JP2003252949A - Polyurethane composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-pack moisture-curable polyurethane composition with good curability and thermally resistant adhesivity, preventing lowering of stability and over-functionalizing of the composition which occurred in a conventional one-pack moisture-curable polyurethane composition, and further exhibiting excellent adhesivity to glass, a metal, a plastic, a coated steel sheet, etc., without using a primer. <P>SOLUTION: This one-pack moisture-curable polyurethane composition is a reaction product of a polyisocyanate containing a biuret group and/or an isocyanurate group with a secondary aminoalkoxysilane in which an aromatic ring of a prescribed structure is directly bonded to a nitrogen atom, has a compound A having one or more hydrolyzable alkoxysilyl groups in the molecule and less than 2,000 average molecular weight and a urethane prepolymer B having an isocyanate group and not less than 2,000 average molecular weight. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-component moisture-curable polyurethane composition, and more specifically, a one-component moisture-curable polyurethane which has excellent adhesion to glass, metal, plastic, coated steel sheet and the like without using a primer. It relates to a composition.

[0002]

2. Description of the Related Art Conventionally, various polyurethane compositions have been widely used as sealing materials, adhesives and the like. Such a polyurethane composition is known to be a two-pack type composition composed of a polyol compound and an isocyanate group compound, and a one-pack type composition which is cured by moisture in the air. The use of the one-component moisture-curable polyurethane composition is expanding in that it does not require mixing and adjustment of the composition and is easy to handle.

Regarding a one-component moisture-curable polyurethane composition, for example, Patent Document 1 discloses a polyurethane sealant containing a prepolymer having two or more alkoxysilyl groups in one molecule by reacting a urethane prepolymer with a secondary aminosilane. Patent Document 2 describes a sealant containing a urethane prepolymer having an alkoxysilane as a pendant group. However, these polyurethane sealants cure slowly, and for example, there is a safety problem in the application of an automobile window glass to an automobile body, and physical properties as a structural member are insufficient. Further, Patent Document 3 describes a composition in which an isocyanurate body, a biuret body, or a pentaerythritol addition reaction product of hexamethylene diisocyanate (HDI) is reacted with a mercaptosilane, and the isocyanate silane is mixed with a urethane resin. . However, since all of these functional groups have low reactivity, a catalyst and heating were required during the synthesis of isocyanate silane. for that reason,
The produced isocyanate silanes may further react with each other, resulting in higher functionality and lower stability.
In the case of the pentaerythritol addition reaction product, the number of functional groups was too high, and when a large amount was added, the physical properties of the cured product became brittle. Further, Patent Document 4 describes a polyurethane sealant containing a reaction product of a secondary aminosilane and a polyisocyanate such as an isophorone diisocyanate trimer, a biuret modification of hexamethylene diisocyanate, and polyphenyl polymethylene isocyanate. However, the polyurethane sealant containing these reactants has good adhesion to glass,
There is a problem that the adhesiveness to paints and the like, especially the heat resistant adhesiveness, is insufficient. Further, Patent Document 5 describes a method for applying a tile to an outer wall material, in which a urethane prepolymer obtained from a trifunctional polyol and a polyisocyanate compound contains an amino-based and glycidyl-based silane coupling agent and the like. Described is a one-part moisture-curable urethane adhesive that has been compounded.

On the other hand, in the one-component moisture-curable urethane composition, carbon dioxide gas is generated by the reaction between free isocyanate in the urethane prepolymer and water during the curing reaction.
It is known to have the problem of foaming. In particular, under high temperature and high humidity conditions, there is a problem that foaming is more likely to occur, which makes it difficult to use in applications where the composition is exposed to high temperature and high humidity during the curing stage (for example, sealing materials, automobile sealants, etc.).

Therefore, the above-mentioned various problems are solved,
It has been desired to realize a polyurethane sealant having excellent adhesion to glass, metal, plastic, painted steel plate, etc. without using a primer. Therefore, as a one-component moisture-curable polyurethane composition having excellent adhesiveness to glass, resin, metal, etc., and having good elongation, curability, and foaming resistance even without using a primer, (A) urethane prepolymer, (B) A silane obtained by adding a secondary aminoalkoxysilane and a polyisocyanate compound having a triol or more polyol having a molecular weight of 500 or less and a diisocyanate and having three or more NCO groups in one molecule. At least one selected from the group consisting of compound (B-1), and silane compound (B-2) having a lysine skeleton obtained by adding lysine isocyanate having two or three isocyanate groups and a secondary aminoalkoxysilane. Includes one type and has an average of 1.5 or more NCO groups and an average of 1.5 or more hydrolyzable alkoxy groups per molecule. 1-component moisture-cure polyurethane composition containing a silane compound have been proposed by the present applicant (refer to Patent Document 6.).

[0006]

[Patent Document 1] US Pat. No. 4,374,237

[Patent Document 2] US Pat. No. 4,687,533

[Patent Document 3] JP-A-6-212141

[Patent Document 4] US Pat. No. 5,623,044

[Patent Document 5] JP-A-9-32239

[Patent Document 6] Japanese Patent Laid-Open No. 2000-128949

[0007]

DISCLOSURE OF THE INVENTION The present inventors have found that the one-part moisture-curable polyurethane composition described in JP 2000-128949 A has an adhesive property after heat aging (hereinafter, also referred to as heat-resistant adhesive property). As a result of diligent examination, the room for improvement was found. Therefore, the present invention prevents the functionalization and stability deterioration of the composition in the conventional one-component moisture-curable polyurethane composition, and has excellent adhesiveness to glass, metal, plastic, coated steel plate, etc. without using a primer. Another object of the present invention is to provide a one-pack moisture-curable polyurethane composition having excellent curability and heat-resistant adhesiveness.

[0008]

The present inventors have found that a one-part moisture-curable polyurethane composition containing a urethane prepolymer and a reaction product of a specific secondary aminoalkoxysilane and a polyisocyanate is made of glass, They have found that they are suitable as a non-primer polyurethane sealant used for bonding materials such as metals, plastics, coated steel plates, etc., and have completed the present invention.

That is, the present invention is a reaction product of a polyisocyanate containing a biuret group and / or an isocyanurate group and a secondary aminoalkoxysilane having an aromatic ring having a structure of the following formula (1) directly bonded to a nitrogen atom. And a compound A having one or more isocyanate groups and one or more hydrolyzable alkoxysilyl groups in one molecule and having an average molecular weight of less than 2000, and an average molecular weight of 2
And a urethane prepolymer B having an isocyanate group and a one-component moisture-curable polyurethane composition.

[Chemical 2] (In the formula, R ¹ is an aromatic residue, R ² is an alkylene group having 1 to 18 carbon atoms and which may be branched. R ³ and R ⁴ are
Each is an independently branched alkyl group having 1 to 18 carbon atoms. n is an integer of 1 to 3. )

There is provided the one-part moisture-curable polyurethane composition, wherein the compound A is contained in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the urethane prepolymer B.

Also provided is a sealing material containing the above polyurethane composition.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The one-part moisture-curable polyurethane composition of the present invention (hereinafter referred to as the polyurethane composition of the present invention) will be described in detail below. The polyurethane composition of the present invention is a reaction product of a polyisocyanate containing a biuret group and / or an isocyanurate group and a secondary aminoalkoxysilane having an aromatic ring having the structure of the above formula (1) directly bonded to a nitrogen atom. Compound A having one or more isocyanate groups and one or more hydrolyzable alkoxysilyl groups in one molecule and having an average molecular weight of less than 2000, and an average molecular weight of 2000 or more and an isocyanate group A one-component moisture-curable polyurethane composition containing the urethane prepolymer B.

The polyisocyanate is a compound containing a biuret group and / or an isocyanurate group, and preferably has an average molecular weight of 2000 or less,
More preferably, it is 1500 or less. Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI) and 4,4 ′.
-Diphenylmethane diisocyanate (4,4'-MD
I), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) and modified products thereof, 1,5-
Naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IP
DI), xylene diisocyanate (XDI), 1,4
-Phenylene diisocyanate, transcyclohexane-1,4-diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate (TMXDI), lysine ester triisocyanate, 1,6,11-undecane Triisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate (T
Examples of the polyisocyanate include a biuret body and / or an isocyanurate body represented by the following formula (2): HDI isocyanurate body represented by the following formula (2); and HDI biuret body represented by the following formula (3). To be done. As the polyisocyanate, various exemplified polyisocyanates may be used alone, or two or more thereof may be used in combination, and further reaction products of various exemplified polyisocyanates and polyol compounds may be used. . Further, it may be a derivative containing a biuret body and / or an isocyanurate body of various exemplified polyisocyanates.

[0014]

[Chemical 3]

The secondary aminoalkoxysilane has a structure represented by the above formula (1) in which an aromatic ring is directly bonded to a nitrogen atom, and has a secondary amino group and an alkoxysilyl group in the molecule. It is a compound that has. R in the above formula (1)
¹ is an aromatic residue, and specific examples thereof include a phenyl group and a p-toluyl group. R ² has 1 carbon
To 18 branched alkylene groups. It is preferably an alkylene group having 2 to 6 carbon atoms. R ³ and R ⁴
Are each independently an optionally branched alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. n is an integer of 1 to 3 and a plurality of R ³ or R ⁴
May be the same or different. Here, the alkylene group and the alkyl group may be linear or branched, and may be a hetero atom (O, N, S).
Etc.) may be included. In addition, the secondary aminoalkoxysilane has a rigid structure because the aromatic ring is directly bonded to the nitrogen atom, and the polyurethane composition of the present invention containing the secondary aminoalkoxysilane is a glass composition. It shows good heat-resistant adhesion to metals, plastics, coated steel sheets, etc. As such a secondary aminoalkoxysilane, specifically, γ-phenylaminopropyltrimethoxysilane (trade name: Y-9669 (manufactured by Nippon Unicar)) represented by the following formula (4) is preferably exemplified. To be done.

[0016]

[Chemical 4]

The compound A is an isocyanate silane compound which is a reaction product of the polyisocyanate and the secondary aminoalkoxysilane. Here, the compound A has an average of 1 or more isocyanate (NCO) groups and an average of 1 or more hydrolyzable alkoxysilyl groups in one molecule, and preferably 1 or more in an average of 1 molecule. And an average of two or more hydrolyzable alkoxysilyl groups, and more preferably one or more isocyanate groups and three hydrolyzable alkoxysilyl groups on average in one molecule. Is a compound having The average molecular weight of the compound A is less than 2000, preferably 600 to 1800, and 600 to 1800.
It is more preferably 1500. The reaction between the polyisocyanate and the secondary aminoalkoxysilane is
Isocyanate group / amino group (ratio of isocyanate group in polyisocyanate per amino group in secondary aminoalkoxysilane) (hereinafter referred to as NCO / NH)
Is 1.5 / 1.0 to 9.0 / 1.0, preferably 1.5
/1.0-6.0/1.0. At this time, unreacted polyisocyanate may remain.
When NCO / NH is in this range, the effect of improving the heat resistant adhesiveness of the compound A is sufficiently exhibited, which is preferable. The production of the compound A can be carried out in the same manner as in the production of a usual polyurethane, and for example, it can be carried out by stirring the polyisocyanate and the secondary aminoalkoxysilane in the above equivalent ratio at room temperature. Also, if necessary,
It is also possible to use a urethane-forming catalyst such as an organic tin compound, organic bismuth, and amine.

The above-mentioned urethane prepolymer B may be any one having a free isocyanate group and used in an ordinary one-pack type polyurethane composition. The polyol compound and the excess polyisocyanate compound (that is, OH groups are included). It is a reaction product with an excess of isocyanate groups. The average molecular weight of the urethane prepolymer B is 2000 or more, preferably 2000-15000, and more preferably 2000-10000. Here, the polyol compound is a general term for a polyhydroxyl compound having a structure in which a plurality of hydrogens in a hydrocarbon are substituted with hydroxyl groups, and specifically, for example, ethylene oxide, propylene oxide, butylene oxide. , A product obtained by addition-polymerizing one or more alkylene oxides such as tetrahydrofuran with a compound having two or more active hydrogens. As the compound having two or more active hydrogens, specifically,
For example, ethylene glycol, propylene glycol,
Butanediol, diethylene glycol, glycerin,
Hexanetriol, trimethylolpropane, pentaerythritol, and the like, and polyether polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene diol, polyoxypropylene triol, and polyoxyptytylene glycol; Polyolefin polyols such as butanediene polyol and polyisoprene glycol; adipate polyols; lactone polyols; polyhydric alcohols such as polyester polyols such as castor oil; and polyhydric phenols such as resorcinol and bisphenol can be used. As the above-mentioned polyol compound, various exemplified polyol compounds may be used alone or in combination of two or more kinds, but in any case, the average molecular weight of each polyol compound is 500 to 10,000, preferably Is 1000-10
000, more preferably 2,000 to 10,000.

As the polyisocyanate compound for forming the urethane prepolymer B, those used in ordinary one-pack type polyurethane compositions can be used, and the above-mentioned polyisocyanate can be used. Specific examples of this polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI) and 2,6-
Tolylene diisocyanate (2,6-TDI), 4,
4'-diphenylmethane diisocyanate (4,4'-
Aromatic polyisocyanates such as MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate and triphenylmethane triisocyanate, and hydrogenated compounds thereof. Aliphatic polyisocyanates such as ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate; arylaliphatic polyisocyanates such as xylylene diisocyanate and hydrogenated compounds thereof are suitable. These may be used alone or in combination of two or more.

The urethane prepolymer B can be produced by reacting the above-mentioned polyol compound with an excess amount of a polyisocyanate compound. Isocyanate group / hydroxyl group (ratio of isocyanate group in polyisocyanate compound per one hydroxyl group in polyol compound) of the above polyisocyanate compound and the above polyol compound is 1.2 to 2.5, preferably 1.5 to Mix and react at a ratio of 2.4. If the isocyanate group / hydroxyl group is within this range, the resulting urethane prepolymer B
It is preferable because the viscosity of is suitable. Further, the production of the urethane prepolymer B can be carried out by the same method as that for the ordinary urethane prepolymer. For example, the polyol compound and the polyisocyanate compound having the above-mentioned equivalent ratios of
It can be performed by heating and stirring at 0 to 100 ° C. Further, if necessary, a urethanization catalyst such as an organic tin compound, organic bismuth or amine can be used.

Further, the obtained urethane prepolymer B
Preferably has an average of 2.0 or more isocyanate groups per molecule, more preferably 2.1 or more. Isocyanate group content (NCO
%), The NCO% is preferably 0.3% or more, and more preferably 0.5% or more. Here, NCO% represents the weight% of the isocyanate group with respect to the total weight of the urethane prepolymer. When the NCO% of the urethane prepolymer B is within this range, the obtained polyurethane composition of the present invention is preferable because it has good viscosity, adhesiveness, and properties as a sealant after curing (for example, hardness and modulus).

The polyurethane composition of the present invention is characterized in that the urethane prepolymer B contains an isocyanate silane compound (compound A) which is a reaction product of the above-mentioned secondary aminoalkoxysilane and polyisocyanate. A one-part moisture-curable polyurethane composition. In the polyurethane composition of the present invention, it is preferable to add 0.1 to 15 parts by weight of the compound A to 100 parts by weight of the urethane prepolymer B.
It is more preferable to contain 10 parts by weight, and 0.2
It is more preferable to contain -5 parts by weight. When the content of the compound A is within this range, it is preferable because the resulting polyurethane composition has excellent adhesiveness and heat resistant adhesiveness when used as a sealing material.

In order to use the polyurethane composition of the present invention as a sealing material or an adhesive composition, an inorganic filler, a plasticizer or the like may be added within a range not impairing the object of the present invention.
Specific examples of the inorganic filler include calcium carbonate, clay, talc, silica and carbon black. As the plasticizer, any one that is inactive to the isocyanate group can be used, and generally, dibutyl phthalate, dioctyl phthalate, tetrahydrophthalic acid ester, azelaic acid ester, maleic acid ester, phthalic acid ester, trimellitic acid ester, Adipic acid ester or the like is used.

The polyurethane composition of the present invention comprises, in addition to the above-mentioned essential components, a curing catalyst, other fillers, a thixotropy-imparting agent, a pigment, a dye, as long as the effects of the present invention are not impaired.
An antiaging agent, an antioxidant, an antistatic agent, a flame retardant, an adhesion promoter, a dispersant, a solvent and the like may be contained, respectively. Specifically, examples of the curing catalyst include dioctyltin dilaurate, dibutyltin laurate, tin octylate, lead octylate, tertiary amines, and the like, and solvents such as toluene, xylene, hexane, and heptane can be used. .

The method for producing the polyurethane composition of the present invention is not particularly limited. For example, the compound A and the urethane prepolymer B, optionally added fillers, plasticizers, other additives and the like are mixed, and a ball mill is used. It can be obtained by sufficiently kneading using a mixing device such as the above and uniformly dispersing.

The polyuree of the present invention having such a constitution
The tongue composition is a combination of excellent adhesiveness to various materials.
It is useful because it becomes a product. This is glass or silicon
The silyl group shows high adhesiveness to vinyl substrates.
In addition, for the surface of acrylic paint, isocyanate
It is believed that the
Polyurethane composition of the present invention having a isocyanate group
Has excellent adhesion to any material
It Furthermore, the structure of secondary aminoalkoxysilane
And R shown in the above formula (1) ¹Is an aromatic residue,
Rigid structure, glass, metal, plastic, painting
Considered to have high adhesiveness and heat resistant adhesiveness to steel plates, etc.
To be Also, as described in Japanese Patent Laid-Open No. 2000-128949.
Listed compound (compound represented by the following formula (5))
Since the same effect cannot be obtained in the case of
It can be seen that the urethane composition is excellent.

[0027]

[Chemical 5]

[0028]

The present invention will be described in detail with reference to the following examples. However, the present invention is not limited to this. <Synthesis of Urethane Prepolymer 1> The urethane prepolymer 1 is a mixture of 500 g of polyoxypropylene diol having an average molecular weight of 2000, 750 g of polyoxypropylene triol having an average molecular weight of 5000, and 1460 g of dioctyl phthalate which is a plasticizer. 110
After dehydration under reduced pressure at 16 ° C for 16 hours, 214 g of MDI was added to the mixture so that NCO / OH = 1.8, and the mixture was reacted at 80 ° C for 24 hours in a nitrogen stream to give an isocyanate group of 1.1. Obtained as a polymer containing wt%.

<Synthesis of Urethane Prepolymer 2> The urethane prepolymer 2 has 400 g of polyoxypropylene diol having an average molecular weight of 2000 and an average molecular weight of 40.
600 g of polyoxypropylene triol which is 00,
And a mixture of 510 g of isodecyl phthalate, which is a plasticizer, was dehydrated under reduced pressure at 110 ° C. for 16 hours, and the MDI of the mixture was adjusted to NCO / OH = 1.75.
6.6 g was added and reacted at 80 ° C. for 24 hours in a nitrogen stream to obtain a polymer containing 1.5% by weight of an isocyanate group.

<Synthesis of Adducts 1 to 10> An isocyanate silane compound, which is a reaction product of polyisocyanate and a secondary aminoalkoxysilane, is also called an adduct, and the following adducts 1 to 10 are used in Examples and Comparative Examples. Using. The obtained adducts 1 to 10 are shown in Table 1 below. a) Adduct 1 (HDI isocyanurate / Y-966
9 reaction product (NCO / NH = 3/1)) HDI isocyanurate body (trade name:
D170N, containing 21.0% of isocyanate groups, manufactured by Takeda Pharmaceutical Co., Ltd., 100 g, and diisononyl phthalate (trade name: DINP, manufactured by Shin Nippon Science Co., Ltd.) (hereinafter, abbreviated as DINP) 28.6 g were put in an N ₂ stream While stirring at N
Γ-phenylaminopropyltrimethoxysilane (trade name: Y-966 so that the CO / NH value becomes 3/1)
9, manufactured by Nippon Unicar Co., Ltd. (hereinafter abbreviated as Y-9669)
Adduct 1 was obtained by reacting at 4Og for 4 hours while dropping 42.5g (adduct concentration 83%). The obtained adduct 1 contained an average of 2 isocyanate groups and an average of 3 alkoxysilyl groups in one molecule.

B) Adduct 2 (HDI isocyanurate / Y-9669 reaction product (NCO / NH = 3 / 1.5)) An HDI isocyanurate (trade name: in a four-necked flask).
D170N, containing 21.0% of isocyanate groups, manufactured by Takeda Pharmaceutical Co., Ltd.) 100 g, and 33.5 g of DINP were added,
While stirring in N ₂ gas flow, the NCO / NH value is 3 /
The adduct 2 was obtained by adding 63.8 g of Y-9669 dropwise to make it 1.5 and reacting at 40 ° C. for 4 hours (adduct concentration 83%). The resulting adduct 2 contained an average of 1.5 isocyanate groups and an average of 3 alkoxysilyl groups in one molecule.

C) Addition body 3 (HDI biuret body / Y-
9669 reaction product (NCO / NH = 3/1)) HDI biuret body (trade name: D16) in a 4-neck flask.
5N, containing 23.4% of isocyanate groups, manufactured by Takeda Pharmaceutical Co., Ltd.) 100 g, and 30.2 g of DINP were added, and N ₂
While stirring in an air stream, 47.4 g of Y-9669 was added dropwise such that the NCO / NH value became 3/1.
Adduct 3 was obtained by reacting at 4 ° C. for 4 hours (adduct concentration 83%). The obtained adduct 3 contained an average of 2 isocyanate groups and an average of 3 alkoxysilyl groups in one molecule.

D) Addition body 4 (HDI biuret body / Y-
9669 Reaction product (NCO / NH = 3 / 1.5)) HDI biuret body (trade name: D16) in a 4-neck flask.
5 N, containing 23.4% of isocyanate groups, manufactured by Takeda Pharmaceutical Co., Ltd.) 100 g, and 35.0 g of DINP were added, and N ₂
NCO / NH value is 3 / 1.5 while stirring in airflow
Then, 71.0 g of Y-9669 was added dropwise and the mixture was reacted at 40 ° C. for 4 hours to obtain an adduct 4 (adduct concentration: 83%). The obtained adduct 4 contained an average of 1.5 isocyanate groups and an average of 3 alkoxysilyl groups in one molecule.

E) Adduct 5 (IPDI isocyanurate / Y-9669 reaction product (NCO / NH = 3/1)) An IPDI isocyanurate (trade name: VESTANATT-1890-100, isocyanate group) was placed in a four-necked flask. 15.3% content, manufactured by Degussa Huls) 100
g, and 100 g of DINP, while stirring in an N ₂ gas flow so that the NCO / NH value becomes 3/1, Y
Adduct 5 was obtained by adding 31.0 g of -9669 dropwise and reacting at 40 ° C. for 4 hours (adduct concentration 57%).
The obtained adduct 5 contained an average of 2 isocyanate groups and an average of 3 alkoxysilyl groups in one molecule.

F) Adduct 6 (IPDI isocyanurate / Y-9669 reaction product (NCO / NH = 3/1.
5)) IPDI isocyanurate body (trade name: VESTANATT-1890-100, containing 15.3% of isocyanate groups, manufactured by Degussa Huls) in a 4-necked flask.
g, and 100 g of DINP, 46.5 g of Y-9669 was added dropwise while stirring in an N ₂ stream so that the NCO / NH value became 3 / 1.5 at 40 ° C.
Adduct 6 was obtained by reacting for a time (adduct concentration 59
%). The obtained adduct 6 contained an average of 1.5 isocyanate groups and an average of 3 alkoxysilyl groups in one molecule.

G) Adduct 7 (HDI isocyanurate / A-1170 reaction product (NCO / NH = 3/1)) HDI isocyanurate (trade name: in a four-necked flask).
D170N, containing 21.0% of isocyanate groups, manufactured by Takeda Pharmaceutical Co., Ltd.) 100 g, and DINP 32.1 g,
The value of NCO / NH is 3/1 while stirring in N ₂ stream.
Bistrimethoxypropylamine (trade name: A-1170, manufactured by Nippon Unicar Co., Ltd.) (hereinafter referred to as A-1
170) (abbreviated as 170) was added dropwise and reacted for 4 hours at 40 ° C. to obtain an adduct 7 (adduct concentration 83
%). The obtained adduct 7 contains an average of 2 isocyanate groups in one molecule and an average of 3 alkoxysilyl groups.
It contained one.

H) Adduct 8 (HDI biuret / A-
1170 reaction product (NCO / NH = 3/1)) HDI biuret body (trade name: D16) in a 4-neck flask.
5 N, containing 23.4% of isocyanate groups, manufactured by Takeda Pharmaceutical Co., Ltd.) 100 g, and 33.4 g of DINP were added, and N ₂
While stirring in an air stream, 63.3 g of A-1170 was added dropwise so that the NCO / NH value became 3/1.
Adduct 8 was obtained by reacting at 4 ° C. for 4 hours (adduct concentration 83%). The obtained adduct 8 had an average of 2 isocyanate groups and an average of 3 alkoxysilyl groups in one molecule.

I) Adduct 9 (HDI pentaerythritol)
Ru adduct / Y-9669 reaction product (NCO / NH = 2 /
1)) Pentaerythritol 136g, HDI672g acetic acid
Add 270 g of ethyl and react at 80 ° C.
Addition of HDI pentaerythritol having cyanate group
To obtain a product (containing 14.5% of isocyanate groups). 4 mouths
The above HDI pentaerythritol adduct 10 in the Rasco
Put 0g, N ₂NCO / NH while stirring in an air stream
4-9g of Y-9669 so that the value of becomes 2/1.
Addition product 9 by reacting at 40 ° C for 4 hours while dropping
Was obtained (adduct concentration 82%). The obtained adduct 9 is 1
It contains an average of 2 isocyanate groups in the molecule,
It contained 6 xylyl groups on average.

J) Adduct 10 (HDI-PPG adduct /
Y-9669 Reactant (NCO / NH = 3/1) 1000 g of dehydrated polyoxypropylene triol having an average molecular weight of 2000, and dehydrated DINP5
252.3 g of HDI was added to the mixture of 00 g,
Was reacted for 24 hours to obtain an HDI-PPG adduct having an isocyanate group at the end (containing 3.6% of an isocyanate group). 100 g of the above HDI-PPG adduct was placed in a 4-necked flask, and NCO was added while stirring in an N ₂ stream.
7. Y-9669 so that the value of / NH becomes 3/1.
Adduct 10 was obtained by reacting at 40 ° C. for 4 hours while dropping 3 g (adduct concentration 71%). Obtained adduct 1
No. 0 contained 2 isocyanate groups on average and 3 alkoxysilyl groups on average in 1 molecule.

[0040]

[Table 1]

[0041]

[Table 2]

(Examples 1 to 30 and Comparative Examples 1 to 4) Carbon black and isononyl phthalate were prepared by using the composition components (parts by weight) shown in Table 2 below with respect to 100 parts by weight of the urethane prepolymers 1 and 2. , Dioctyltin dilaurate, dimethylaminoethylmorpholine (trade name: XD
M, manufactured by Sankyo Air Products Co., Ltd.) and the above adduct were added to obtain polyurethane compositions of Examples 1 to 30 and Comparative Examples 1 to 4. The adhesiveness of each obtained polyurethane composition was examined under the following conditions. The results are shown in Table 2 below.

<Measurement of Adhesiveness> The adhesiveness of the polyurethane compositions of Examples 1 to 30 and Comparative Examples 1 to 4 was measured by the following method. Each of the obtained polyurethane compositions was applied to a plate glass in a thickness of 3 mm to prepare a test piece. 20 for each specimen
After leaving in an atmosphere of 65 ° C and 65% RH for 7 days, a hand peel test by knife cutting was performed. Furthermore, 20 ℃, 65%
A test body left for 7 days in an RH atmosphere was immersed in 40 ° C. water for 14 days or in an 80 ° C. oven for 14 days, and a hand peel test was conducted in the same manner as above. As a value indicating the adhesiveness, a sealant pseudo-aggregation failure CF (number is a ratio (%) to the adhesive area) and an adhesive failure AF (a number is a ratio (%) to the adhesive area) were used. CF10
0% indicates that the composition layer has undergone cohesive failure over the entire coating area, and that there is no peeling on the adhesive surface with the glass. The results are shown in Table 2.

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

[Table 6]

From the results shown in Table 2, the polyurethane compositions of Examples 1 to 30 have high adhesiveness with respect to the plate glass, and further, the adhesive properties even when heat-aged in an oven at 80 ° C. for 14 days. It was found that it has heat-resistant adhesive property because it is not lost. With respect to curability and foaming resistance, effects equivalent to or higher than those of Comparative Example were obtained.

[0049]

As described above, the polyurethane composition of the present invention has excellent adhesiveness to glass, metal, plastic, coated steel plate and the like without using a primer, and also has excellent heat resistant adhesiveness. . Therefore, the polyurethane composition of the present invention is very useful as a sealing material such as a sealing material for automobiles and a coating material for construction.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor, Kiminori Araki             2-1, Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd.             Ceremony Company Hiratsuka Factory F-term (reference) 4J034 AA01 CA03 CA04 CA13 CB08                       DA01 DA03 HA06 HA13 HB16                       JA41 JA42 QB11 QB12 RA08

Claims (2)

[Claims] 1. A reaction product of a polyisocyanate containing a biuret group and / or an isocyanurate group with a secondary aminoalkoxysilane having an aromatic ring having a structure of the following formula (1) directly bonded to a nitrogen atom, Compound A having at least one isocyanate group and at least one hydrolyzable alkoxysilyl group therein and having an average molecular weight of less than 2000; and urethane prepolymer having an average molecular weight of 2000 or more and having an isocyanate group. A one-pack moisture-curable polyurethane composition containing polymer B. [Chemical 1] (In the formula, R ¹ is an aromatic residue, R ² is an alkylene group having 1 to 18 carbon atoms and which may be branched. R ³ and R ⁴ are
Each is an independently branched alkyl group having 1 to 18 carbon atoms. n is an integer of 1 to 3. ) 2. The one-part moisture-curable polyurethane composition according to claim 1, wherein the compound A is contained in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the urethane prepolymer B. .