B) dicarboxylic acid, (C) nuclear hydrogenated terpene phenol resin. In addition to the method of obtaining by dehydration condensation reaction with two components as essential components, (B) dicarboxylic acid ester instead of (B) dicarboxylic acid, (A) polyol, (C) nuclear hydrogenated terpene phenol It may be obtained by transesterification with a resin.
Here, the above-mentioned dehydration condensation reaction and transesterification reaction may use the usual dehydration condensation reaction and transesterification reaction.
In addition, (A) polyol, (B) dicarboxylic acid, (C) three components of hydrogenated terpene phenol resin, (B) dicarboxylic acid, (C) two components of hydrogenated terpene phenol resin ((A) + (C)) :( B) = 4.0-0.8: 1.0 (molar ratio), or (C) :( B) = 4.0-0.8: 1 0.0 (molar ratio) is preferred.
When the blending amount of (A) + (C) or (C) is less than 0.8 times the mole of (B), the number of carboxylic acid molecules at the end increases, and the reactivity with the isocyanate compound decreases. Therefore, the molecular weight of the urethane resin is not increased, which is not preferable. On the other hand, if it exceeds 4.0 moles, the molecular weight of the polyester polyol does not increase, which is not preferable.
The same applies when (b) dicarboxylic acid ester is used instead of (B) dicarboxylic acid.

  The polyol (A) of the present invention includes, for example, glycols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, poly (ethylene adipate), poly (1,4-butylene adipate), poly ( 1,6-hexane adipate), poly (propylene adipate), poly (neopentylene adipate), polyester polyol such as polycarbonate polyol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene oxide / polypropylene oxide copolymer, amine Polyether polyols such as modified polyols, and others such as acrylic polyols, polybutadiene polyols, phenolic polyols, epoxy polyols, flame retardant polyols, polyether polyols Although the like can be exemplified, but the invention is not limited thereto. These hydroxy components can be used alone or in combination of two or more.

The (B) dicarboxylic acid or (b) dicarboxylic acid ester of the present invention is not particularly limited, but if it is (B) a dicarboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4,4′- Aromatic dicarboxylic acids such as dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-decahydronaphthalene Dicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydro In the case of phthalenedicarboxylic acid, 2,7-decahydronaphthalenedicarboxylic acid, and (b) dicarboxylic acid ester, dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dicyclohexyl ester, diphenyl of the above-mentioned dicarboxylic acid Examples include esters and di (methylphenyl) esters.
You may use these individually or in combination of 2 or more types.

  As the isocyanate compound (D) used in the present invention, various isocyanate compounds such as a diisocyanate compound or a polyisocyanate compound are usually used. As an isocyanate compound suitable for applications requiring weather resistance, for example, 1,6-hexa Examples include methylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated MDI, hydrogenated XDI, and derivatives of these isocyanate compounds. On the other hand, this is not limited to applications where initial hue, light, and heat discoloration are not regarded as problems, and generally used isocyanate compounds such as tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI). ), Xylylene diisocyanate (XDI), 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate (TODI), lysine diisocyanate, polymeric MDI, and derivatives of these isocyanate compounds are not particularly limited.

  (D) As an isocyanate compound, as a derivative thereof, a polyisocyanate compound, a urethane modified product obtained by modifying a polyisocyanate with a polyether polyol or a polyester polyol, an allophanate modified product, a burette modified product, an isocyanurate modified product, or a carbodiimide modified product. Although a body etc. may be used, it is not limited to these.

In the present invention, these (D) isocyanate compounds can be used alone or in combination of two or more.
Moreover, in this invention, as long as the effect of this invention appears, you may mix | blend and use another polyol.
Specific examples of other polyols include glycols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, poly (ethylene adipate), poly (1,4-butylene adipate), poly ( 1,6-hexane adipate), poly (propylene adipate), poly (methylpentylene adipate): (trade name: Kuraray polyol P3050, manufactured by Kuraray) Polyester polyol such as polycarbonate polyol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol , Polyethylene oxide / polypropylene oxide copolymers, polyether polyols such as amine-modified polyols, and others such as acrylic polyols, polybutadiene polyols, phenolic polyols, epoxy resins Polyol, there is such as flame-retardant polyols and the like.
(A) 3 components of polyol, (B) dicarboxylic acid, (C) nuclear hydrogenated terpene phenol resin or 2 components of (B) dicarboxylic acid, (C) nuclear hydrogenated terpene phenol resin are reacted as essential components. As for the reaction ratio of the obtained polyester polyol and (D) isocyanate compound, the isocyanate group is preferably 0.8 to 5.0 times moles relative to the hydroxyl group of the polyol.
When the blending amount of (D) is less than 0.8 times mol, the molecular weight of the urethane resin composition does not increase, which causes a decrease in strength and a decrease in adhesive strength. Moreover, when it exceeds 5.0 times, since many unreacted isocyanate compounds remain | survive and cause the fall of adhesive force, it is unpreferable.
In particular, in the case of the urethane resin composition according to claim 1, which is a moisture curable type, the isocyanate group is preferably 1.1 to 5.0 times moles of the hydroxyl group of the polyol.

  (C) Since the nuclear hydrogenated terpene phenol resin has a terpene skeleton having excellent weather resistance and high hydrophobicity in the molecule, it can be used alone in a urethane resin composition or as a raw material for a polyester polyol. In addition, hydrolysis resistance can be imparted without lowering the weather resistance of the urethane resin composition, and adhesion to various adherends is improved.

  The urethane resin composition of the present invention is not particularly limited, but can be used as a thermoplastic urethane resin, a moisture curable urethane resin, or a two-component curable urethane resin.

  In the urethane resin composition of the present invention, a tertiary amine catalyst or an organometallic catalyst can be used as needed to promote the reaction. Examples of the tertiary amine catalyst include, but are not limited to, triethylenediamine, pentamethylenediethylenetriamine, triethylamine, N, N-dimethylethanolamine, and ethylmorpholine. Examples of the organometallic catalyst include, but are not limited to, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, and sodium bicarbonate.

  The urethane resin composition of the present invention has excellent weather resistance and hydrolysis resistance as well as adhesives, adhesives, paints, inks, coating agents, adhesives, sealants, binders and other applications that require adhesiveness. Taking advantage of these characteristics, it can be used as a liquid crystal display element substrate, an optical sheet such as a color filter substrate, and a buffer material for display.

  In the urethane resin composition of the present invention, a crosslinking agent, a flame retardant, an antioxidant, an ultraviolet absorber, an antifungal agent, and a hydrolysis inhibitor can be used as necessary.

  In carrying out the urethane resin composition of the present invention, if necessary, pigments and dye colorants, inorganic fillers, leveling agents, surfactants, antifoaming agents, tackifier resins, plasticizers, solvents Components such as a storage stabilizer and water can be added.

The method for producing the urethane resin composition of the present invention is not particularly limited, but a polyester polyol, (D) isocyanate compound, and various additives that are optionally added, a container with a stirrer, other rolls, kneaders, extrusions. The method of mixing by a machine is mentioned.
Moreover, when using the urethane resin composition of this invention as one liquid, it may be stored, blocking | blocking from the water in air. Moreover, you may use as a two-component type, and in that case, it consists of two components, the composition which usually consists of an isocyanate compound, and the composition which consists of a hydroxy compound, and this two components are mixed and used at the time of use.

  In addition to the polyol component of the urethane resin composition, the polyester polyol of the present invention can be used as a raw material for polyester, epoxy resin, and other polymer modifiers.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(C) The synthesis example of a nuclear hydrogenated terpene phenol resin is shown below.
Synthesis example 1
(Synthesis of terpene phenol resin B (compound B))
Using a 2-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser tube, 580 g of toluene and 15 g of aluminum chloride as a catalyst were charged, and then stirred while maintaining a temperature of 75 ° C. Then, 400 g (equivalent to about 3 mol) of α-pinene (Yasuhara Chemical Co., Ltd. α-pinene, purity 95%) and 180 g (equivalent to about 2 mol) of phenol (phenol, purity 99%) manufactured by Kanto Chemical Co., Ltd. The solution was added dropwise over a period of time, and then reacted by stirring for 4 hours.
Next, the mixed solution was washed with water to remove the catalyst, and then toluene, unreacted monomers and low molecular weight compounds were distilled off by distillation at a maximum temperature of 250 ° C. under a reduced pressure of 5 mmHg. The terpene phenol resin B 560g was obtained. The terpene phenol resin B had a softening point of 125 ° C., an OH value of 91 mgKOH / g, a GPC number average weight molecular weight of 610, a weight average molecular weight of 800, and a Z average weight molecular weight of 1020.

Synthesis example 2
(Synthesis of nuclear hydrogenated terpene phenol resin A)
After charging 100 g of terpene phenol resin B obtained in Synthesis Example 1, 400 g of cyclohexane, and 2.0 g of powdered 5% palladium-supported alumina catalyst, this was sealed and the atmosphere was replaced with nitrogen gas. Hydrogen gas was introduced while applying a pressure of 10 kg / cm 2. Then, when heated to 150 ° C. while stirring, the hydrogen pressure was set to 80 kg / cm 2, and the reaction was carried out for 14 hours while maintaining the pressure at 80 kg / cm 2 by supplementing the absorbed hydrogen. 100 g of phenol resin A was obtained.
The nuclear hydrogenated terpene phenol resin A had a softening point of 120 ° C., an OH value of 90 mgKOH / g, a GPC number average weight molecular weight of 620, a weight average molecular weight of 800, and a Z average weight molecular weight of 1000. Moreover, when IR analysis was performed (Spectrum One system B type | mold by Perkin Elmer), it was confirmed that the peak of the phenol-derived aromatic ring was lose | disappeared.

Synthesis example 3
(Synthesis of polyester polyol A)
20 g of ethylene glycol and hydrogenated terpene phenol resin A (Synthesis Example 2) 80 g of hydroxyl group / carboxyl group of adipic acid = 1 / 0.8 (molar ratio) was charged in a four-necked flask with 45 g of adipic acid, While maintaining the reduced pressure state, the temperature was raised to a maximum temperature of 250 ° C. to carry out a dehydration condensation reaction.
The obtained polyester polyol had a weight average molecular weight of 5,000 and an OH value measured by an acetylation method was 57 mgKOH / g.

Example 1 (Moisture-curing urethane resin composition)
Using polyester polyol A obtained in Synthesis Example 3 above, 100 g of this polyester polyol A and 12 g of hexamethylene diisocyanate as an isocyanate compound (isocyanate group / hydroxyl molar ratio [NCO] / [OH] ratio of 1.3) In a four-necked flask under a nitrogen stream at 80 ° C. for 3 hours to obtain a urethane resin composition.
The physical properties of this urethane resin composition were evaluated by the methods shown below.

  [Adhesive strength] It was applied between aluminum plate and SUS316 plate or polypropylene plate so as to have a thickness of 120 μm, and allowed to stand for 24 hours under conditions of 60 ° C. and 80% RH, and then tensioned according to ASTM D1002. Shear strength was measured.

  [Hydrolysis resistance] A SUS316 plate and an aluminum plate were coated so as to have a thickness of 120 μm, allowed to stand at 60 ° C. for 24 hours, and then immersed in water at 80 ° C. for 7 days. Thereafter, the tensile shear strength of the test piece was measured according to ASTM D1002.

[Weather resistance] The obtained test piece was irradiated with a xenon weather meter X75 manufactured by Suga Test Instruments Co., Ltd., and the yellow index (YI) value after 3100 hours was measured using JIS standard COH-300A manufactured by Nippon Denshoku Industries Co., Ltd. This was carried out in accordance with K3761 and the difference in YI values was determined.
The results are listed in Table 1.

Example 2
Using polyester polyol A obtained in Synthesis Example 3, 100 g of polyester polyol A isocyanurate-modified hexamethylene diisocyanate (trimer-modified type) 18 g (isocyanate group / hydroxyl molar ratio [NCO] / The amount of [OH] ratio is 1.0) was charged into a four-necked flask and mixed at 30 ° C. under a nitrogen stream, and the same method as in Example 1 except that 85% RH of the curing conditions was changed to 25% RH. The physical properties were evaluated. The results are listed in Table 1.

Comparative Example 1 (moisture curable urethane resin composition)
Urethane resin composition in the same manner as in Example 1 except that polyester polyol B: polyester polyol having an average molecular weight of 3000 (polymethylpentanethylene adipate. Kuraray Kuraray Polyol P3050) was used instead of polyester polyol A used in Example 1. I got a thing. The obtained composition was evaluated for physical properties in the same manner as in Example 1.
The results are listed in Table 1.

Comparative Example 2
A urethane resin composition was obtained in the same manner as in Example 2 except that polyester polyol B was used instead of polyester polyol A used in Example 2. The obtained composition was evaluated for physical properties in the same manner as in Example 1. The results are listed in Table 1.

  The urethane resin composition of the present invention is suitable as a urethane-based adhesive because it has excellent weather resistance, high adhesion, and good hydrolysis resistance. In addition to adhesives, adhesives, paints, inks, coating materials, sealing materials, binders, and the like can be used by taking advantage of performances such as adhesion, hydrolysis resistance, and weather resistance.

Claims (2)

  (A) polyol, (B) dicarboxylic acid, (C) three components of nuclear hydrogenated terpene phenol resin and / or (B) dicarboxylic acid, (C) two components of nuclear hydrogenated terpene phenol resin are reacted as essential components. The urethane resin composition obtained by making the polyester polyol obtained by reacting (D) isocyanate compound react.   (A) polyol, (B) dicarboxylic acid, (C) three components of nuclear hydrogenated terpene phenol resin and / or (B) dicarboxylic acid, (C) two components of nuclear hydrogenated terpene phenol resin are reacted as essential components. The urethane resin composition according to claim 1, wherein the polyester polyol obtained in the step (D) has a reaction ratio of 1.1 to 5.0 times mol of the isocyanate compound.