JP2000297264A - Thixotropic one-pack curing-type polyurethane-based adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject adhesive with good comb-patterned trowel smothness in its coating operation using a comb-patterned trowel, capable of forming comb-patterned stripes favorable for bonding without the need of addition of any volatile or high-boiling solvent under the addition of a thixotropic agent by incorporating a specific urethane prepolymer with a paraffin, or the like. SOLUTION: This adhesive is obtained by incorporating (A) 100 pts.wt. of an isocyanate group-terminated urethane prepolymer prepared by reaction of a compound having at least two active hydrogen groups in the molecule with a polyisocyanate compound having at least two isocyanate groups in the molecules so as to be an excess of the isocyanate groups with (B) pref. 0.1-50 pts.wt. of a paraffin, pref. i-paraffin and (C) pref. 0.1-50 pts.wt. of an organic ester such as di-2-ethylhexyl phthalate. The adhesive which is appropriately viscous has excellent thixotropy, exhibiting high adhesion to e.g. plastics including polyvinyl chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thixotropic one-component curing type polyurethane adhesive, and more particularly, to applying an adhesive using a comb iron without adding a volatile solvent or a high boiling point solvent. It has good comb-teeth handling properties, and it can form a good pile of combs with good adhesion, suitable viscosity, excellent thixotropic properties, plastics such as polyvinyl chloride, olefin resin, polyester and plastic foam. One-part curable polyurethane-based adhesive with excellent storage stability and excellent storage stability to inorganic materials including glass and ceramics, metal materials such as iron and aluminum, and wood materials. About.

[0002]

2. Description of the Related Art Polyurethane-based adhesives are prepared by one-component (one-component) or two-component (two-component) mixing a polyisocyanate compound alone or by mixing it with a substance containing active hydrogen which easily reacts with isocyanate. Liquid type). That is, it is used in various forms such as a polyisocyanate monomer, a prepolymer, and an isocyanate-modified polymer. The prepolymer comprises a polyol having two or more active hydrogen groups such as a hydroxyl group (OH) or an amine group in a molecule and a polyisocyanate compound having two or more isocyanate groups (NCO) in a molecule, wherein the isocyanate group is It is obtained by mixing and reacting both so as to be excessive, that is, so that the NCO / OH equivalent ratio is greater than 1. In an adhesive application, it may be used together with an appropriate curing agent as a two-pack type. There is also a one-part type that cures with moisture in the air or surface moisture of the material to be adhesively coated. The two-pack type requires work such as weighing and mixing the main agent and the curing agent, and the workability is inferior to that of the one-pack type. Is coming. One-component urethane prepolymer-based adhesives are used for various purposes such as shoe production and automobile parts attachment, and in particular, in the construction field, are used for production of building members in factories and construction site construction. However, in general, the bonding surfaces of the adherends are not smooth, and when they are overlapped, many gaps are generated between the adherends. Normally, the adhesive completely fills the gap and joins each material,
If the gap is large, it is necessary to apply a large amount of adhesive in advance. In addition, even if there is a gap between the adherends, the adhesive may be partially and evenly adhered without prioritizing the adhesive completely with priority given to economy. In this case, the adhesive is applied in a beat shape or in a point with the adhesive raised. In both cases, it is better that the adhesive has no fluidity. However, to perform the coating operation, it is better to have a low viscosity. To this end, thixotropic properties are often imparted to the adhesive. However, one-part urethane prepolymers are usually
Since there is little thixotropy, a thixotropic agent is added to impart thixotropy. However, the addition of the thixotropic agent increases the viscosity and reduces the workability of coating. In the conventional example, the viscosity is reduced by adding a volatile solvent or a high boiling point solvent. However, when a volatile solvent is used, it becomes a factor of causing a risk of fire and deteriorating the environment in which the adhesive is used. Further, when a high boiling point solvent is added, the effect of reducing the viscosity is low, so that a large amount of the addition is required, and as a result, the adhesive performance is reduced. Furthermore, when applying the adhesive using a comb iron in the above-mentioned bonding, the adhesive has good shaping property, and has an appropriate viscosity so as to form a comb peak that is good for bonding. While it is required to be excellent in denaturation, plastics such as polyvinyl chloride, olefin resin, polyester and plastic foam, inorganic materials including glass and ceramics, metal materials such as iron and aluminum, and wood materials There is a need for polyurethane-based adhesives that exhibit excellent adhesion to a wide variety of materials such as. Further, the adhesive is required to have good storage stability.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned disadvantages of the prior art, and uses a comb iron to add a volatile solvent or a high-boiling solvent without adding a volatile solvent or a high boiling point solvent. Plastics such as polyvinyl chloride, olefin-based resin, polyester, etc. have good comb-tease handling property when applying the agent, and can form good comb-shaped peaks for adhesion, suitable viscosity, excellent thixotropic properties. And plastic foam,
To provide a polyurethane-based adhesive that exhibits excellent adhesion to a wide variety of materials such as inorganic materials including glass and ceramics, metal materials such as iron and aluminum, and wood materials, and has good storage stability. Aim. Other objects of the present invention will become clear from the description throughout the present specification.

[0004]

According to the present invention, a compound having two or more active hydrogen groups in a molecule and a polyisocyanate compound having two or more isocyanate groups in a molecule are mixed so that the isocyanate group becomes excessive. The present invention relates to a thixotropic one-component curable polyurethane-based adhesive obtained by mixing a paraffin and an organic acid ester with a terminal isocyanate group urethane prepolymer obtained by the reaction. In particular, a specific amount of paraffins and organic acid esters is blended in the urethane prepolymer having terminal isocyanate groups, and the paraffins are, inter alia, i-paraffins and the distillation property temperature range is A preferred range is a specific range.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The compound having two or more active hydrogen groups in the molecule (hereinafter referred to as an active hydrogen group-containing compound) used in the present invention includes, for example, a monomer or prepolymer having a terminal hydroxyl group or an amine group. Can be
Specific examples thereof include polymer polyols such as polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, and polyether polyamine, polymer polyamines, castor oil, and saccharides. As an active hydrogen group-containing compound, a chain extender such as a low molecular weight alcohol such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, and cyclohexane dimethanol or propylene for the purpose of adjusting the molecular weight or introducing a hydroxyl group. Diamines such as diamine and hexamethylene diamine, low molecular weight amino alcohols, and water may be used. Other active hydrogen group-containing compounds include monoalcohols and monoamines, and these and the aforementioned low-molecular-weight amino alcohols are also used as reaction terminators. One or more of these can be used. Among the above-mentioned polymer polyols, specific examples of the polyester polyol include ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol. Butanediol, 1,4-butanediol, neopentyl glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,5-pentane Diol,
3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3 -Propanediol, 2
So-called low molecular weight glycols such as -n-butyl-2-ethyl-1,3-propanediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, and mixtures thereof; succinic acid, adipic acid, Dehydration condensation with dicarboxylic acids such as sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid, naphthylene dicarboxylic acid, their acid esters, acid anhydrides, and mixtures thereof Examples thereof include polyesters having hydroxyl groups at both ends obtained by the reaction, and polycaprolactone diol obtained by ring-opening polymerization of ε-caprolactone. Specific examples of the polyether polyol include, for example, ethylene oxide, propylene oxide, oxirane compounds such as butylene oxide, ethylene glycol, propylene glycol, trimethylolpropane, obtained by polymerizing with a low molecular weight polyol such as glycerin or water as an initiator. Polyether polyols and ethylene oxide,
Examples thereof include polyether polyols obtained by ring-opening polymerization of epoxides such as propylene oxide alone or mixtures, and polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran. Specific examples of the polycarbonate polyol include those obtained by a dephenol reaction between low-molecular glycols used in the synthesis of the polyester polyol and diphenyl carbonate. In order to achieve the object of the present invention, the number average molecular weight of such a polymer polyol is 500
It is preferably in the range of 10,000 to 10,000. Examples of the low molecular alcohol include low molecular glycols used for the synthesis of the polyester polyol described above.
Specific examples of the low-molecular polyamine include aliphatic diamines such as ethylenediamine and hexamethylenediamine, alicyclic diamines such as isophoronediamine and cyclohexyldiamine, and aromatic diamines such as diaminodiphenylmethane and diaminodiphenylsulfone. . Specific examples of the low-molecular-weight amino alcohol include monoethanolamine and diethanolamine. Specific examples of the monoalcohol include methanol, ethanol, propanol, isopropanol and the like. Specific examples of the monoamine include -monoamines such as ethylamine and butylamine, and secondary monoamines such as diethylamine and dibutylamine.

The polyisocyanate compound used in the present invention includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate (I
PDI), phenylene diisocyanate, cyclohexyl diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated trimethyl xylylene diisocyanate, 2-
Methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-
Trimethylhexamethylene-1,6-diisocyanate, 2,4,4, trimethylhexamethylene-1,6-diisocyanate
MDl isomers such as diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), and 2,4'-diphenylmethane diisocyanate; 4,4'-diphenylmethane diisocyanate; MDI), 4,4-dibenzyl diisocyanate, 1,5-naphthalenediisocyanate,
Paraphenylene diisocyanate, 2,4- or 2,
Examples include aromatic diisocyanates such as 6-tolylene diisocyanate or a mixture thereof, tetramethyl xylylene diisocyanate, 4,4-diphenyl ether diisocyanate, and araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof. Can be Also, triphenylmethane-4,4
Dimer, trimer, burette derived from the above polyisocyanate monomer such as', 4 ''-triisocyanate, and 2,4,6-oxaziridine obtained from carbon dioxide and the above polyisocyanate monomer Polyisocyanates having a trione ring, adducts of low molecular weight polyols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, and cyclohexane dimethanol with polyisocyanates, modified isocyanate compounds with carbodiimide, or Examples include NCO-terminated compounds such as adducts of polyester polyols, polyether polyols and the like with polymer polyols of polyisocyanates, and mixtures of two or more of these. The polyisocyanate compound may be used alone or in combination of two or more.

The paraffins used in the present invention include (1) i-paraffin, and (2) liquid paraffin which is a mixture of liquid saturated hydrocarbons belonging to a lubricating oil fraction in terms of boiling point (for example, crude oil is usually used). Gas under pressure and vacuum distillation,
Except for gasoline, kerosene, and light oil, a fraction of engine oil can be obtained from spindle oil and extracted with a solvent such as liquid sulfurous acid or furfural. ), (3)
n-paraffin; (4) chlorination of n-paraffin or molten solid paraffin; chlorinated paraffin which can be produced by passing chlorine gas through a solution of solid paraffin in carbon tetrachloride; (5) raw materials such as naphtha in a tubular furnace An olefinic hydrocarbon obtained by thermal decomposition through a hydrocarbon and steam (by a tubular decomposition method). (6) Mainly composed of n-paraffin, containing small amounts of i-paraffin and naphthene, and having 20 carbon atoms. To 35, paraffin waxes obtained by a lubricating oil press dewaxing method and a solvent dewaxing method industrially. The above-mentioned chlorinated paraffin can be obtained in the form of solid powder or liquid depending on its chlorine content, but is preferably liquid. Among them, i-paraffin is preferable for achieving the object of the present invention, that is, the addition of the i-paraffin hydrocarbon oil uses a comb iron even without adding a volatile solvent or a high boiling point solvent. It has good comb-tease handling when applying adhesive, and also can form good comb-like peaks for bonding.
Appropriate viscosity, excellent thixotropic properties, polyvinyl chloride, olefin resin, polyester and other plastics and plastic foams, inorganic materials including glass and pottery, iron,
It is preferable for obtaining a one-part curable polyurethane-based adhesive which exhibits excellent adhesiveness to a wide variety of materials such as metal materials such as aluminum and wood materials, and has good storage stability.

The paraffins are added in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 35 parts by weight, based on 100 parts by weight of the urethane prepolymer. If the amount of the paraffins is less than 0.1, the effect of reducing the viscosity is small, the handling with a comb is heavy, and it becomes difficult to apply the adhesive. On the other hand, if it exceeds 50 parts by weight, it is difficult to form a good peak of combs when separated with a comb iron.

[0010] The above-mentioned paraffins have a distillation property temperature range of:
The temperature is preferably from 150 to 360 ° C. If the distillation property temperature range is lower than 150 ° C, the paraffins are easily volatilized. If the temperature exceeds 360 ° C, the viscosity reducing effect and thixotropic property of the adhesive are reduced.

The organic acid esters used in the present invention include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and di-n-octyl phthalate. , Di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), dioctyldecyl phthalate, diisodecyl phthalate (DIDP), butylbenzyl phthalate (BBP), dilauryl phthalate (DLP), dicyclohexyl phthalate (DCHP) ), Phthalic esters such as hydrophthalic anhydride (esters derived from hydrophthalic anhydride), adipates such as dioctyl adipate (DOA), isodecyl adipate (DIDA), and triethyl phosphate ( TE
P), phosphates such as tributyl phosphate (TBP), trioctyl phosphate (TOP), tris (chloroethyl) phosphate (TCEP), and tris (dichloropropyl) phosphate (TDCPP) Propylene glycol adipate, butylene glycol adipate polyester, alkyl epoxystearate, epoxidized soybean oil and the like. These can be used alone or in combination.

The organic acid ester is added in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 35 parts by weight, based on 100 parts by weight of the urethane prepolymer. When the amount of the organic acid ester is less than 0.1, the viscosity of the adhesive becomes high, the combing operation becomes heavy, and it becomes difficult to apply the adhesive. Adhesion to the material is poor.

The total amount of the paraffins and organic acid esters is 0.2 to 50 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the urethane prepolymer.
It is advisable to add 35 parts by weight. The total addition amount is 0.2
If the amount is less than the above, the effect of reducing the viscosity is small, the combing operation becomes heavy, and it becomes difficult to apply the adhesive. On the other hand, if the amount exceeds 50 parts by weight, the adhesiveness to the adherend is deteriorated.

The adhesive of the present invention has a thixotropic property by adding a thixotropic agent. Specific examples of thixotropic agents include fatty acid amide wax, ultrafine silica, asbestos powder, rock wool powder, inorganic thixotropic agents such as sepiolite, organic bentonite, modified polyester polyol-based organic thixotropic agents, amide-based wax, and the like. Surface-treated calcium carbonate, mica powder, short fiber polyethylene, and the like.

[0015] A filler is added to the adhesive of the present invention. Specific examples of the filler include, for example, clay, calcined clay, talc, silica, alumina, calcium carbonate, magnesium oxide, calcium silicate, calcium aluminate, sodium aluminate, magnesium silicate, calcium hydroxide, barium sulfate, Examples include inorganic fillers such as carbon black, silica sand, mica, titanium oxide, silica balloon, glass balloon, and zeolite, and organic powders such as vinyl chloride powder, rubber powder, and organic balloon.

The adhesive of the present invention may further contain, if necessary, an adhesion-imparting agent, a tackifier, a catalyst, and the like. Examples of the adhesion-imparting agent include various titanate-based or silane-based coupling agents, reaction products of a coupling agent and an isocyanate compound, and reaction products of two or more coupling agents (for example, various aminosilanes and epoxysilanes). And a condensation reaction product of an alkoxy group of two or more molecules of the coupling agent) and the like, and these can be used alone or as a mixture. Specific examples of the tackifier include rosin and the like, and can be used alone or as a mixture. Specific examples of the catalyst include organometallic catalysts such as dibutyltin dilaurate, tin octenoate, lead octenoate and lead naphthenate, N-triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N , N ', N ".
N ", N" -pentamethyldiethylenetriamine,
N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N
Tertiary amines such as -methyl-N'-dimethylaminoethylpiperazine, and an imidazole compound in which the secondary amine functional group of the imidazole ring is linearized with a cyanoethyl group, and the like, and one or a mixture of two or more thereof can be used. As other additives, stabilizers, various antioxidants, ultraviolet absorbers and the like can also be added.

[0017]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, parts mean parts by weight.

Example 1 Polypropylene glycol having an average molecular weight of 2000
8.8 parts by weight of 4,4'-diphenylmethane diisocyanate and 8.8 parts by weight of polymethylene polyphenyl isocyanate were added to 4 parts by weight, and reacted at 80 ° C. for 4 hours in a nitrogen stream to obtain an NCO group content of 14%. Was obtained. After adding 22.2 parts by weight of dehydrated and dried calcium carbonate and 15.8 parts by weight of surface-treated calcium carbonate to the urethane prepolymer, G2
6 parts by weight of ethylhexyl phthalate and 16 parts by weight of i-paraffin hydrocarbon oil having a distillation property temperature range of 213 to 262 ° C. are stirred in a nitrogen stream to obtain a one-part curable polyurethane adhesive having a resin content of 40%. Obtained.

Example 2 To the urethane prepolymer obtained in Example 1, 22.2 parts by weight of dehydrated and dried calcium carbonate and 15.8 parts by weight of surface-treated calcium carbonate were added, and then dioctyl phthalate was added. 10 parts by weight and the distillation property temperature range is 2
16 parts by weight of i-paraffin hydrocarbon oil at 77 to 353 ° C. was added, and the mixture was stirred in a nitrogen stream to obtain a one-component curable polyurethane-based adhesive having a resin content of 40%.

Example 3 Polypropylene glycol having an average molecular weight of 3000
To 34 parts by weight, 4.33 parts by weight of 4,4'-diphenylmethane diisocyanate and 7.33 parts by weight of polymethylene polyphenyl isocyanate were added, and 80
The reaction was carried out at 4 ° C. for 4 hours to obtain a urethane prepolymer having an NCO group content of 12%. In this urethane prepolymer,
After adding 34.2 parts by weight of dehydrated and dried calcium carbonate, 10 parts by weight of surface-treated calcium carbonate, and 0.8 parts by weight of hydrophobized ultrafine silica, i-paraffin having a distillation property temperature range of 213 to 262 ° C. 10 parts by weight of a hydrocarbon oil, 4 parts by weight of an i-paraffinic hydrocarbon oil having a distillation property temperature range of 116 to 202 ° C., and 6 parts by weight of di-2-ethylhexyl phthalate were added, and the mixture was stirred in a nitrogen stream to give a resin content of 35%. One-part curing type polyurethane adhesive was obtained.

Example 4 34.2 parts by weight of dehydrated and dried calcium carbonate, 10 parts by weight of surface-treated calcium carbonate, and 0.8 parts by weight of hydrophobized ultrafine silica were added to the urethane prepolymer obtained in Example 3 After the addition, the distillation property temperature range is 226.
12 parts by weight of n-paraffin hydrocarbon oil at ~ 229 ° C;
8 parts by weight of di-2-ethylhexyl phthalate was added, and the mixture was stirred in a nitrogen stream to obtain a one-part curable polyurethane-based adhesive having a resin content of 35%.

Comparative Example 1 In Example 1, the distillation property temperature range was 213 to 262.
A one-part curable polyurethane-based adhesive was obtained in the same manner as in Example 1, except that i-paraffin hydrocarbon oil at a temperature of ° C was not used and 22 parts by weight of di-2-ethylhexyl phthalate alone was used.

Comparative Example 2 In Example 1, n-ethylhexyl phthalate having a distillation property temperature range of 213 to 262 ° C. was added without adding di-2-ethylhexyl phthalate.
-Except for 22 parts by weight of paraffin hydrocarbon oil alone,
A one-component curable polyurethane-based adhesive was obtained in the same manner as in Example 1.

Comparative Example 3 Example 3 was repeated except that i-paraffinic hydrocarbon oil and di-2-ethylhexyl phthalate were not added, and dioctyl phthalate alone was added in an amount of 20 parts by weight.
A one-component curable polyurethane-based adhesive was obtained in the same manner as described above.

Comparative Example 4 In Example 4, di-2-ethylhexyl phthalate was not added, and the distillation property temperature range was 226 to 229 ° C.
One-part curable polyurethane-based adhesive was obtained in the same manner as in Example 4, except that the n-paraffin hydrocarbon oil alone was changed to 20 parts by weight.

<Test Method and Performance Evaluation> Examples 1 to 4
Each of the one-component curable polyurethane-based adhesives obtained in Comparative Examples 1 to 4 was subjected to the following tests, and the results of each test evaluation are shown in Table 1. <Viscosity> Each viscosity at 2 rpm and 20 rpm was measured according to the viscosity test method of a liquid resin according to JIS K7117 using a rotational viscometer, and the SVI value was calculated by the following equation. S = η1 / η2, where S: SVI value η1: Viscosity at 2 rpm (mPa · s) η2: Viscosity at 20 rpm (mPa · s) <Applicability> Application of adhesive for vinyl floor tile / vinyl floor sheet of JIS A5536 According to the test method for the properties, the combing and combing were evaluated in the following four stages. X: Comb eyes spread immediately after coating. Δ: After a while after application, the mountain of combs spreads. ：: Mount Kushime stands and does not spread. ◎: Comb peaks stand more than ○ and clear peaks are formed. <Storage Stability> 500 g of the adhesive was put in a metal can, sealed with nitrogen, covered, and left in a thermostat at 40 ° C. for one month. The viscosity (20 rpm) and the separation state of the adhesive after the test were measured, and the thickening ratio was determined by the following equation, and the separation state was determined as follows.
It was evaluated on a scale. M = η3 / η2, where M: Thickening ratio η2: Viscosity before test at 20 rpm (Pa · s) η3: Viscosity after test at 20 rpm (Pa · s) ：: None ○: Slightly separated △: Slightly large (Separated on one side but less than 1 mm) X: Many (separation of 1 mm or more on one side) <Adhesive strength> 4 mm thick according to the tensile test method for adhesives for vinyl floor tiles and vinyl floor sheets of JIS A5536 400 g / m ^{2 of} each adhesive was applied to a flexible board (manufactured by Asano Slate) using a comb iron,
The following adherends were bonded together within 5 minutes after application. Then
After loading a 1 kg weight for 5 seconds, it was cured for 7 days in a constant temperature room at 20 ° C., and the tensile adhesive strength was measured. Polystyrene foam: Styrofoam (manufactured by Dow Chemical) Inorganic filled polyethylene foam: Softlon FBQ
(Manufactured by Sekisui Chemical)

[0027]

[Table 1]

[0028]

As described above, according to the present invention, even when a volatile solvent or a high-boiling-point solvent is not added, the combing iron can be easily removed when the adhesive is applied using the combing iron. It is possible to form a good pile of combs, with appropriate viscosity, excellent thixotropic, plastics such as polyvinyl chloride, olefin resin, polyester and plastic foam, inorganic materials including glass and pottery, iron, A one-component curable polyurethane-based adhesive exhibiting excellent adhesiveness to a wide variety of materials such as metal materials such as aluminum and wood materials and having good storage stability can be provided.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Koji Fukuda 4-13-1, Itabashi, Itabashi-ku, Tokyo Oshika Shinko Co., Ltd. F term (reference) 4J040 BA172 EC242 ED052 ED162 EF101 EF111 EF121 EF131 EF181 EF201 EF321 GA20 HA306 HA356 HB02 HB32 HB34 HB44 HC10 HD24 JA12 JB04 KA25 LA05 LA06 MA02 MA03 MA04 MA05 MA08 MA10 MA11 NA05 NA12 NA16

Claims (4)

[Claims] 1. A terminal isocyanate obtained by mixing and reacting a compound having two or more active hydrogen groups in a molecule with a polyisocyanate compound having two or more isocyanate groups in a molecule such that the isocyanate group becomes excessive. A thixotropic one-part curable polyurethane-based adhesive comprising a base urethane prepolymer blended with paraffins and organic acid esters. 2. Paraffins are added in an amount of 0.1 to 50 parts by weight per 100 parts by weight of a urethane prepolymer having terminal isocyanate groups.
The thixotropic one-component curable polyurethane-based adhesive according to claim 1, wherein 0.1 to 50 parts by weight of an organic acid ester is mixed with 0.1 to 50 parts by weight. 3. The thixotropic one-component curing type polyurethane adhesive according to claim 1, wherein the paraffin is i-paraffin. 4. The distillation property temperature range of i-paraffin is 1
The thixotropic one-component curing type polyurethane adhesive according to claim 1, wherein the temperature is 50 to 360 ° C.