JP4539298B2 - One-part moisture-curing urethane composition - Google Patents

Description

  The present invention relates to a one-component moisture-curable urethane composition.

  Conventionally, various urethane compositions utilizing moisture curing have been proposed and used in various fields such as the field of automobiles such as adhesion between a vehicle body and a window glass, and the field of architecture. Such urethane compositions are known as a two-component type composed of a polyol compound and an isocyanate compound, and a one-component type composition that is cured by moisture in the air. The use of a one-component moisture-curing urethane composition is expanding in that it does not require mixing adjustment of the composition and is easy to handle.

In general, adhesion between an automobile body and a window glass is performed by applying a primer to both the body and the glass side, and applying a sealant composition between the primers. In particular, the primer is applied to the vehicle body side by hand in most cases, but there is a concern about the influence of the volatile organic solvent (VOC) used during primer application on the human body. Moreover, reduction of VOC is also demanded from the viewpoint of environmental problems. Furthermore, if the primer adheres to a portion other than the portion to be applied, a great amount of labor and cost are required for the repair. There is a demand for a one-component moisture-curing urethane composition that can solve these problems and has excellent non-primer adhesion that can simplify the work process. In addition, non-primer adhesiveness means the adhesiveness with respect to a to-be-adhered body when a primer is not used.
However, it has been difficult to make non-primer adhesion to so-called difficult-to-adhere coating plates painted with recent high solid paints, acid rain resistant paints, easy maintenance paints, and the like.

  As a solution to non-primer adhesion to a difficult-to-adhere coating plate, for example, Patent Document 1 discloses a moisture-curable one-component urethane adhesive composition mainly composed of an isocyanate group-terminated urethane prepolymer. (1) Silane coupling agent as adhesion agent, and (2) as curing catalyst, (a) 2,2′-dimorpholinodiethyl ether and / or di (2,6-dimethylmorpholinoethyl) ether, and (b) dibutyltin A moisture-curable one-component urethane-based adhesive composition containing diacetylacetonate is described. However, Patent Document 1 does not discuss various properties required for a one-component moisture-curing urethane composition such as shape maintaining property, elongation at break, and heat-resistant adhesive properties. When it is used for adhesion between the glass and the window glass, there is a risk that the composition will not adhere to the portion other than the portion to be applied due to insufficient shape maintenance, or a problem of mechanical strength of the cured product of the composition, or There are problems such as the possibility of causing a decrease in mechanical strength when heated by direct sunlight and left at a high temperature for a long time.

International Publication No. 01/053423 Pamphlet

  In other words, due to recent technological innovation, optimization of materials, etc., simplification and shortening of manufacturing processes, etc., the properties required for a one-component moisture-curing urethane composition are becoming more sophisticated. There are no moisture-curing urethane compositions that satisfy a high level of shape maintenance, elongation at break, heat-resistant adhesion, non-primer adhesion to various adherends, etc., and further improvements in these properties are required. .

  Therefore, the present invention is a one-component moisture-curing urethane composition that is excellent in properties such as shape maintenance, elongation at break, and heat-resistant adhesion, and further excellent in non-primer adhesion to various adherends such as difficult-to-adhere coating plates. The purpose is to provide.

As a result of intensive studies by the inventor to achieve the above object, a preliminary composition comprising a urethane prepolymer, a filler, and a plasticizer, a specific adhesion-imparting agent, and a content of an organotin compound are specified. In terms of relationship, we provide a one-component moisture-curing urethane composition that excels in properties such as shape retention, elongation at break, and heat-resistant adhesion, as well as non-primer adhesion to various adherends such as hard-to-adhere coatings. As a result, the present invention has been completed.
That is, this invention is made | formed based on the said knowledge, and provides the following (1)-(6).

(1) A mixture of polyether triol having a number average molecular weight of 1000 to 7000 and polyether diol is reacted with diphenylmethane diisocyanate so that the equivalent ratio of NCO group to OH group is 1.1 to 2.5. 100 parts by mass of a preliminary composition comprising a urethane prepolymer, a filler and a plasticizer,
A compound obtained by reacting trimethylolpropane with a bifunctional isocyanate such that the equivalent ratio of NCO group to OH group is 0.8 to 1.5, has an imino group in which an aryl group is directly bonded to a nitrogen atom, And a compound (A) obtained by reacting a compound having a hydrolyzable silyl group such that the equivalent ratio of NCO group to NH group is 1.8 to 3.5, and / or
An imino group in which an aryl group is directly bonded to a nitrogen atom is bonded to at least one compound selected from the group consisting of isocyanurates of bifunctional isocyanates, burettes, and compounds obtained by reacting bifunctional isocyanates with triols. And a compound (B) obtained by reacting a compound having a hydrolyzable silyl group with an NCO group and NH group equivalent ratio of 1.8 to 3.5,
Containing 0.0006 to 0.20 parts by mass of an organic tin compound,
When the content of the preliminary composition is X parts by mass, the content of the compound (A) is A parts by mass, and the content of the compound (B) is B parts by mass, the following formula (1) is satisfied. Liquid moisture curable urethane composition.

  0.1X ≦ 100 (A + B) ≦ 6.5X (1)

  (2) When the content of the preliminary composition is X parts by mass, the content of the compound (A) is A parts by mass, and the content of the compound (B) is B parts by mass, the following formula (2) The one-component moisture-curable urethane composition according to (1), which satisfies the above.

  0.3X ≦ 100 (A + B) ≦ 5.0X (2)

(3) Further, it contains at least one compound (C) selected from the group consisting of isocyanurate bodies of bifunctional isocyanates, burette bodies, and compounds obtained by reacting bifunctional isocyanates and triols,
The content of the preliminary composition is X parts by mass, the content of the compound (A) is A parts by mass, the content of the compound (B) is B parts by mass, and the content of the compound (C) is C parts by mass. The one-component moisture-curable urethane composition according to (1), which satisfies the following formula (3):

  0.1X ≦ 100 (A + B + C) ≦ 6.5X (3)

  (4) The content of the preliminary composition is X parts by mass, the content of the compound (A) is A parts by mass, the content of the compound (B) is B parts by mass, and the content of the compound (C) is The one-component moisture-curable urethane composition according to (3), which satisfies the following formula (4) when C parts by mass is satisfied.

  0.3X ≦ 100 (A + B + C) ≦ 5.0X (4)

  (5) The one-component moisture-curable urethane composition according to any one of the above (1) to (4), containing 0.001 to 0.05 parts by mass of the organotin compound.

  (6) The compound having an imino group in which the aryl group is directly bonded to a nitrogen atom and having a hydrolyzable silyl group is γ-N-phenylaminopropyltrimethoxysilane, and the bifunctional isocyanate is hexagonal. The one-component moisture-curable urethane composition according to any one of the above (1) to (5), which is methylene diisocyanate.

  The one-component moisture-curable urethane composition of the present invention is excellent in properties such as shape maintenance, elongation at break and heat-resistant adhesiveness, and is excellent in non-primer adhesiveness to various adherends such as hard-to-adhere coating plates.

Hereinafter, the one-component moisture-curable urethane composition of the present invention will be described in detail.
In the present invention, a mixture of polyether triol and polyether diol having a number average molecular weight of 1000 to 7000 is reacted with diphenylmethane diisocyanate so that the equivalent ratio of NCO groups to OH groups is 1.1 to 2.5. 100 parts by mass of a pre-composition comprising a urethane prepolymer, a filler and a plasticizer, and a trifunctional roll propane with bifunctional isocyanate so that the equivalent ratio of NCO groups to OH groups is 0.8 to 1.5. The compound obtained by reacting the compound having an imino group in which an aryl group is directly bonded to a nitrogen atom and having a hydrolyzable silyl group has an equivalent ratio of NCO group to NH group of 1.8 to 3.5. The compound (A) and / or the bifunctional isocyanate isocyanurate, burette, and bifunctional isocyanate NCO is a compound having an imino group in which an aryl group is directly bonded to a nitrogen atom and a hydrolyzable silyl group in at least one compound selected from the group consisting of compounds obtained by reacting an nate and a triol. Containing the compound (B) obtained by reacting so that the equivalent ratio of the group and the NH group is 1.8 to 3.5, and 0.0006 to 0.20 part by mass of the organotin compound, the preliminary composition The one-component moisture-curing type satisfying the following formula (1) when the content of X is X parts by mass, the content of the compound (A) is A parts by mass, and the content of the compound (B) is B parts by mass. It is a urethane composition.

  0.1X ≦ 100 (A + B) ≦ 6.5X (1)

<Preliminary composition>
The urethane prepolymer blended in the preliminary composition contained in the one-component moisture-curable urethane composition of the present invention (hereinafter also referred to as “the urethane prepolymer used in the present invention”) is 3 per molecule. A mixture of a polyether triol having a number average molecular weight of 1000 to 7000 having a hydroxyl group and a polyether diol having a number average molecular weight of 1000 to 7000 having two hydroxyl groups per molecule is mixed with diphenylmethane diisocyanate in an equivalent ratio of NCO group and OH group. It is obtained by reacting such that (NCO / OH) is 1.1 to 2.5.

The polyether triol used to synthesize the urethane prepolymer used in the present invention (hereinafter also referred to as “polyether triol used in the present invention”) has a number average molecular weight of 1000 to 7000. From the point that the viscosity of the obtained one-component moisture-curable urethane composition of the present invention and the physical properties of the cured product of the composition are excellent, 2000 to 5000 is preferable.
Specific examples of the polyether triol include polyoxypropylene triol, polyoxyethylene triol, polytetramethylene triol, polyethylene triol, polypropylene triol, and polyoxybutylene triol. Among these, polyoxypropylene triol and polyoxyethylene triol are preferable from the viewpoint of balance between physical properties and cost.
In the polyether triol used in the present invention, the polyether triol may be used alone or in combination of two or more.

The polyether diol used to synthesize the urethane prepolymer used in the present invention (hereinafter also referred to as “polyether diol used in the present invention”) has a number average molecular weight of 1000 to 7000. From the point that the viscosity of the obtained one-component moisture-curable urethane composition of the present invention and the physical properties of the cured product of the composition are excellent, 2000 to 5000 is preferable.
Specific examples of the polyether diol include polypropylene ether diol, polyethylene ether diol, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol. Among these, polypropylene ether diol and polyethylene ether diol are preferable from the viewpoint of good balance between physical properties and cost.
In the polyether diol used in the present invention, the above polyether diols may be used alone or in combination of two or more.

  The isocyanate used to synthesize the urethane prepolymer used in the present invention is diphenylmethane diisocyanate (MDI). The MDI may be any of 4,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and mixtures thereof (for example, crude MDI, etc.). From a certain point, 4,4′-diphenylmethane diisocyanate is preferred.

  The urethane prepolymer used in the present invention can be produced by a known production method. For example, after mixing and dehydrating the polyether triol and the polyether diol, the molten MDI It can be obtained by adding an amount such that the equivalent ratio of the MCO NCO group to the OH group of the above mixture is 1.1 to 2.5, and stirring while purging with nitrogen.

  The preliminary composition contained in the one-component moisture-curable urethane composition of the present invention (hereinafter also referred to as “preliminary composition used in the present invention”) includes the urethane prepolymer, a filler, and a plasticizer. It is the composition which consists of.

The filler to be blended in the preliminary composition used in the present invention is not particularly limited. For example, calcium carbonate, aluminum hydroxide, carbon black, white carbon, silica, glass, kaolin, talc (magnesium silicate), fume Silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, clay, calcined clay, glass, bentonite, glass fiber, asbestos, glass filament, ground quartz, diatomaceous earth, aluminum silicate, zinc oxide, magnesium oxide, titanium oxide Or inorganic fillers such as these surface-treated products; carbonates, organic bentonite, high styrene resin, coumarone-indene resin, phenol resin, formaldehyde resin, modified melamine resin, cyclized rubber, lignin, ebonite powder, shellac, cork Powder, bone meal, wood meal, Organic fillers such as lurose powder, coconut palm, wood pulp; inorganic pigments such as lamp black, titanium white, bengara, titanium yellow, zinc white, red lead, cobalt blue, iron black, aluminum powder and neozabon black RE And organic pigments such as Neo Black RE, Orazole Black CN, Orazole Black Ba (all manufactured by Ciba Geigy) and Spiron Blue 2BH (manufactured by Hodogaya Chemical Co., Ltd.). Of these, carbon black and calcium carbonate are preferably used in order to impart desired characteristics. These carbon black and calcium carbonate are not particularly limited, and commercially available products can be used. For example, carbon black includes N110, N220, N330, N550, N770, etc., or a mixture thereof according to the American Society for Testing Materials standard, and calcium carbonate includes heavy calcium carbonate, precipitated calcium carbonate, and the like. Among these, heavy calcium carbonate is preferable in that it can impart deep part curability to the obtained one-component moisture-curable urethane composition of the present invention.
These fillers can be used singly or in combination of two or more.

The above-mentioned urethane prepolymer is blended in the above-mentioned amount of carbon black in that the obtained one-component moisture-curing urethane composition of the present invention has sufficient mechanical strength and can impart viscosity and thixotropy excellent in handleability. It is preferable that it is 10-100 mass parts with respect to 100 mass parts. 20 to 90 mass parts is more preferable at the point which is excellent by this characteristic.
The blending amount of the calcium carbonate is 2 to 30 parts by mass with respect to 100 parts by mass of the urethane prepolymer, in that the deep part curability of the obtained one-part moisture curable urethane composition of the present invention is good. It is preferable. 3-20 mass parts is more preferable at the point which is excellent by this characteristic.

  The reaction between the mixture and the MDI is performed by mixing the mixture and MDI so that the equivalent ratio of NCO groups to OH groups is 1.1 to 2.5. If the amount ratio falls within this range, the resulting one-part moisture-curing urethane composition of the present invention has good adhesion and crosslink density, and the cured product does not become brittle. It is preferably 1.5 to 2.0 because it is more excellent in this characteristic.

The plasticizer blended in the preliminary composition used in the present invention is not particularly limited, but phthalic acid derivatives such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, tetrahydrophthalic acid, azelaic acid, maleic acid, trimellitic acid, Examples thereof include derivatives such as isophthalic acid, adipic acid, itaconic acid, citric acid, and the like.
The amount of the plasticizer blended is 100 parts by mass of the urethane prepolymer in that the obtained one-component moisture-curing urethane composition of the present invention has appropriate flexibility and has a viscosity excellent in handleability. It is preferable that it is 3-40 mass parts with respect to. 5-30 mass parts is more preferable at the point which is excellent by this characteristic.

  The production method of the preliminary composition used in the present invention is not particularly limited, and the amount of each component is not particularly limited as long as it does not deviate from the object of the present invention. 70 parts by mass of carbon black, 15 parts by mass of calcium carbonate, and 20 parts by mass of a plasticizer can be added per 80 parts by mass of the polymer, and stirred under reduced pressure to obtain a preliminary composition used in the present invention.

<Compound (A)>
The trifunctional roll propane (TMP) contains bifunctional isocyanate contained in the one-component moisture curable urethane composition of the present invention as an adhesion-imparting agent, and the equivalent ratio of NCO group to OH group (NCO / OH) is 0.8 to 1. .5 (hereinafter also referred to as “compound (A-1)”) having an imino group in which an aryl group is directly bonded to a nitrogen atom, and a hydrolyzable silyl group Compound (hereinafter also referred to as “compound (A-2)”) having an NCO group-NH group equivalent ratio (NCO / NH) of 1.8 to 3.5 ( A) (hereinafter also referred to as “compound (A) used in the present invention”) is a compound having an average of one or more NCO groups and hydrolyzable silyl groups in each molecule.

  The bifunctional isocyanate contained in the compound (A-1) is not particularly limited as long as it is a compound having two isocyanate groups in one molecule. Specific examples of the bifunctional isocyanate include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and 4,4′-diphenylmethane. Diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylidene diisocyanate (TMXDI), tolidine Aromatic diisocyanates such as diisocyanate (TODI) and 1,5-naphthalene diisocyanate (NDI); hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate Aliphatic diisocyanates such as nate methyl (NBDI); alicyclic diisocyanates such as transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H6XDI (hydrogenated XDI), H12MDI (hydrogenated MDI); carbodiimides of the above diisocyanates Modified diisocyanates or these isocyanurate-modified diisocyanates may be used, and one kind may be used alone, or two or more kinds may be used in combination. Among these, it is preferable to use HDI and XDI because the adhesive property of the obtained one-component moisture-curable urethane composition of the present invention is excellent.

The reaction between the bifunctional isocyanate and TMP is carried out by mixing the bifunctional isocyanate and TMP so that the equivalent ratio of NCO groups to OH groups is 0.8 to 1.5. If the amount ratio falls within this range, the resulting one-part moisture-curing urethane composition of the present invention has good adhesion and crosslink density, and the cured product does not become brittle. In the point which is excellent by this characteristic, Preferably it is 0.9-1.2.
Moreover, manufacture of the said compound (A-1) can be performed by the method similar to manufacture of a normal urethane prepolymer, for example, TMP and bifunctional isocyanate of the above-mentioned equivalent ratio are heated at 50-100 degreeC. This can be done by stirring. Moreover, if necessary, a urethanization catalyst such as an organic tin compound, organic bismuth, or amine can be used.

The compound (A-1) preferably has at least three isocyanate groups in one molecule. When expressed in terms of isocyanate group content (NCO%), the NCO% is preferably 10% or more, more preferably 12% or more. Here, NCO% represents the mass% of the isocyanate group with respect to the total mass of the compound (for example, compound (A-1)).
If NCO% of a compound (A-1) is this range, since the hardened | cured material of the one-component moisture hardening type urethane composition of this invention obtained will not become weak, it is preferable.

As such a compound (A-1), specifically, an HDI-TMP adduct obtained by reacting TMP and HDI, an XDI-TMP adduct obtained by reacting TMP and XDI, and the like are preferable. Illustrated. The structural formula of the HDI-TMP adduct is shown in the following formula (a).
As said compound (A-1), what is marketed can also be used, for example, D160N made by Takeda Pharmaceutical Co., Ltd. as an HDI-TMP adduct, Takeda Pharmaceutical Co., Ltd. as an XDI-TMP adduct, for example. D110N made from the company etc. are mentioned.
In addition, the compound (A-1) may not be a complete adduct in which a hydroxyl group and an isocyanate group are completely reacted, and may contain an unreacted raw material.

Next, the compound (A-2) will be described.
The compound (A-2) is a compound having a structure represented by the following formula (b) and having at least an imino group (secondary amino group) and a hydrolyzable silyl group.

In the formula (b), R ¹ , R ² and R ³ each independently represent a hydrolyzable group or an alkyl group, and at least one of these is a hydrolyzable group. It is preferable that two or three hydrolyzable groups are bonded to the silyl group, since the adhesion-imparting effect of the compound (A) used in the present invention is further enhanced, and R ¹ , R ² and R ³ are all A group having hydrolyzability is more preferable. By R ^1, R ² and R ^3, depending on the application, it is possible to adjust the rate of hydrolysis and adhesiveness expression time. Specific examples of the hydrolyzable group include a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a mild hydrolyzable alkoxy group is preferable, and a methoxy group is particularly preferable because it is easily available.

  The alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec. -Butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group and the like. It may contain a heavy bond or a triple bond.

In the above formula (b), R ⁴ represents an alkylene group having 1 to 12 carbon atoms. Preferably, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, etc. are mentioned, and a trimethylene group is more preferable from the viewpoint of excellent adhesiveness.

In the above formula (b), R ⁵ represents an aryl group. Preferred examples of the aryl group include a phenyl group, a phenyl ether group, an anilino group, a phenyl thioether group, a methylphenyl group, and an ethylphenyl group.

  Preferred examples of the compound (A-2) used in the present invention having such a structure include γ-N-phenylaminopropyltrimethoxysilane having a structure represented by the following formula (c).

  The compound (A) used in the present invention is produced by a reaction between the NCO group of the compound (A-1) and the imino group of the compound (A-2). A urea group is generated by this reaction, but conventionally, the reactivity of the active hydrogen of this urea group is high, so that it has been difficult to store without losing the activity for a long time. However, in the compound (A-2) used in the present invention, since the phenyl group is directly bonded to the nitrogen atom, the reactivity of the active hydrogen of the generated urea group is suppressed by the steric hindrance and the electron withdrawing effect, Even if stored for a long period of time, the activity is not impaired, and it is considered that high adhesiveness can be imparted.

The compound (A) used in the present invention is a reaction product of the compound (A-1) and the compound (A-2) having a structure represented by the formula (b), and the compound (A-1). ) And the compound (A-2) are reacted at an equivalent ratio such that the equivalent ratio of NCO group to NH group (NCO / NH) is 1.8 to 3.5, preferably 2.0 to 3.3. The reaction product obtained.
Moreover, manufacture of the said compound (A) can be performed by the method similar to manufacture of a normal polyurethane, for example, the compound (A-1) and compound (A-2) of the above-mentioned equivalent ratio are 20 It can be carried out by stirring at ˜40 ° C., for example 30 ° C. Moreover, if necessary, a urethanization catalyst such as an organic tin compound, organic bismuth, or amine can be used.

The one-component moisture-curing urethane composition containing the compound (A) used in the present invention does not impair properties such as shape maintenance, elongation at break, and heat-resistant adhesion, and various adherends such as difficult-to-adhere coating plates. It is useful because it is a composition excellent in non-primer adhesion to
The reason for this excellent adhesiveness is that the silyl group exhibits high adhesion to silyl groups on the surface of glass or silicone-based substrates, and isocyanate to hydroxyl groups on the surface of acrylic paints. This is probably because the group exhibits high adhesiveness. The one-component moisture-curing urethane composition of the present invention having a silyl group and an isocyanate group is very excellent in adhesion to any material. For this reason, for example, even when a part of the glass is applied with a hard-to-adhere acrylic paint, it is possible to bond with the one-component moisture-curable urethane composition of the present invention.
Moreover, since the compound (A-1) is a compound obtained by reacting TMP with a bifunctional isocyanate as described above, the polarity is higher than that of a burette body having three isocyanate groups, an isocyanurate body, It is considered that the adhesiveness is excellent because it has an affinity for a hardly adhesive coating plate.

<Compound (B)>
Selected from the group consisting of a bifunctional isocyanate isocyanurate body, a burette body, and a compound obtained by reacting a bifunctional isocyanate and a triol, contained as an adhesion-imparting agent in the one-part moisture-curable urethane composition of the present invention. A compound having an imino group in which an aryl group is directly bonded to a nitrogen atom and having a hydrolyzable silyl group (hereinafter referred to as “compound (B-1)”). Compound (B) (hereinafter also referred to as “compound (B-2)”) is reacted so that the equivalent ratio of NCO group to NH group is 1.8 to 3.5. The compound (B) ”) is a compound having one or more NCO groups and hydrolyzable silyl groups on average in the molecule.

  The bifunctional isocyanate compounded in the compound (B-1) used in the present invention is basically the same as the bifunctional isocyanurate used in the compound (A-1), and is an HDI represented by the following formula (d). The isocyanurate body, and the compound (B) from which the HDI burette body represented by the following formula (e) can be obtained are preferable because of high adhesion imparting effect.

  The triol to be reacted with the bifunctional isocyanate is not particularly limited as long as it has three hydroxyl groups in one molecule. Specifically, for example, 1,2,5-hexanetriol, 1,2, Examples include 6-hexanetriol, 1,2,3-propanetriol, 1,2,3-benzenetriol, 1,2,4-benzenetriol, and the like. Among these, propanetriol is preferable from the viewpoint of physical property adjustment and compatibility.

The reaction between the bifunctional isocyanate and the triol is performed by mixing the bifunctional isocyanate and the triol so that the equivalent ratio of NCO group to OH group (NCO / OH) is 1.5 to 2.5. . If the amount ratio falls within this range, the resulting one-part moisture-curing urethane composition of the present invention has good adhesion and crosslink density, and the cured product does not become brittle. It is preferably 1.8 to 2.2 because it is more excellent in this characteristic.
The production of the compound obtained by reacting the above bifunctional isocyanate and the above triol can be carried out in the same manner as in the production of an ordinary urethane prepolymer. For example, the above-mentioned equivalent ratio of triol and bifunctional isocyanate is 50 It can be performed by heating and stirring at ~ 100 ° C. Moreover, if necessary, a urethanization catalyst such as an organic tin compound, organic bismuth, or amine can be used.

  The isocyanurate body, burette body, and compound obtained by reacting the bifunctional isocyanate and triol may be used singly or in combination of two or more.

  The said compound (B-2) is the same as the said compound (A-2) mix | blended with the compound A used for this invention.

The compound (B) used in the present invention is a reaction product of the compound (B-1) and the compound (B-2), and the compound (B-1) and the compound (B-2) are combined. It is preferable that the reaction product is obtained by reacting at an equivalent ratio of NCO group to NH group (NCO / NH) of 1.8 to 3.5, preferably 2.0 to 3.3. .
Moreover, manufacture of the said compound (B) can be performed by the method similar to manufacture of a normal polyurethane, for example, the compound (B-1) and the compound (B-2) of the above-mentioned equivalent ratio are 20 It can be carried out by stirring at ˜40 ° C., for example 30 ° C. Moreover, if necessary, a urethanization catalyst such as an organic tin compound, organic bismuth, or amine can be used.

The one-component moisture-curable urethane composition containing the compound (B) used in the present invention does not impair properties such as shape maintenance, elongation at break, and heat-resistant adhesive properties, and various adherends such as difficult-to-adhere coating plates. It is useful because it is a composition excellent in non-primer adhesion to
The reason why this adhesiveness is excellent is the same as that of the above compound (A). In particular, by containing the above compound (B-1), the compatibility is changed and the adhesiveness is easily transferred to the interface. it is conceivable that.

  In the one-component moisture-curable urethane composition of the present invention, the content of the preliminary composition is X parts by mass, the content of the compound (A) is A parts by mass, and the content of the compound (B) is B parts by mass. The following formula (1) is satisfied.

  0.1X ≦ 100 (A + B) ≦ 6.5X (1)

When satisfying the above formula (1), the resulting one-component moisture-curing urethane composition is excellent in shape maintenance and elongation at break, and is further excellent in non-primer adhesion to various adherends such as a difficult-to-adhere coating plate. .
It is preferable to satisfy the following formula (2) in that it is more excellent in this characteristic.

  0.3X ≦ 100 (A + B) ≦ 5.0X (2)

<Compound (C)>
The one-component moisture-curable urethane composition of the present invention further comprises, in addition to the above-mentioned components, a bifunctional isocyanate isocyanurate body, a burette body, and a compound obtained by reacting a bifunctional isocyanate and a triol. It is preferable to contain at least one compound (C) selected from: The compound (C) not only imparts non-primer adhesion to various adherends such as difficult-to-adhere adhesive plates to the obtained one-component moisture-curable urethane composition, but also includes trifunctional compounds (C) and 2 By adjusting the content of the functional compound (A) and / or the compound (B), the resulting one-component moisture-curing urethane composition has characteristics such as high-temperature and high-humidity curability, strength development, hardness, and extensibility. Can be adjusted according to the application.
The compound (C) used in the present invention is basically the same as the compound (B-1).

  In the one-component moisture-curable urethane composition of the present invention, the content of the preliminary composition is X parts by mass, the content of the compound (A) is A parts by mass, and the content of the compound (B) is B parts by mass. When the content of the compound (C) is C parts by mass, the following formula (3) is satisfied.

  0.1X ≦ 100 (A + B + C) ≦ 6.5X (3)

When satisfy | filling said Formula (3), it is excellent in the high-temperature high-humidity curability, strength expression, and adhesive expression of the obtained one-component moisture-curing urethane composition.
It is preferable to satisfy the following formula (4) in that it is more excellent in this characteristic.

  0.3X ≦ 100 (A + B + C) ≦ 5.0X (4)

<Organic tin compounds>
The one-component moisture-curable urethane composition of the present invention contains 0.0006 to 0.20 parts by mass of an organic tin compound with respect to 100 parts by mass of the preliminary composition. Since the organotin compound catalyzes the reaction between the isocyanate group of the urethane prepolymer and the active hydrogen on the surface of the adherend, the resulting one-part moisture-curing urethane composition can be applied to various adherends such as difficult-to-adhere coating plates. Excellent adhesion to the body.
When the content of the organotin compound is in the above range, the adhesiveness to various adherends such as a hardly adhesive coating plate is excellent, and the heat resistant adhesiveness is excellent. From the point which is excellent by this characteristic, 0.001-0.05 mass part is preferable, and 0.002-0.03 mass part is especially preferable.

  The organotin compound contained in the one-component moisture-curable urethane composition of the present invention is not particularly limited, and specifically, for example, dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin maleate, stannous octate, dibutyltin diacetylacetate Nate, dioctyl tin maleate and the like. Among these, dioctyltin laurate is preferable from the viewpoint of excellent adhesion to difficult-to-adhere coating plates.

  The organotin compound contained in the one-component moisture-curable urethane composition of the present invention may be used alone or in combination of two or more.

In the one-component moisture-curable urethane composition of the present invention, in addition to the above components, an organic solvent can be contained in order to improve the ease of preparation and the workability of the coating process.
The organic solvent is not particularly limited as long as it is inert to the above components and has an appropriate volatility.
Specific examples of the organic solvent include methyl ethyl ketone, dimethylacetamide, acetone, ethyl acetate, butyl acetate, cellosolve acetate, mineral spirit, toluene, xylene, n-hexane, isohexane, methylene chloride, tetrahydrofuran, ethyl ether, dioxane. Etc. Among these organic solvents, toluene, mineral spirit, and methyl ethyl ketone are preferable.
These organic solvents are preferably used after sufficiently dried.
In the one-component moisture-curable urethane composition of the present invention, one kind of the above organic solvent may be used, or two or more kinds thereof may be used in combination. The organic solvent may not be used from the viewpoint of VOC reduction.

Furthermore, the one-component moisture-curable urethane composition of the present invention may contain other additives as necessary. For example, when UV absorbers such as Siasolv (Cyasorb UV24 Light Absorber, manufactured by American Cyanamid), Ubinur (Uvinul D-49, D-50, N-35, N-539, manufactured by General Aniline), etc. It is effective in improving the light resistance by shielding or absorbing ultraviolet rays and visible rays.
Furthermore, you may contain stabilizers, such as a thickener and diethyl malonate.

  The production method of the one-component moisture-curable urethane composition of the present invention is not particularly limited. Specifically, for example, the compound (A) and / or the compound (B) is added to the preliminary composition in an organic solvent. Alternatively, it is preferably dissolved in a plasticizer and further added with the above organotin compound and sufficiently kneaded under reduced pressure to obtain a one-component moisture-curable urethane composition of the present invention.

  The one-component moisture curable urethane composition of the present invention comprises a preliminary composition comprising a urethane prepolymer, a filler and a plasticizer, the compound (A) and / or the compound (B), and the organotin compound. In the above-mentioned range, it is excellent in properties such as high-temperature and high-humidity curability, shape maintenance, storage stability and the like, and also excellent in non-primer adhesion to various adherends such as hard-to-adhere coating plates. .

  The use, application conditions, etc. of the one-component moisture-curable urethane composition of the present invention are not particularly limited, but are suitable for the field of automobiles such as adhesion between a vehicle body and a window glass because of the above-described excellent characteristics. Used for.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
(Examples 1, 2, 4, and 7, Comparative Examples 1 to 4, 6 to 11, Reference Examples 1 to 4)
<Preparation of pre-composition>
Polyether triol (Exenol 5030, number average molecular weight of about 5000, manufactured by Asahi Glass Co., Ltd.) and polyether diol (Exenol 2020, number average molecular weight of about 2000, manufactured by Asahi Glass Co., Ltd.) were mixed at a mass ratio of 70/30, and at 120 ° C. After dehydration under reduced pressure, melted 4,4′-diphenylmethane diisocyanate (Isonate 125M, manufactured by Mitsui Takeda Urethane Co., Ltd.) was added in an amount such that the equivalent ratio of NCO group / OH group was 1.7. After mixing and stirring for a time, a urethane prepolymer was obtained. The urethane prepolymer thus obtained has 80 parts by mass of the urethane prepolymer, 70 parts by mass of carbon black (Elf Tech 8, manufactured by Cabot), and diisodecyl phthalate (DIDP, manufactured by Mitsubishi Chemical) as a plasticizer. Part by mass and 15 parts by mass of calcium carbonate (SB Blue, manufactured by Shiroishi Calcium Co., Ltd.) were added and mixed for 1 hour using a mixer under vacuum to obtain a preliminary composition.

<Synthesis of Compound (A)>
To 100 g of an HDI-TMP adduct (D160N, manufactured by Mitsui Takeda Urethane Co., Ltd., NCO%: 12.8%), a value of γ-N-phenylaminopropyltrimethoxysilane (NCO / NH) is 3/1. Compound (A) (NCO%: 6.8%) was obtained by reacting while adding 26 g of Y9669 (manufactured by Nihon Unicar).

<Synthesis of Compound (B)>
To 100 g of a modified HDI isocyanurate (D170N, manufactured by Mitsui Takeda Urethane Co., Ltd., NCO%: 27%), the value of NCO / NH is 3/1, so that γ-N-phenylaminopropyltrimethoxysilane (Y9669, Compound (B) (NCO%: 15.3%) was obtained by reacting while adding 18 g of Nippon Unicar Co., Ltd. dropwise.

Subsequently, with respect to 100 parts by mass of the preliminary composition, the amount of compound (A), compound (B), compound (C) shown in Table 1 below (modified HDI isocyanurate, D170N, manufactured by Mitsui Takeda Urethane Co., Ltd., NCO%: 27%) and dioctyltin dilaurate (DOTL) (U-810, manufactured by Nitto Kasei Co., Ltd.), and diethyl malonate (DEM, manufactured by Inoue Fragrance Co., Ltd.) as a stabilizer are added and mixed for 10 minutes. A one-component moisture-curable urethane composition was obtained.
With respect to the obtained one-component moisture-curable urethane composition, the drooping property, elongation at break, heat resistant adhesiveness, and adhesiveness to various coated plates were evaluated according to the following methods. The results are shown in Table 1.

(Droop test)
A drooping test was conducted to evaluate the shape maintenance of the applied one-component moisture-curing urethane composition. FIG. 1 is a conceptual diagram illustrating an example of a drooping test.
As shown in FIG. 1, the one-component moisture-curing urethane composition 1 is extruded into a glass plate 3 with a right triangle bead having a base of 6 mm and a height of 10 mm, and a holder 4 is immediately attached to the glass plate 3 at an angle of 90 °. Was held at 20 ° C. and 65% RH for 30 minutes, and the distance h at which the top of the one-component moisture-curing urethane composition 2 hangs down was measured.

(Elongation at break)
The cured product of the obtained one-component moisture-curable urethane composition was cut into a dumbbell-shaped test piece (dumbbell-shaped No. 3) having a thickness of 2 mm, and the elongation at break (%) was measured according to JIS K6251-1993. .

(Heat resistant adhesion test)
After applying the one-component moisture-curing urethane composition to an adherend for curing test evaluation (glass coated with a primer (MS-90, manufactured by Yokohama Rubber Co., Ltd.)) and leaving it at 20 ° C. and 60 RH% for 7 days, The mixture was allowed to stand at 120 ° C. for 5 days and gradually cooled to 20 ° C. One end of the one-component moisture-curing urethane composition cured product was gripped and peeled 180 degrees, and the fracture state was observed. The cohesive failure of the cured product is CF (the numerical value is the area (%) where the cohesive failure of the cured product occurs relative to the area of the portion where the cured product is peeled off), and the interface peeling between the primer and the cured product is PS (the numerical value is The area (%) where interfacial peeling between the primer and the cured product occurred relative to the area of the part from which the cured product was peeled.

(Adhesion test for coated plates A and B)
The one-component moisture-curing urethane composition was directly applied to each of the coated plates A and B each having the following coating materials A and B applied to the steel plate without using a primer, and allowed to stand at 20 ° C. and 60 RH% for 168 hours. One end of the one-component moisture-curing urethane composition cured product is gripped and peeled 180 degrees, and the fracture state is observed. The cohesive failure of the cured product is CF (the numerical value is the area (%) where the cohesive failure of the cured product occurs relative to the area of the portion where the cured product is peeled off), and the interface peeling between the coated plate / cured product is AF (the numerical value is The area (%) where interface peeling between the coated plate and the cured product occurred relative to the area of the portion where the cured product was peeled.
Paint A: 540-DS405 / RK8010 (manufactured by DuPont)
Paint B: 545-DS435 / RK8046 (DuPont)

FIG. 1 is a conceptual diagram illustrating an example of a drooping test.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 One-component moisture curable urethane composition in initial state 2 One-component moisture curable urethane composition after standing for 30 minutes 3 Glass plate 4 Holder

Claims (6)

A urethane prepolymer obtained by reacting a mixture of a polyether triol having a number average molecular weight of 1000 to 7000 and a polyether diol with diphenylmethane diisocyanate so that the equivalent ratio of NCO groups to OH groups is 1.1 to 2.5. 100 parts by weight of a preliminary composition comprising a polymer, a filler and a plasticizer;
An imino group in which an aryl group is directly bonded to a nitrogen atom is bonded to at least one compound selected from the group consisting of isocyanurates of bifunctional isocyanates, burettes, and compounds obtained by reacting bifunctional isocyanates with triols. And a compound (B) obtained by reacting a compound having a hydrolyzable silyl group with an NCO group and NH group equivalent ratio of 1.8 to 3.5,
Containing 0.0006 to 0.20 parts by mass of an organic tin compound,
Furthermore, it contains at least one compound (C) selected from the group consisting of isocyanurate bodies of bifunctional isocyanates, burette bodies, and compounds obtained by reacting bifunctional isocyanates with triols , The reaction with the triol is performed so that the equivalent ratio of NCO group to OH group (NCO / OH) of the bifunctional isocyanate and the triol is 1.5 to 2.5,
When the content of the preliminary composition is X parts by mass, the content of the compound (B) is B parts by mass, and the content of the compound (C) is C parts by mass, the following formula (3) is satisfied. Liquid moisture curable urethane composition.
0.1X ≦ 100 (B + C) ≦ 6.5X (3) Claims satisfying the following formula (4) when the content of the preliminary composition is X parts by mass, the content of the compound (B) is B parts by mass, and the content of the compound (C) is C parts by mass. Item 2. A one-component moisture-curable urethane composition according to Item 1.
0.3X ≦ 100 (B + C) ≦ 5.0X (4) A compound obtained by reacting trimethylolpropane with a bifunctional isocyanate such that the equivalent ratio of NCO group to OH group is 0.8 to 1.5, has an imino group in which an aryl group is directly bonded to a nitrogen atom, And a compound (A) obtained by reacting a compound having a hydrolyzable silyl group so that the equivalent ratio of NCO group to NH group is 1.8 to 3.5,
The one-component moisture curable urethane composition according to claim 1, which satisfies the following formula (3) when the content of the compound (A) is A parts by mass.
0.1X ≦ 100 (A + B + C) ≦ 6.5X (3) The content of the preliminary composition is X parts by mass, the content of the compound (A) is A parts by mass, the content of the compound (B) is B parts by mass, and the content of the compound (C) is C parts by mass. The one-component moisture-curable urethane composition according to claim 3, which satisfies the following formula (4):
0.3X ≦ 100 (A + B + C) ≦ 5.0X (4)   The one-component moisture-curable urethane composition according to any one of claims 1 to 4, comprising 0.001 to 0.05 parts by mass of the organotin compound.   The compound in which the aryl group has an imino group directly bonded to a nitrogen atom and has a hydrolyzable silyl group is γ-N-phenylaminopropyltrimethoxysilane, and the bifunctional isocyanate is hexamethylene diisocyanate. The one-component moisture-curable urethane composition according to any one of claims 1 to 5.