JP3330439B2 - Two-part reactive polyurethane composition for bonding or sealing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an elongation after curing.
Adhesive or sealing with large and suitable flexibility
The present invention relates to a two-component reaction type polyurethane composition for use .

[0002]

2. Description of the Related Art A polyurethane composition can impart various physical properties to a cured product obtained by changing the kind of polyisocyanate or polyol constituting the composition and the curing conditions. Such a polyurethane composition comprises
It is widely used in applications such as adhesives, sealing materials, and paints.It has excellent adhesiveness and impact resistance. It is suitably used as a sealing material.

[0003] In recent years, polyurethane compositions have been applied to bonding and sealing of large structures. However, as for the polyurethane composition as an adhesive or a sealing material applied to a large-sized structure, the cured product is required to have sufficient flexibility to withstand a large deformation force, and specifically, Improvement in elongation properties is required as a physical property in a cured product.

[0004] Moisture-curable one-part urethane compositions are commercially available as urethane-based adhesives and sealing materials that meet such demands, but the curing speed is extremely slow.
Further, it has a problem that the curing speed is greatly affected by environmental conditions such as humidity, and is not practical.

[0005] As a means for improving elongation characteristics after curing of a polyurethane composition, the following techniques have been conventionally introduced. Japanese Patent Application Laid-Open No. 5-78447 discloses a technique of forming a highly elastic rubber elastic cured product from a heat-curable one-part composition containing a polyoxyalkylene ether polyol having a high molecular weight (8,000 to 40,000). reference). A technique for improving elongation properties by a two-pack reaction type composition containing a polyoxyalkylene ether polyol having a low degree of unsaturation and a high molecular weight (see JP-A-2-263818).

[0006]

However, in the above-mentioned technique, it is difficult to cure the composition.
It is necessary to heat to about 100 ° C., and it is practically difficult to apply to a large structure.

Further, in the above technique, although the elongation characteristics can be improved to some extent by increasing the molecular weight of the polyoxyalkylene polyol, the obtained cured product does not have sufficient strength. Therefore, when applied to a sealing material or the like, it is necessary to use a low molecular weight chain extender as a component of the composition. However, by using the chain extender in combination, the Young's modulus of the cured product increases. The adhesive or sealing portion made of a cured product having a high Young's modulus is subjected to an excessive load due to the deformation, and the structure is damaged or damaged.
There is a risk of damage.

The present invention has been made based on the above circumstances. An object of the present invention is a two-component reaction type polyurethane composition that cures at room temperature, and can provide a cured product having a large elongation, excellent flexibility, a small Young's modulus, and a small load accompanying deformation, Suitable for use as an adhesive or sealing material for large structures
Is to provide a two-part reactive polyurethane composition for sealing .

[0009]

According to the present invention, there is provided a method for bonding or printing a sheet.
The two-component reactive polyurethane composition for cooling comprises a first component mainly composed of a polyisocyanate prepolymer (A) and a second component mainly composed of a polyol compound (B).
Be one of the additional level, the first component of the polyisocyanate prepolymer (A) is a polyisocyanate compound having an isocyanate group of two or more and (a), poly having hydroxyl groups at both ends (3-methyl - 1 , 5 - Monodea obtained by the reaction of pentanediol adipate)
Ri, the second component of the polyol compound (B) is a hydroxyl group
Low molecular weight diol with a molecular weight of 150 or less per
The derived hydroxyl group and the molecular weight per hydroxyl group are 1500 or less
High molecular weight with 3 or more hydroxyl groups in the molecule
It has a hydroxyl group derived from a polyol .

[0010] In the polyurethane composition of the present invention,
It is preferable to satisfy the following conditions. 30 to 100 mol% of the isocyanate groups contained in the polyisocyanate compound (a) contain isocyanate groups in a ratio of 15 to 30% by weight obtained by reacting 4,4′-diphenylmethane diisocyanate with a low molecular weight diol. Being an isocyanate group derived from a urethane prepolymer. Of the hydroxyl groups contained in the polyol compound (B), 50 to 70 mol% have a molecular weight of 15
A hydroxyl group derived from a low molecular weight diol having a molecular weight of 15 or less, and 50 to 30 mol% having a molecular weight of 15 or less per hydroxyl group.
A hydroxyl group derived from a high molecular weight polyol having at least 00 and having at least 3 hydroxyl groups in the molecule. When the number of moles of isocyanate groups contained in the first component is a and the number of moles of hydroxyl groups contained in the second component is b, the value of (a / b) is in the range of 0.9 to 1.4. That is, the first component and the second component are mixed.

Hereinafter, the present invention will be described specifically.
The first component constituting the composition of the present invention is mainly composed of the polyisocyanate prepolymer (A). The polyisocyanate prepolymer (A) is composed of a polyisocyanate compound (a) containing two or more isocyanate groups and a poly (3-methyl-
1.5-pentanediol adipate).

As the polyisocyanate compound (a), for example, various polyisocyanate compounds such as aliphatic, aromatic and alicyclic compounds can be used. Specific examples of the polyisocyanate compound (a) include, for example, xylylene diisocyanate, polyphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate,
Isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, diisocyanate compounds such as dicyclohexylmethane diisocyanate, and polymers thereof can be mentioned. Allophanate bond, isocyanurate bond, having a carbodiimide bond and the like, a polyisocyanate compound having a plurality of isocyanate groups, for example, a dimer or trimer of the above diisocyanate compound,
Polymeric phenylmethane diisocyanate may be used. These compounds can be used alone or in combination of two or more to constitute the polyisocyanate compound (a).

In the present invention, the polyisocyanate compound (a) has an isocyanate group of 30 to 10
It is preferable that 0 mol% is an isocyanate group derived from a urethane prepolymer obtained by reacting 4,4′-diphenylmethane diisocyanate with a low molecular weight diol (hereinafter, also referred to as “specific urethane prepolymer”). When the proportion of the isocyanate group derived from the specific urethane prepolymer is less than 30 mol%, the cured product of the polyurethane composition is unlikely to have large elongation characteristics and small Young's modulus. In the specific urethane prepolymer, the isocyanate group content is preferably 15 to 30% by weight,
More preferably, the content is 22 to 24% by weight. Examples of such a specific urethane prepolymer include “Sumidur PF” (manufactured by Sumitomo Bayer Urethane Co., Ltd.).

Poly (3-methyl-1.5-pentanediol adipate) having hydroxyl groups at both ends, which is subjected to a reaction with the polyisocyanate compound (a) to obtain a polyisocyanate prepolymer (A) Examples thereof include a copolymer of 3-methyl-1.5-pentanediol and adipic acid having a molecular weight of 500 to 10,000. Specifically, "Kurapol P series"
[Manufactured by Kuraray Co., Ltd.]. Particularly, from the viewpoint of imparting a large elongation property and a small Young's modulus to a cured product of the polyurethane composition, "Kurapol P-40"
It is preferable to use "10".

The method for obtaining the polyisocyanate prepolymer (A) is not particularly limited. For example, a polyisocyanate compound (a) and a poly (3-methyl-1) having hydroxyl groups at both terminals are used. .5-pentanediol adipate) at a molar ratio of isocyanate groups to hydroxyl groups (NCO / OH) of from 2 to 20 and the mixture was heated at 20 to 90 ° C. for 1 to 6 hours to react. There is a method to make it.

The second component constituting the composition of the present invention comprises a polyol compound (B) as a main component. Specific examples of the polyol compound (B) include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, diethylene glycol, triethylene glycol,
Polyhydric alcohols such as hexamethylene glycol, glycerin, 1,3-butylene glycol, 1,4-butanediol, hexanetriol, pentaerythritol derivatives, sorbitol and neopentyl glycol;
A polyether polyol obtained by addition polymerization of the polyhydric alcohol and an alkylene oxide (eg, ethylene oxide, propylene oxide, etc.); the polyhydric alcohol and a polybasic acid (eg, maleic acid,
Polyester polyol obtained by condensation reaction with succinic acid, adipic acid, sebacic acid, tartaric acid, terephthalic acid, isophthalic acid, etc .; polyester obtained by ring-opening polymerization of lactones (eg, ε-caplactone, γ-valerolactone) Polyol; a polymerizable monomer containing a hydroxyl group (eg, hydroxyethyl acrylate, hydroxybutyl acrylate, trimethylolpropane monoacrylate, etc.) alone or a monomer copolymerizable therewith (eg, acrylic acid, methacrylic acid) ,
Styrene, acrylonitrile, α-methylstyrene, etc.)
And castor oil and derivatives thereof; epoxy polyols obtained by reacting an epoxy resin having epoxy groups at both ends with monoethanolamine, diethanolamine, and the like. These compounds have a single structure or a combination of two or more polyol compounds (B).
Can be configured.

In the present invention, the hydroxyl group contained in the polyol compound (B) is preferably a hydroxyl group derived from a low molecular weight diol in an amount of 50 to 70 mol%,
It is preferable that 50 to 30 mol% of the hydroxyl groups be hydroxyl groups derived from a high molecular weight polyol.

Here, "low molecular weight diol" refers to a diol having a molecular weight per hydroxyl group of 150 or less. As the low molecular weight diol, polyoxypropylene ether diol having a molecular weight of 300 or less can be exemplified as a preferable one from the viewpoints of viscosity and reactivity.

On the other hand, the term "high molecular weight polyol" refers to a polyol having a molecular weight per hydroxyl group of 1500 or more and having three or more hydroxyl groups in the molecule. Preferred examples of the high molecular weight polyol include polyoxypropylene ether triol and polyoxypropylene ether tetraol from the viewpoints of viscosity and physical properties of the cured product.

When the ratio of hydroxyl groups derived from the low molecular weight diol is 5
When the proportion is less than 0 mol% , and when the proportion of the hydroxyl group derived from the high molecular weight polyol exceeds 50 mol% , the effect of improving the elongation property in the cured product is recognized, but the cured product has sufficient strength. Hateful. On the other hand, if the proportion of the hydroxyl group derived from a low molecular weight diol is more than 70 mol%, the proportion of hydroxyl group derived from a high molecular weight polyol is 30 Mo
When the content is less than 1 % , the cured product of the composition is unlikely to have large elongation characteristics and small Young's modulus.

The second component constituting the composition of the present invention includes:
An amine compound may be contained as needed. Specific examples of such an amine compound include ethylenediamine, diethylenetriamine, triethylenetetramine,
Aliphatic polyamine compounds such as tetraethylenepentamine, pentaethylenehexamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, cyclohexylenediamine, isophoronediamine, piperazine, melamine and derivatives thereof; o-phenylenediamine, m-phenylene Diamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4 '
-Diaminodiphenyl ether, 2,4-diaminodiphenylamine, 1,5-diaminonaphthalene, 1,8-
Examples thereof include aromatic polyamine compounds such as diaminonaphthalene and 2,4-diaminotoluene. The amount of the amine compound to be added is generally 0.1 to 2 parts by weight based on 100 parts by weight of the second component.

Further, the second component may contain a curing catalyst for accelerating the curing reaction. Such curing catalysts include, for example, stannous carboxylate such as stannous acetate, stannous octoate, stannous laurate, stannous oleate; dibutyltin acetate, dibutyltin dilaurate, dibutyltin maleate Dialkyltin salts of carboxylic acids such as ethate, dibutyltin di-2-ethyl-hexoate, dilauryltin diacetate, dioctyltin diacetate; trimethyltin hydroxide;
Trialkyltin hydroxides such as tributyltin hydroxide and trioctyltin hydroxide; dialkyltin oxides such as dibutyltin oxide, dioctyltin oxide and dilauryltin oxide; dialkyltin chlorides such as dibutyltin dichloride and dioctyltin dichloride; triethylamine and benzylmethyl Tertiary amines such as amines, triethylenediamine, tetramethylbutanediamine, and 2-methyl-triethylenediamine; 1,8-diaza-bicyclo (5.4.
0) phenolic salt of undecene-7, stearic acid salt,
Oleates, formates, phenol novolak salts and the like can be mentioned. The amount of the curing catalyst added is the second component 1
It is usually 0.01 to 4 parts by weight with respect to 00 parts by weight.

Further, the first component and / or the second component constituting the composition of the present invention may contain various fillers as necessary. Examples of such a filler include talc, calcium carbonate, clay, synthetic silica, synthetic zeolite, bentonite, zinc white, titanium dioxide, carbon black, glass particles and the like. It is preferable that these fillers have been subjected to a surface treatment.

It is preferable that the composition of the present invention is constituted by mixing the first component and the second component at a specific ratio. Specifically, when the number of moles of isocyanate groups contained in the first component is a and the number of moles of hydroxyl groups contained in the second component is b, the value of (a / b) is 0.9.
It is preferable that they are mixed so as to be in the range of ~ 1.4. When this value is less than 0.9, the water resistance of the cured product tends to decrease due to the excessively remaining hydroxyl groups. On the other hand, if this value is less than 1.4, the cured product will not have sufficient strength, and the excess isocyanate groups will be moisture-cured and the effect of improving elongation properties will be impaired. Tend. The first component and the second component
The means for mixing with the components is not particularly limited, and can be mixed with, for example, a static mixer or a dynamic mixer.

[0025]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In addition,
Hereinafter, "parts" means "parts by weight".

Example 1 (1) Preparation of First Component Polymeric 4,4′-diphenylmethane diisocyanate “Sumidur 44V-20” [manufactured by Sumitomo Bayer Urethane Co., Ltd .: polyisocyanate compound (a)]
3 parts, 8.3 parts of hydrogenated xylylene diisocyanate “Takenate 600” [manufactured by Takeda Pharmaceutical Co., Ltd .: polyisocyanate compound (a)], and reaction of 4,4′-diphenylmethane diisocyanate with a low molecular weight polyol Obtained urethane prepolymer "Sumidur PF"
[Sumitomo Bayer Urethane Co., Ltd .: polyisocyanate compound (a)] 16.7 parts and poly (3-methyl-1.
5-pentanediol adipate) "Clapol P-4
010 "[manufactured by Kuraray Co., Ltd .: molecular weight 4,000]
5 parts of the mixture, and the mixture was reacted by heating at 90 ° C. for 2 hours.
A first component was prepared by adding 2 parts. In the first component, 38.5 mol% of the isocyanate groups of the polyisocyanate compound (a) are derived from the urethane prepolymer “Sumidur PF”.

(2) Preparation of the second component Polyether triol "Exenol 823" (manufactured by Asahi Glass Co., Ltd .: high molecular weight polyol having a molecular weight of 5,000)
64.2 parts and the polyether diol “Exenol 2”
20 "[manufactured by Asahi Glass Co., Ltd .: 10.8 parts of low molecular weight diol having a molecular weight of 200], 25 parts of talc, 0.5 parts of pentaethylenehexamine [amine compound], and triethylenediamine" DABCO "[Sankyo Air Product ( stock)
Production: curing catalyst] was mixed with 0.05 part to prepare a second component. Among the hydroxyl groups of the polyol compound (B) constituting the second component, the ratio of the hydroxyl groups derived from “exenol 823” which is a high molecular weight polyol is 3%.
0.8 mol%, and the ratio of hydroxyl groups derived from low molecular weight diol “Exenol 220” is 69.2 mol%.

(3) Production of Polyurethane Composition The first component and the second component are mixed at a ratio of 1: 1.5 (weight ratio) to give the composition 1 of the present invention.
Was manufactured. In this composition 1, the molar ratio of the isocyanate group to the hydroxyl group (NCO / OH) is 1.2.

Example 2 (1) Preparation of First Component Urethane prepolymer “Sumidur PF” 31.35
Part of the mixture and 33.65 parts of “Klapol P-4010” were heated at 90 ° C. for 2 hours to cause a reaction. Then, 35 parts of dried calcium carbonate powder was added thereto, and the first mixture was added.
The components were prepared. In the first component, 100% of the isocyanate groups of the polyisocyanate compound (a)
Molar% is urethane prepolymer "Sumidur PF"
It is derived from.

(2) Preparation of second component Polyether triol "Exenol 823"
4 parts and polyether diol “Exenol 220”
A second component was prepared by mixing 6.6 parts, 25 parts of talc, and 0.05 parts of triethylenediamine “DABCO”. The polyol compound (B) constituting the second component
The ratio of the hydroxyl group derived from “Exenol 823” which is a high molecular weight polyol among the hydroxyl groups of
Mol%, and the ratio of hydroxyl groups derived from low molecular weight diol “Exenol 220” is 56.3 mol%.

(3) Production of Polyurethane Composition The first component and the second component are mixed at a ratio of 1: 1.5 (weight ratio) to give the composition 2 of the present invention.
Was manufactured. In this composition 2, the molar ratio of the isocyanate group to the hydroxyl group (NCO / OH) is 1.1.

Example 3 (1) Preparation of First Component A first component was prepared in the same manner as in Example 2.

(2) Preparation of Second Component Polyethertetraol "Preminol 7021"
[Made by Asahi Glass Co., Ltd .: high molecular weight polyol having a molecular weight of 13,000] 33.6 parts, polyether triol “Exenol 823” 33.6 parts, polyether diol “Exenol 220” 7.9 parts, and talc 25 Department and
A second component was prepared by mixing with 0.05 parts of triethylenediamine “DABCO”. Among the hydroxyl groups of the polyol compound (B) constituting the second component, the total ratio of the hydroxyl groups derived from the high molecular weight polyol “Preminol 7021” or “Exenol 823” is 3
2.5 mol%, and the ratio of hydroxyl groups derived from low molecular weight diol “Exenol 220” is 67.5 mol%.

(3) Production of Polyurethane Composition The above-mentioned first component and second component are mixed in a ratio of 1: 1.5 (weight ratio) to obtain the composition 3 of the present invention.
Was manufactured. In this composition 3, the molar ratio between the isocyanate group and the hydroxyl group (NCO / OH) is 1.1.

Example 4 (1) Preparation of First Component 26.1 parts of "Sumidur 44V-20", 8.77 parts of urethane prepolymer "Sumidur PF", and "Clapol P-4010" 37 The mixture was heated at 90 ° C. for 2 hours to react, and then 27.72 parts of dried calcium carbonate powder was added to prepare a first component. In the first component, 20.0 of the isocyanate groups of the polyisocyanate compound (a)
Molar% is urethane prepolymer "Sumidur PF"
It is derived from.

(2) Preparation of Second Component A second component was prepared in the same manner as in Example 1.

(3) Production of Polyurethane Composition The above-mentioned first component and second component are mixed at a ratio of 1: 1.5 (weight ratio) to obtain the composition 4 of the present invention.
Was manufactured. In this composition 4, the molar ratio between the isocyanate group and the hydroxyl group (NCO / OH) is 1.2.

Example 5 (1) Preparation of First Component The same operation as in Example 1 was performed to prepare a first component.

(2) Preparation of second component Polyether triol "Exenol 823" 13
5.2 parts and a polyether diol “Exenol 22”
0 "and 5.46 parts of triethylenediamine" DABC
O "was mixed with 0.05 part to prepare a second component. Among the hydroxyl groups of the polyol compound (B) constituting the second component, the proportion of hydroxyl groups derived from the high molecular weight polyol “Exenol 823” is 65.0 mol%, and the low molecular weight diol “Exenol 220” Is 35.0 mol%.

(3) Production of Polyurethane Composition Composition 5 of the present invention was produced by mixing the above first component and second component at a ratio of 1: 2 (weight ratio). In this composition 5, the molar ratio between the isocyanate group and the hydroxyl group (NCO / OH) is 1.2.

Example 6 (1) Preparation of First Component The same operation as in Example 1 was performed to prepare a first component.

(2) Preparation of Second Component Polyether triol “Exenol 823” 41.
6 parts and polyether diol “Exenol 220”
12.48 parts and triethylenediamine "DABCO"
The second component was prepared by mixing with 0.05 part. This second
Among the hydroxyl groups of the polyol compound (B) constituting the component, “exenol 82” which is a high molecular weight polyol
The ratio of hydroxyl groups derived from 3 "is 20.0 mol%,
The ratio of hydroxyl groups derived from the low molecular weight diol “Exenol 220” is 80.0 mol%.

(3) Production of Polyurethane Composition The above-mentioned first component and second component are mixed at a ratio of 1: 0.8 (weight ratio) to give the composition 6 of the present invention.
Was manufactured. In this composition 6, the molar ratio of the isocyanate group to the hydroxyl group (NCO / OH) is 1.2.

Example 7 (1) Preparation of First Component The same operation as in Example 1 was performed to prepare a first component.

(2) Preparation of Second Component A second component was prepared in the same manner as in Example 1.

(3) Production of Polyurethane Composition The above first component and second component are combined at 1.25: 1.5
The composition 7 of the present invention was produced by mixing at a ratio of (weight ratio). In this composition 7, the molar ratio between the isocyanate group and the hydroxyl group (NCO / OH) is 1.5.

Example 8 (1) Preparation of First Component In place of "Clapol P-4010", 37.5 parts of polyether polyol "Exenol 510" (manufactured by Asahi Glass Co., Ltd., molecular weight: 4,000) was used. A first component was prepared by performing the same operation as in Example 1 except that it was used.

(2) Preparation of Second Component The same operation as in Example 1 was performed to prepare a second component.

(3) Production of Polyurethane Composition The above-mentioned first component and second component are mixed at a ratio of 1: 1.5 (weight ratio) to obtain composition 8 of the present invention.
Was manufactured. In this composition 8, the molar ratio of the isocyanate group to the hydroxyl group (NCO / OH) is 1.2.

<Test Example> Each of the compositions 1 to 8 of the present invention obtained as described above was poured into a mold and cured at room temperature for 3 days to obtain a 1 mm thick sheet-like cured product. Was. Tumbell-shaped test pieces (JIS-2) were prepared from each of these cured products, and were pulled at a pulling speed of 100 mm / min using a tensile tester “Autograph AG-5000B” (manufactured by Shimadzu Corporation). Tests were performed to measure tensile strength (T _B ), elongation (E _B ) and Young's modulus.
Table 1 shows the results.

[0051]

[Table 1]

From the results shown in Table 1, according to the composition of the present invention, particularly the compositions 1 to 3, a cured product having a sufficient tensile strength, a large elongation and a small Young's modulus can be obtained. It is understood that.

[0053]

The polyurethane composition of the present invention can be cured at room temperature and has sufficient strength.
A cured product having large elongation and excellent flexibility, and having a small Young's modulus and a small load due to deformation can be formed, and is particularly suitable for bonding plastics. Therefore,
The polyurethane composition of the present invention can be suitably used as an adhesive or a sealing material for large structures such as septic tanks, panels, water tanks, tanks, various types of housing equipment, vehicles, ships, and water leisure vehicles.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 C09D 175/06 C09K 3/10

Claims (1)

(57) [Claims] 1. Polyisocyanate prepolymer (A)
For bonding or sealing, comprising a first component mainly composed of a polyol and a second component mainly composed of a polyol compound (B)
A two-component reactive polyurethane composition for use in a fuel cell , wherein the first component is a polyisocyanate prepolymer (A)
Is a polyisocyanate compound (a) containing two or more isocyanate groups, and poly (3-methyl- 1,5 -pentanediol adipate) having hydroxyl groups at both ends.
Are those obtained by reaction of the second component of the polyol compound (B) is a hydroxyl group per
Derived from low molecular weight diols with a molecular weight of 150 or less
And the molecular weight per hydroxyl group is 1500 or more
High-molecular-weight polyhaving three or more hydroxyl groups in the molecule
A two-part reactive polyurethane composition for bonding or sealing , which has a hydroxyl group derived from an all .