JP2003026750A - Urethane prepolymer composition bearing terminal isocyanate group and reactive hot melt adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane prepolymer composition bearing a terminal isocyanate group, which exhibits excellent adhesion to a molded article made of various plastics such as polyethylene, polypropylene, nylon, polyethylene terephthalate and the like when used as an adhesive and excellent in color tone, heat resistance, oil resistance and stability, and a reactive hot melt adhesive containing the prepolymer composition. SOLUTION: The reactive hot melt adhesive comprises a terminal isocyanate group-bearing urethane prepolymer composition, which is composed of a reaction product of a hydrogenated product (1) of a petroleum resin bearing an active hydrogen, a polymeric polyol (2) and a diisocyanate compound (3), or a terminal isocyanate group-bearing urethane prepolymer composition, which is obtained by reacting a polyol (4) constituted of a hydrogenated product (1) of a petroleum resin bearing an active hydrogen with a diisocyanate compound (3).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a urethane prepolymer composition having an isocyanate group at a terminal and a reactive hot melt type adhesive containing the prepolymer composition.

[0002]

2. Description of the Related Art A hot melt type adhesive is an adhesive which exhibits a strong adhesive property by being instantly cured by cooling after heating and melt coating. In addition, since hot melt adhesives do not use solvents, there is no risk of fire caused by solvents, it is difficult to cause poisoning symptoms such as so-called sick house syndrome, and further, it is essential for solvent-based and water-based adhesives. Since it does not require an evaporation or drying process, it can save energy required for drying, a drying equipment, and a space for installing equipment, and is an adhesive with high productivity and small environmental load, and thus is used in various fields. However, a general hot melt adhesive has a limit in heat resistance because it is used by melting a thermoplastic resin. To compensate for this, high-melting hot-melt adhesives such as low-crystalline polyester resin and nylon have been developed, but there are problems that they cannot be used for heat-sensitive base materials and that the open time is short.

In order to improve the drawbacks of such a hot melt type adhesive, a reactive hot melt type adhesive in which the adhesive is crosslinked by a chemical reaction after the adhesion to improve the performance such as adhesive strength, heat resistance and oil resistance. Agents are being developed. Examples of the cross-linking method include cross-linking with moisture, heat, cross-linking with energy rays, and cross-linking by mixing two liquids. However, the use of heat and energy rays is currently limited in usage due to the fact that auxiliary equipment is required and the type of mixing two liquids complicates the process. On the other hand, the type utilizing moisture is widely used particularly for adhesion of wood or the like in which moisture is contained in the adherend because the crosslinking reaction proceeds by utilizing the moisture in the air or the adherend.

Examples of the reactive hot-melt type adhesive utilizing moisture curing include those utilizing an isocyanate group and those utilizing an alkoxysilyl group. As an example of the former, for example, a method is known in which a urethane prepolymer having an isocyanate group at the terminal is obtained by reacting a polyol with an excess amount of a polyisocyanate compound. As an example of the latter, a method of introducing an alkoxysilyl group into a prepolymer or oligomer using a silane coupling agent is known. In the latter case, since the silane coupling agent is expensive, there are disadvantages such as the cost of the adhesive.Therefore, at present, the method using the terminal isocyanate group-containing urethane prepolymer is widely used. Has been done.

Generally, polyurethane adhesive compositions have insufficient adhesion to general-purpose films such as polyethylene films and polypropylene films. Therefore, in order to improve the adhesion, rosin ester resins, ketone resins, styrene oligomers and petroleum oils are used. A method of blending a tackifying resin such as a resin is known. However,
Generally, the tackifying resin has a low molecular weight, so that the heat resistance,
There is a problem that physical properties such as oil resistance are deteriorated.

[0006]

The present invention solves the above problems, that is, it has excellent adhesiveness to various plastic molded products such as polyethylene, polypropylene, nylon and polyethylene terephthalate when used as an adhesive. And to provide a urethane prepolymer composition having an isocyanate group at the terminal, which is excellent in color tone, heat resistance, oil resistance, and stability, and a reactive hot melt adhesive containing the prepolymer composition. And

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventors have found that a urethane prepolymer composition having an isocyanate group at the terminal and the prepolymer composition are contained. The inventors have found that the problems of the above-mentioned conventional techniques can be solved by using a reactive hot melt type adhesive, and have completed the present invention.

That is, the present invention provides a urethane prepolymer composition having an isocyanate group at the terminal, which is composed of a reaction product of a hydride (1) of a petroleum resin having active hydrogen, a polymer polyol (2) and a diisocyanate compound (3). The present invention relates to a urethane prepolymer composition having an isocyanate group at the terminal, which is obtained by reacting a polyol (4) containing a hydride (1) of a petroleum resin having active hydrogen as a constituent, and a diisocyanate compound (3). The present invention also relates to a reactive hot melt type adhesive containing a urethane prepolymer composition having an isocyanate group at the terminal as a main component.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The hydride (1) of a petroleum resin having active hydrogen used in the present invention is a reaction product of a polymerizable monomer contained in a petroleum fraction and an active hydrogen-containing compound described later. It means a product obtained by hydrogenating a petroleum resin having active hydrogen.

The above-mentioned petroleum resin having active hydrogen is a reaction product composed of a polymerizable monomer contained in a petroleum fraction and an active hydrogen-containing compound, and examples of the polymerizable monomer include isoprene, normal pentene and cyclopentadiene. C5 fraction such as C9 fraction, styrene, vinyltoluene, α-methylstyrene, indene and the like C9 fraction, a mixture thereof or a purified product thereof, and the above-mentioned separately synthesized polymerizable monomer can be used.

As the active hydrogen-containing compound, a hydroxyl group capable of reacting with an isocyanate group in the polyisocyanate compound which is one of the constituents of the polyurethane adhesive composition,
A compound having active hydrogen such as an amino group and a carboxyl group can be used. Specific examples thereof include hydroxyl group-containing compounds such as allyl alcohol and phenol compounds, carboxylic acid compounds such as maleic acid and its anhydride, and amine compounds such as aniline and allylamine. Of these, a hydroxyl group-containing compound, particularly an alcohol type hydroxyl group, is more preferable from the viewpoint of odor and colorability of the obtained resin, and ease of production.

In order to produce a petroleum resin having active hydrogen, a method in which an active hydrogen-containing compound is allowed to exist in the reaction system when the polymerizable monomer is polymerized and cationic polymerization or thermal polymerization is mentioned. By these methods, an active hydrogen group derived from an active hydrogen-containing compound is introduced into a petroleum resin having active hydrogen.

As a method other than the above-mentioned method of introducing an active hydrogen group, there is also a method of hydrolyzing a reaction product comprising the above-mentioned polymerizable monomer and a compound having a functional group such as ester. Specifically, there may be mentioned a method in which a hydrocarbon resin having an ester group introduced therein is converted into hydroxyl groups by saponification using a monomer such as vinyl acetate.

Among these methods for introducing an active hydrogen group, the method of reacting the above-mentioned polymerizable monomer with the above-mentioned compound having an active hydrogen group such as a hydroxyl group, an amino group and a carboxyl group is preferred because of its simplicity. preferable. When the polymerizable monomer is an aromatic hydrocarbon, phenol or the like is preferable as the active hydrogen-containing compound to be reacted therewith, and when the polymerizable monomer is a dicyclopentadiene hydrocarbon, the activity to be reacted with this is preferable. Allyl alcohol and the like are preferable as the hydrogen-containing compound.

As the petroleum resin having active hydrogen, the active hydrogen group introduced into the resin as described above is further modified and used in order to change it into a more reactive active hydrogen group. You can also do it. For example,
When the active hydrogen group introduced into the resin is a hydroxyl group or a phenolic hydroxyl group, an adduct obtained by adding an alkylene oxide or an epoxy compound to these functional groups can be used, and the active hydrogen group is a carboxyl group. In the case of a group, it is also possible to use an amidated product with a hydroxyamine compound.

Since the petroleum resin having active hydrogen thus obtained has active hydrogen, it can react with an isocyanate group. An amino group as the active hydrogen group,
A carboxyl group and the like are preferable in terms of reactivity with isocyanate, but a hydroxyl group is particularly preferable in terms of no odor or coloration and easy production. Examples of these include phenol-modified C9 petroleum resin obtained by cationically polymerizing C9 petroleum fraction in the presence of phenol, and alcohol-modified diene obtained by thermal polymerization of cyclopentadiene and dicyclopentadiene in the presence of allyl alcohol. Examples thereof include cyclopentadiene-based resins, but alcohol-modified dicyclopentadiene-based resins having a large average hydroxyl group content per molecule are preferable because the resulting urethane prepolymer can have a high molecular weight.

The hydride (1) of the petroleum resin having active hydrogen used in the present invention is obtained by hydrogenating the above-mentioned petroleum resin having active hydrogen. The content of active hydrogen in the hydride (1) of the petroleum resin having active hydrogen is preferably such that when the group having active hydrogen is, for example, a hydroxyl group, the hydroxyl value is 70 to 250.
-220 is more preferable. When the hydroxyl value is 70 or more, the reactivity with the isocyanate compound is improved, and sufficient adhesiveness, heat resistance and oil resistance can be obtained. Also,
When the hydroxyl value is 250 or less, workability is improved, and the color tone and stability of the resulting reactive hot-melt adhesive can be improved.

The hydride (1) of a petroleum resin having active hydrogen has a hydrogenation ratio of 5 to 100% and is a resin having an excellent color tone. Usually, the color tone is the Gardner color number (JIS.
K 5400) is 3 or less.

As the hydrogenation conditions for producing the hydride (1) of petroleum resin having active hydrogen, the hydrogenation pressure is about 1 to 30 MPa (the lower limit is preferably 3 MPa, and the upper limit is preferably 25 MPa). The reaction temperature is about 50 to 400 ° C. (the lower limit is preferably 100 ° C. and the upper limit is preferably 350 ° C.). Hydrogenation pressure is 1M
When it is less than Pa or when the reaction temperature is less than 50 ° C., the hydrogenation reaction is difficult to proceed. Hydrogenation pressure is 30
If it exceeds MPa, special equipment is required, and if the reaction temperature exceeds 400 ° C., the decomposition reaction of the resin becomes remarkable, which is not preferable. Also,
The reaction time for hydrogenation is usually about 10 minutes to 10 hours, preferably about 20 minutes to 7 hours. When the reaction time is less than 10 minutes, the hydrogenation reaction is difficult to proceed, so that it is necessary to use a large amount of the catalyst, and when the reaction time exceeds 10 hours, there is a problem that productivity is deteriorated. . The above description does not exclude hydrogenation conditions outside the above range, and hydrogenation can be carried out by using a catalyst that can react even at a hydrogenation pressure of less than 1 MPa, for example.

As the hydrogenation catalyst, various kinds such as metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium, rhenium or metal compounds such as oxides or sulfides thereof can be used. Such a hydrogenation catalyst may be used by supporting it on a carrier such as porous alumina having a large surface area, silica, silica alumina (diatomaceous earth), carbon or titania. The amount of the catalyst used is usually 0.01 to 10% by weight based on the modified hydrocarbon resin (A) which is the raw material resin.
It is a degree.

The hydrogenation reaction is carried out in a state where the petroleum resin having active hydrogen is melted or dissolved in a solvent.
The solvent is not particularly limited as long as it is inert in the reaction and can dissolve the petroleum resin having active hydrogen as the raw material resin and the hydride (1) of the petroleum resin having active hydrogen as the product. Not limited. For example, tetrahydrofuran, dioxane, n-hexane, n-heptane, n-octane, 2-ethylhexane, cyclohexane, decalin, terpene, isopropyl alcohol, n
-Butanol, 2-methyl-2-propanol, cyclohexanol, n-hexanol, 2-ethylhexanol and the like can be mentioned, and these can be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but is usually 5% by weight with respect to the modified hydrocarbon resin (A).
It is above, and preferably in the range of 10 to 70% by weight.

Regarding the amount of the catalyst used and the reaction time, the case of using the batch system as the reaction system has been described, but other reaction systems such as the flow system (fixed bed system, fluidized bed system, etc.) are also adopted. It is also possible.

The number average molecular weight of the hydride (1) of the petroleum resin having active hydrogen is not particularly limited, but it is usually preferably about 200 to 3,000. When the number average molecular weight is 200 or more and 3000 or less, workability can be improved.

Next, a description will be given of a urethane prepolymer composition containing a terminal isocyanate group containing a hydride (1) of a petroleum resin having active hydrogen as a constituent. The terminal isocyanate group-containing urethane prepolymer composition of the present invention is a terminal isocyanate group-containing urethane prepolymer composition in addition to a hydride (1) of a petroleum resin having active hydrogen and a diisocyanate compound (3) as its constituent components. The polymer polyol (2) is used in order to make the above-mentioned flexibility suitable.

As the polymer polyol (2) which is a constituent component of the urethane prepolymer composition containing a terminal isocyanate group of the present invention, various known ones can be used. For example, polyether polyols such as polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc .; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,
3-propanediol, 1,3-butanediol, 1,
4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol,
1,6-hexanediol, octanediol, 1,4
-Saturated or unsaturated known low-molecular-weight glycols such as butynediol and dipropylene glycol, or n
-Alkyl glycidyl ethers such as butyl glycidyl ether and 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, and terephthalic acid ,
Polyester polyols obtained by dehydration condensation with dibasic acids such as succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, or their corresponding acid anhydrides and dimer acids. Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds; Other polycarbonate polyols, polybutadiene glycols, bisphenol A
Examples thereof include various known polymer polyols generally used in the production of polyurethane resins, such as glycols obtained by adding ethylene oxide or propylene oxide.

In the case of the high-molecular polyester polyol obtained by reacting a glycol with a dibasic acid among the high-molecular polyols, glycerin, trimethylolpropane, trimethylolethane, 1, 2,
It is also possible to use polyhydric alcohols such as 6-hexanetriol, 1,2,4-butanetriol, sorbitol and pentaerythritol. However, since gelation occurs when a large amount of polyhydric alcohol is used, the amount of polyhydric alcohol used is preferably up to 5 mol% of the glycols. As the polymer polyol (2), a polyol (4) containing a hydride (1) of a petroleum resin, which will be described later, as a constituent component may be used. In this case, 3% by weight or more, 6% or more in the urethane prepolymer finally obtained.
It is preferable to determine the amounts of various components so as to contain the hydride (1) of petroleum resin of 0% by weight or less.

As the diisocyanate compound (3) which is a constituent of the terminal isocyanate group-containing urethane prepolymer composition of the present invention, various known diisocyanates such as aromatic, aliphatic or alicyclic compounds can be used. . Specifically, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1, 4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, hydrogen Xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, Cyclohexyl-4,4 '
Typical examples thereof include diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexanediisocyanate, m-tetramethylxylylene diisocyanate, and dimerisocyanate obtained by converting the carboxyl group of dimer acid into an isocyanate group.

The urethane prepolymer composition containing a terminal isocyanate group of the present invention is, as described above, a reaction product of a hydride (1) of a petroleum resin having active hydrogen, a polymer polyol (2) and a diisocyanate compound (3). It consists of things. By containing the diisocyanate compound (3) in an excess amount with respect to the amount of active hydrogen groups in the hydride (1) of the petroleum resin having active hydrogen and the high molecular weight polyol (2), the terminal isocyanate group-containing It becomes a urethane prepolymer composition. Usually, the equivalent of the isocyanate group of the diisocyanate compound (3) is 1.2 / 1 to 3.5 / 1 equivalent to the total of the active hydrogen group of the petroleum resin having active hydrogen and the polymer polyol (2). It is preferably within the range. By setting the equivalent ratio of the isocyanate group to 1.2 or more, the moisture curing reaction is likely to proceed, and heat resistance and oil resistance can be improved, which is preferable, and by setting it to 3.5 or less,
Suppresses the remaining free isocyanate groups, foaming and heat resistance decrease during moisture curing, stability decrease during storage (increased viscosity)
Is preferable because it can suppress

In the urethane prepolymer composition containing a terminal isocyanate group of the present invention, a hydride (1) of a petroleum resin having active hydrogen which is the above-mentioned constituent, a polymer polyol (2) and a diisocyanate compound (3). Besides, a chain extender may be used as an additional component.
By adding the chain extender, the flexibility of the urethane prepolymer composition containing a terminal isocyanate group can be adjusted. Various known chain extenders can be used. Specific examples include ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, and dicyclohexylmethane-4,4'-diamine. Also, 2-hydroxyethylethylenediamine,
The diamines having a hydroxyl group in the molecule such as 2-hydroxyethyl propylene diamine, di-2-hydroxy ethyl ethylene diamine, di-2-hydroxy ethyl propylene diamine, 2-hydroxy propyl ethylene diamine, and di-2-hydroxy propyl ethylene diamine, and the above-mentioned. Representative examples thereof include the low-molecular glycol described in the section of polyester diol and dimer diamine obtained by converting the carboxyl group of dimer acid into an amino group.

Even when a chain extender is used, the isocyanate group of the diisocyanate compound (3) is added to the total amount of the active hydrogen groups of the petroleum resin having active hydrogen, the polymer polyol (2) and the chain extender. It is preferably in the range of 1.2 to 3.5 equivalent times.

A urethane prepolymer composition containing a terminal isocyanate group is produced by reacting the petroleum resin (1) having active hydrogen, the polymer polyol (2) and the active hydrogen group of the chain extender with the isocyanate of the diisocyanate compound (3). Other than reacting so that the equivalents of groups become excessive,
A general urethane prepolymer manufacturing method can be adopted. Specifically, the petroleum resin hydride (1) having a predetermined amount of active hydrogen (1), the polymer polyol (2) and the diisocyanate compound (3) are added in a temperature range of about 50 to 150 ° C. for about 1 to 5 hours. React. In addition, these reactions can be performed in the presence or absence of various solvents. The solvent is not particularly limited as long as it does not inhibit the formation of the urethane prepolymer composition containing a terminal isocyanate group, and examples thereof include aromatic solvents such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. System solvent; dioxane,
An ether solvent such as tetrahydrofuran may be used alone or in combination.

In the production of the urethane prepolymer composition having an isocyanate group at the terminal, a catalyst for accelerating the reaction may be used if necessary. The type of catalyst is not particularly limited, but examples thereof include tertiary amine-based catalysts such as triethylenediamine and triethylamine, and tin-based catalysts such as dibutyltin dilaurate, dibutyltin diacetate and dibutyltin dimaleate.

The melt viscosity of the urethane prepolymer composition containing a terminal isocyanate group of the present invention thus obtained is 1
100 Pa · s or less at 20 ° C., preferably 1 to 50 Pa
・ S. The number average molecular weight is usually 5,000 to 100.
It is about 000.

A urethane prepolymer composition having an isocyanate group at the terminal obtained by reacting a polyol (4) containing a hydride (1) of a petroleum resin having active hydrogen (1) as a constituent and a diisocyanate compound (3) of the present invention are , Hydrides of petroleum resins having said active hydrogen (1)
Is obtained by reacting the diisocyanate compound (3) with a polyol obtained by using, for example, an alcohol component or an acid component of the polyester polyol.

The polyol (4) having a hydride (1) of a petroleum resin having active hydrogen as a constituent is, for example, when the hydride (1) of a petroleum resin having active hydrogen has a carboxylic acid group or a hydroxyl group. Examples include polyester polyols and the like. In the case of polyester polyol, a general polyester production method can be adopted. Specifically, a predetermined amount of a dibasic acid component, a hydride (1) of a petroleum resin having active hydrogen, a polyol, and a catalyst are present. Esterification is performed by dehydration condensation in the temperature range of about 200 to 280 ° C. for about 3 to 20 hours in the presence or absence of the solvent. As the catalyst, a general esterification catalyst can be used, and examples thereof include a production method using dibutyltin oxide, zinc acetate, titanium tetrabutoxide, antimony trioxide and the like. The end point of the esterification is usually the time when the acid value becomes 3 or less, preferably 1 or less.

In the case of producing a polyester polyol, in order to promote esterification, an organic solvent may be added at the stage of esterification and the mixture may be refluxed at about 200 to 280 ° C. Reflux with an organic solvent is usually for about 2 to 8 hours, and the organic solvent is removed after the reflux. In addition,
The organic solvent is not particularly limited as long as it does not have active hydrogen such as a hydroxyl group, and examples thereof include hydrocarbon solvents such as toluene and xylene; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

The petroleum resin hydride (1) having active hydrogen and the polymer polyol (2) may be used in combination with the polyol (4). In this case, it is preferable to determine the amounts of various components so that the urethane prepolymer finally obtained contains the hydrogenated product (1) of 3% by weight or more and 60% by weight or less of the petroleum resin.

As the reaction conditions of the polyol (4) and the diisocyanate compound (3), the above method can be adopted.

The urethane prepolymer composition having an isocyanate group at the terminal obtained by these methods can be used as it is as a reactive hot-melt type adhesive, and the prepolymer as a main component,
Further, auxiliary materials and additives such as plasticizers, thermoplastic polymers, tackifiers, fillers, antioxidants and the like used for ordinary reactive hot melt adhesives may be added.

[0040]

The reactive hot melt type adhesive using the prepolymer of the present invention has excellent adhesiveness to various plastic molded products such as polyethylene, polypropylene, nylon and polyethylene terephthalate and has a good color tone. is there. It also has excellent heat resistance, which is a problem when it is used as a hot-melt adhesive, and has good oil resistance, weather (light) resistance, and stability.

[0041]

EXAMPLES The present invention will be described in more detail with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. Parts and% are based on weight.

Production Example 1 (Production of hydride (1) of petroleum resin having active hydrogen) An alcohol-modified dicyclopentadiene-based petroleum resin (trade name "Quinton 170" was placed in an autoclave having a volume of 1 liter.
0 ", manufactured by Nippon Zeon Co., Ltd., softening point 102.0 ° C., number average molecular weight 360) 500 parts, nickel / diatomaceous earth catalyst (nickel loading 50% by weight) 7 parts, and kept at 260 ° C. under hydrogen pressure. Hydrogenation was carried out at 20 MPa for 5 hours. Then, the hydride of the obtained alcohol-modified dicyclopentadiene-based petroleum resin was taken out, dissolved in 500 parts of toluene, and the catalyst was removed by filtration.
The solvent was removed under reduced pressure at 2.7 kPa for 30 minutes to give a softening point of 100.
450 parts of hydride of alcohol-modified dicyclopentadiene-based petroleum resin at 0 ° C. Table 1 shows the color tone, hydroxyl value, hydrogenation rate of unsaturated bonds, and number average molecular weight of the hydride of the obtained alcohol-modified dicyclopentadiene-based petroleum resin (hereinafter referred to as "resin A").

The softening point is the ring and ball method (JIS K220).
It is the measured value according to 7). The color tone is based on Hazen Standard Color (H) (ASTM D1209). The hydroxyl value is determined by potentiometric titration (JIS K0070). The hydrogenation rate of unsaturated bonds was calculated by measuring a proton nuclear magnetic resonance spectrum ( ¹ H-NMR). That is, a deuterium-substituted chloroform (CDCl ₃ ) solution having the same concentration of the raw material resin and the obtained hydride was prepared, and ¹
H-NMR was measured and calculated from the H-spectrum of the unsaturated double bond appearing around 5 to 6 ppm and the H-spectrum area of the conjugated double bond of the aromatic ring appearing near 7 ppm based on the following formula. Hydrogenation rate = {1- (spectrum area of obtained hydride / spectrum area of raw material resin)}
× 100 (%). The number average molecular weight is gel permeation chromatography (manufactured by Tosoh Corporation, HLC8120,
Column used: TSKgel Super HM-L × 3,
It was measured with a developing solvent: tetrahydrofuran.

Production Example 2 460 parts of "Resin B" was obtained by the same procedure as in Production Example 1 except that the nickel / diatomaceous earth catalyst was changed to 4 parts. .

Production Example 3 In Production Example 1, 500 parts of phenol-modified C9 petroleum resin (“Neopolymer E-100”, softening point 93.0 ° C., number average molecular weight 580, manufactured by Nippon Petrochemical Co., Ltd.) was used as a raw material. 480 parts of "resin C" was obtained by performing the same operation except that 2.0 parts of nickel / diatomaceous earth catalyst (supported amount of nickel: 50% by weight) was used for the resin and the reaction temperature was changed to 280 ° C.

Production Example 4 430 parts of "Resin D" was obtained by performing the same operation except that the nickel / diatomaceous earth catalyst was changed to 10 parts in Production Example 1.

[0047]

[Table 1]

Production Example 5 (Production of Polyester Polyol Composition) 375.3 parts of adipic acid and "resin B" were placed in a flask equipped with a thermometer, a nitrogen inlet tube, a reflux dehydrator and a stirrer.
00.0 parts, 1,6-hexanediol 362.8 parts (hydroxyl / carboxyl group equivalent ratio = 1.2) and dibutyltin oxide 0.0175 parts were charged, and the raw materials were melted and allowed to stir. Start stirring 1
The temperature was gradually raised from 50 ° C to 250 ° C over 5 hours. The water generated at this time was distilled out of the system. Next, after charging 15.6 parts of xylene, the temperature was raised to 260 ° C. and xylene was refluxed to further promote esterification. Then, 0.7 part of phosphorous acid was added, and after keeping the temperature for 30 minutes,
Xylene is distilled off for 30 minutes under a reduced pressure of 50 mmHg,
An acid value of 0.4, a hydroxyl value of 40, and a number average molecular weight of 55, which contains a hydride (1) of a petroleum resin having active hydrogen as a constituent component.
00 polyester polyol (A) was obtained.

Example 1 A round bottom flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas introducing tube was charged with 200 parts of "resin A" and a molecular weight of 2000.
Poly (3-methyl-1,5-pentylene adipate)
Glycol (Kuraray Co., Ltd., trade name "Kurapol P2
010 ″) was charged, and after the raw materials were melted and the stirring became possible, stirring was started and the temperature was raised to 80 ° C. Then isophorone diisocyanate (IPDI)
A colorless polyurethane adhesive composition was obtained by charging 280 parts of (equivalent ratio of isocyanate group / hydroxyl group = 2) and reacting at 140 ° C. for 6 hours under a nitrogen stream.

Examples 2 to 4 The same as Example 1 except that the kind of hydride of the petroleum resin containing an active hydrogen group and the charged amount of IPDI were changed as shown in Table 2. Thus, a colorless polyurethane-based adhesive composition was obtained.

[0051]

[Table 2]

Example 5 In Example 1, 300 parts of a polyester polyol (A) containing a hydride (1) of a petroleum resin having active hydrogen as a polyol component as a constituent component was used as a diisocyanate compound (3) at 4,4 '. -In the same manner as in Example 1 except that 53.3 parts of diphenylmethane diisocyanate (so that the equivalent ratio of isocyanate group / hydroxyl group = 2) was changed to a reaction temperature of 90 ° C and a reaction time of 3 hours, A colorless polyurethane adhesive composition was obtained.

Comparative Example 1 Poly (3-methyl-) having a molecular weight of 2000 in Example 1
1,5-Pentylene adipate) glycol (manufactured by Kuraray Co., Ltd., trade name "Kurapol P2010") 1000
Parts, and a colorless polyurethane composition was obtained in the same manner as in Example 1 except that 222 parts of IPDI was used.

Comparative Example 2 Instead of "resin A" in Example 1, 200 parts of rosin ester (trade name: super ester S-115, pentaerythritol ester of disproportionated rosin, manufactured by Arakawa Chemical Industry Co., Ltd.) A brownish polyurethane adhesive composition was obtained in the same manner as in Production Example 1, except that 178 parts of IPDI was used.

Comparative Example 3 Instead of "resin A" in Example 1, 200 parts of C9 petroleum resin hydride (trade name: Alcon P-100, manufactured by Arakawa Chemical Industry Co., Ltd.) and 178 parts of IPDI were used. A colorless polyurethane adhesive composition was obtained in the same manner as in Production Example 1 except for the above.

<Evaluation Method of Adhesiveness of Polyurethane Adhesive Composition> The obtained urethane adhesive composition was melted in a corona discharge treated polypropylene film (thickness: 0.3 mm, width: 25 mm) using a dedicated applicator. , Coated (coating amount: 30 g / m ² ), corona discharge treated polypropylene film (thickness 0.3 mm, width 25 m
m) were overlaid and pressure was applied at 0.2 MPa for 5 seconds to bond them together to prepare an evaluation film. The evaluation film was subjected to the following tests. The evaluation results are shown in Table 3.

(Evaluation of Adhesiveness) After the evaluation film was prepared, the film was allowed to stand at room temperature for 10 days (relative humidity 60%), and the peel strength and heat resistant creep were evaluated under the following conditions. Peel strength: T-type peel strength was measured at a pulling speed of 100 mm / min. Heat-resistant creep: At an environmental temperature of 70 ° C and a load of 1 kg,
The number of days until peeling by 1 mm was measured.

(Adhesive Composition Colorability) The color tone of the obtained polyurethane adhesive was visually confirmed.

(Evaluation of Stability of Adhesive Composition) The viscosity at 120 ° C. immediately after preparation of the obtained polyurethane adhesive and the viscosity at 120 ° C. after standing for 24 hours in a nitrogen atmosphere were measured to obtain a composition. Calculated as stability. (Viscosity after leaving for 24 hours / viscosity immediately after preparation) × 100 = less than 200 is ◯, 2
A value of 00 or more and less than 300 was evaluated as Δ and a value of 300 or more was evaluated as x. The results are shown in Table 3.

[0060]

[Table 3]

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J034 BA08 CA15 CC23 CC26 CC61                       CC62 DA01 DF02 DF16 DF20                       DF22 DG03 DG04 DG05 DG14                       DP06 GA06 GA33 HA01 HA07                       HA18 HC03 HC09 HC12 HC13                       HC17 HC22 HC46 HC52 HC64                       HC67 HC71 HC73 JA42 RA08                 4J040 EF101 EF181 EF281 EF321                       JB01

Claims (5)

[Claims] 1. A urethane prepolymer composition having an isocyanate group at the terminal, which comprises a reaction product of a hydride (1) of a petroleum resin having active hydrogen, a polymer polyol (2) and a diisocyanate compound (3). 2. A urethane prepolymer composition having an isocyanate group at the terminal, which is obtained by reacting a polyol (4) containing a hydride (1) of a petroleum resin having active hydrogen as a constituent and a diisocyanate compound (3). 3. The urethane prepolymer composition having an isocyanate group at the terminal according to claim 1, wherein the hydride (1) of a petroleum resin having active hydrogen is a hydride of an alcohol-modified dicyclopentadiene resin. 4. The urethane having a terminal isocyanate group according to any one of claims 1 to 3, wherein the urethane prepolymer contains 3 to 60% by weight of a hydride (1) of a petroleum resin having active hydrogen. Prepolymer composition. 5. A reactive hot-melt adhesive containing the urethane prepolymer composition having an isocyanate group at the terminal according to claim 1 as a main component.