JP4546708B2 - Polyol composition and adhesive composition using the same - Google Patents

Description

The present invention relates to a polyol composition for polyisocyanate reaction and an adhesive composition using the same. More specifically, when used in an adhesive composition, non-ferrous metals such as aluminum can be bonded with sufficient strength without particularly cleaning the surface, and a low boiling point for reducing the viscosity. Since a solvent is not required, the present invention relates to a polyisocyanate reaction polyol composition having a good working environment and an adhesive composition using the same.

Conventionally, polyurethane adhesives with various compositions have been proposed. For example, organic polyisocyanates and organic polyols are mixed with phosphoric acids, amine compounds, and epoxy resins. What is used for adhesion | attachment with metal foils, such as foil, is known (for example, refer patent document 1).
Furthermore, an adhesive containing a polyol composition obtained by adding a compound having an active hydrogen group such as a secondary amine or a phenol compound to an epoxy resin, and a polyisocyanate as a curing agent is used for various substrates. It is used for bonding, and because it forms an adhesive film with excellent heat resistance, chemical resistance, electrical properties, mechanical properties, etc., it is used in a wide range of applications such as electrical, electronic, vehicle, civil engineering, and architectural fields. Yes. Conventionally, this adhesive was generally used by dissolving in various low-boiling solvents such as benzene, toluene, xylene, methyl ethyl ketone, and ethyl acetate. Due to problems such as adverse effects, the use of solvents has been restricted, and it has become necessary to reduce the amount of solvent and further eliminate the use of solvents. Therefore, the amount of solvent can be sufficiently reduced, and it has a low viscosity and excellent workability. By curing with polyisocyanate, non-ferrous metals such as aluminum can be bonded with sufficient strength. A proposed polyol resin composition has been proposed (see, for example, Patent Document 2).

JP 7-11225 A Japanese Patent Laid-Open No. 11-171979

However, Patent Document 1 does not describe or examine the presence or absence of hydroxyl groups of phosphoric acids that are components of the adhesive composition, the number of carbons, and the correlation between the number of carbons and adhesion performance. . Moreover, in the adhesive using the polyol resin composition described in Patent Document 2, there is a problem that the adhesiveness is lowered because a large amount of polyol is used in combination for reducing the viscosity. Therefore, it is necessary to develop an adhesive that can bond a non-ferrous metal such as aluminum with sufficient strength and has a good working environment.
The present invention solves the above-described conventional problems, and when used in an adhesive composition, can be bonded with sufficient strength without particularly cleaning the surface of a non-ferrous metal such as aluminum, A polyol composition that does not require a low-boiling solvent and has a good working environment, and does not require the use of a large amount of polyol for viscosity reduction, and does not require a decrease in adhesion, and adhesion using the same An object is to provide an agent composition.

The present invention is as follows.
1. A castor oil-based polyol and an acidic phosphate compound having a total carbon number of 12 or more ,
The acidic phosphate compound is a compound having an epoxy group,
At least one phosphoric acid selected from orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and phosphinic acid compound and polyisocyanate reactant polyol composition, characterized in acidic phosphoric acid ester compound der Rukoto produced by the reaction of.
2. The above-mentioned 1. The compound having an epoxy group is at least one of an epoxidized animal and vegetable oil and an epoxidized animal and vegetable oil ester. The polyol composition for polyisocyanate reaction described in 1.
3. Furthermore, the above-mentioned 1. containing terpene phenols. Or 2. The polyol composition for polyisocyanate reaction described in 1.
4). A castor oil-based polyol, an acidic phosphate compound having 12 or more carbon atoms, and a polyisocyanate ;
The acidic phosphate compound is a compound having an epoxy group,
At least one phosphoric acid selected from orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and phosphinic acid compound, adhesive composition, characterized in acidic phosphate ester compound der Rukoto produced by the reaction of.
5). The above- mentioned 4. wherein the compound having an epoxy group is at least one of an epoxidized animal and vegetable oil and an epoxidized animal and vegetable oil ester. The adhesive composition described in 1.
6). Furthermore, the above 4. containing terpene phenols. Or 5. The adhesive composition described in 1.
The above 2. And 5. The term “epoxidized animal and vegetable oil” means an animal and vegetable oil having an unsaturated group, an animal and vegetable oil having an epoxy group obtained by epoxidizing an animal and vegetable oil having an unsaturated group and a hydroxyl group, or an epoxy group and a hydroxyl group. Means animal and vegetable oils. The “epoxidized animal and vegetable oil ester” is an alkyl ester of an epoxidized animal and vegetable oil, and this alkyl ester is particularly preferably a lower alkyl ester such as methyl ester, ethyl ester, propyl ester, and butyl ester.

The polyol composition of the present invention can adhere non-ferrous metals such as aluminum with sufficient strength and does not require a low-boiling solvent when blended with this composition to form an adhesive composition. The working environment is also good.
In addition, when the acidic phosphoric acid ester compound is obtained by reacting an epoxidized hydrocarbon oil ester or the like with phosphoric acids, a non-ferrous metal such as aluminum can be bonded with particularly high strength.
Furthermore, when it contains terpene phenols, the adhesiveness to a to-be-adhered body improves, and adhesive strength can be enlarged more.
Since the adhesive composition of the present invention uses polyisocyanate as a curing agent, non-ferrous metals such as aluminum can be bonded with sufficient strength, and the working environment is also good. In addition, since the strength reduction | decrease when immersed in warm water is small and it is excellent also in water resistance etc., it can be used also in the use which may contact with water.
In addition, when the acidic phosphoric acid ester compound is obtained by reacting an epoxidized hydrocarbon oil ester or the like with phosphoric acids, a non-ferrous metal such as aluminum can be bonded with particularly high strength.
Furthermore, when it contains terpene phenols, the adhesiveness to a to-be-adhered body improves, and adhesive strength can be enlarged more.

Hereinafter, the present invention will be described in detail.
(1) Polyisocyanate reaction polyol composition (hereinafter simply referred to as “polyol composition”)
The “castor oil-based polyol” is a polyol containing a polyester polyol having two or more hydroxyl groups and having a castor oil fatty acid as a skeleton. The castor oil-based polyol includes a transesterified product of at least one of castor oil and an alkylene oxide adduct of castor oil and at least one of alcohol, polyester polyol and polyether polyol; castor oil fatty acid; (It is a fatty acid obtained from castor oil, and is usually a mixture of ricinoleic acid and oleic acid. It may be ricinoleic acid alone) and at least one of alcohol, polyester polyol and polyether polyol A diol-type partially dehydrated or partially acylated product of castor oil; a transesterified product, an ester compound and a hydrogenated product of each compound of the partially dehydrated or partially acylated product, and the like. As a castor oil type polyol, only 1 type may be used and 2 or more types may be used.
In addition, an oligomer can also be used as a castor oil and a castor oil fatty acid. As this oligomer, a 2-7mer, especially a 3-5mer is preferable, and it can also be set as a multimer. A saturated oligomer produced by hydrogenation of an unsaturated group can also be used.

  Said transesterification product can be produced by reacting at least one of castor oil and an alkylene oxide adduct of castor oil with at least one of alcohol, polyester polyol and polyether polyol. The ratio of castor oil or the like and alcohol used in the transesterification reaction is not particularly limited, but 0.1 to 5 of alcohol or the like is used per 1 mol of castor oil (in the case of multimer, converted to multimer). It is preferable to set it as mol, especially 0.2-4 mol. The molecular weight of the alcohol used in the transesterification reaction is not particularly limited, but is preferably a low molecular weight alcohol having 1 to 12, particularly 2 to 8, and further 2 to 4 carbon atoms. The alcohol may be a polyol or a monool, and a polyol is particularly preferable. Monools include methanol, ethanol, propanol and the like. Examples of the polyol include polyethylene glycols such as ethylene glycol, diethylene glycol and triethylene glycol, polypropylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol, 1,3-butanediol, 1,4-butanediol, 2, 3-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, trimethylolethane, glycerin, diglycerin and other polyglycerin, pentaerythritol, dipentaerythritol and other polypentaerythritol, sorbitol , And shulksol. As alcohol, only 1 type may be used and 2 or more types may be used. Furthermore, monools and polyols may be used in combination. Polyols having different valences can be used in combination, and it is particularly preferable to use a trivalent or higher polyol at least in part. Moreover, it is particularly preferable that the total amount is a trivalent or higher polyol.

Furthermore, said ester compound can be produced by reacting castor oil fatty acid with at least one of alcohol, polyester polyol and polyether polyol. The ratio of castor oil fatty acid to alcohol used in the production of this ester compound is not particularly limited, but 0% of alcohol or the like is used per 1 mol of castor oil fatty acid (in the case of multimer, converted to multimer). 0.05 to 2 mol, particularly 0.1 to 2 mol is preferable. Although the molecular weight of the alcohol used for the production | generation of an ester compound is not specifically limited, It is preferable that the carbon number is 1-12, especially 2-8, Furthermore, it is a low molecular weight alcohol of 2-4. As the alcohol used for the production of the ester compound, the above monools and polyols can be used. However, when the castor oil fatty acid is a monomer, it is necessary to use a polyol. As this alcohol, only 1 type may be used, 2 or more types may be used, and monool and a polyol may be used together. Furthermore, polyols having different valences can be used in combination, and it is particularly preferable to use at least a part of a trivalent or higher polyol. Moreover, it is particularly preferable that the total amount is a trivalent or higher polyol.
Instead of castor oil, hydrogenated castor oil, which is a hydrogenated product thereof, can be used. Further, hydrogenated castor oil fatty acid which is a hydrogenated product instead of castor oil fatty acid and mainly contains 12-hydroxystearic acid can be used. Furthermore, also when using an oligomer as a castor oil and a castor oil fatty acid, each hydrogenated material can be used similarly.

Moreover, as a castor oil-type polyol, the reaction product of a castor oil fatty acid and amines can also be used. In this case, an amide-based polyol is used, and this amide-based polyol is also included in the castor oil-based polyol used in the present invention. The total amount of castor oil-based polyol may be an amide-based polyol, and this amide-based polyol may be used in combination with another castor oil-based polyol. As amines, primary amines and secondary amines can be used, and polyamines, hydroxylamines and the like can also be used. Examples of the primary amine include methylamine, ethylamine, and butylamine. Examples of the secondary amine include dimethylamine and diethylamine. Furthermore, examples of the polyamine include tetramethylethylenediamine and pentamethyldiethylenetriamine. As amines, only 1 type may be used and 2 or more types may be used.
The amines may contain a tertiary amine as long as the properties of the castor oil-based polyol are not impaired.

The “acidic phosphate compound” has a total carbon number of 12 or more. This carbon number is preferably 14 or more, particularly 16 or more. Moreover, this carbon number is 60 or less normally. The total number of carbon atoms of 12 or more means any of a group having 12 or more carbon atoms and a case of having a plurality of groups having less than 12 carbon atoms and the total number of carbon atoms being 12 or more. Also means. This acidic phosphoric ester compound has an effect of improving adhesiveness to the adherend, anticorrosion, and the like when a polyol composition is used in the adhesive composition. As the acidic phosphoric acid ester compound, those produced by the reaction of various compounds having a hydroxyl group and / or an epoxy group and phosphoric acids can be used, but the acidic phosphoric acid ester compound of the present invention is an epoxy group. And at least selected from orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and phosphinic acid It is produced by reaction with phosphoric acid which is one kind of phosphoric acid compound. As the compound having a hydroxyl group and / or an epoxy group, a polyol, a carboxylic acid having a hydroxyl group and / or an epoxy group, and an ester thereof, an animal and vegetable oil having a hydroxyl group and / or an epoxy group, and an ester thereof are preferable. . As an acidic phosphate ester compound, only 1 type may be used and 2 or more types may be used.

  Polyols include polyethylene glycols such as ethylene glycol, diethylene glycol and triethylene glycol, polypropylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3- Polyglycerin such as butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, trimethylolethane, glycerin and diglycerin, polypentaerythritol such as pentaerythritol and dipentaerythritol, sorbitol, shulc Sol and the like. As a polyol, only 1 type may be used and 2 or more types may be used.

  As the carboxylic acid having a hydroxyl group, a hydroxycarboxylic acid having one or more hydroxyl groups, for example, 11- or 16-hydroxyhexadecanoic acid, 16-hydroxyhexadecenoic acid, 2- or 18-hydroxyoctadecanoic acid, 22-hydroxy Examples include docosanoic acid, 2-hydroxytetracosanoic acid, dihydroxymyristic acid, dihydroxypalmitic acid, dihydroxystearic acid, dihydroxyarachidic acid, and trihydroxypalmitic acid. In addition, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, etc. are decomposed into fatty acids, and hydroxylated fatty acids that have been ring-opened and tall oils etc. have been epoxidized and hydroxylated by ring opening Fatty acids and the like can also be used. Further, alkyl esters of these carboxylic acids can be used as esters of carboxylic acids having a hydroxyl group. As the alkyl group forming this ester, a lower alkyl group is preferable, and methyl ester, ethyl ester and the like are preferable.

  Examples of the carboxylic acid having an epoxy group include those obtained by epoxidizing a carboxylic acid having an unsaturated group such as oleic acid, linoleic acid, and linolenic acid. Moreover, what epoxidized soybean oil fatty acid, olive oil fatty acid, etc. containing these carboxylic acids are mentioned. Further, examples of the carboxylic acid having a hydroxyl group and an epoxy group include those obtained by epoxidizing a carboxylic acid having a hydroxyl group and an unsaturated group such as ricinoleic acid. Moreover, what epoxidized the castor oil fatty acid etc. containing these carboxylic acid is mentioned. Furthermore, as esters of carboxylic acids having an epoxy group, alkyl esters of these carboxylic acids can be used. As the alkyl group forming this ester, a lower alkyl group is preferable, and methyl ester, ethyl ester and the like are preferable. As a carboxylic acid having a hydroxyl group and / or an epoxy group and an ester thereof, only one kind may be used, or two or more kinds may be used.

  Examples of animal and vegetable oils having a hydroxyl group include castor oil and resclair oil. Examples of animal and vegetable oils having an epoxy group (epoxidized animal and vegetable oils) include those obtained by epoxidizing castor oil, soybean oil, linseed oil, cottonseed oil, olive oil, rapeseed oil and the like. Furthermore, as an animal and vegetable oil (epoxidized animal and vegetable oil) having a hydroxyl group and an epoxy group, those obtained by epoxidizing castor oil and the like can be mentioned. Moreover, as the ester of animal and vegetable oils having a hydroxyl group and / or an epoxy group, alkyl esters of these animal and vegetable oils can be used. As the alkyl group forming this ester, a lower alkyl group is preferable, and methyl ester, ethyl ester and the like are preferable. As animal and vegetable oils having hydroxyl groups and / or epoxy groups, and esters thereof, only one kind may be used, or two or more kinds may be used.

  As what reacts with phosphoric acid, the epoxidized animal and vegetable oil which epoxidized animal and vegetable oil, for example, epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, etc. are preferable. Further, it is particularly preferable to use alkyl esters of these epoxidized animal and vegetable oils. The alkyl group forming the ester is preferably a lower alkyl group, preferably a methyl ester, an ethyl ester, or the like. Examples of the epoxidized animal and vegetable oil ester include epoxidized soybean oil methyl, epoxidized soybean oil ethyl, and epoxidized castor oil methyl. And epoxidized castor oil ethyl. Epoxidized animal and vegetable oils and alkyl esters thereof can be used in combination. In these epoxidized animal and vegetable oils and alkyl esters thereof, phosphoric acids and / or phosphate esters react with epoxy groups to form hydroxyl groups with the formation of esters.

  When the carboxylic acid and its ester and the animal and vegetable oil and its ester are compounds having an epoxy group, the number of epoxy groups in each compound is not particularly limited, but is preferably two. One epoxy group is not preferable because the molecular weight of the phosphoric ester compound is reduced. On the other hand, if the number of epoxy groups is 3 or more, the phosphate ester compound may be gelled, which is not preferable. Therefore, when using a compound having an epoxy group, it is preferable to use the compound having two epoxy groups in combination with a compound having one or more epoxy groups, and the total amount is two epoxy groups. Particularly preferred is a compound having

As the phosphoric acids, at least selected from orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and phosphinic acid It is a kind of phosphoric acid compound . As phosphoric acid, only 1 type may be used and 2 or more types may be used together.

  The ratio of carboxylic acid and its ester, oxycarboxylic acid and its ester, animal and vegetable oil and its ester, etc. and phosphoric acid is not particularly limited, but carboxylic acid and its ester, oxycarboxylic acid and its ester, animal and vegetable oil and its It is preferable to make phosphoric acid 0.1-5 mol with respect to 1 mol of ester (in the case of a multimer, it is conversion of multimer), especially 0.2-3 mol.

  The contents of each of the castor oil-based polyol and the acidic phosphate ester compound in the polyol composition of the present invention are not particularly limited, but when the total of the castor oil-based polyol and the acidic phosphate ester compound is 100% by mass, The castor oil-based polyol is preferably 90 to 99% by mass, particularly 91 to 98% by mass, and more preferably 92 to 98% by mass. If the content of the castor oil-based polyol is 90 to 99% by mass, that is, the acid phosphate ester compound is 1 to 10% by mass, when this polyol composition is used in the adhesive composition, the adhesive strength is increased. It can be enlarged and the adhesion to the adherend can be improved.

  The polyol composition may further contain terpene phenols in addition to the castor oil-based polyol and the acidic phosphate ester compound. These terpene phenols are produced by adding an alkylphenol compound such as phenol or orthocresol to a cyclic terpene compound, and examples thereof include compounds represented by the following chemical formulas (1) to (6). . By containing these terpene phenols, adhesion to an adherend can be further improved when the polyol composition is used in an adhesive composition. As terpene phenols, only 1 type may be used and 2 or more types may be used.

  Furthermore, this polyol composition can contain other polyols in addition to the castor oil-based polyol. Other polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, Examples include low molecular weight polyols such as hexamethylene glycol, 2-methylpentanediol, 12-hydroxystearyl alcohol, dimer diol, hydrogenated bisphenol A, bis (hydroxyethoxyphenyl) propane, glycerin, trimethylolpropane, and pentaerythritol.

  Other polyols include (1) ethylene oxide adducts and / or propylene oxide adducts of the above low molecular weight polyols, (2) copolymers of alkylene glycols such as polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, (3) ethylene oxide adduct and / or propylene oxide adduct of polyhydric phenols such as resorcin, hydroquinone, bisphenol A, bisphenol F, bisphenol S, (4) ammonium, ethylenediamine, hexamethylenediamine, ethanolamine, propanolamine, etc. Examples include polyether polyols such as ethylene oxide adducts and / or propylene oxide adducts of amines. In addition, the above low molecular weight polyols and succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, pyro Examples thereof include polyester polyols that are condensates of polybasic acids such as merit acid, hydroxycarboxylic acids such as 12-hydroxystearic acid and castor oil fatty acid, and at least one acid of carbonic acid. Moreover, polycarbonate polyol etc. can also be used as another polyol. Of these various polyols, those having an average molecular weight of less than 3000 are preferred. Such low molecular weight polyols generally have a low viscosity, and when used together with the low viscosity polyol, the viscosity of the adhesive composition can be lowered when the polyol composition is used in the adhesive composition. And it can be set as the adhesive composition which is low viscosity and excellent in workability | operativity, without using an organic solvent. These other polyols may be used alone or in combination of two or more.

  Although content of the other polyol used together is not specifically limited, When a castor oil-type polyol is 100 mass parts, it is preferable that it is 50 mass parts or less, especially 40 mass parts or less. If the content of other polyols is too small, the viscosity of the adhesive composition using this polyol composition may not be sufficiently lowered. On the other hand, if it exceeds 40 parts by mass, particularly 50 parts by mass, the adhesion to non-ferrous metals such as aluminum, corrosion resistance, etc. tend to decrease, which is not preferable.

  Further, this polyol composition includes a plasticizer such as dioctyl phthalate, a diluent such as methylacetylated ricinolate and trimethyl phosphate, glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, To contain various additives such as bentonite, talc, silica, titania, carbon black, graphite, iron oxide, bituminous materials and other fillers or pigments, thickeners, thixotropic agents, flame retardants, antifoaming agents, etc. Can do. Furthermore, resins having adhesiveness such as xylene resin, petroleum resin, rosin, rosin ester, and terpene resin can be contained.

  The polyol composition of the present invention can be used in various applications. For example, it can mix | blend and use as components, such as an adhesive agent, a coating material, a sealing material, a sealing material, a casting material, and an elastomer. Furthermore, it can also be set as a foam, and this foam can also be used as a shock absorbing material, a soundproof material, a vibration isolator, a heat insulating material, etc.

(2) Adhesive composition The adhesive composition of the present invention contains a castor oil-based polyol, an acidic phosphate compound, and a polyisocyanate. Examples of the castor oil-based polyol and acidic phosphate ester compound include the castor oil-based polyol and acidic phosphate ester compound in the above-mentioned (1) polyol composition, and for each of these, the above description is applied as it is. Can do.

  The “polyisocyanate” is not particularly limited, and various polyisocyanates can be used. As this polyisocyanate, diphenylmethane diisocyanate (MDI), carbodiimide-modified MDI, crude MDI, hydrogenated MDI, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, tri And phenylmethane diisocyanate. In addition, urethane modified products, dimers, trimers, carbodiimide modified products, allophanate modified products, urea modified products, biuret modified products, blocked products (phenols, oximes, imides, mercaptans, Alcohols, ε-caprolactam, ethyleneimine, α-pyrrolidone, diethyl malonate, sodium bisulfite, boric acid and the like), prepolymers, and the like can also be used. In particular, when weather resistance is required, it is preferable to use a non-yellowing polyisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate. As polyisocyanate, only 1 type may be used and 2 or more types may be used.

  The isocyanate index representing the amount ratio between the polyisocyanate in the adhesive composition and the castor oil-based polyol (the total amount of polyol when other polyols are contained) is 0.95 to 1.3, particularly 1.0. It is preferable that it is -1.2. If this isocyanate index is 0.95-1.3, it can be hardened more easily and it can be set as the adhesive composition excellent in adhesiveness, adhesive strength, etc.

  In addition to the castor oil-based polyol, the adhesive composition can further contain other polyols. As other polyols, those exemplified as the other polyols in the above polyol composition can be used. These other polyols may not be contained in the polyol composition but may be blended at the time of preparing the adhesive composition, or may be blended into the polyol composition and further blended at the time of preparing the adhesive composition. Good. In addition, preferable content of these other polyols is as above-mentioned, and the problem when it remove | deviates from an upper and lower limit is also the same as the above.

  The adhesive composition of the present invention has a sufficiently low viscosity and excellent workability without using a solvent, but can contain a solvent as required. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, butyl acetate, ethyl acetoacetate and 2-ethoxyethyl acetate, diethylene glycol dimethyl ether, propylene glycol monoethyl ether and propylene glycol. Examples include ethers such as monoethyl ether acetate, hydrocarbons such as xylene, toluene and mineral spirits, N, N-dimethylformamide, N, N-dimethylacetamide, and terpenes. As a solvent, only 1 type may be used and 2 or more types may be used.

  The adhesive composition includes various additives such as plasticizers, diluents, fillers or pigments, thickeners, thixotropic agents, flame retardants, antifoaming agents, and the like as in the case of the polyol composition. In addition, resins having adhesiveness and the like can also be contained. These additives and resins may not be contained in the polyol composition, but may be blended when preparing the adhesive composition, or may be blended into the polyol composition and further added when preparing the adhesive composition. May be.

  The adherend that can be bonded by the adhesive composition of the present invention is not particularly limited, and examples thereof include metal, concrete, cement mortar, leather, glass, rubber, plastic, wood, cloth, and paper. This adhesive composition is preferably used as an adhesive for metals such as aluminum, titanium, stainless steel, mild steel, and plated steel, and is particularly useful as an adhesive for non-ferrous metals such as aluminum. In addition, this adhesive composition not only can bond metals, for example, non-ferrous metals such as aluminum with sufficient strength, but also provides sufficient strength between the metal and various adherends other than the above metals. It can also be glued with. Practically, there are more products that require adhesion between the metal and various adherends other than the above metals than products that require adhesion between metals, and the adhesive composition of the present invention is a wall panel, door panel. In addition, it can be suitably used for adhesion between a metal and other adherends in various products such as interior materials for cold storage vehicles.

  Further, the method for applying the adhesive composition of the present invention to an adherend is not particularly limited, and brush coating, roller coating, spray coating, gravure coating, reverse roll coating, air knife coating, bar coating, curtain roll coating, dip coating. It can apply | coat by various methods, such as a coat, a rod coat, and a doctor blade coat.

  Furthermore, this adhesive composition can be bonded with sufficient strength without cleaning the surface of a non-ferrous metal such as aluminum, and is advantageous in terms of work process. When the adherend is a metal, the surface cleaning treatment is not particularly necessary as described above, but degreasing, blasting, alkali cleaning, phosphate treatment, chromate treatment with an organic solvent such as acetone or alcohol. Various surface treatments such as fluoride treatment may be performed.

Hereinafter, the present invention will be described specifically by way of examples.
Synthesis example 1
2. In a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser, 3720 g (4 mol) of castor oil, 410 g (3.1 mol) of trimethylolpropane, and a 28% by weight methanol solution of sodium methylate 0 g was added and reacted at 220 ° C. for 3 hours under a nitrogen stream. Then, it cooled to 100 degrees C or less, 2.7g of 75 mass% concentration aqueous solution of orthophosphoric acid was added, and the catalyst was neutralized and removed. Thus, a castor oil-based polyol having an acid value of 1.0, a hydroxyl value of 270, a viscosity at 25 ° C. of 900 mPa · s, and a number average molecular weight of 600 was synthesized.

Synthesis example 2
Into a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel, epoxidized soybean oil methyl ester 1500 g (6.5 mol) was charged, and at 50-100 ° C. under nitrogen flow, 500 g of 75% strength by weight aqueous solution (3.8 mol of orthophosphoric acid) was added dropwise over 2 hours and reacted at 100 ° C. for another 2 hours to bind orthophosphoric acid to the epoxy group of epoxidized soybean oil methyl ester. In this way, an acidic phosphate ester compound having an acid value of 170 and a viscosity of 28000 mPa · s at 25 ° C. was synthesized.

Synthesis example 3
Into a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel, 1,6-hexanediol diglycidyl ether 1500 g (6.5 mol) was charged, and at 50 to 100 ° C. under a nitrogen stream, 500 g of a 75% strength by weight aqueous solution of orthophosphoric acid (3.8 mol of orthophosphoric acid) was added dropwise over 2 hours and reacted at 100 ° C. for a further 2 hours, so that orthophosphoric acid was an epoxy of 1,6-hexanediol diglycidyl ether. Attached to the group. Thus, an acidic phosphate compound having an acid value of 200 and a viscosity of 100000 mPa · s at 25 ° C. was synthesized.

Comparative Synthesis Example 1
A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel was charged with 1400 g (10 mol) of butyl glycidyl ether, and a 75% by mass concentration of orthophosphoric acid at 50 to 100 ° C. in a nitrogen stream. 300 g of aqueous solution (2.3 mol of orthophosphoric acid) was added dropwise over 2 hours, and the mixture was further reacted at 100 ° C. for 2 hours. In this way, an acidic phosphate compound having an acid value of 120 and a viscosity of 20,000 mPa · s at 25 ° C. was synthesized.

Examples 1-11 and Comparative Examples 1-7
Castor oil-based polyol of Synthesis Example 1, Synthesis Example 2, Synthesis Example 3 and Acidic Phosphate Ester Compound of Comparative Synthesis Example 1, and Table 1 (Examples 1 to 11) and Table 2 (Comparative Examples 1 to 7) These compounds were blended so as to have the compositions shown in Tables 1 and 2. Further, an adhesive composition was prepared by blending crude MDI so that the isocyanate index was 1.05.

上記ヒマシ油系ポリオールは合成例１のものであり、上記炭素数１８（Ｃ数１８）の酸性リン酸エステル化合物は合成例２のものであり、上記炭素数１２（Ｃ数１２）の酸性リン酸エステル化合物は合成例３のものである。また、上記炭素数３（Ｃ数３）のリン酸エステル化合物はリン酸トリメチルであり、希釈剤として作用するものである。更に、上記ＡＡ／ＭＰＤはポリエステルポリオールである。

The castor oil-based polyol is that of Synthesis Example 1, the above-described acidic phosphate compound having 18 carbon atoms (C number 18) is that of Synthesis Example 2, and the above-mentioned acidic phosphorus compound having 12 carbon atoms (C number 12). The acid ester compound is that of Synthesis Example 3. The phosphoric acid ester compound having 3 carbon atoms (C 3) is trimethyl phosphate and acts as a diluent. Further, the AA / MPD is a polyester polyol.

上記ヒマシ油系ポリオールは合成例１のものである。また、上記炭素数１０（Ｃ数１０）の酸性リン酸エステル化合物はイソデシルアシッドフォスフェート（モノエステルとジエステルの混合物であり、平均分子量は３０８である。）であり、上記炭素数６（Ｃ数６）の酸性リン酸エステル化合物は、比較例５ではジブチルフォスフェート、比較例６では比較合成例１のものである。更に、上記ＣＯＦＡは酸価１８０のヒマシ油系脂肪酸である。
尚、表１及び２においてテルペンフェノール類としては、ヤスハラケミカル社製、商品名「ＹＳ−８５」を用いた。

The castor oil-based polyol is that of Synthesis Example 1. Further, the acidic phosphate compound having 10 carbon atoms (10 C atoms) is isodecyl acid phosphate (a mixture of monoester and diester, having an average molecular weight of 308), and has 6 carbon atoms (C The acidic phosphoric acid ester compound of Formula 6 is that of dibutyl phosphate in Comparative Example 5 and that of Comparative Synthesis Example 1 in Comparative Example 6. Further, the COFA is a castor oil fatty acid having an acid value of 180.
In Tables 1 and 2, as the terpene phenols, the product name “YS-85” manufactured by Yasuhara Chemical Co., Ltd. was used.

The adhesive strengths of the adhesive compositions described in Table 1 and Table 2 were evaluated as tensile shear adhesive strength by the following method.
Each adhesive composition is applied to an area 12.5 mm long from one end of one of two aluminum sheets of length 100 mm × width 25 mm × thickness 2 mm, and the thickness is 0.2 mm. The coating film was formed. Thereafter, one end of the other sheet was laminated on the coating film, and then allowed to stand at 25 ° C. for 24 hours and further at 40 ° C. for 48 hours to cure the adhesive composition. The tensile shear bond strength was measured at a tensile speed of 50 mm / min with a tensile tester (manufactured by Shimadzu Corporation, model “AGS-10KNG”) using the specimen thus prepared.
In addition, after each specimen was immersed in warm water at 40 ° C. for 48 hours, the tensile shear adhesive strength was measured in the same manner, and the strength retention after the warm water immersion was evaluated.
Tensile shear bond strength retention (%) = (tensile shear bond strength before warm water immersion / tensile shear bond strength after warm water immersion) × 100
The results of Examples 1 to 10 are shown in Table 3, and the results of Comparative Examples 1 to 7 are shown in Table 4, respectively.
In addition, the pot life in Tables 3 and 4 is measured according to the time from the start of measurement until the viscosity reaches 100,000 mPa · s by measuring the viscosity of the adhesive composition left at 25 ° C. in the same manner as described above. It has been evaluated.

  According to the results of Table 3, in the adhesive composition containing the specific castor oil-based polyol and the acidic phosphate ester compound, the tensile shear adhesive strength before immersion in warm water is 7.4 MPa or more, and sufficient adhesive strength is obtained. Have Moreover, when terpene phenol is contained, there exists a tendency for a tensile shear adhesive strength to become larger, and even if compared with the epoxy-type adhesive agent mounted in Table 2 and Table 4 as a reference example, nothing is inferior. Further, after immersion in warm water, the tensile shear bond strength is reduced in any of the examples, but the retention rate is 74% or more, and it can be seen that there is no significant decrease in strength due to immersion in warm water. Moreover, any adhesive composition of Examples 1-11 has an appropriate pot life of 6 to 13 minutes.

On the other hand, according to the results in Table 4, each comparative example does not contain the specific acidic phosphate ester compound in the present invention, so that the tensile shear adhesive strength is 4.9 MPa or less, and the strength is small. Moreover, in Comparative Examples 5-7 containing a phosphoric acid ester compound with few carbon atoms, intensity | strength is falling rather by containing them. Further, it can be seen that the decrease in strength after immersion in warm water is larger than that in Examples, except when the strength before immersion in warm water is extremely low.

Claims (6)

A castor oil-based polyol and an acidic phosphate compound having a total carbon number of 12 or more ,
The acidic phosphate compound is a compound having an epoxy group,
At least one phosphoric acid selected from orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and phosphinic acid compound and polyisocyanate reactant polyol composition, characterized in acidic phosphoric acid ester compound der Rukoto produced by the reaction of. The polyol composition for polyisocyanate reaction according to claim 1, wherein the compound having an epoxy group is at least one of an epoxidized animal and vegetable oil and an epoxidized animal and vegetable oil ester. Furthermore , the polyol composition for polyisocyanate reaction of Claim 1 or 2 containing terpene phenols. A castor oil-based polyol, an acidic phosphate compound having 12 or more carbon atoms, and a polyisocyanate ;
The acidic phosphate compound is a compound having an epoxy group,
At least one phosphoric acid selected from orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, methanephosphonic acid, benzenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and phosphinic acid compound, adhesive composition, characterized in acidic phosphoric acid ester compound der Rukoto produced by the reaction of. The adhesive composition according to claim 4, wherein the compound having an epoxy group is at least one of an epoxidized animal and vegetable oil and an epoxidized animal and vegetable oil ester.   Furthermore, the adhesive composition of Claim 4 or 5 containing terpene phenols.