JP2022086248A - Adhesive for nonwoven fabric - Google Patents

Abstract

To provide an adhesive that has high workability when applied to nonwoven fabric and is cured into a product having high followability and adhesion to the nonwoven fabric.SOLUTION: The present invention discloses an adhesive for nonwoven fabric. Before curing, the adhesive has a viscosity of 1200 mPa s or less as measured at 23°C. After curing, the cured product of it has a hardness of A50-A80 as measured at 23°C. The adhesive is preferably used for bonding nonwoven fabric.SELECTED DRAWING: None

Description

The present technology relates to adhesives for non-woven fabrics.

In recent years, non-woven fabrics are widely used in various applications such as civil engineering materials, building materials, agricultural materials, automobile materials, aircraft materials, electronic equipment materials, and electrical equipment materials.
For example, in order to cover a soil structure such as an embankment or an embankment or a building structure, a moisture-permeable and waterproof non-woven fabric is used as a civil engineering material or a building material. Patent Document 1 proposes to provide an excellent waterproof sheet having high strength capable of withstanding wind pressure and capable of maintaining good waterproof performance for a long period of time, and a sheet waterproofing method using the same.

Japanese Unexamined Patent Publication No. 2001-241118

The present inventors have studied an adhesive that has good workability before curing and good followability and adhesiveness of the cured product to the nonwoven fabric after curing.
That is, it is a main object of the present invention to provide an adhesive having excellent workability when applied to a nonwoven fabric and having excellent followability and adhesiveness to the cured product after curing.

As a result of diligent studies, the present inventors have found that a specific adhesive can form a cured product having excellent workability when applied to a nonwoven fabric and excellent followability and adhesiveness to the nonwoven fabric. rice field.

That is, in the present invention, when the viscosity of the adhesive before curing is 1200 mPa · s or less when measured at 23 ° C, and the hardness of the cured product after curing is measured at 23 ° C, A non-woven fabric adhesive of A50 to A80 can be provided.
The adhesive may contain a polyol and an isocyanate compound.
The polyol may be a polyester polyol.
The polyol may be a castor oil-based polyester polyol.

According to the present invention, it is possible to provide an adhesive which is excellent in workability when applied to a nonwoven fabric and has excellent followability and adhesiveness to a cured product after curing. The effect of the present invention is not necessarily limited to the effect described here, and may be any effect described in the present specification.

FIG. 1 shows an example of joining of sheets formed when they are bonded with the adhesive of the present invention. FIG. 1A shows joining by overlapping hands, and FIG. 1B shows joining by hands to one side. Is shown. FIG. 2 is a diagram showing a manufacturing example of a flat joint test piece 10 for a simple water stoppage test. FIG. 3 is a side view of a simple water stoppage test using a joint test piece 20 having a substantially quadrangular pyramid shape. FIG. 4 is an upper view of a simple water stoppage test using a joint test piece 20 having a substantially quadrangular pyramid shape. FIG. 5 is a perspective view from above of a simple water stop test using a folded joint test piece 20 having a substantially quadrangular pyramid shape. FIG. 6 is a photograph of an upward observation of a simple water stoppage test using a joint test piece 20 having a substantially quadrangular pyramid shape.

Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the embodiments described below show examples of typical embodiments of the present invention, and the present invention is not limited to these embodiments. Further, the upper limit value and the lower limit value of each numerical value range can be arbitrarily combined as desired.

1. 1. Description of Adhesive of the Present Invention

The adhesive of the present invention has a viscosity of the adhesive before curing of 1200 mPa · s or less when measured at 23 ° C., and the hardness of the cured product after curing is measured at 23 ° C. , A50 to A80. The adhesive of the present invention may be for a non-woven fabric or may be used for adhering a non-woven fabric.
Further, the adhesive of the present invention may contain a polyol and an isocyanate compound.
The adhesive of the present invention has excellent workability when applied to a non-woven fabric by coating or the like, and the cured product after curing has excellent followability and adhesiveness to a substrate.

2. 2. Adhesive properties

In a preferred embodiment of the present invention, the viscosity of the adhesive before curing of the present invention is preferably 1200 mPa · s or less, more preferably 1000 mPa · s or less, still more preferably 1000 mPa · s or less, as an upper limit value when measured at 23 ° C. It is 900 mPa · s or less, and the lower limit is not particularly limited, but is preferably 300 mPa · s or more, more preferably 400 mPa · s or more, still more preferably 500 mPa · s or more, still more preferably 600 mPa · s or more. Even more preferably, it is 700 mPa · s or more. The suitable numerical range is more preferably 300 to 1200 mPa · s, still more preferably 500 to 1000 mPa · s, still more preferably 600 to 900 mPa · s.
By making the adhesive before curing have a specific appropriate viscosity, the impregnation property of the adhesive when applied to a non-woven fabric can be made appropriate, and the adhesiveness of this cured product after curing can be improved. Further, the watertightness of the non-woven fabric joint portion after being applied to the non-woven fabric and cured can be improved. Further, by making the adhesive have a specific viscosity, it is possible to easily perform the coating work on the non-woven fabric, and further, it is possible to secure the working time when adhering the base material and shorten the curing time at the same time. Workability can be improved when the agent is applied to the non-woven fabric.

<Measuring method of adhesive viscosity before curing>
The viscosity of the adhesive before curing can be measured according to JIS K 7117-1, K 7117-2 and JIS K 1557-5. JIS K 1557-5 is a standard for a test method (method for determining viscosity, etc.) of a polyurethane raw material polyol, and this standard is a method using a Brookfield type rotational viscometer JIS K 7117-1, determined by a rotational viscometer. Method for measuring viscosity at shear rate JIS K 7117-2 is cited. Specifically, after the temperature of the adhesive is adjusted to 23 ° C., the measurement is immediately performed with a BM type viscometer. In the case of a two-component adhesive, the temperature of each of the liquids A and B is adjusted to 23 ° C., the two liquids are mixed, and the measurement is immediately performed with a BM type viscometer.
Measurement conditions: Viscometer B type series BM type viscometer 12 rotations No. 3 rotor Measurement time 1 minute, measurement temperature 23 ° C

In a preferred embodiment of the present invention, the hardness of the cured product after curing in the adhesive of the present invention is preferably A80 or less, more preferably A75 or less, still more preferably A75 or less, as an upper limit value when measured at 23 ° C. It is A70 or less, and the lower limit is preferably A50 or more, more preferably A55 or more, and further preferably A60 or more. The suitable numerical range is preferably A55 to A80, and more preferably A60 to A70.
By setting the hardness of the cured product after curing to a specific appropriate hardness, it is possible to improve the followability and adhesiveness of the cured product existing inside the non-woven fabric and on the adhesive surface, and to make the non-woven fabric The watertightness of the non-woven fabric joint portion after being applied and cured can also be improved.

<Measuring method of hardness of cured adhesive>
The hardness (shore hardness) of the cured product after curing of the adhesive can be measured according to JIS K 7215. Specifically, the adhesive was put into a mold (depth / thickness: 8 mm × diameter: 60 mm) and cured at 23 ° C. One day later, the cured product was taken out from the mold, and the removed cured product was shored. -Measure with an A hardness tester. The range of measurement of the hardness of the cured product by the Shore-A hardness tester is A10 to 90, and when it exceeds A90, the hardness is measured by the Shore-D hardness tester.
Measurement conditions: Shore-A hardness tester Instantaneous value, measurement temperature 23 ° C, shape of cured product: thickness 8 mm x diameter 60 mm.

In a preferred embodiment of the present invention, the tensile strength of the cured product of the present invention after curing is not particularly limited, but the lower limit is preferably 2.0 MPa or more, more preferably 3.0 MPa or more. It is more preferably 3.5 MPa or more, still more preferably 4.0 MPa or more, even more preferably 4.5 MPa or more, still more preferably 5.0 MPa or more, and the upper limit is preferably 15 MPa or less, more preferably 13 MPa or less. It is more preferably 10 MPa or less, still more preferably 8.0 MPa or less, more preferably 7.5 MPa or less, still more preferably 7.0 MPa or less, still more preferably 6.5 MPa or less, and even more preferably 6.0 MPa or less. The suitable numerical range is preferably 2.0 to 15 MPa, more preferably 4.0 to 7.5 MPa, and further preferably 5.0 to 6.5 MPa.
By making the cured product have a specific appropriate tensile strength after curing, it is possible to improve the followability and adhesiveness of the cured product existing inside the non-woven fabric and on the adhesive surface, and also to make the non-woven fabric watertight. Can be better.

<Measurement method of tensile strength under normal conditions of cured adhesive>
The tensile strength test of the cured product of the adhesive under normal conditions can be performed at 23 ° C. according to JIS K7113. As the test machine used, Autograph ASG-X (Shimadzu Corporation) can be used, and the test can be performed at a test speed of 200 mm / min and N = 2 to 5 (average value of these values).

In a preferred embodiment of the present invention, the gel time of the adhesive of the present invention is not particularly limited, but is preferably 30 to 120 minutes, more preferably 50 to 90 minutes, still more preferably 60 to 80 minutes. It is possible to secure the pot life, secure the work time when adhering the base material, and shorten the curing time, and improve the workability when applying the adhesive to the non-woven fabric. can.
This gel time can be determined by taking 100 g of the adhesive in a cylindrical cup (diameter 5 cm x height 9 cm), allowing it to stand at 23 ° C., and measuring the time until the fluidity disappears due to the influence of curing as the gel time. .. In the case of measuring the gel time of the two-component adhesive, it can be carried out according to <Measuring method of gel time> in the following example.

In the present invention, it is preferable to contain an adhesive component so as to have a specific viscosity and a specific hardness as described above, and a more suitable adhesive component can be obtained from the following "3. Adhesive composition". It can be adopted as appropriate.

3. 3. Adhesive Composition In a preferred embodiment of the present invention, the adhesive comprises a component (A) polyol and a component (B) isocyanate compound. The adhesive of the present invention is preferably a urethane-based adhesive, and the urethane-based adhesive is cured by, for example, reacting a hydroxy group (OH group) of a polyol with an isocyanate group (NCO group) of an isocyanate compound. It is possible to form a resin of a urethane polymer which is a product.
Thereby, it is possible to provide an adhesive which is excellent in workability when applied to a nonwoven fabric and also has excellent followability and adhesiveness of a cured product after curing to the nonwoven fabric. An example of the composition of the adhesive of the present invention will be described below.

<Component (A) Polyol>
The polyol of the component (A) used in the present invention is not particularly limited, and examples thereof include, but are not limited to, polyester polyols and polyether polyols. One kind or two or more kinds selected from these may be used. As these polyols, commercially available products may be used, or those obtained by a known production method may be used.
Further, as the polyol, for example, a polyol derived from a vegetable oil or fat may be mentioned, and the polyol may be either a natural system or a synthetic system, and as a natural system, a vegetable oil or fat such as castor oil may be mentioned, and as a synthetic system, a vegetable oil or fat may be used. Examples thereof include those obtained by condensing carboxylic acid (preferably fatty acid) and the like contained in the above with polyhydric alcohol and the like, but the present invention is not limited thereto. Of these, a castor oil-derived polyol containing castor oil and the like is preferable.

The viscosity of the polyol is not particularly limited, but when measured at 23 ° C., the upper limit is preferably 1200 mPa · s or less, more preferably 1000 mPa · s or less, still more preferably 900 mPa · s or less, and the lower limit. The value is preferably 200 mPa · s or more, more preferably 500 mPa · s or more, and further preferably 600 mPa · s or more.

<Measuring method of viscosity of polyols, etc.>
The viscosity in the present specification can be measured in accordance with JIS K 7117-1, K 7117-2 and JIS K 1557-5 in the same manner as in the above <Method for measuring the viscosity of the adhesive before curing>. Specifically, after the temperature of the sample is adjusted to 23 ° C., the sample is measured at 23 ° C. with a BM type viscometer.
Measurement conditions: Viscometer B type series BM type viscometer 12 rotations No. 3 rotor Measurement time 1 minute, measurement temperature 23 ° C

The hydroxyl value of the polyol is not particularly limited, but the upper limit is preferably 160 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 145 mgKOH / g or less, still more preferably 140 mgKOH / g or less, and the lower limit. The value is preferably 100 mgKOH / g or more, more preferably 110 mgKOH / g or more, and further preferably 120 mgKOH / g or more.
The hydroxyl value (mgKOH / g) in the present specification can be measured according to JIS K 0070 and JIS K 1557-5.

The number of functional groups (terminal hydroxyl groups) of the polyol is not particularly limited, but the upper limit is preferably 4 or less, more preferably 3 or less, still more preferably 2.5 or less, and the lower limit is preferably 1 or more. It is preferably 1.5 or more, and more preferably 2 or more.
The number of functional groups (terminal hydroxyl group) in the present specification can be calculated by the formula 1 from the hydroxyl group value and the number average molecular weight by GPC. Number of functional groups (terminal hydroxyl group) = hydroxyl group value (mgKOH / g) × number average molecular weight / (1000 × 56.1) ... (Equation 1).

The mass content of the polyol in the adhesive is not particularly limited, but is preferably 60% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, as a lower limit value with respect to the mass of the adhesive. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less.
The volume content of the polyol in the adhesive is not particularly limited, but is preferably 65% by volume or more, more preferably 68% by volume or more, still more preferably 70% by volume or more as the lower limit value with respect to the volume of the adhesive. It is even more preferably 73% by volume or more, and the upper limit value is preferably 90% by volume or less, more preferably 85% by volume or less, still more preferably 80% by volume or less.

<Component (A) Polyester Polyol>
The polyester polyol is not particularly limited, but may be a natural system or a synthetic system. As the polyester polyol, a commercially available product may be used, or a polyester polyol obtained by a known production method may be used.

The natural polyester polyol is not particularly limited, and examples thereof include vegetable oil and fat polyols, and the vegetable oil and fat polyol is not particularly limited, and examples thereof include sunflower oil, rapeseed oil, flaxseed oil, cottonseed oil, millet oil, and coconut oil. , Vegetable oils and fats such as poppy oil, corn oil, castor oil and peanut oil, and one or more selected from these can be used. These vegetable oils and fats may contain, for example, polyester polyols of polyglycerin fatty acid esters.

Examples of the synthetic polyester polyol include, but are not limited to, those obtained by condensation of a carboxylic acid (preferably a fatty acid) contained in these vegetable oils and fats with a polyhydric alcohol. For example, hydrogenated vegetable fats and oils, reaction products of hydrogenated vegetable fats and oils and polyhydric alcohols, esterification reactants of fatty acids derived from vegetable fats and oils or hydrogenated vegetable fats and oils and polyhydric alcohols, and alkylene oxides thereof. Examples thereof include polyols obtained by hydrogenation of the above, and one or more selected from these can be used.

The viscosity of the polyester polyol is not particularly limited, but is preferably 1200 mPa · s or less, more preferably 1000 mPa · s or less, still more preferably 900 mPa · s or less, and further preferably 900 mPa · s or less, as an upper limit value when measured at 23 ° C. The lower limit is preferably 200 mPa · s or more, more preferably 500 mPa · s or more, and further preferably 600 mPa · s or more.

The hydroxyl value of the polyester polyol is not particularly limited, but the upper limit is preferably 160 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 145 mgKOH / g or less, still more preferably 140 mgKOH / g or less. The lower limit is preferably 100 mgKOH / g or more, more preferably 110 mgKOH / g or more, and further preferably 120 mgKOH / g or more.

The number of functional groups (terminal hydroxyl groups) of the polyester polyol is not particularly limited, but the upper limit is preferably 4 or less, more preferably 3 or less, still more preferably 2.5 or less, and the lower limit is preferably 1 or more. It is more preferably 1.5 or more, still more preferably 2 or more.

The mass content of the polyester polyol in the adhesive is not particularly limited, but is preferably 60% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass, as a lower limit value with respect to the mass of the adhesive. As described above, the upper limit value is preferably 85% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and the more preferable numerical range is preferably 60 to 80% by mass, more preferably. Is 65 to 75% by mass.

The volume content of the polyester polyol in the adhesive is not particularly limited, but is preferably 65% by volume or more, more preferably 68% by volume or more, still more preferably 70% by volume, as a lower limit value with respect to the volume of the adhesive. As described above, it is more preferably 73% by volume or more, and the upper limit value is preferably 90% by volume or less, more preferably 85% by volume or less, still more preferably 80% by volume or less, and it is preferable as a more preferable numerical range. Is 68 to 85% by volume, more preferably 70 to 80% by volume.

Of the polyester polyols, castor oil-based polyester polyols are preferable. As the castor oil-based polyester polyol, a commercially available product may be used, or a product obtained by a known production method may be used.
The castor oil-based polyester polyol is not particularly limited, but is, for example, a natural polyester polyol of castor oil, a castor oil fatty acid, a hydrogenated castor oil, a hydrogenated castor oil fatty acid, or a synthetic system produced by using these. Examples include polyester polyols and mixtures thereof, and one or more selected from these can be used.

As the castor oil-based polyester polyol, a commercially available product may be used, for example, castor oil (hydroxyl value 160 mgKOH / g, functional group number 2.7), H-81 (hydroxyl value 330 to 350 mgKOH / g, functional group number 3). 1000-1400 mPa.s (25 ° C), manufactured by Ito Essential Oil Co., Ltd.), H-1824 (hydroxyl value 55-77 mgKOH / g, number of functional groups 2.3, 700-1600 mPa.s (25 ° C), manufactured by Ito Essential Oil Co., Ltd.), HF-2009 (hydroxyl value 44 mgKOH / g, number of functional groups 2.2, 1500 mPa.s (25 ° C), manufactured by Ito Essential Oil Co., Ltd.), HF-1300 (hydroxyl value 75-105 mgKOH / g, number of functional groups 2, 170-250 mPa. s (25 ° C.), manufactured by Ito Essential Oil Co., Ltd.), etc., but is not limited thereto. One kind or two or more kinds selected from these can be used.

The castor oil-based polyester polyol is preferably a mixture of two or more kinds having different properties. The mixture of castor oil-based polyester polyol is preferably a combination of two or more so as to be within the range of the specific viscosity described in the above-mentioned "Viscosity of polyol", and is a suitable upper limit value when measured at 23 ° C. It is preferably 1200 mPa · s or less. Further, the mixture may contain one or more selected from polyester polyols other than castor oil polyester polyols, polyether polyols such as polypropylene glycol, and the like, as long as the effects of the present invention are not impaired. ..
Further, the mixture of castor oil-based polyester polyols may be a combination of two or more kinds of polyester polyols having different hydroxyl values. At this time, it may be a mixture of a castor oil-based polyester polyol having a high hydroxyl value and a castor oil-based polyester polyol having a low hydroxyl value. It is intended to show a relative relationship that is lower than the hydroxyl value of. This "high" is also intended to indicate the relative relationship that the hydroxyl value of a certain polyol is higher than the hydroxyl value of the certain polyol. The "low" preferably has a hydroxyl value of 10 to 150 mgKOH / g, more preferably 50 to 100 mgKOH / g, and may be a combination of two or more polyester polyols having different hydroxyl values. .. The "high" preferably has a hydroxyl value of 170 to 380 mgKOH / g, more preferably a hydroxyl value of 250 to 350 mgKOH / g, and may be a combination of two or more polyester polyols having different hydroxyl values. ..

The hydroxyl value of the mixture of castor oil-based polyester polyol is preferably in the range of the specific hydroxyl value described in the above-mentioned "hydroxyl value of the polyol", and it is preferable to combine two or more kinds, which is preferable as a suitable upper limit value. Is 160 mgKOH / g or less. Further, the number of functional groups of the mixture is preferably 2 to 3.

As a mixture of castor oil-based polyester polyol, for example, a mixture of castor oil and castor oil-based polyester polyol having a hydroxyl value of 330 to 350 mgKOH / g, and a castor oil-based polyester polyol having a hydroxyl value of 330 to 350 mgKOH / g and a hydroxyl value of 55 to 77 mgKOH. A mixture of / g of castor oil-based polyester polyol is preferable, and more preferably, a mixture of castor oil-based polyester polyol having a hydroxyl value of 330 to 350 mgKOH / g and castor oil-based polyester polyol having a hydroxyl value of 55 to 77 mgKOH / g. The castor oil-based polyester polyol used in the mixture preferably has 2 to 3 functional groups. The mixture may contain a polyol other than castor oil-based polyester polyol as long as the effect of the present invention is not impaired.

The mass content ratio of the castor oil-based polyester polyol having a low hydroxyl value and the castor oil-based polyester polyol having a high hydroxyl value in the mixture of the castor oil-based polyester polyol is not particularly limited, but each of them is preferably 30 in the adhesive. It is -80: 70-20, more preferably 65-75: 35-25.
The mass content of the low hydroxyl value castor oil-based polyester polyol in the mixture of castor oil-based polyester polyol is not particularly limited with respect to 100 parts by mass of the mixture of castor oil-based polyester polyol, but is preferably 10 to 80 parts by mass. , More preferably 20 to 70 parts by mass, still more preferably 20 to 50 parts by mass, and even more preferably 20 to 30 parts by mass.
The mass content of the high hydroxyl value castor oil-based polyester polyol in the mixture of castor oil-based polyester polyol is not particularly limited with respect to 100 parts by mass of the mixture of castor oil-based polyester polyol, but is preferably 20 to 90 parts by mass. , More preferably 30 to 80 parts by mass, still more preferably 50 to 80 parts by mass, and even more preferably 70 to 80 parts by mass.

The viscosity of the castor oil-based polyester polyol is not particularly limited, but when measured at 23 ° C., the upper limit is preferably 1200 mPa · s or less, more preferably 1000 mPa · s or less, and further preferably 900 mPa · s or less. Further, the lower limit value is preferably 200 mPa · s or more, more preferably 500 mPa · s or more, and further preferably 600 mPa · s or more.

The hydroxyl value of the castor oil-based polyester polyol is not particularly limited, but as an upper limit value, it is preferably 160 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 145 mgKOH / g or less, still more preferably 140 mgKOH / g or less. The lower limit is preferably 100 mgKOH / g or more, more preferably 110 mgKOH / g or more, and further preferably 120 mgKOH / g or more.

The number of functional groups (terminal hydroxyl groups) of the castor oil-based polyester polyol is not particularly limited, but is preferably 4 or less, more preferably 3 or less, still more preferably 2.5 or less as the upper limit value, and preferably 2.5 or less as the lower limit value. It is 1 or more, more preferably 1.5 or more, still more preferably 2 or more.

The mass content of the castor oil-based polyester polyol in the adhesive is not particularly limited, but is preferably 60% by mass or more, more preferably 65% by mass or more, still more preferably 65% by mass or more, as a lower limit value with respect to the mass of the adhesive. It is 70% by mass or more, and the upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and more preferably 60 to 80% by mass as a numerical range. , More preferably 65 to 75% by mass.

The volume content of the castor oil-based polyester polyol in the adhesive is not particularly limited, but is preferably 65% by volume or more, more preferably 68% by volume or more, still more preferably 68% by volume or more, as a lower limit value with respect to the volume of the adhesive. It is 70% by volume or more, more preferably 73% by volume or more, and the upper limit value is preferably 90% by volume or less, more preferably 85% by volume or less, still more preferably 80% by volume or less, and a more preferable numerical range. It is preferably 68 to 85% by volume, more preferably 70 to 80% by volume.

<Component (A) Polyether Polyol>
The polyether polyol is not particularly limited, and for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like can be added to a single material or a mixture of two or more selected from monool, diol, polyol, and other active hydrogen-containing compounds. Examples thereof include those obtained by addition polymerization by a known method using one kind or two or more kinds selected from the above alkylene oxides. One kind or two or more kinds selected from these can be used.
The monool of the polyether polyol is not particularly limited, and examples thereof include methanol, ethanol, propanol, butanol, octanol, and lauryl alcohol.
The diol of the polyether polyol is not particularly limited, and is, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6. -Hexylene diol and the like can be mentioned.
The polyol of the polyether polyol is not particularly limited, and examples thereof include glycerin, trimethylolpropane, and pentaerythritol.
Examples of the active hydrogen-containing compound other than these include, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, diglycerin, sorbitol, sucrose and the like.
As the polyether polyol, a commercially available product may be used, or a product obtained by a known production method may be used. Examples of commercially available products include, but are not limited to, polypropylene glycol such as P-2000 (hydroxyl value 56 mgKOH / g, functional group number 2, manufactured by ADEKA CORPORATION). One kind or two or more kinds selected from these can be used.

The mass content of the polyether polyol in the adhesive is not particularly limited, but is preferably 60 to 80% by mass, more preferably 65 to 75% by mass, based on the mass of the adhesive.
The volume content of the polyether polyol in the adhesive is not particularly limited, but is preferably 68 to 85% by volume, more preferably 70 to 80% by volume, based on the volume of the adhesive.

<Component (B) Isocyanate compound>
The component (B) isocyanate compound used in the present invention is not particularly limited, and examples thereof include aromatic isocyanates, aliphatic isocyanates, and alicyclic isocyanates, and one or two selected from these. The above can be used. As the isocyanate compound, a commercially available product may be used, or a product obtained by a known production method may be used.
As the isocyanate compound, a polyisocyanate compound having two or more isocyanate groups in the molecule is preferable. As the polyisocyanate compound, an organic polyisocyanate, a modified polyisocyanate, an isocyanate-based prepolymer, or a mixture thereof may be used.

The aromatic polyisocyanate compound is not particularly limited, and is, for example, MDI (for example, methylenebis (4,1-phenylene) = diisocyanate (also known as 4,4'-diphenylmethane diisocyanate (4,4'-MDI)), 2,4. Diphenylmethane diisocyanate such as ′ -diphenylmethane diisocyanate (2,4'-MDI) and mixtures thereof, polymethylene = polyphenylene polyisocyanate (PMDI)), TDI (for example, 2,4-toluene diisocyanate (2,4-TDI), 2 , 6-Toluene diisocyanate (2,6-TDI) and toluene diisocyanates such as mixtures thereof), 1,4-phenylene diisocyanate, diphenyl diisocyanate, trizine diisocyanate (TODI), 1,5-naphthalene diisocyanate (1,5-NDI) ), Diphenyl ether diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate (XDI), phenylene diisocyanate (PDI) and the like, and one or more selected from these can be used.
Among the aromatic polyisocyanate compounds, MDI is preferable, and among the MDIs, polymethylene = polyphenylene polyisocyanate (PMDI) is preferable.

In addition, "MDI" can be generally used as a general term for diphenylmethane diisocyanate and polymethylene = polyphenylene polyisocyanate. The term "diphenylmethane diisocyanate" refers to 2,2'-diphenylmethane diisocyanate (2,2'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) and 4,4'-diphenylmethane diisocyanate (4). , 4'-MDI) isomers may be included. These isomers collectively mean "monomeric MDI" or "MMDI". Further, the term "polymethylene = polyphenylene sulfide (PMDI)" means "polymer MDI" or "PMDI". These may include higher homologues of the monomeric MDI and optionally the monomeric MDI.

Examples of the aliphatic polyisocyanate compound include 1,6-hexaethylene diisocyanate (HDI), L-leucine diisocyanate (LDI), 1,6,11-undecane diisocyanate and the like, and one or more selected from these. Can be used.

Examples of the alicyclic polyisocyanate compound include 4-4'-methylenebiscyclohexyldiisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), cyclohexanediisocyanate (hydrogenated XDI) and the like, and one selected from these. Alternatively, two or more types can be used.

Of the polyisocyanate compounds, a bifunctional aromatic polyisocyanate compound is preferable. Further, among the polyisocyanate compounds, PMDI is preferable from the viewpoint of followability to non-woven fabric, adhesiveness, workability and environmental standard.

The NCO amount (%) of the isocyanate compound is not particularly limited, but is, for example, 20 to 30%, preferably 25 to 30%, more preferably 26 to 29%, still more preferably 27 to 28%. The amount of NCO in the present specification can be measured according to "JIS K 1603-2007 plastic-polyurethane raw material aromatic isocyanate test method".
The viscosity of the isocyanate compound is not particularly limited, but is preferably 10 to 500 mPa · s, more preferably 50 to 300 mPa · s, and even more preferably 100 to 200 mPa · s when measured at 23 ° C. The viscosity of the isocyanate compound can be measured according to the above <method for measuring the viscosity of a polyol or the like>.

The mass content of the isocyanate compound in the adhesive is not particularly limited, but is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass, as a lower limit value with respect to the mass of the adhesive. As described above, the upper limit value is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.
The volume content of the isocyanate compound in the adhesive is not particularly limited, but is preferably 10% by volume or more, more preferably 15% by volume or more, still more preferably 20% by volume, as a lower limit value with respect to the volume of the adhesive. As described above, the upper limit value is preferably 35% by volume or less, more preferably 32% by volume or less, still more preferably 30% by volume or less, still more preferably 25% by volume or less.

The NCO amount (%) of the bifunctional aromatic polyisocyanate compound is not particularly limited, but is, for example, 20 to 30%, preferably 25 to 30%, more preferably 26 to 29%, still more preferably 27 to 28%. ..
The viscosity of the bifunctional aromatic polyisocyanate compound is not particularly limited, but is preferably 10 to 500 mPa · s, more preferably 50 to 300 mPa · s, and even more preferably 100 to 200 mPa · s.

The mass content of the bifunctional aromatic polyisocyanate compound in the adhesive is not particularly limited, but is preferably 15% by mass or more, more preferably 20% by mass or more, and further, as a lower limit value with respect to the mass of the adhesive. It is preferably 25% by mass or more, the upper limit value is preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, and the more preferable numerical range is preferably 20 to 40. It is by mass, more preferably 25 to 35% by mass.
The volume content of the bifunctional aromatic polyisocyanate compound in the adhesive is not particularly limited, but is preferably 10% by volume or more, more preferably 15% by volume or more, and further, as a lower limit value with respect to the volume of the adhesive. It is preferably 20% by volume or more, and the upper limit value is preferably 35% by volume or less, more preferably 32% by volume or less, still more preferably 30% by volume or less, still more preferably 25% by volume or less, and more preferably. The numerical range is preferably 15 to 32% by volume, more preferably 20 to 30% by volume.

<Mass content ratio and volume content ratio of component (A) and component (B)>
The mass content ratio of the component (A) polyol and the component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) in the adhesive is not particularly limited, but is 100 parts by mass of the component (A) polyol. On the other hand, the component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, and further preferably 30 to 40 parts by mass. ..
The mass content ratio of the component (A) polyester polyol in the adhesive and the component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) is not particularly limited, but the component (A) polyester polyol 100 mass. The component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, and further preferably 30 to 40 parts by mass with respect to parts. Is.
The mass content ratio of the component (A) castor oil-based polyester polyol and the component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) in the adhesive is not particularly limited, but the component (A) isocyanate. The component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, and further preferably 20 to 50 parts by mass with respect to 100 parts by mass of the oil-based polyester polyol. Is 30 to 40 parts by mass.

The volume content of the component (A) polyol and the component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) in the adhesive is not particularly limited, but the volume of the component (A) polyol is 100. The component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) is preferably 10 to 50 parts by volume, more preferably 15 to 40 parts by volume, and further preferably 25 to 35 parts by volume. Is.
The volume content of the component (A) polyester polyol and the component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) in the adhesive is not particularly limited, but the component (A) polyester polyol is not particularly limited. The component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) is preferably 10 to 50 parts by volume, more preferably 15 to 40 parts by volume, and further preferably 25 to 35 parts by volume with respect to 100 parts by volume. It is a volume part.
The volume content of the component (A) castor oil polyester polyol and the component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) in the adhesive is not particularly limited, but the component (A). The component (B) isocyanate compound (preferably a bifunctional aromatic polyisocyanate compound) is preferably 10 to 50 parts by volume, more preferably 15 to 40 parts by volume, based on 100 parts by volume of the castor oil-based polyester polyol. More preferably, it is 25 to 35 parts by volume.

<Arbitrary ingredient>
The adhesive of the present invention may appropriately contain various additives and the like other than the above-mentioned components as optional components as long as the effects of the present invention are not impaired. Examples of the optional component include a solvent, a curable component, a curing accelerator, a photocuring agent, a filler, a plasticizer, an antioxidant, an antioxidant, a pigment, a dye, an ultraviolet absorber, a flame retardant, and a surfactant. Dispersants, dehydrators, adhesives, antistatic agents and the like can be mentioned, and one or more selected from these can be used.

The method for producing an adhesive of the present invention is not particularly limited, and can be prepared, for example, by mixing one or more adhesive components contained in the adhesive simultaneously or separately.

Further, in the present invention, in the case of a two-component adhesive composed of a component (A) as a main agent and a component (B) as a curing agent, the component (A) and the component (B) are placed in separate containers. It may be filled and stored, and the inside of either or both containers may be replaced with an inert gas such as nitrogen gas. The mass usage ratio and volume usage ratio of the component (A) and the component (B) are the mass content ratio and the volume content ratio described in the above <mass content ratio and volume content ratio of the component (A) and the component (B)>. The volume content ratio can be appropriately adopted. It is also possible to prepare a two-component adhesive by sufficiently mixing the main agent and the curing agent at the time of use. For example, using an adhesive tool such as a cartridge gun, at the tip of this cartridge, the component (A) and the component ( The two components of B) may be applied to the substrate while being mixed.

In the present invention, as described above, it is preferable that the adhesive containing the polyol and the isocyanate compound has specific properties, and the more suitable properties of the adhesive are appropriately determined from the above "2. Adhesive properties". Can be adopted.

The form of use of the adhesive of the present invention is not particularly limited, but may be, for example, hot melt type, solvent type, or water type, and one-component curing type, two-component curing type, room temperature curing type, thermosetting type, etc. And UV curable type and the like. The adhesive of the present invention is preferably used in a non-solvent system. Further, as the usage form of the adhesive of the present invention, a two-component curing type and / or a room temperature curing type is preferable because the work when the adhesive is applied to the substrate can be easily performed.

The adhesive or adhesive component of the present invention is preferably used for adhering a non-woven fabric that can be used for applications such as civil engineering, construction, agriculture, automobiles, aircraft, electronic equipment, and electrical equipment. Specific examples thereof include civil engineering materials, building materials, agricultural materials, automobile materials, aircraft materials, electronic equipment materials, electrical equipment materials, and the like, and one or two selected from these. More than seeds are more preferred.
Of these, the adhesive or adhesive component of the present invention is preferably used for adhering a non-woven fabric that can be used for civil engineering materials, building materials, or agricultural materials, and is used for soil structures such as embankments and embankments or building structures. It is preferable to use it for adhering a non-woven fabric that can be used for coating, and since the cured product after curing has excellent followability and adhesiveness, and also has watertightness and water resistance, it is moisture permeable to be laid on embankments and the like. It is more preferable to use it for adhering a waterproof non-woven fabric.

INDUSTRIAL APPLICABILITY The present invention may use an adhesive component or a urethane-based adhesive component in which the adhesive has a specific viscosity and the cured product has a specific hardness, in order to produce an adhesive. .. The adhesive may be a one-component type or a two-component type, or may be an adhesive kit composed of a container containing a main agent and a container containing a curing agent.
The present invention can also provide an adhesive method for adhering a base material using an adhesive or an adhesive component to the base material.

The adhesive of the present invention can form a cured product having excellent followability and adhesiveness to a substrate when the hardness of the cured product is within a specific range after curing.
Further, since the adhesive of the present invention has an appropriate viscosity before curing, it can be cured while being well impregnated in the nonwoven fabric while being present on the adhesive surface of the nonwoven fabric. Therefore, after curing, the cured product of the adhesive is well present inside the nonwoven fabric and also well on the adhesive surface, so that the cured product has excellent adhesiveness to the nonwoven fabric. The cured product has excellent water resistance and also has excellent followability and adhesiveness to the non-woven fabric, and therefore has excellent watertightness.
Further, since the adhesive of the present invention does not cure for a predetermined time to secure an appropriate pot life and has an appropriate curing time so that the curing time does not become long, the adhesive is applied to the non-woven fabric. It is possible to improve the work efficiency when giving. Further, the adhesive of the present invention has an appropriate viscosity, so that the coating work on the non-woven fabric can be easily performed. Further, with the adhesive of the present invention, it is not necessary to perform the heat-sealing bonding work, and it is possible to secure the pot life by curing at room temperature and perform the bonding work, so that the bonding work of the non-woven fabric is easy. Can be easily done. As described above, the adhesive of the present invention is excellent in workability when the adhesive is applied to the non-woven fabric.

As described above, the adhesive of the present invention can form a cured product having excellent workability when applied to a nonwoven fabric by coating or the like, and also having excellent followability and adhesiveness to the nonwoven fabric. Further, the cured product obtained by applying the adhesive of the present invention to a non-woven fabric and curing it has excellent watertightness and water resistance.

4. How to use the adhesive of the present invention

The method for applying the adhesive of the present invention to the substrate is not particularly limited, and a known method can be used. For example, in the method of using the adhesive of the present invention, an adhesive is applied to a base material by coating or the like, the base materials are brought into contact with each other on an adhesive surface, and the adhesive is cured to bond a plurality of base materials. Can be made to.

The base material is not particularly limited, and examples thereof include a base cloth such as a woven fabric or a non-woven fabric, a metal material, a synthetic resin material, and the like, and one or more selected from these can be used. It is preferable to use an adhesive at least to bond the base cloths, and more specifically, to bond the base cloths to each other, or to bond the base cloth and a base material other than the base cloth (for example, a metal material or a synthetic resin material). Is preferable.

Of the base materials, the adhesive of the present invention can sufficiently impregnate the inside of the nonwoven fabric while remaining partially on the surface of the nonwoven fabric when applied, so that the cured product can be formed inside and on the surface after curing, which is good. A non-woven fabric is more preferable because it can exhibit a good adhesiveness, and the adhesive of the present invention is used for adhering a non-woven fabric, more specifically, between non-woven fabrics, or between a non-woven fabric and a metal material (for example, a non-woven fabric fixing pin). It is more preferable to use it.

The non-woven fabric is not particularly limited, but is preferably a long-fiber non-woven fabric. Further, the nonwoven fabric may have a single layer or a laminated structure.
The thickness of the non-woven fabric is not particularly limited, but is preferably a thickness that can be used for civil engineering materials, building materials, or agricultural materials, for example, 0.1 to 20 mm, more preferably 0.5 to 10 mm, still more preferably 1 to 6 mm or. It is 1 to 5 mm.

The non-woven fabric is not particularly limited, and examples thereof include natural fibers such as cellulose and synthetic fibers such as polyester. As the material of the synthetic fiber, for example, a polyolefin-based material such as polyethylene and polypropylene, a polyester-based material such as polyethylene terephthalate, polybutylene terephthalate and polymethylene terephthalate, and a thermoplastic resin such as a polyamide-based material such as nylon 6, nylon 66 and nylon 46 are used. It is possible.
Of these, polyester-based non-woven fabrics (for example, polyethylene terephthalate non-woven fabrics) and polyolefin-based (polyethylene and the like) non-woven fabrics are preferable.
Further, as the non-woven fabric, a breathable waterproof non-woven fabric which is a non-woven fabric having a function of moisture-permeable waterproof is more preferable, and examples of the breathable waterproof non-woven fabric include a moisture-permeable waterproof sheet conforming to JIS A 6111. ..

Examples of the method for forming the fleece in the non-woven fabric include a dry method, a wet method, a spunbond method, a meltblown method, a thermal bond method, a chemical bond method (impregnation method, a spray method, etc.), and any method is used. You may. Examples of the method for bonding the fibers of the non-woven fabric include a needle punching method, a water flow entanglement method, an adhesive method, and the like, and any method may be used. It is possible to provide a dry non-woven fabric or the like manufactured by such a manufacturing method such as a dry method.

The adhesive of the present invention can be used outdoors or indoors, and is preferably a room temperature curing type. For example, it can be cured by moisture such as humidity, and can be cured without irradiation with light such as ultraviolet rays. It is possible. More specifically, the adhesive of the present invention can cure the adhesive of the present invention under the conditions of, for example, 5 to 90 ° C. and a relative humidity (RH) of 5 to 95%.
The curing temperature of the adhesive of the present invention is, for example, −20 to + 90 ° C., preferably 5 to 90 ° C., more preferably 4 to 50 ° C., still more preferably 10 to 40 ° C.
The curing time of the adhesive of the present invention is not particularly limited, but is preferably about 0.1 to 3 hours, more preferably about 0.5 to 2 hours from the viewpoint of improving workability and securing working time. , More preferably 1 to 2 hours.
The amount of the adhesive of the present invention applied is not particularly limited, but is preferably 250 to 550 g, more preferably 300 to 500 g, still more preferably 350 to 450 g with respect to the adhesive area of 1000 cm ² .

Hereinafter, the present technique will be described in more detail based on test examples and the like. It should be noted that the test examples and the like described below show examples of typical examples and the like of the present technique, and the scope of the present technique is not narrowly interpreted by this.

Weigh the volume (mL) of liquid A and liquid B and the mass (g) at this time so that the composition is as shown in the table below, and mix liquid A and liquid B together. A liquid adhesive was obtained. When there were a plurality of components of solution A, the mass (g) of each component was weighed, these components (polyols 1 and 2 derived from castor oil) were mixed, and this mixed solution was used as solution A. .. A two-component adhesive was applied to the surface of the adhesive surface of the test piece, another test piece was adhered to the applied adhesive surface to cure the two-component adhesive, and the two-component adhesive was cured for a predetermined period after curing. The work was carried out in the laboratory at room temperature (23 ° C.). As a result, it was possible to obtain a bonded test piece in which a plurality of test pieces were bonded with a cured product obtained by curing the adhesive.

<Each material>
The compound names of the test pieces and materials shown in this test example are as follows. Commercially available products were used as these test pieces and materials.
[Test piece, joint]
Moisture-permeable waterproof non-woven fabric (compatible with JIS A 6111) (thickness 6 mm): Includes protective polyester non-woven fabric and waterproof polyethylene porous film as materials. The moisture-permeable and waterproof non-woven fabric is manufactured by a spunbond manufacturing method.
[Liquid A]
Castor oil-based polyester polyol (castor oil-derived polyol)
(1) Castor oil; hydroxyl value 160 mgKOH / g, number of functional groups 2.7, viscosity 670 mPa · s (measurement temperature 23 ° C)
(2) Castor oil-based polyester polyol U1; hydroxyl value 55 to 77 mgKOH / g, number of functional groups 2.3, viscosity 700 to 1600 mPa · s (measurement temperature 23 ° C.))
(3) Castor oil-based polyester polyol U8; hydroxyl value 330 to 350 mgKOH / g, number of functional groups 3, viscosity 1000 to 1400 mPa · s (measurement temperature 23 ° C)
[Liquid B]
Bifunctional aromatic isocyanate compound (1) Cosmonate PM-35 (manufactured by Mitsui Chemicals Polyurethane Co., Ltd.): Polyisocyanate compound (modified isocyanate); Polymethylenepolyphenyl = Polyisocyanate (PMDI) (Methylenebis (4,1-phenylene) = Diisocyanate), NCO%: 27.0 to 28.0%, viscosity 100 to 200 mPa · s (23 ° C.)

Various measurements and tests were performed according to the following methods. These results are shown in Table 1.

<Calculation method of hydroxyl value>
When the liquid A is a single polyol, this hydroxyl value can be measured according to JIS K 0070 and JIS K 1557-1. When the A liquid contains a plurality of polyols, the hydroxyl value includes (mass part of A1 liquid x hydroxyl value + mass part of A2 liquid x hydroxyl value + ... mass part of Ax liquid x hydroxyl value) / mass of A1 liquid. It can be calculated by the part + the mass part of the A2 liquid + ... the mass part of the Ax liquid (total amount of the mass part)). For example, in the case of Test Example 1, (U1: 75 × OHV 66 + U8: 25 × OHV 340) ÷ 100 (total amount) = OHV 134.5 can be obtained.

<Measuring method of viscosity of each material before curing>
The viscosity of each of the polyol and the polyisocyanate compound can be measured according to the above <method for measuring the viscosity of the polyol and the like>. Measurement conditions: JIS K 7117-1, K 7117-2 and JIS K 1557-5, Viscometer B type series BM type viscometer 12 rotations No. 3 rotor Measurement time 1 minute, measurement temperature 23 ° C.
The viscosity of the mixture after mixing the polyol and the polyisocyanate compound can be measured according to the above <method for measuring the viscosity of the adhesive before curing>. Specifically, after adjusting the temperature of each of the liquids A and B to 23 ° C., stirring the two liquids, the mixed liquid is immediately mixed with a BM viscometer at 23 ° C. and the measurement time is 1 minute. , Can be measured. Measurement conditions: JIS K 7117-1, K 7117-2 and JIS K 1557-5, Viscometer B type series BM type viscometer 12 rotations No. 3 rotor Measurement time 1 minute, measurement temperature 23 ° C.

<Measuring method of hardness of cured product after curing of adhesive>
The hardness (shore hardness) of the adhesive after curing can be determined according to the above <method for measuring the hardness of the cured product of the adhesive>. Measurement conditions: JIS K 7215, Shore-A hardness tester Instantaneous value, measurement temperature 23 ° C, shape of cured product: thickness 8 mm x diameter 60 mm.

<Adhesive strength test of joining test piece>
Method for manufacturing the lap joint test piece: Using two strip-shaped test pieces (width 2.5 cm x length 15 cm x thickness 6 mm) 1, 1, the adhesive surface at the end of one strip-shaped test piece 1. 4 (width 2.5 cm × length 5 cm) was coated with an adhesive of 5 g / (2.5 cm × 5 cm) at room temperature of 23 ° C. The adhesive surface 4 (width 2.5 cm × length 5 cm) of the other strip-shaped test piece 1 was superposed and adhered to the adhesive surface 4 coated with this adhesive, and cured at room temperature 23 ° C. After curing, it was cured at 23 ° C. for one week to obtain a "superposition joint test piece" 10a (width 2.5 cm x length 25 cm, joint thickness 12 mm) (see FIG. 1A).
According to the method for producing the laminated bonding test piece, the adhesives of Test Examples 1 to 5 were applied to obtain the lapped bonding test pieces of Test Examples 1 to 5, and these were used for the adhesive strength test of the bonding test pieces.

The adhesive strength test was carried out at 23 ° C. according to JIS 7214 using the superposition bonding test piece manufactured in the above <Adhesive strength test of bonding test piece>. An autograph AGS-X (Shimadzu Corporation) was used as the test machine used, and the test speed was 100 mm / min and N = 2 (the average value of these values).

The elongation test and the tensile strength test can be performed at 23 ° C. according to JIS K7113 using a 5B type test piece prepared according to JIS K 7161-2. The 5B type test piece is a resin of a cured product cured only with an adhesive. An autograph AGS-X (Shimadzu Corporation) was used as the test machine used, and the test speed was 200 mm / min and N = 3 (the average value of these values).

The unit in the elongation test is%, the unit in the tensile strength test is MPa, and the unit in the adhesive strength test is N / 5 cm.
Under normal conditions, the test is performed in an environment of 23 ± 2 ° C. and 50 ± 5% RH.
In water immersion, the bonding test piece is immersed in water for 30 days in an environment of 23 ± 2 ° C. and 50 ± 5% RH, and then the test is performed.

<Evaluation of broken state>
After the above <adhesive strength test (normal state)>, the fractured state of the bonded test piece was observed, and the substrate fracture (SF), interface peeling (AF), and cohesive fracture (CF) were visually evaluated. If the moisture-permeable and waterproof non-woven fabric that is the base material is destroyed, the base material is destroyed, and if it is destroyed at the joint interface between the moisture-permeable and waterproof non-woven fabric that is the base material and the cured adhesive, the interface When the inside of the cured product (resin) layer in which the adhesive was cured was destroyed without peeling or destroying the non-woven fabric as the base material, it was evaluated as coagulation failure.

<Measurement method of gel time>

<Simple water stop test>
A method for manufacturing a joining test piece used in the simple water stoppage test will be described with reference to FIG. The bonding test pieces of Test Examples 1 to 5 were produced by using the two-component adhesives of Test Examples 1 to 5 obtained by mixing the solutions A and B before coating. The following will be described in more detail.
Two test pieces (30 cm × 30 cm × thickness 6 mm) were used, and the ends of these test pieces 1 and 1 were butted against each other (FIG. 2A). Adhesive surfaces 4 (adhesive area 30 cm x 10 cm) for applying the adhesive were provided on 10 cm of 5 cm each in the left-right direction from the butt end of the two test pieces 1 and 1 and 30 cm from the upper end to the lower end in the vertical direction. An adhesive was applied on the entire surface of the adhesive surface 4 at 120 g / (30 cm × 10 cm) at room temperature of 23 ° C. so that the adhesive layer had a uniform thickness. A test piece 3 (30 × 10 cm × thickness 6 mm) serving as a contact was placed on the adhesive surface 4 coated with the adhesive (FIG. 2B).
At this time, the cartridge gun for applying the two-component adhesive may be used for application, and the cartridge gun for applying the two-component adhesive includes a container containing the liquid A and a container containing the liquid B. A specific amount (mL) of each of the liquid A and the liquid B is extruded at the same time, and the extruded liquid A and the liquid B are mixed at the nozzle portion, and the adhesive of the mixed liquid can be applied to the test piece.

After the contact 3 was placed on the adhesive surface 4 and pressed, the adhesive was cured at room temperature of 23 ° C. After curing, the cured product of the adhesive was cured for 7 days. As a result, a joint test piece 10 (30 cm × 60 cm, joint thickness 12 mm) having a joint portion 21 in which the adhesive surface 4 of the test pieces 1 and 1 and the adhesive surface of the joint 3 are adhered with a cured product of an adhesive is formed. Manufactured. This was used as a joining test piece 10 for a simple water stoppage test.

As shown in FIGS. 3 to 6, the tips of the folds come inward from both ends of the obtained planar joint test piece 10 (30 cm × 60 cm, joint thickness 12 mm) in the lateral direction (10 cm) of the joint 3. As described above, four points were folded to form a substantially quadrangular frustum shape, and a joining test piece 20 having a substantially quadrangular frustum shape was obtained.

A joint test piece 20 for a simple water stoppage test of 30 cm × 60 cm was installed as shown in FIGS. 3 to 6, and after pouring 1 kg of water into the joint portion, it was left at room temperature of 23 ° C. for 1 hour and then flooded for 1 hour. The presence or absence of water leakage from the joint portion 21 of the later joint test piece was confirmed.
Further, the joint test piece 20 after the test was cut in the longitudinal direction (60 cm), and the state of the cross section of the joint portion 21 was observed.
In the cross-sectional observation of the joint portion 21, the state of the cured product (resin) in which the adhesive on the non-woven fabric is cured is defined as the state of being impregnated with the adhesive, and the adhesive surface 4 of the test piece coated with the adhesive is set as the starting point (0 mm). The distance (mm) of the tip of the cured product impregnated from the adhesive surface is measured, and the impregnation rate is determined by [distance from the adhesive surface to the tip of the cured product (mm) / thickness of the test piece (mm)] × 100 (%). be able to. When there are a plurality of test pieces, the impregnation rates thereof can be obtained, and the average value of the impregnation rates can be obtained.

<Evaluation of impregnation>
Visually check to what layer the test piece is impregnated.
× (impossible): 50% or more impregnated with no resin remaining on the adhesive surface, or 50% or more impregnated △ (good to slightly poor): 50% or more with resin partially on the adhesive surface Impregnated 〇 (excellent): 50% or more is impregnated while the adhesive surface has resin. If the adhesive surface of the contact 3 is at least partially adhered to the adhesive surface 4 of the test piece 1. Pass with △ (good to slightly bad). However, in the cross section of the joined portion 21, it is preferable that there are more portions in the joined state, for example, [longitudinal length (cm) of the joined state portion / longitudinal length (60 cm) of the cross section of the joined portion 21]. The joining ratio can be obtained and evaluated at × 100, and a joining ratio of 50% or more is desirable.

3 to 6 are schematic views and observation photographs of a simple water stoppage test using the joining test piece 20 folded so as to have a substantially quadrangular pyramid trapezoidal shape. Specifically, FIG. 3 is a side view of the simple water stop test, FIG. 4 is an upward observation view of the simple water stop test, and FIG. 5 is a perspective view from above of the simple water stop test. be. FIG. 6 is a photograph when the simple water stoppage test is observed upward.
As the support container 30 for installing the test piece, a 5 L plastic container (height 26 cm × diameter 20 cm) with a handle was used.
FIG. 3 shows a state in which the joint test piece 20 having a substantially quadrangular pyramid shape is inserted into the support container 30 for installing the test piece up to about 12 cm, and water 25 is poured into the inserted joint test piece 20 from the side. It is a schematic diagram at the time.
In FIGS. 4 and 6, the butt portion of the test pieces 1 and 1 is arranged so as to pass through the center of the support container 30 for installing the test piece (on the line between the spout and the handle), and the folds are folded inward. It is a schematic diagram and a photograph when the state which water 25 was poured into the quadrangular frustum-shaped joining test piece 20 was seen from above.

<Test results of Test Examples 1 to 5>
The test results of Test Examples 1 to 5 are shown in Table 1.
From the results of the <simple water stop test>, the bonding test pieces 20 of Test Examples 2 to 4 had no water leakage, and when the cross section was visually inspected, the resin which was the cured product of the adhesive was 50% or more of the non-woven fabric. The adhesive surface 4 of the test pieces 1 and 1 and the adhesive surface of the contact 3 were adhered to each other, and a joint portion 21 in which water leakage did not occur was formed. Since these adhesives had appropriate thixotropy and viscosity, it was confirmed that these adhesives were impregnated into the non-woven fabric but adhered to the joint after curing.
Even when the vicinity of the joint portion of the joint test pieces of Test Examples 2 to 4 was bent, there was no gap in the joint test piece that caused water leakage, and it was considered that the hardness of the resin after curing was appropriate. ..
On the other hand, it was confirmed that in the bonding test piece 10 of Test Example 1, when the vicinity of the bonding portion was bent, the cured resin was hard and could not follow the non-woven fabric, and a gap was formed in the bonding test piece.
From this, it was confirmed that the adhesives of Test Examples 2 to 4 had excellent followability and adhesiveness to the non-woven fabric after curing. Furthermore, it was confirmed that the adhesives of Test Examples 2 to 4 were excellent in watertightness after curing.

Furthermore, from the results of <Measurement method of gel time>, since the gel time of the adhesives of Test Examples 2 to 4 was 65 to 75 minutes, positioning between the base materials, application to the base materials, and adhesion between the base materials were performed. It was confirmed that it was possible to secure an appropriate working time (usable time) when performing such things.

The adhesives of Test Examples 2 to 4 have a viscosity of the adhesive before curing of 1000 mPa · s or less when measured at 23 ° C., and the hardness of the resin which is a cured product after curing is high. It was A50 to A80 when measured at 23 ° C.

Further, a polyol other than castor oil is used as liquid A, and an adhesive is applied so that the viscosity of the mixed liquid containing the liquid A and the liquid B (PMDI) becomes about 1500 mPa · s when measured at 23 ° C. Made. A flat bonding test piece 10 to which this adhesive was applied and cured was obtained, and a bonding test piece 20 having a substantially quadrangular pyramid shape was further produced. As a result of performing a simple water stop test using this joint test piece 20, it was confirmed that water leaked from the joint portion 21 and the watertightness of the cured resin after curing was poor. When the cross section of the joint portion 21 was observed, it was confirmed that the adhesive was impregnated to less than 50% of the thickness of the non-woven fabric, and the reason is that the viscosity of this adhesive exceeds 1500 mpa · s. Since it was high, it was considered that the impregnation of the adhesive was not sufficient.

Further, in the case of the solvent product of Test Example 5, a bonding test piece 20 having a substantially square cone trapezoidal shape was obtained using this solvent product, and when the cross section of the bonding portion 21 was observed, the adhesive was 50% or more of the non-woven fabric. Although it was impregnated, it was confirmed that the adhesive was not left on the surface of the non-woven fabric because it was impregnated too much, so that there was no resin as a cured product on the adhesive surface of the joint after curing and a gap was formed, resulting in poor watertightness. ..

Furthermore, from the results of the <tensile strength test> shown in Table 1 and the results of the <evaluation of the fractured state>, the resin strength when the adhesives of Test Examples 1 to 5 were cured was examined. Further, the adhesiveness of the cured product of the adhesive to the non-woven fabric was comprehensively judged by the following evaluation in consideration of the above <evaluation of impregnation property> and the above <evaluation of the broken state>.
<Evaluation of adhesiveness of cured product>
Very good adhesiveness (◎): Excellent impregnation (○) and broken state SF Good adhesiveness (○): Excellent impregnation (○) and broken state CF or Those with SF Adhesiveness is slightly poor (△): Impregnation is good to slightly poor (△), and the fractured state is partially CF. Adhesive is poor (×): Impregnation is not possible (×). Or, the broken state is AF

When the adhesive of Test Example 1 was applied to the non-woven fabric, the evaluation of the broken state was SF, but the followability of this cured product according to the result of the simple water stoppage test was lacking.
When the adhesive of Test Example 2 is applied to the non-woven fabric, the adhesive is slightly impregnated into the non-woven fabric and the evaluation of the broken state is somewhat unfavorable, but the followability and adhesiveness of this cured product are good according to the results of the simple water stoppage test. Met.
When the adhesive of Test Example 3 is applied to the non-woven fabric, the tensile strength (normal state) is slightly weak, so the evaluation of the fractured state has SF and CF, and the resin strength is slightly weak. The followability and adhesiveness were good.
When the adhesive of Test Example 4 was applied to the non-woven fabric, the evaluation of the broken state was as good as SF, and the followability and adhesiveness of the cured product according to the results of the simple water stoppage test were also good. Regarding <evaluation of adhesiveness of cured product>, Test Example 2 was Δ, Test Example 3 was ○, and Test Example 4 was ⊚, and the adhesiveness of the cured product obtained by curing the adhesive of Test Example 4 was the highest. It was good. Further, the cured product obtained by curing Test Examples 2 to 4 has water resistance such that the cured product is not easily hydrolyzed by contact with water and the properties of the resin can be easily maintained. Among them, the water resistance of the cured product of Test Example 4 was the best, and it was considered that the type and combination of the polyols were involved in this water resistance.
Further, when the tensile strength (normal state) of the resin which is the cured product when the adhesive is cured is 4.0 MPa or more, it is possible to provide an adhesive capable of forming a cured product having better resin strength. It could be confirmed.

Therefore, among the adhesives of Test Examples 1 to 5, the adhesives of Test Examples 2 to 4 are preferable from the viewpoints of workability, resin strength, followability, adhesiveness, watertightness, and water resistance. , More preferably, the adhesives of Test Example 3 and Test Example 4. A particularly preferable adhesive is the adhesive of Test Example 4, which is excellent in workability, resin strength, followability, adhesiveness, watertightness, and water resistance, and the balance between them is very good. It was confirmed that it was a good one.
In the adhesive of Test Example 4, liquid A contains a mixture of two kinds of castor oil-based polyester polyols having different properties, liquid B contains a bifunctional aromatic isocyanate compound of PMDI, and liquids A and B are mixed. Since it was a mixture, it was confirmed that such an adhesive component and volume content ratio can provide an adhesive having excellent workability, resin strength, followability, adhesiveness, watertightness, and water resistance. did it. Furthermore, it was also confirmed that such an adhesive component, a volume content ratio, and the like are appropriate for producing an adhesive having specific properties.

From this example, in order to provide an adhesive which is excellent in workability when applied to a nonwoven fabric and has excellent followability and adhesiveness to the cured product after curing, adhesion before curing is performed. The specific property that the viscosity of the agent is 1200 mPa · s or less when measured at 23 ° C. and the hardness of the cured product after curing is A50 to A80 when measured at 23 ° C. It was confirmed that the adhesive to have was good.
From this example, in order to provide an adhesive having excellent workability when applied to a nonwoven fabric and having excellent followability and adhesiveness to the cured product after curing, a polyol and an isocyanate compound can be obtained. It was confirmed that an adhesive containing the above is preferable, and the polyol is more preferably a polyester polyol, and more preferably an adhesive having a specific composition of being a castor oil-based polyester polyol.
Furthermore, it was confirmed that a specific adhesive having both this property and composition is more preferable from the viewpoints of workability, followability and adhesiveness.

That is, from this embodiment, by using the above-mentioned specific adhesive, this specific adhesive is excellent in workability before curing when the adhesive is applied to a base material by coating or the like, and also for a non-woven fabric. It was confirmed that a cured product having excellent followability and adhesiveness could be formed. Further, the cured product obtained by applying this specific adhesive to the non-woven fabric and curing the non-woven fabric can be present well inside the non-woven fabric and on the adhesive surface with appropriate hardness, and has excellent watertightness and water resistance. It could be confirmed. As described above, the present inventors have been able to provide an adhesive suitable for non-woven fabrics.

<Investigation of water pollutants contained in adhesives>
The adhesives of Test Examples 2 to 4 were soaked in water and eluted, according to the test contents of the Ministry of the Environment_uniform drainage standard (www.env.go.jp/water/impure/haisui.html).

Analysis results below the standard values were obtained for all of the adhesives of Test Examples 2 to 4, and these adhesives or their cured products have little effect on the water quality around them even when used for a long period of time in rivers, etc., and are safe. It was confirmed that the sex was high.

When a breathable waterproof non-woven fabric is laid on an embankment or embankment of a river or lake, water leakage from the gap between the joints of the breathable waterproof non-woven fabric is suppressed in order to maintain the condition of the embankment or embankment. Since it was necessary to maintain the strength of the jointed portion, a professional worker used a heat-sealed sheet and a heat-sealed machine to perform heat-sealing of the bonded surfaces.

On the other hand, with the specific adhesive of the present invention, even a general worker can easily and easily bond the nonwoven fabrics to each other, and after curing, the cured product having excellent watertightness and water resistance and the curing thereof. A breathable waterproof non-woven fabric containing an object can be obtained. As described above, the adhesive of the present invention is excellent in adhesive workability when applying the adhesive to the moisture-permeable and waterproof non-woven fabric installed on the embankment as described above and when the base material is cured with the adhesive. Further, it is possible to provide a cured product having excellent watertightness and water resistance, and a moisture-permeable and waterproof non-woven fabric containing the cured product. Further, since the influence of the adhesive component on the water quality is less than the standard value, the embankment, etc. It can also be used to adhere a moisture-permeable and waterproof non-woven fabric to be laid on the structure of.

1 non-woven fabric, 3 joints, 4 adhesive surfaces, 10 bonded non-woven fabric, 20 substantially truncated cone-shaped bonded non-woven fabric, 21 joints, 25 water, 30 support containers

That is, the present invention contains a polyester polyol and an isocyanate compound, and the viscosity of the adhesive before curing is 200 mPa · s or more and 1200 mPa · s or less when measured at 23 ° C., and the cured product after curing. A non-woven fabric adhesive having a hardness of A50 to A80 when measured at 23 ° C. can be provided.
The isocyanate compound may be an aromatic polyisocyanate compound.
The polyester polyol may be a castor oil-based polyester polyol.
The form of use of the adhesive may be a two-component curing type.
Further, the present invention is composed of a main agent containing the component (A) polyester polyol and a curing agent containing the component (B) isocyanate compound, and the main agent and the curing agent are mixed at the time of use to form an adhesive before curing. For non-woven fabrics, the viscosity of the cured product is 200 mPa · s or more and 1200 mPa · s or less when measured at 23 ° C, and the hardness of the cured product after curing is A50 to A80 when measured at 23 ° C. It is possible to provide a two-component adhesive kit for a non-woven fabric used for preparing an adhesive.

Claims (4)

The viscosity of the adhesive before curing is 1200 mPa · s or less when measured at 23 ° C., and the hardness of the cured product after curing is A50 to A80 when measured at 23 ° C. Adhesive for non-woven fabric. The adhesive according to claim 1, wherein the adhesive contains a polyol and an isocyanate compound. The adhesive according to claim 2, wherein the polyol is a polyester polyol. The adhesive according to claim 2 or 3, wherein the polyol is a castor oil-based polyester polyol.

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