JP2003034709A - Polyisocyanate composition and sealing material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyisocyanate composition having less content of high molecular weight fraction in a resin and low viscosity, and a moisture-curing sealing material using the same that is superior in a low modulus, stainproof and weather resistance. SOLUTION: The polyisocyanate composition contains a pre-polymer (A) with an isocyanate terminal group that is obtained by a reaction between at least one kind of an aliphatic and/or an alicyclic diisocyanate monomer and a polyether diol having a number-average molecular weight or 500 to 10,000 with its unreacted diisocyanate monomer and solvent being removed and does not contain an allophanate bond, and a pre-polymer (B) with an isocyanate terminal group that is obtained by a reaction between a polyether triol having a number-average molecular weight of 500 to 10,000 with the unreacted diisocyanate monomer and solvent being removed and does not contain an allophanate bond. And the sealing material using it is provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polyisocyanate composition useful as a sealing material for construction and automobiles, and a sealing material using the same.

[0002]

2. Description of the Related Art Polymers having isocyanate groups at the ends are used in moisture-curable compositions which react with moisture in the air and cure. This composition is used in the fields of construction, civil engineering, automobiles, etc., and is particularly frequently used as a sealing material for construction and automobiles. Regarding the sealing material for construction, in JP-A-3-111448, polypropylene glycol having an average molecular weight of 3,000 and 5,000 and 4,4′-diphenylmethane diisocyanate (hereinafter referred to as MDI) are disclosed in JP-A-4-370146. Then, polyoxypropylene glycol having an average molecular weight of 3,000, polyoxypropylene triol having an average molecular weight of 300 and MDI are used. In JP-A-6-080755, a polyoxypropylene glycol having an average molecular weight of 3,000 and an average molecular weight of 3,000 are used. Polyoxypropylene triol and xylylene diisocyanate are disclosed in
-256499 discloses a polyalkylene ether triol having an average molecular weight of 7,000 and an average molecular weight of 5,000.
Of polyalkylene triol and MDI from JP-A-3-2
In JP 15554, a polyether triol having a molecular weight of 3,000 is reacted with MDI, and in JP-A 5-209165, a polyoxypropylene ether diol having a molecular weight of 4,000 and a polyoxypropylene triol having a molecular weight of 10,000 are reacted with tolylene diisocyanate. However, the obtained isocyanate group-terminated high molecular weight product is disclosed.

Urethane-based sealing materials for construction have no surface tack and are desired to have improved stain resistance, low modulus, high curability, low viscosity and foaming resistance. However, the above-mentioned proposal has limitations. All of these are carried out in the reaction between the polyol and the diisocyanate monomer in a state where the equivalents of the hydroxyl group and the isocyanate group are relatively close. Since such a method basically has the following problems, various prescriptions are available. Therefore, there were many restrictions.

1) Since a large amount of high molecular weight compounds are formed in the resin synthesized in a state where the equivalents of the hydroxyl group and the isocyanate group are relatively close to each other and the resin viscosity is high, the viscosity of the sealing material when compounding as it is Has the problem of becoming high. 2) The higher molecular weight due to the urethane bond results in an increase in viscosity due to the urethane bond and an increase in the modulus of the cured resin. Therefore, plasticizers, solvents, etc. are used, which cause pollution. 3) In the high molecular weight product obtained under such conditions, unreacted diisocyanate monomer remains, and during curing, it reacts with moisture and easily foams. As a means for solving the above problems, a method of adding a reactive diluent has also been reported. For example, JP-A-54-302
Japanese Patent Laid-Open No. 95 discloses a method of adding a specific amount of an adduct of 1 mol of an organic diisocyanate monomer and 1 mol of a compound represented by a monoalcohol to a urethane prepolymer as a high solid type coating, thereby reducing the amount of solvent used. It is described that it is possible.

However, the reaction conditions for synthesizing the above urethane prepolymer are NCO / OH equivalent ratio of 2-8.
Therefore, even under these conditions, it is conceivable that the prepolymer tends to have a higher molecular weight and the resin viscosity increases.
Further, under the above reaction conditions, the adduct of monoalcohol also dimerizes. In that case, since it is not reactive by itself, it exists as a diluent when used as a sealing material, and causes contamination. Become. Therefore, the present inventors previously prepared a sealing material using a specific polyisocyanate product obtained by reacting a high molecular weight polyol and a diisocyanate monomer in a large excess diisocyanate monomer state, and removing the unreacted diisocyanate monomer after the reaction. Proposed (WO99 / 52960). This proposal has achieved the above-mentioned object. Furthermore, the present inventors have studied to achieve the above-mentioned object by using a prepolymer that can be produced under relatively mild reaction conditions and has excellent mechanical properties.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a low-viscosity polyisocyanate composition and a moisture-curable sealant using the same, which has a particularly low modulus.

[0007]

In order to solve the above-mentioned problems, the present inventors have prepared an isocyanate-terminated prepolymer containing no allophanate bond, which is obtained from a diisocyanate monomer and a polyether diol, from the diisocyanate monomer and a polyether triol. It has been found that the above-mentioned problems can be achieved by blending the resulting isocyanate-terminated prepolymer containing no allophanate bond, and the present invention has been accomplished. The polyisocyanate composition comprising an isocyanate-terminated prepolymer derived from a polyether diol and a polyether triol used in the present invention has a high molecular weight due to a urethane bond because the synthesis is carried out under the condition that the ratio of the isocyanate groups is in excess of the hydroxyl groups. In addition, the resin content is low, and the viscosity is significantly lower than the conventional isocyanate-terminated prepolymer synthesized under the condition that the ratio of isocyanate groups to hydroxyl groups is close. Further, since a mixture of polyether diol and polyether triol is used as a urethane, there is no need to generate an allophanate bond in the prepolymer, the reaction conditions are mild, and a low molecular weight polyether triol is used. Viscosity and excellent mechanical strength. When this polyisocyanate composition is used as a sealing material, surprisingly, even if a formulation in which the amount of plasticizer used is greatly reduced or a formulation in which it is not used at all is set, low viscosity, good extrudability, low modulus, and non-use are obtained. Low pollution due to bleed-out can be achieved all at once. Further, it was discovered that when a predetermined amount of various additives is added, further lower modulus, lower stain resistance, and higher weather resistance can be achieved, and the present invention has been completed.

That is, the present invention is as follows. I) At least one or more kinds of aliphatic and / or alicyclic diisocyanate monomers and a number average molecular weight of 500 to
It is obtained by reacting a polyether diol of 10,000 at an isocyanate group / hydroxyl group equivalent ratio of 5/1 to 100/1, and then removing unreacted diisocyanate monomer and solvent, which does not contain an allophanate bond. Isocyanate-terminated prepolymer (A) and at least one or more of aliphatic and / or alicyclic diisocyanate monomers, and polyether triol having a number average molecular weight of 500 to 10,000 are used in an isocyanate group / hydroxyl group equivalent ratio. Is obtained by removing unreacted diisocyanate monomer and solvent after the reaction at 5/1 to 100/1, and contains an isocyanate-terminated prepolymer (B) containing no allophanate bond. Composition.

II) The content of the isocyanate-terminated prepolymer (B) is 1 part by mass or more and less than 200 parts by mass with respect to 100 parts by mass of the isocyanate-terminated prepolymer (A). Polyisocyanate composition. III) Further, at least one selected from a photocurable substance, a polymer plasticizer, a plasticizer, an inert organic solvent, a thixotropic agent, and an oxygen curable substance is contained, and II) is described. Polyisocyanate composition. IV) A moisture-curable resin composition comprising the polyisocyanate composition according to any one of I) to III). V) A sealing material comprising the polyisocyanate composition according to any one of I) to III).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The isocyanate-terminated prepolymers (A) and (B) will be described. The diisocyanate monomer used for the synthesis of the isocyanate-terminated prepolymers (A) and (B) is aliphatic and / or alicyclic. Aromatic diisocyanate monomers can also be used unless the weather resistance is required.

The aliphatic diisocyanate monomer preferably has 4 to 30 carbon atoms, and the aromatic diisocyanate monomer preferably has 8 to 30 carbon atoms.
For example, tetramethylene-1,4-diisocyanate,
Pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamylene-1,6-diisocyanate, lysine diisocyanate, isophorone diisocyanate, 1,3-
Bis (isocyanatomethyl) -cyclohexane, 4,
4'-dicyclohexyl methane diisocyanate etc. can be mentioned. Among them, hexamethylene diisocyanate (hereinafter referred to as H
DI), isophorone diisocyanate (hereinafter I
PDI) is preferable, and they may be used alone or in combination. Of these, HDI is preferable.

Next, the polyether polyol used in the present invention will be described. Polyether diol is used for the synthesis of the isocyanate-terminated prepolymer (A), and polyether triol is used for the synthesis of the isocyanate-terminated prepolymer (B). 1.5-2.5 are preferable and, as for the hydroxyl group average number of functional groups of polyether diol, 1.8-2.2 are more preferable. If it is less than 1.5, the curability is poor, and if it exceeds 2.5, the modulus at the time of curing tends to increase. Moreover, 2.5-3.5 are preferable and, as for the hydroxyl group average number of functional groups of polyether triol, 2.8-3.2 are more preferable. If it is less than 2.5, the curability tends to be poor, and if it exceeds 3.5, the modulus upon curing tends to increase.

In the case of producing a polyether polyol, polyhydric alcohols, polyhydric phenols, polyamines, alkanolamines, etc. are specifically mentioned, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4. -Butanediol, 1,6-hexanediol, dihydric alcohols such as bisphenol A, trihydric alcohols such as glycerin and trimethylolpropane, diamines such as ethylenediamine, alone or in a mixture, for example, water such as lithium, sodium and potassium. Strongly basic catalysts such as oxides, alcoholates, and alkylamines, metal porphyrins, complex metal cyanide complexes, complexes of metals with chelating agents having three or more coordinations, and zinc hexacyanocobaltate complex complexes. Using a metal complex,
It is obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide and styrene oxide, alone or in a mixture. The preferred alkylene oxide is propylene oxide.

The number average molecular weight of the polyol is 500 to 3
10,000 is preferable, and more preferably 1,000 to
20,000, particularly preferably 1,000 to 1
It is 10,000. When the molecular weight is less than 500, physical properties of the cured resin such as elongation deteriorate, and when it is 10,000 or more, the effect of reducing the viscosity becomes small. The diisocyanate monomer and polyether diol or polyether triol are used in an isocyanate group / hydroxyl group equivalent ratio of 5/1 to 1
It is preferable to react at 00/1. The equivalent ratio is 5
If it is less than 1/1, the viscosity of the reaction solution tends to increase, and if it exceeds 100/1, the yield tends to decrease.

A solvent may be used in the reaction of the diisocyanate monomer and the polyol, but in that case, a solvent inert to isocyanate should be used. The reaction temperature is preferably 20 to 170 ° C, more preferably 60 to 130 ° C. When the reaction temperature is lower than 20 ° C., the reaction rate is slow and the productivity tends to decrease. Also, 1
If it exceeds 70 ° C, side reactions such as coloring may occur. A catalyst may be used in the reaction. It is also preferable that the catalyst generally has basicity. For example, a tetraalkylammonium hydroxide or an organic weak acid group such as acetic acid or capric acid can be used as a catalyst.
Primary amine compounds such as trioctylamine, 1,
4-diazabicyclo (2,2,2) octane, 1,8-
Diazabicyclo (5,4,0) undecene-7,1,5
A catalyst such as a tertiary amine compound such as diazabicyclo (4,3,0) nonene-5, for example, an acetylacetone metal salt such as zinc, a weak organic metal salt of zinc, tin, lead, iron, or the like is also effective.

Usually, the catalyst concentration is preferably in the range of 10 ppm to 1.0% with respect to the isocyanate compound. The bonds between the isocyanate groups of the diisocyanate monomer and the hydroxyl groups of the polyether polyol that are present in the reaction solution are substantially all urethane bonds. The allophanate groups in the composition have a binding ratio (described below) of less than 0.05.
When comparing with prepolymers of the same molecular weight, rather than including allophanate groups at the ends of the polyol for crosslinking, it is possible to more evenly distribute the crosslinking points by using triol, which increases the strength at break, It is advantageous in terms of mechanical properties. In addition, the reaction conditions for forming allophanate bonds are higher than those for forming urethane bonds, and a long reaction time is required. Therefore, the present invention in which only urethanation is used is advantageous in terms of production conditions.

After the reaction, the unreacted diisocyanate monomer and the solvent are removed by a method such as thin film distillation or extraction to obtain an isocyanate-terminated prepolymer (A) or an isocyanate-terminated prepolymer (B). The concentration of unreacted diisocyanate monomer and solvent contained is 5% or less, preferably 3% or less, and more preferably 0.
It is 2% or less.

The isocyanate-terminated prepolymer (A) thus obtained preferably has an isocyanate functionality of 1.5 to 2.5, more preferably 1.8 to.
2.2 Viscosity at 25 ° C is 500 to 10,000 mPas
-S (more preferably 1,000 to 8,000 mPa-
s), the isocyanate group concentration is 0.5 to 10 wt%, more preferably 0.5 to 5 wt%, and further preferably 0.5.
~ 3 wt%. If the viscosity is less than 500, sufficient thixotropy cannot be obtained in the sealing material after compounding, and if it exceeds 10,000, a sufficient effect of viscosity reduction cannot be obtained and the viscosity of the sealing material tends to increase. If the isocyanate group concentration is less than 0.5 wt%, it is difficult to obtain sufficient curability, and if it exceeds 10 wt%, it is difficult to obtain a sufficiently low modulus. The isocyanate-terminated prepolymer (B) preferably has an isocyanate functionality of 2.5 to 3.5, more preferably 2.8 to 3.2.
Viscosity at 5 ° C. is 500 to 10,000 mPa · s (more preferably 1,000 to 8,000 mPa · s), isocyanate group concentration is 1.0 to 13 wt%, more preferably 1.0 to 8 wt%. Preferably 1.0-5 wt%
Is. If the viscosity is less than 500, it is difficult to obtain sufficient thixotropy in the sealing material after compounding.
If it exceeds 10,000, the effect of sufficient viscosity reduction cannot be obtained, and the viscosity of the sealing material tends to increase. If the isocyanate group concentration is less than 1.0 wt%, it is difficult to obtain sufficient curability, and if it exceeds 13 wt%, it is difficult to obtain a sufficiently low modulus.

In obtaining a polyisocyanate composition from the above-mentioned isocyanate-terminated prepolymers (A) and (B) obtained as described above, the content of the isocyanate-terminated prepolymer (B) is adjusted to A) 1 part by mass or more per 100 parts by mass 2
It is preferable to mix within the range of less than 00 parts by mass, more preferably the isocyanate-terminated prepolymer (A) 10
10 parts by mass or more and less than 100 parts by mass with respect to 0 parts by mass, more preferably an isocyanate-terminated prepolymer (A) 1
It is 10 parts by mass or more and less than 50 parts by mass with respect to 00 parts by mass. When the content of the isocyanate-terminated prepolymer (B) is less than 1 part by mass, it is difficult to obtain sufficient curability, and when it is 200 parts by mass or more, the cured resin becomes too hard and the modulus becomes higher than necessary. Tend.

In obtaining the polyisocyanate composition of the present invention, the isocyanate-terminated prepolymers (A) and (B) may be separately prepared and then mixed to obtain a polyisocyanate composition. It is also possible to obtain a polyisocyanate composition all at once by simultaneously supplying two kinds of polyether triol to the same reactor at a predetermined amount ratio and reacting them at the NCO / OH equivalent ratio under the above-mentioned appropriate reaction conditions. It is possible.
It is also possible to obtain a polyisocyanate composition by simultaneously adding the isocyanate-terminated prepolymers (A) and (B) to another polyisocyanate. In that case, the isocyanate should be adjusted so as to satisfy the above composition. It is necessary to adjust the addition amount of the terminal prepolymers (A) and (B).

A polyisocyanate composition which is a mixture of the isocyanate-terminated prepolymer (A) and the isocyanate-terminated prepolymer (B) thus obtained is
Isocyanate group concentration is preferably 0.5-10 wt
%, More preferably 0.5 to 5 wt%, still more preferably 0.5 to 3 wt%, and the viscosity at 25 ° C. is preferably 500 to 10,000 mPa · s, more preferably 1,000 to It is 8,000 mPa · s. If the isocyanate group concentration is less than 0.5 wt%, it is difficult to obtain sufficient curability, and if it exceeds 10 wt%, it is difficult to obtain a sufficiently low modulus. Also, the viscosity is 500 mPa · s
If the amount is less than that, sufficient thixotropy is difficult to be obtained in the sealing material after compounding, and if it exceeds 10,000 mPa · s, the viscosity of the sealing material becomes high and workability tends to be deteriorated.

Next, a stabilizer that can be used in the present invention,
The photocurable substance, polymer plasticizer, plasticizer, inert organic solvent, thixotropic agent, and oxygen-curable substance will be described. Examples of stabilizers that can be used in the present invention include benzotriazole-based ultraviolet absorbers, phosphite-based antioxidants, organic sulfur-based antioxidants, hindered phenol-based antioxidants,
A hindered amine light stabilizer is mentioned. As the benzotriazole-based ultraviolet absorber, one containing benzotriazole in its chemical structural formula, specifically, for example, tinuvin P, tinuvin 213, tinuvin 234, tinuvin 32.
0, tinuvin 326, tinuvin 327, tinuvin 32
8, TINUVIN 329, TINUVIN 571 (all of which are trademarks of Ciba Specialty Chemicals Co., Ltd.), Sumisolve 250, Sumisolve 310 (all of which are trademarks of Sumitomo Chemical Co., Ltd.), ADEKA STAB LA-31 (trademark of Asahi Denka Kogyo Co., Ltd.) , Etc., but especially Tinuvin 327, that is, 2,4-di-t-butyl-6- (5
-Chlorobenzotriazol-2-yl) phenol is preferred.

As the phosphite type antioxidant, those containing phosphite in its chemical structural formula, specifically, for example, Irgafos 38, Irgafos P-EPQ, Irgafos 126 (all of these are Ciba Specialty.
Chemicals Co., Ltd.), Sumilizer TNP, Sumilizer TPP-P, Sumilizer P-16 (all of which are trademarks of Sumitomo Chemical Co., Ltd.), ADEKA STAB PEP
-4C, ADEKA STAB PEP-8, ADEKA STAB 11
C, ADEKA STAB PEP-36, ADEKA STAB HP-1
1, Adeka Stub 260, Adeka Stub 522A, Adeka Stub 329K, Adeka Stub 1500, Adeka Stub C, Adeka Stub 135A, Adeka Stub 3010
(All of the above are trademarks of Asahi Denka Kogyo Co., Ltd.) and the like, but Sumilizer P-16, that is, tris (2,4-di-t-butylphenyl) phosphite is particularly preferable.

As the organic sulfur-based antioxidant, those containing thioether in the chemical structural formula, specifically, for example, Irganox PS800FL, Irganox PS80
2FL (all are trademarks of Ciba Specialty Chemicals Co., Ltd.), Sumilizer TPM, Sumilizer TP-D, Sumilizer TL, Sumilizer MB (all are trademarks of Sumitomo Chemical Co., Ltd.), ADEKA STAB A
O-23 (trademark of Asahi Denka Co., Ltd.) and the like can be mentioned, but in particular, Sumilizer TP-D, that is, pentaerythrityl tetrakis (3-lauryl thiopropionate).
Is preferred.

As the hindered phenolic antioxidant, one having 2,6-alkylphenol in the chemical structural formula, specifically, for example, Irganox 245, Irganox 259, Irganox 565, Irganox 1010, Irganox. 1035, Irganox 1076, Irganox 1098, Irganox 1222, Irganox 1330, Irganox 1
425, Irganox 3114, Irganox 15
20, Irganox 1135, Irganox 114
1, Irganox (all of which are trademarks of Ciba Specialty Chemicals Co., Ltd.), Sumilizer BHT,
Sumilizer MDP-S, Sumilizer GA-80, Sumilizer BBM-S, Sumilizer WX-R, Sumilizer GM, Sumilizer GS (all of which are manufactured by Sumitomo Chemical Co., Ltd.), Adeka Stab AO-30 (trademark of Asahi Denka Kogyo Co., Ltd.), etc. In particular, Irganox 245, that is, triethylene glycol-bis [3
-(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred.

As the hindered amine light stabilizer, those containing 2,2,6,6-tetramethylpiperidine in the chemical structural formula, specifically, for example, tinuvin 123S, tinuvin 144, tinuvin 765, timasolve 119FL,
Cimasolve 2020FDL, Cimasolve 944, Cimasolve 622LD (all of these are Ciba Specialty
Chemicals Co., Ltd.), Sumisolve 577 (Sumitomo Chemical Co., Ltd.), ADEKA STAB LA-52, ADEKA STAB LA-57, ADEKA STAB LA-62, ADEKA STAB LA-67, ADEKA STAB LA-63P, ADEKA STAB LA-68LD, ADEKA STAB LA-. 82, ADEKA STAB LA-87, ADEKA STAB LA-503, ADEKA STAB LA-601 (all above are trademarks of Asahi Denka Kogyo Co., Ltd.) SANOL LS-2626, SANOL LS-74
4, Sanol LS-440 (all of which are trademarks of Sankyo Co., Ltd.) and the like, and in particular, ADEKA STAB LA-62.
Is preferred.

The polyisocyanate composition of the present invention contains a benzotriazole type ultraviolet absorber group, a phosphite type antioxidant group, an organic sulfur type antioxidant group, a hindered phenol type antioxidant group, a hindered amine light stabilizer group. 1 group or more to 2 types or more, preferably 2 groups or more to 2 types or more, and more preferably 2 groups or more to 3 types or more can be added. Benzotriazole-based UV absorbers, phosphite-based antioxidants, organic sulfur-based antioxidants, hindered phenol-based antioxidants, hindered amine light stabilizers are isocyanate-terminated prepolymer 10 respectively.
0 to 10 parts by mass, preferably 0.01 to 10 parts by mass,
It is more preferably used in a proportion of 0.05 to 5 parts by mass.
If the amount used is less than 0.01 parts by mass, the effect of addition is difficult to be exhibited, and if the amount used exceeds 10 parts by mass, cost performance tends to decrease.

The photocurable resin which can be used in the present invention is one which is cured and crosslinked by light. Various substances such as organic monomers, oligomers, resins or compositions containing these are known as this type of substance, and any commercially available substance can be used in the present invention. For example, an unsaturated acrylic compound, polyvinyl cinnamate, azide resin, etc. can be mentioned. The unsaturated acrylic compound is a monomer, an oligomer, or a mixture thereof having one to several acrylic or methacrylic unsaturated groups, which is propylene (or butylene,
Monomers or molecular weights of ethylene) glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, isocyanuric acid ethylene oxide modified triacrylate, etc.
The following oligoesters may be mentioned.

Examples of polyvinyl cinnamate include cinnamic acid esterification products of polyvinyl alcohol, which is known as a photosensitive resin having a cinnamoyl group as a photosensitive group, and many polyvinyl cinnamate derivatives.
The azide compound is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive liquid to which a diazide compound is added as a photosensitizer, a "photosensitive resin" is used.
(Published March 17, 1972, published by Japan Society of Printing, page 93-, page 106-, page 117-), there are detailed examples. These may be used alone or in combination, and increased as necessary. A sensitizer can be added and used.

One or more photocurable substances may be added to the polyisocyanate composition of the present invention. The photocurable substance is preferably used in an amount of 0.001 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the isocyanate-terminated prepolymer. If the amount used is less than 0.001 part by mass, the effect of addition is difficult to be exhibited, and if it exceeds 30 parts by mass, the physical properties may be adversely affected. The polymer plasticizer that can be used in the present invention is a polyester-based, polyether-based, polystyrene-based, polybutadiene-based, alkyd resin, polychloroprene, butadiene-acrylonitrile copolymer, ethylene glycol-having a number average molecular weight of 300 to 20,000.
Propylene glycol copolymer, polyoxyalkylene monoether, natural oil, epoxidized natural oil, paraffins, and polyolefin wax.

Examples of the polymer plasticizer containing an ester group include an aliphatic linear polyester, a vinyl acetate type copolymer, a methyl methacrylate type copolymer and the like. Aliphatic linear polyesters are synthesized by polycondensation of dibasic acids such as adipic acid, sebacic acid, phthalic acid, and glycols such as 1,2-propylene glycol and 1,3-butylene glycol, for example polypropylene glycol adipate. and so on. The vinyl acetate-based copolymer is represented by a copolymer of ethylene and vinyl acetate.
The methyl methacrylate-based copolymer is a copolymer of methyl methacrylate and alkyl acrylate.

The polymer plasticizer containing an ether group is a polyoxyalkylene glycol ether, such as polyethylene glycol or polypropylene glycol. In addition, poly-α-methylstyrene, epoxidized natural oil such as epoxidized soybean oil, castor oil, chlorinated paraffin, liquid paraffin, liquid polybutene, liquid polyisobutylene, liquid polybutadiene, liquid polyisoprene, hydrogenated liquid polybutadiene, Hydrogenated liquid polyisoprene, other polyolefin waxes, etc. are used, but those compatible with the isocyanate-terminated prepolymer of the present invention can be used.

One or more polymer plasticizers may be added to the polyisocyanate composition of the present invention. The addition amount of the above-mentioned polymer plasticizer is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and further preferably 5 to 30 parts by mass with respect to 100 parts by mass of the isocyanate-terminated prepolymer of the present invention. Is. If the addition amount is less than 0.1 parts by mass, the effect of adding the polymer plasticizer is difficult to be exhibited, and if it is more than 100 parts by mass, mechanical properties such as elongation may deteriorate. The plasticizer that can be used in the present invention is, for example, phthalic acid ester, phosphoric acid ester, glycol ester, citric acid ester, aliphatic dibasic acid ester, fatty acid ester, or epoxy plasticizer.

As phthalic acid esters, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-
2-ethylhexyl phthalate, di-n-octyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, di-n-decyl phthalate, di-n-dodecyl phthalate, ditridecyl phthalate, diisotridecyl phthalate, dibenzyl phthalate, Examples include dinonyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, methyl oleyl phthalate, n-octyl-n-decyl phthalate, heptyl nonyl phthalate, di-2-ethylhexyl isophthalate, dicapryl phthalate, and di (79 alkyl) phthalate. .

Examples of the phosphoric acid esters include tributyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate and the like.
Examples of glycol esters include diethylene glycol dibenzoate, dipentaerythritol hexaester, and pentaerythritol ester. Examples of the citric acid esters include triethyl citrate and acetyl triethyl citrate. Examples of the aliphatic dibasic acid esters include diisodecyl succinate, dioctyl adipate, diisodecyl adipate, di-n-decyl adipate, dioctyl azelate, di-n-ethylhexyl azelate, dibutyl sebacate, dioctyl sebacate, Dioctyl tetrahydrophthalate and the like can be mentioned.

The fatty acid esters include butyl oleate, methoxyethyl oleate ,. Examples thereof include butyl stearate, acetylated methyl ricinoleate, methoxyethyl acetylated ricinoleate, glycerin triheptanoate, chlorinated fatty acid methyl, and methoxychlorinated fatty acid methyl. Examples of the epoxy plasticizer include butyl epoxystearate, octyl epoxystearate, benzyl epoxystearate, dioctyl epoxyhexahydrophthalate, and the like.

In addition, trioctyl trimellitate, tris-2-ethylhexyl trimellitate, ethylphthalylethyl glycolate, butylphthalylbutyl glycolate, tributyl acetylcitrate, etc. may be used. Use a material that is compatible with the polymer. One or more plasticizers may be added to the polyisocyanate composition of the present invention. The addition amount of the above plasticizer is preferably 1 part by mass or more and less than 20 parts by mass, more preferably 5 to 15 parts by mass, relative to 100 parts by mass of the isocyanate-terminated prepolymer of the present invention. When the addition amount is less than 1 part by mass, a sufficiently low modulus may not be achieved, and when it is 20 parts by mass or more, the stain resistance tends to be deteriorated.

Organic solvents usable in the present invention include aromatic hydrocarbon-based, aliphatic / alicyclic hydrocarbon-based, petroleum-based solvents and esters which are inert to the isocyanate-terminated prepolymer and other added substances. , Ketones, and ether esters. As the aromatic hydrocarbon-based organic solvent, toluene, mixed xylene, o-xylene, m-
Examples thereof include xylene, p-xylene, ethylbenzene, diethylbenzene, cumene, mesitylene, p-cymene, tetralin and butylbenzene. Examples of the aliphatic / alicyclic hydrocarbon-based organic solvent include hexane, heptane, octane, nonane, and cyclohexane. Examples of petroleum-based solvents include gasoline, kerosene fraction, and process oil.

As the organic solvent for the esters, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate,
Examples include isopentyl acetate, isohexyl acetate, ethyl propionate, butyl propionate, ethylene diacetate and the like. As the organic solvent for ketones, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-
Hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, isophorone, cyclohexanone, camphor and the like can be mentioned.

As the organic solvent of ether ester,
2-Methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like can be mentioned. One or more kinds of organic solvents can be added to the polyisocyanate composition of the present invention. The amount of the above solvent added is 1 to 100 parts by mass of the isocyanate-terminated prepolymer of the present invention.
The amount is preferably 20 parts by mass, more preferably 5 to 10 parts by mass. If the addition amount is less than 1 part by mass, a sufficiently low modulus may not be achieved, and if it is more than 20 parts by mass, the amount of organic solvent remaining on the surface is large and the tackiness deteriorates, resulting in deterioration of stain resistance. Tend to do.

As the thixotropic agent which can be used in the present invention, various thixotropic agents which are usually added for imparting thixotropic properties can be used. As thixotropic agent, hydrogenated castor oil, amide wax,
Aluminum stearate, calcium stearate,
Zinc stearate, fine powder silica, organic bentonite,
Benton, silicic acid anhydride, silicic acid derivatives, urea derivatives, aerosil and the like are known, and any commercially available substance can be used in the present invention, but hydrogenated castor oil, fine powder silica and aerosil are particularly preferable.

One or more thixotropic agents may be added to the polyisocyanate composition of the present invention. The thixotropic agent is used in an amount of preferably 0.001 to 50 parts by mass, and more preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the isocyanate-terminated prepolymer. If the amount used is 0.001 parts by mass or less, the effect becomes small, and if it is 50 parts by mass or more, the workability may be adversely affected.

The oxygen-curing substance that can be used in the present invention generally includes an air-oxidation-curing substance which is said to be a compound having an unsaturated group in the molecule which causes polymerization by oxygen in the air. Specifically, for example, tung oil, dry oil such as linseed oil, various alkyd resins obtained by modifying the compound, acrylic polymers modified with a drying oil, epoxy resins, silicone resins, 1, Polymers and copolymers of 2-polybutadiene, 1,4-polybutadiene, C ₅ -C ₈ diene, and various modified products of the polymers and copolymers (maleized modified product, boiled oil modified product, etc.) There is.

Of these, liquid products (liquid diene polymers) of tung oil, linseed oil and diene polymers and modified products thereof are preferable. Specific examples of the liquid diene polymer include, for example, butadiene, chloroprene, isoprene,
A liquid polymer obtained by polymerizing or copolymerizing a diene compound such as 1,3-pentadiene or the like, and a diene compound as a main component of a monomer such as acrylonitrile or styrene copolymerized with these diene compounds. Examples thereof include polymers such as NBS and SBR obtained by copolymerization as described above, and various modified products thereof (malein compounds, boil oil modified products, etc.) and the like.

These may be used alone or in combination of two or more. Among these liquid diene polymers, liquid polybutadiene is preferable. The unsaturated compounds capable of reacting with oxygen in the air may be used alone or in combination of two or more. Further, the effect may be enhanced by using a catalyst and a metal drier that accelerate the oxidative curing reaction together with the unsaturated compound that can react with oxygen in the air. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate and zirconium octylate, and amine compounds. The unsaturated compound capable of reacting with oxygen in the air is preferably 0.001 with respect to 100 parts by mass of the isocyanate-terminated prepolymer of the present invention.
To 30 parts by mass, more preferably 0.01 to 20 parts by mass. If the amount used is 0.001 parts by mass or less, the effect becomes small, and if it is 30 parts by mass or more, the physical properties may be adversely affected.

In the present invention, at least one of the above-mentioned stabilizers, photocurable substances, polymer plasticizers, plasticizers, inert organic solvents, thixotropic agents, and oxygen-curable substances can be used. . A filler, a curing catalyst, titanium oxide, an adhesion promoter, a dye, a pigment, a flame retardant and the like are mixed with the polyisocyanate composition of the present invention to form a moisture-curable sealing material. Examples of the filler include silicic acid derivative, talc, metal powder, calcium carbonate, titanium oxide, clay, carbon black and the like. As the curing catalyst, for example,
Organotin compounds such as dibutyltin laurate and dioctyltin dilaurate, organozinc compounds such as zinc octylate,
There are amine compounds such as triethyleneamine, triethylenediamine, laurylamine, morpholine, diazabicyclocycloundecene, and diazabicyclooctane, which may be used in combination.

Specific examples of titanium oxide include, for example,
TYPEK R-820, TYPEK R-830, TYPEK R-930, TYPEK R-850, TYPEK R
-855, Typeay CR-57, Typeay CR-8
0, Taipaque CR-90, Taipaque CR-93, Taipaque CR-95, Taipaque CR-97, Taipaque CR-85 (all of which are trademarks of Ishihara Sangyo Co., Ltd.). Examples of the adhesion-imparting agent include 3-glycidylpropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane and the like. Silane coupling agents of

The polyisocyanate composition of the present invention is mixed with a one-part moisture effect type sealing material containing it alone and reacting with moisture in the atmosphere to cure and a compound containing active hydrogen capable of reacting with an isocyanate group, and reacting and curing. It can be used as a two-component sealing material. As a compound containing active hydrogen capable of reacting with an isocyanate group, which is mixed when used as a two-pack type sealing material, for example, an activity which is usually used for a two-pack urethane type sealing material such as a polyether type, a polyester type or an acrylic type is used. Hydrogen compounds can be used.

As the polyether type, a polyether polyol having an average number of hydroxyl functional groups in one molecule of 2 to 3 can be used. As the acrylic type, it is possible to use an acrylic polyol having an average number of hydroxyl functional groups of 2 to 3 in one molecule, for example, a hydroxyl-terminated telechelic polymer described in JP-A-4-132706. Further, as the fluorine-containing acrylic polyol, a fluorine-containing acrylic polymer derived from a polymerizable monomer such as tetrafluoroethylene, trifluoroethylene, chlorotolufluoroethylene, vinyl fluoride, hexafluoropropylene, etc. can be used.

The obtained sealing material of the present invention can be used as a curtain wall, a ceramic siding board, various exterior panels for ALC, concrete, etc., a working joint for metal fittings, etc., and a non-working joint. In addition to the sealing material, the polyisocyanate composition of the present invention can also be used as an adhesive, an adhesive, a waterproof material, a floor material, a resin, an elastomer and the like. The present invention will be described based on examples, but the present invention is not limited to the following examples. In addition, "part" represents a "mass part."

The measuring method is as follows. (Measurement of number average molecular weight) The number average molecular weight is measured by gel permeation chromatograph (hereinafter referred to as GP
This is the number average molecular weight based on polystyrene measured. Device: Tosoh Corp. HLC-802A Column: Tosoh Corp. G1000HXL × 1 bottle G2000HXL 〃 G3000HXL 〃 Carrier: Tetrahydrofuran Detection method: Differential refractometer

(Mixing) Mixing of the polyisocyanate composition with various additives and fillers was carried out using Twinmix (manufactured by Dalton Co.). (Viscosity) The viscosity at a temperature of 25 ° C. was measured by an E-type viscometer. (Allophanate bond ratio) FT-NMR manufactured by JEOL Ltd.
"FT90Q" is used, the solvent is acetone d6,
As a result of 1 H-NMR measurement, the peak integrated value of allophanate bond and urethane bond was represented by allophanate bond / (allophanate bond + urethane bond). When this ratio was less than 0.05, it was determined that the allophanate content was absent.

(Tensile test) Polyisocyanate was poured into a mold so as to have a thickness of 1 mm, left at 20 ° C. and humidity of 65 RH% for 3 weeks, and then allowed to stand at 20 ° C. for 50% modulus at a pulling speed of 50 mm / min. The breaking strength and breaking elongation were measured. (Contamination test) Using a siding board (trade name "Kanbeki" of Toray Glasl Co., Ltd.), a groove having a width of 12 mm, a depth of 10 mm and a length of 300 mm is formed, and a compound of a polyisocyanate composition is applied thereto. , 20 ℃,
Humidity of 65 RH% After curing for 3 weeks, an outdoor exposure test was conducted. The evaluation was conducted by visual inspection, and was expressed in three grades of good, good, and bad in the order of ◯, Δ, and ×.

[0054]

[Manufacturing Example 1] A 4-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was filled with a nitrogen atmosphere and 1008 parts of HDI and polyether diol (trade name “Axenol 2020” of Asahi Glass) averaged. A molecular weight of 2000) (400 parts) (isocyanate group / hydroxyl group equivalent ratio 30/1) was charged, and the temperature in the reactor was maintained at 120 ° C. for 10 hours while stirring in a nitrogen atmosphere. The temperature of the reaction solution was lowered, and unreacted HDI was removed using a thin film evaporator. The number average molecular weight of the isocyanate-terminated prepolymer (hereinafter, prepolymer A) of the obtained polyol raw material was 240.
0, isocyanate group concentration 3.7%, viscosity 1100
mPa · s, diisocyanate monomer concentration is 0.1%
, The average number of isocyanate functional groups was 2.0, and the allophanate bond ratio was less than 0.05.

[0055]

[Production Example 2] A 4-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was filled with a nitrogen atmosphere, and 1008 parts of HDI and polyethertriol (trade name “Axenol 3030” manufactured by Asahi Glass Co., Ltd. averaged. A molecular weight of 3000) (400 parts (equivalent ratio of isocyanate group / hydroxyl group: 30/1) was charged, and the temperature inside the reactor was maintained at 120 ° C. for 10 hours while stirring in a nitrogen atmosphere. The temperature of the reaction solution was lowered, and unreacted HDI was removed using a thin film evaporator. The number average molecular weight of the isocyanate-terminated prepolymer (hereinafter, prepolymer B) of the obtained polyol raw material was 360.
0, isocyanate group concentration 3.7%, viscosity 1400
mPa · s, diisocyanate monomer concentration is 0.1%
, The average number of isocyanate functional groups was 3.0, and the allophanate bond ratio was less than 0.05.

[0056]

[Production Example 3] A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was filled with a nitrogen atmosphere, and 504 parts of HDI and polyether diol (trade name "Preminol PML4002" of Asahi Glass Co., Ltd. average) A molecular weight of 4000) (400 parts (equivalent ratio of isocyanate group / hydroxyl group: 30/1) was charged, and the temperature inside the reactor was maintained at 120 ° C. for 10 hours while stirring in a nitrogen atmosphere. The temperature of the reaction solution was lowered, and unreacted HDI was removed using a thin film evaporator.
The number average molecular weight of the isocyanate-terminated prepolymer (hereinafter, prepolymer C) of the obtained polyol raw material is 430.
0, isocyanate group concentration 1.9%, viscosity 1500
mPa · s, diisocyanate monomer concentration is 0.1%
, The average number of isocyanate functional groups was 2.0, and the allophanate bond ratio was less than 0.05.

[0057]

[Production Example 4] A 4-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was placed in a nitrogen atmosphere, and 605 parts of HDI and polyethertriol (trademark "Preminol PML3005" manufactured by Asahi Glass Co., Ltd. average) A molecular weight of 5000) (400 parts) (isocyanate group / hydroxyl group equivalent ratio 30/1) was charged, and the temperature inside the reactor was maintained at 120 ° C. for 10 hours while stirring in a nitrogen atmosphere. The temperature of the reaction solution was lowered, and unreacted HDI was removed using a thin film evaporator. The number average molecular weight of the isocyanate-terminated prepolymer (hereinafter, prepolymer D) of the obtained polyol raw material is 5
600, isocyanate group concentration 2.4%, viscosity 25
00 mPa · s, diisocyanate monomer concentration is 0.
It was less than 1%, the average number of isocyanate functional groups was 3.0, and the allophanate bond ratio was less than 0.05.

[0058]

[Production Example 5] A 4-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was placed in a nitrogen atmosphere, and 43 parts of HDI was added to the divalent polyether polyol (trade name “EXCENOL 3020” manufactured by Asahi Glass Co., Ltd.). "Average molecular weight 3200) 389 parts, trivalent polyether polyol (trademark" Axenol 4030 "of Asahi Glass" average molecular weight 4
000) 102 parts (equivalent ratio of isocyanate group / hydroxyl group: 1.6 / 1) was charged, and the temperature inside the reactor was maintained at 120 ° C. for 10 hours while stirring in a nitrogen atmosphere. The obtained polyol raw material had an isocyanate-terminated prepolymer (hereinafter referred to as prepolymer E) having a molecular weight of 23,000, an isocyanate group concentration of 1.3%, a viscosity of 14,000 mPa · s, and an allophanate bond ratio of less than 0.05.

[0059]

[Production Example 6] A 4-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was filled with a nitrogen atmosphere, HDI was 778 parts, and polyether diol (Asahi Glass's trademark "Excelen 3020" average) was used. Molecular weight 3
200) 476 parts (isocyanate group / hydroxyl group equivalent ratio 31/1) were charged, and the temperature inside the reactor was maintained at 160 ° C. for 5 hours while stirring in a nitrogen atmosphere. The temperature of the reaction solution was lowered, and unreacted HDI was removed using a thin film evaporator. The number average molecular weight of the isocyanate-terminated prepolymer (hereinafter, prepolymer F) of the obtained polyol raw material was 3700, the isocyanate group concentration was 3.7%, and the viscosity was 1500 mPa.
s, the diisocyanate monomer concentration was less than 0.1%, and the allophanate bond ratio was 0.5.

[0060]

Example 1 A mass ratio of the prepolymer A obtained in Production Example 1 and the prepolymer B obtained in Production Example 2 was 100: 20.
Were mixed in a mixing machine at a ratio of to obtain a polyisocyanate composition. The viscosity of the composition obtained is 1500 at 25 ° C.
mPa · s, isocyanate group concentration is 1.4%,
The inclusion of allophanate linkages was not observed. next,
A mixture of heavy calcium carbonate and light calcium carbonate (trade name "Super SS" of Maruo Calcium Co., Ltd. as heavy calcium carbonate and trade name "Calfine 200M" of Maruo Calcium Co., Ltd. as light calcium carbonate in a mass ratio. (Mixed at 70:30) 100 parts in a mixer 120
After drying for 2 hours at a temperature of 133 ° C. or less and 133 Pa and cooling, 100 parts of the above-mentioned polyisocyanate composition, titanium dioxide (trademark “Taipaque CR-90” of Ishihara Sangyo Co., Ltd.) 20
Parts, 5.5 parts of Tinuvin 327 dissolved in tetrahydrofuran at 20 wt%, 30 parts in tetrahydrofuran
3.7 parts of Sumilizer TP-D dissolved in wt%,
2.2 parts of Irganox 245 dissolved in tetrahydrofuran at 50 wt%, 1.1 parts of ADEKA STAB LA-62, 0.2 parts of dibutyltin dilaurate (BTL) as a curing catalyst, a photocurable substance ( Toagosei Co., Ltd.
Trademark "Aronix M309"), polymer plasticizer (trademark "PF-X716" alkyl end PPG of Asahi Glass Co., Ltd.) 10 parts, hydrogenated castor oil (trademark "Disparon 305" of Kusumoto Kasei Co., Ltd.) 5 Parts and 5 parts of linseed oil were added and sufficiently kneaded and dispersed while degassing under reduced pressure to prepare a curable composition. A sheet having a thickness of 1 mm was prepared using the curable composition, cured at 20 ° C. and 65 RH% for 3 weeks, and then subjected to a tensile test and a stain test by a predetermined method. The results are shown in Table 1.

[0061]

Example 2 A mass ratio of the prepolymer C obtained in Production Example 3 to the prepolymer D obtained in Production Example 4 was 100: 20.
The same procedure as in Example 1 was carried out except that the mixture was mixed with the mixer at the ratio. The results are shown in Table 1.

[0062]

Example 3 A mass ratio of the prepolymer A obtained in Production Example 1 and the prepolymer B obtained in Production Example 2 was 100: 30.
The same procedure as in Example 1 was carried out except that mixing was carried out in a mixer at a ratio of 0. The results are shown in Table 1.

[0063]

Comparative Example 1 The same procedure as in Example 1 was carried out except that only the prepolymer A obtained in Production Example 1 was used as it was for preparing a cured composition. The results are shown in Table 1.

[0064]

Comparative Example 2 The procedure of Example 1 was repeated, except that only the prepolymer B obtained in Production Example 1 was used as it was for the preparation of the cured composition. The results are shown in Table 1.

[0065]

Comparative Example 3 Only the prepolymer E obtained in Production Example 5 was used as it was in the preparation of a cured composition, and a polymer plasticizer was added to
The same procedure as in Example 1 was carried out except that some parts were used. The results are shown in Table 1.

[0066]

Comparative Example 4 The prepolymer A obtained in Production Example 1 and the prepolymer F obtained in Production Example 6 were mixed in a mass ratio of 100: 20.
The same procedure as in Example 1 was carried out except that the mixture was mixed with the mixer at the ratio. The results are shown in Table 1.

[0067]

[Table 1]

[0068]

EFFECTS OF THE INVENTION The polyisocyanate composition of the present invention has a low viscosity and, after curing, has a lower modulus and a high breaking strength and a rupture by a composition in which the amount of the plasticizer used is greatly reduced or is not used at all. Indicates elongation. Therefore, the composition of the present invention includes a sealing material, an adhesive,
It can be advantageously used as a waterproof material, floor material, resin, elastomer, paint, and the like. In particular, when it is used as a sealing material for buildings and automobiles, various functions can be added by adjusting the type of polyol, in addition to good tackiness due to the absence of plasticizer. By further blending a specific additive, further low modulus, low stain resistance and high weather resistance can be achieved.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H017 AA03 AA04 AB04 AB05 AB13                       AB17 AC05 AD03 AE03 AE05                 4J002 AC03Y AC07Y AC09Y AC11U                       AE00U AE00Y AE05Y AE05Z                       BB00Y BC03Y BE02X CD16Y                       CF00Y CF01Y CH00Y CH02Y                       CH05Y CK04W DJ018 EG048                       EH047 EH076 EH147 EL027                       ET018 EW047 FD02Y FD027                       FD20U FD20X FD20Z FD206                       FD208                 4J034 BA03 DA01 DB03 DG03 DG04                       DG05 DG14 DG16 DG18 DG20                       DG22 HA01 HA02 HA07 HC03                       HC09 HC17 HC22 HC46 HC52                       HC61 HC64 HC67 HC71 HC73                       JA41 KA01 QA03 QA05

Claims (5)

[Claims] 1. At least one or more kinds of aliphatic and / or alicyclic diisocyanate monomers and a polyether diol having a number average molecular weight of 500 to 10,000,
Isocyanate group / hydroxyl group equivalent ratio is 5/1 to 100 /
After reacting with 1, the unreacted diisocyanate monomer and the solvent are removed to obtain an isocyanate-terminated prepolymer (A) containing no allophanate bond and at least one kind of aliphatic and / or alicyclic diisocyanate monomer. Above, the number average molecular weight is 500 to 10,0.
Polyethertriol No. 00 was reacted at an isocyanate group / hydroxyl group equivalent ratio of 5/1 to 100/1, and then unreacted diisocyanate monomer and solvent were removed to obtain an isocyanate terminal containing no allophanate bond. A polyisocyanate composition comprising the prepolymer (B) of 2. Isocyanate-terminated prepolymer (B)
Content of isocyanate-terminated prepolymer (A) 1
The polyisocyanate composition according to claim 1, which is 1 part by mass or more and less than 200 parts by mass with respect to 00 parts by mass. 3. A photocurable substance, a polymer plasticizer,
The polyisocyanate composition according to claim 2, containing at least one selected from a plasticizer, an inert organic solvent, a thixotropic agent, and an oxygen-curing substance. 4. A moisture curable resin composition comprising the polyisocyanate composition according to claim 1. 5. A sealing material comprising the polyisocyanate composition according to any one of claims 1 to 3.