JP2022134107A - Curable urethane composition, and cured product thereof - Google Patents

Abstract

To provide a curable urethane composition excellent in adhesiveness to a substrate after cured.SOLUTION: A curable urethane composition contains a hydroxy group component (A) and an isocyanate component (B) and satisfies at least one of following (i) - (iii). (i) The hydroxy group component (A) contains a compound (S) represented by following general formula (1). (ii) The hydroxy group component (A) contains an urethane prepolymer that is obtained by reacting a hydroxy group component containing the compound (S) and an isocyanate component and has a hydroxy group at the terminal. (iii) The isocyanate component (B) contains an urethane prepolymer that is obtained by reacting a hydroxy group component containing the compound (S) and an isocyanate component and has an isocyanate group at the terminal.SELECTED DRAWING: None

Description

The present invention relates to a curable urethane composition and its cured product.

Curable urethane compositions are used in a wide range of fields such as adhesives (binders), pressure-sensitive adhesives, sealants, etc., due to their excellent toughness and wear resistance due to the intermolecular hydrogen bonds formed by urethane bonds. A two-part curable adhesive composed of polyol and polyisocyanate is known (see, for example, Patent Document 1). In recent years, however, adhesives and pressure-sensitive adhesives have become thinner, and there is a demand for adhesives and pressure-sensitive adhesives that are thin but have excellent adhesive strength.
It is also known to incorporate various inorganic fillers such as potassium titanate, alumina, magnesium oxide and iron oxide into curable urethane compositions and use them as binders and adhesives for electronic materials. . However, in the above applications, although a large amount of inorganic filler must generally be contained in many cases, the dispersibility of the filler in the curable urethane composition is poor, resulting in poor handling of the curable urethane composition. It is bad and has problems such as difficulty in coating. Therefore, in order to solve this problem, it is known to add a low-molecular-weight surfactant, a plasticizer, or the like to the curable urethane composition to improve the handleability (see, for example, Patent Document 2). However, the addition of a low-molecular-weight surfactant or a plasticizer poses a problem that the substrate adhesion of a cured product of a curable urethane composition containing an inorganic filler is insufficient.

JP-A-03-182584 JP 2011-94134 A

An object of the present invention is to provide a curable urethane composition having good adhesion to a substrate after curing.

［一般式（１）中、Ｘ^１及びＸ^２は水酸基を２個有する化合物から１個の水酸基を除いた残基を表し、Ｘ^１とＸ^２はそれぞれ同一でも異なっていてもよく；Ｒは炭素数２～１０の三価の鎖式飽和炭化水素基を表し；ＳＯ_３Ｚはスルホン酸塩基を表す。］ The present inventors arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is a curable urethane composition containing a hydroxyl group component (A) and an isocyanate component (B), wherein the curable urethane composition satisfies at least one of the following (i) to (iii): be.
(i) the hydroxyl group component (A) contains a compound (S) represented by the following general formula (1); (ii) the hydroxyl group component (A) contains the compound (S); a hydroxyl group component and an isocyanate component; (iii) the isocyanate component (B) containing a urethane prepolymer having a hydroxyl group at the end obtained by reacting an isocyanate group at the end obtained by reacting a hydroxyl group component containing the compound (S) and an isocyanate component contains a urethane prepolymer having

[In general formula (1), X ¹ and X ² represent a residue obtained by removing one hydroxyl group from a compound having two hydroxyl groups, and X ¹ and X ² may be the same or different; SO 3 Z represents a trivalent chain saturated hydrocarbon group having 2 to 10 carbon atoms; SO ₃ Z represents a sulfonate group. ]

The curable urethane composition of the present invention has the effect of having excellent adhesion to substrates after curing of the curable urethane composition.

［一般式（１）中、Ｘ^１及びＸ^２は水酸基を２個有する化合物から１個の水酸基を除いた残基を表し、Ｘ^１とＸ^２はそれぞれ同一でも異なっていてもよく；Ｒは炭素数２～１０の三価の鎖式飽和炭化水素基を表し；ＳＯ_３Ｚはスルホン酸塩基を表す。］ The curable urethane composition of the present invention is a curable urethane composition containing a hydroxyl group component (A) and an isocyanate component (B), wherein at least one of the following (i) to (iii) is satisfied: It is a flexible urethane composition.
(i) the hydroxyl group component (A) contains a compound (S) represented by the following general formula (1); (ii) the hydroxyl group component (A) contains the compound (S); a hydroxyl group component and an isocyanate component; (iii) the isocyanate component (B) containing a urethane prepolymer having a hydroxyl group at the end obtained by reacting an isocyanate group at the end obtained by reacting a hydroxyl group component containing the compound (S) and an isocyanate component contains a urethane prepolymer having

[In general formula (1), X ¹ and X ² represent a residue obtained by removing one hydroxyl group from a compound having two hydroxyl groups, and X ¹ and X ² may be the same or different; SO 3 Z represents a trivalent chain saturated hydrocarbon group having 2 to 10 carbon atoms; SO ₃ Z represents a sulfonate group. ]

<Compound (S)>
In the present invention, the compound (S) is a compound represented by the general formula (1). In the present invention, since the curable urethane composition satisfies at least one of the above (i) to (iii), the sulfonic acid group (- SO ₃ Z).

X ¹ and X ² in general formula (1) represent residues obtained by removing one hydroxyl group from a compound having two hydroxyl groups. X ¹ and X ² may be the same or different.

R in the general formula (1) represents a trivalent chain saturated hydrocarbon group having 2 to 10 carbon atoms, including straight-chain or branched-chain ones.
R is preferably a trivalent hydrocarbon group having 2 carbon atoms from the viewpoint of adhesion to the substrate and dispersibility of the inorganic filler in the curable urethane composition.

The compound (S) has a structure in which a compound having two hydroxyl groups on two carboxyl groups of an aliphatic dicarboxylic acid (anhydride) having a sulfonic acid group is esterified, and the sulfonic acid group is a sulfonate. and, for example, unsaturated aliphatic dicarboxylic acid (anhydride) {e.g., fumaric acid, maleic acid, maleic anhydride, 2-pentenedioic acid, mesaconic acid, itaconic acid, etc.} 1 mole has two hydroxyl groups To the carbon-carbon double bond of the compound (S0) obtained by esterifying 2 moles of the compound (e.g., fumarate diester, maleate diester, etc.), to a sulfonating agent (e.g., hydrogen sulfite, dipyrosulfite, etc.) It can be obtained by an addition reaction of the derived sulfonic acid group (--SO ₃ Z).
As the unsaturated aliphatic dicarboxylic acid (anhydride), fumaric acid, maleic acid and maleic anhydride are preferable from the viewpoint of adhesion to the substrate and dispersibility of the inorganic filler in the curable urethane composition.

Examples of compounds having two hydroxyl groups include dihydric alcohols having 2 to 20 carbon atoms, dihydric phenol compounds, alkylene oxide (hereinafter abbreviated as AO) adducts thereof, and polyester diols. The compounds having two hydroxyl groups may be used singly or in combination of two or more.

Examples of dihydric alcohols having 2 to 20 carbon atoms include dihydric alcohols having 2 to 20 carbon atoms [aliphatic diols (ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, , neopentyl glycol and 1,10-decanediol), alicyclic diols (cyclohexanediol and cyclohexanedimethanol, etc.) and araliphatic diols [1,4-bis(hydroxyethyl)benzene, etc.].

Any dihydric phenol compound may be used as long as two hydroxyl groups are bonded to an aromatic ring. and polycyclic aromatic dihydroxy compounds such as dihydroxynaphthalene.

As the AO to be added to the dihydric alcohol and dihydric phenol compound having 2 to 20 carbon atoms, AO having 2 to 4 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter, PO), 1,3-propylene oxide, 1,2-, 1,3- or 2,3-butylene oxide and tetrahydrofuran (hereinafter abbreviated as THF).
Among these, EO, PO and THF are preferable from the viewpoint of substrate adhesion after curing of the curable urethane composition, moist heat resistance, and dispersibility of the inorganic filler in the curable urethane composition. Preferred are PO and THF, particularly preferred is THF.
One type of AO may be used alone or two or more types may be used in combination. When two or more types of AO are used in combination, the addition method may be block addition or random addition. It may be used in combination.

Polyester diols include, for example, condensed polyester diols, polylactone diols and polycarbonate diols.

The condensed polyester diols include dihydric alcohols having 2 to 20 carbon atoms and AO adducts thereof and/or AO adducts of dihydric phenol compounds, dicarboxylic acids (acid anhydrides and alkyl esters having 1 to 4 carbon atoms, etc. ) and the like.

Specific examples of dicarboxylic acids include saturated or unsaturated aliphatic dicarboxylic acids having 2 to 40 carbon atoms or more (preferably 2 to 12 carbon atoms) [oxalic acid, succinic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, maleic acid, fumaric acid, itaconic acid and dimer acid]; aromatic dicarboxylic acids having 8 to 15 carbon atoms [dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid etc.); and sulfo group-containing dicarboxylic acids [those obtained by introducing a sulfo group into the above dicarboxylic acids, such as sulfosuccinic acid, sulfomalonic acid, sulfoglutaric acid, sulfoadipic acid and sulfoisophthalic acid, and salts thereof (e.g., metal salts, ammonium salts, amine salts and quaternary ammonium salts); and polymers having terminal carboxyl groups.

Examples of the polymer having a carboxyl group at the end include polyether dicarboxylic acid [for example, carboxymethyl ether of polyol such as low-molecular-weight polyol (a1) having Mn of less than 300 described later or polyether polyol (a21) described later (in the presence of alkali with monochloroacetic acid, etc.)]; polyamide and/or polyester dicarboxylic acid [for example, lactams having 4 to 15 carbon atoms (caprolactam, enantholactam, laurolactam, undecanolactam, etc., using the above dicarboxylic acids as initiators ) or polylactam dicarboxylic acids and polylactone dicarboxylic acids obtained by ring-opening polymerization of lactones having 4 to 15 carbon atoms (γ-butyrolactone, γ-valerolactone, ε-caprolactone, etc.).

Examples of polylactone diols include water, lactones having 4 to 15 carbon atoms (γ-butyrolactone, γ-valerolactone, ε-caprolactone, etc.) using water, the aforementioned dihydric alcohols having 2 to 20 carbon atoms, or AO adducts thereof as initiators. and ring-opening adducts of

Polycarbonate diols include ring-opening addition/polycondensation products of alkylene carbonates starting with the above-mentioned dihydric alcohols having 2 to 20 carbon atoms or AO adducts thereof, and the above-mentioned dihydric alcohols having 2 to 20 carbon atoms or AO addition products thereof. and diphenyl or dialkyl carbonate polycondensation (ester exchange) products.

In the compound (S), the compound having two hydroxyl groups is preferable from the viewpoint of substrate adhesion after curing of the curable urethane composition, moist heat resistance, and dispersibility of the inorganic filler in the curable urethane composition. are AO adducts of dihydric alcohols having 2 to 20 carbon atoms, AO adducts of dihydric phenol compounds and polyester diols, more preferably poly(oxypropylene) glycol, poly(oxytetramethylene) glycol, AO adduct of bisphenol A and polyester diol composed of dihydric alcohol having 2 to 6 carbon atoms and polycarboxylic acid having 2 to 12 carbon atoms, particularly preferred are poly(oxytetramethylene) glycol and AO of bisphenol A It is an adjunct.
In the compound (S), X ¹ and X ² are each independent from the viewpoint of substrate adhesion after curing of the curable urethane composition, moist heat resistance, and dispersibility of the inorganic filler in the curable urethane composition. Preferably, a residue obtained by removing one hydroxyl group from an AO adduct of a dihydric alcohol having 2 to 20 carbon atoms, a residue obtained by removing one hydroxyl group from an AO adduct of a dihydric phenol compound, and a polyester diol A residue obtained by removing one hydroxyl group, more preferably a residue obtained by removing one hydroxyl group from poly(oxypropylene) glycol, a residue obtained by removing one hydroxyl group from poly(oxytetramethylene) glycol, bisphenol A A residue obtained by removing one hydroxyl group from the AO adduct of and a residue obtained by removing one hydroxyl group from a polyester diol composed of a dihydric alcohol having 2 to 6 carbon atoms and a polycarboxylic acid having 2 to 12 carbon atoms, A residue obtained by removing one hydroxyl group from poly(oxytetramethylene)glycol and a residue obtained by removing one hydroxyl group from an AO adduct of bisphenol A are particularly preferred.

In the general formula (1), —SO ₃ Z represents a sulfonate group, Z represents a counter ion, and Z is, for example, an alkali metal (eg, sodium, potassium, etc.) ion, an alkaline earth metal (eg, Calcium, magnesium, etc. (for example, Z=[Ca ²⁺ ] _1/2 , etc.) ions, onium [for example, ammonium, amines {including primary amines (having 1 to 50 carbon atoms, such as methylamine, ethylamine and alkylamines such as butylamine and monoalkanolamines such as monoethanolamine), secondary amines (including those having 2 to 50 carbon atoms, for example, dialkylamines such as dimethylamine, diethylamine and dibutylamine, and diethanolamine dialkanolamine, etc.), tertiary amines (including those having 3 to 50 carbon atoms, for example, trialkylamines such as trimethylamine, triethylamine and tributylamine, trialkylamines such as triethanolamine, N-methyldiethanolamine, etc. ), quaternary ammonium {including those having 4 to 50 carbon atoms, such as tetramethylammonium, etc.}, phosphonium (e.g., tetrabutylphosphonium, tributylbenzylphosphonium etc.), etc.].
Among these, alkali metal ions and onium ions are preferred, more preferably sodium ions, from the viewpoint of substrate adhesion after curing of the curable urethane composition and dispersibility of the inorganic filler in the curable urethane composition. Potassium ions and ammonium ions, particularly preferably sodium ions.

Z in the general formula (1) in the compound (S) is, for example, a salt such as hydrogen sulfite or pyrosulfite used as the sulfonating agent, and the alkali metal salt, alkaline earth metal salt, onium salt or the like is used. can be adjusted by

In the compound (S), the hydroxyl value of the compound having two hydroxyl groups is preferably 50 to 450 mgKOH/g, more preferably 80 to 300 mgKOH/g. When the hydroxyl value of the compound having two hydroxyl groups is within the above range, the concentration of the sulfonate groups in the compound (S) becomes appropriate, and the substrate adhesion after curing of the curable urethane composition is improved. In addition, since the urethane group with high cohesion generated by the reaction of the hydroxyl group in the compound (S) with the isocyanate group and the sulfonic acid group in the compound (S) can exist apart from each other, the curable urethane composition It is presumed that the dispersibility of the inorganic filler, which has a high affinity for the sulfonate group, tends to be good.
Incidentally, in the present invention, the hydroxyl value is measured according to JIS K1557-1.

The concentration of the sulfonate group in compound (S) is preferably 0.22 to 1.8 mmol/g, more preferably 0.3 to 1.6 mmol/g, particularly preferably 0.4 to 1.5 mmol/g. is.
The concentration of sulfonate groups can be determined according to the phase separation titration method (Epton method) for anionic surfactants. Specifically, the compound (S) is phase-separated into a system of chloroform and water, an aqueous solution of methylene blue hydrochloride is added as an indicator, and a 1 mmol/l benzalkonium chloride solution (standard cationic surfactant) is added in this state. Liquid) is added dropwise for phase separation titration, and the end point is determined by observing the migration of the indicator with the naked eye.

Concentration of sulfonate group (mmol/g) = (titration amount of cationic surfactant standard solution (ml)) x (concentration of cationic surfactant standard solution (mmol/l))/(amount of compound (S) ( g) × 1000)

When the concentration of the sulfonate group of the compound (S) is 0.22 mmol/g or more, the substrate adhesion of the curable urethane composition after curing tends to be good, and when it is 1.8 mmol/g or less. Dispersibility of inorganic fillers in curable urethane compositions tends to be good.

The hydroxyl value of compound (S) is preferably 25 to 190 mgKOH/g, more preferably 30 to 180 mgKOH/g, particularly preferably 40 to 170 mgKOH/g.
When the hydroxyl value of the compound (S) is 25 mgKOH/g or more, the concentration of the sulfonate group in the compound (S) becomes appropriate, and the curable urethane composition tends to have good adhesiveness to the substrate after curing. If it is 190 mgKOH / g or less, the urethane group with high cohesion generated by the reaction of the hydroxyl group in the compound (S) with the isocyanate group and the sulfonic acid group in the compound (S) are present apart. Therefore, the dispersibility of the inorganic filler in the curable urethane composition tends to be good.

The primary hydroxyl group ratio of the hydroxyl groups of the compound (S) is preferably 30 to 100%, more preferably 40 to 100%, from the viewpoint of curability of the curable urethane composition.
A method for measuring the ratio of primary hydroxyl groups will be specifically described below.
<Sample preparation method>
About 30 mg of a measurement sample is weighed into an NMR sample tube with a diameter of 5 mm, and dissolved by adding about 0.5 ml of a deuterated solvent. About 0.1 ml of trifluoroacetic anhydride is then added to obtain an analytical sample. Examples of the deuterated solvent include heavy water, deuterated chloroform, deuterated toluene, deuterated dimethylsulfoxide, and deuterated dimethylformamide, and a solvent capable of dissolving the sample is appropriately selected.
<NMR measurement>
¹ H-NMR measurement is performed under general conditions.

<Method for calculating primary hydroxyl group ratio>
By the pretreatment method described above, the hydroxyl group of compound (S) reacts with the added trifluoroacetic anhydride to form a trifluoroacetate. As a result, the signal derived from the methylene group to which the primary hydroxyl group was bound was observed at around 4.3 ppm, and the signal derived from the methine group to which the secondary hydroxyl group was bound was observed at around 5.2 ppm (deuterated chloroform was used as a solvent ). The primary hydroxyl group ratio is calculated by the following relational expression (2).
Primary hydroxyl group ratio (%) = [a / (a + 2 x b)] x 100 (2)
However, in the formula, a is the integrated value of the signal derived from the methylene group bonded to the primary hydroxyl group near 4.3 ppm; b is the integrated value of the signal derived from the methine group bonded to the secondary hydroxyl group near 5.2 ppm. .

The molecular formula weight or number average molecular weight (Mn) of the compound (S) is preferably 590 from the viewpoint of substrate adhesion after curing of the curable urethane composition and dispersibility of the inorganic filler in the curable urethane composition. 4500, more preferably 620-3700.

<Hydroxyl component (A)>
Examples of the hydroxyl group component (A) include the compound (S) and other hydroxyl group components (a) other than the compound (S).
Other hydroxyl group components (a) include a low-molecular-weight polyol (a1) having a number-average molecular weight (hereinafter abbreviated as Mn) of less than 300, a high-molecular-weight polyol (a2) having an Mn of 300 or more, and the "compound Examples include urethane prepolymers having terminal hydroxyl groups obtained by reacting a hydroxyl group component containing (S) with an isocyanate component (a3), and urethane prepolymers having hydroxyl groups other than (a3) (a4). The hydroxyl group component (A) may be used alone or in combination of two or more.

The Mn of the compound (S) and hydroxyl group component (A) in the present invention is measured by gel permeation chromatography using THF as a solvent and poly(oxyethylene) glycol as a standard substance. For example, it can be measured under the following conditions.
Apparatus: "Waters Alliance 2695" [manufactured by Waters]
Column: "Guardcolumn Super HL" (1 piece), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) each connected"
Sample solution: 0.25% by weight tetrahydrofuran solution Injection amount: 10 μl
Flow rate: 0.6 ml/min Measurement temperature: 40°C
Detection device: refractive index detector Reference material: standard polyethylene glycol

Low-molecular-weight polyols (a1) having Mn of less than 300 also include polyols having a chemical formula weight of less than 300, specifically, dihydric alcohols having 2 to 20 carbon atoms, trihydric to 8 carbon atoms having 3 to 20 Polyols having a valence of 5 to 20 and having functional groups other than hydroxyl groups and polyhydric alcohols having a valence of 5 to 20 are included.

Examples of the dihydric alcohol having 2 to 20 carbon atoms include those exemplified as the compound having two hydroxyl groups in the compound (S).

Examples of trihydric to octahydric or higher polyhydric alcohols having 3 to 20 carbon atoms include (cyclo)alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol, di pentaerythritol, 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerols], sugars and their derivatives [sucrose, glucose, fructose, mannose, lactose and glycosides (methyl glucoside, etc.)], and AO adducts of alkylenediamines such as N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine.

Examples of polyols having 5 to 20 carbon atoms having functional groups other than hydroxyl groups include polyols having carboxyl groups, sulfonic acid groups or salts thereof.

Examples of polyols having a carboxyl group include polyhydroxycarboxylic acids having 5 to 20 carbon atoms [e.g., 3,5-dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxymethyl) butanoic acid, 2,2-bis(2-hydroxyethyl)propionic acid, 2,2-bis(3-hydroxypropyl)propionic acid, bis(hydroxymethyl)acetic acid, bis(4-hydroxyphenyl)acetic acid, 2,2 -bis(hydroxymethyl)butyric acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, tartaric acid, N,N-dihydroxyethylglycine and N,N-bis(2-hydroxyethyl)-3-carboxy-propionamide ] is mentioned.

The polyol having a sulfonic acid group is other than the compound (S), and is, for example, a polyester polyol obtained by reacting a dicarboxylic acid containing a sulfonic acid group having 3 to 20 carbon atoms with one or more polyols. etc. Dicarboxylic acids containing a sulfonic acid group include, for example, 5-sulfoisophthalic acid and 2-sulfoterephthalic acid, with 5-sulfoisophthalic acid being preferred. Examples of polyols include alkylene glycols having 2 to 12 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol and 1, 6-hexanediol, etc.). The molar ratio (OH/COOH) of the hydroxyl group of the polyol and the carboxyl group of the dicarboxylic acid containing a sulfo group during esterification is preferably 1.1/1 to 5/1, more preferably 1.5/1 to 3/1.

The counter ion when the carboxyl group or sulfonic acid group forms a salt is not particularly limited, and examples of the salt include alkali metal (sodium and potassium) salts, ammonium salts, primary amines (methylamine, ethylamine, butylamine, etc.). alkylamines and monoalkanolamines such as monoethanolamine) salts, secondary amines (dimethylamine, dialkylamines such as diethylamine and dibutylamine, and dialkanolamines such as diethanolamine) salts, tertiary amines (trimethylamine, triethylamine and tri trialkylamines such as butylamine, trialkylamines such as triethanolamine, and alkyldialkanolamines such as N-methyldiethanolamine) salts and quaternary ammonium salts (tetraalkylammonium, etc.) salts.

Among the low-molecular-weight polyols (a1) having an Mn of less than 300, preferred from the viewpoint of reactivity are trihydric to octahydric or higher polyhydric alcohols having 3 to 20 carbon atoms, and more preferred are glycerin and trihydric alcohols. Methylolpropane and pentaerythritol.
Further, from the viewpoint of adhesiveness to the substrate of the cured product, a polyol having 5 to 20 carbon atoms having a functional group other than a hydroxyl group is preferable, and 2,2-bis(hydroxymethyl) having a carboxyl group is more preferable. Propionic acid and 2,2-bis(hydroxymethyl)butanoic acid.

Examples of polymer polyols (a2) having Mn of 300 or more include polyether polyols (a21), polyester polyols (a22) and other polyols (a23).

Examples of the polyether polyol (a21) include AO adducts of the low-molecular-weight polyol (a1), such as poly(oxyalkylene) glycol [poly(oxyethylene) glycol, poly(oxypropylene) glycol and poly(oxytetra methylene) glycol, poly(oxy-3-methyltetramethylene) glycol, etc.], copolymerized poly(oxyalkylene) diols [EO/PO copolymerized diols, THF/EO copolymerized diols and THF/3-methyltetrahydrofuran copolymerized diols etc. (weight ratio is, for example, 1/9 to 9/1)] and AO adducts of bisphenol-based compounds; and AO adducts of trimethylolpropane, etc.]; and those obtained by coupling one or more of these with methylene dichloride.

Examples of the above bisphenol compounds include bisphenol A, bisphenol B, bisphenol E and bisphenol F, and more specifically those described in JP-A-2008-126108.
The number of moles of AO added in the above is preferably 2 to 100 moles, more preferably 2, from the viewpoint of substrate adhesion after curing of the curable urethane composition and dispersibility of the inorganic filler in the curable urethane composition. to 50 mol, particularly preferably 2 to 30 mol.
In the case of the AO adduct of a bisphenol compound, the number of moles of AO added is preferably 2 to 10 mol, more preferably 2 to 6 mol, particularly preferably 2 to 4 mol.

As the polyester polyol (a22), in addition to the same compounds as those exemplified as the compounds having two hydroxyl groups in the compound (S), castor oil-based polyols and the like can be mentioned.

Castor oil-based polyols include castor oil (ricinoleic acid triglyceride), partially dehydrated castor oil, partially acylated castor oil, hydrogenated castor oil, and modified products thereof [polyether polyol (a21) or low molecular weight Mn less than 300 Ester polyol obtained by transesterification reaction of polyol (a1) with castor oil, partially dehydrated castor oil or hydrogenated castor oil, and polyether polyol (a21) or low-molecular-weight polyol (a1) having Mn of less than 300 and castor oil ester obtained by esterification reaction with fatty acid or hydrogenated castor oil fatty acid] and the like.

Other polyols (a23) include polymer polyols, polyolefin polyols, polyalkadiene polyols, acrylic polyols and amino group-containing polyols.

The polymer polyol is obtained by dispersing and stabilizing polymer particles obtained by polymerizing a vinyl monomer having 3 to 24 carbon atoms (eg, styrene, acrylonitrile) in one or more polyols in the presence of a radical polymerization initiator. Polyols (with a polymer content of, for example, 5 to 30% by weight) may be mentioned.
Polyisobutene polyol etc. are mentioned as a polyolefin polyol.
Polyalkadiene polyols include polyisoprene polyols, polybutadiene polyols, hydrogenated polyisoprene polyols and hydrogenated polybutadiene polyols.

Examples of acrylic polyols include copolymers of alkyl (meth)acrylates (alkyl with 1 to 30 carbon atoms) esters [butyl (meth)acrylate, etc.] and hydroxyl group-containing acrylic monomers [hydroxyethyl (meth)acrylate, etc.]. mentioned.
Examples of amino group-containing polyols include AO adducts of poly(n=2-6) alkylene (having 2-6 carbon atoms) and poly(n=3-7) amines [N,N,N',N',N'' -pentakis(2-hydroxypropyl)-diethylenetriamine, etc.].

As the above (ii) "a urethane prepolymer having a terminal hydroxyl group obtained by reacting a hydroxyl group component containing the compound (S) and an isocyanate component" (a3), the compound (S) and, if necessary, ( reacting at least one selected from the group consisting of a1) and (a2) with at least one selected from the group consisting of isocyanates (b1), (b2), (b3) and modified isocyanates (b4) described later; and a urethane prepolymer having a hydroxyl group at the terminal obtained by
As the urethane prepolymer (a4) having a hydroxyl group other than (a3), at least one selected from the group consisting of (a1) and (a2) and isocyanates (b1), (b2), (b3) and Examples include urethane prepolymers having terminal hydroxyl groups obtained by reacting with at least one selected from the group consisting of isocyanate-modified compounds (b4).

At least one selected from the group consisting of isocyanates (b1), (b2), (b3) and isocyanate-modified products (b4) described later when producing the urethane prepolymers (a3) and (a4) having hydroxyl groups at their ends The molar ratio (NCO/hydroxyl group) between the isocyanate group (NCO group) in the isocyanate component of and the hydroxyl group in at least one hydroxyl group component selected from the group consisting of compounds (S), (a1) and (a2) is , from the viewpoint of substrate adhesion after curing of the curable urethane composition and dispersibility of the inorganic filler in the curable urethane composition, preferably 0.25/1 to 0.99/1, more preferably 0 0.5/1 to 0.95/1, particularly preferably 0.6/1 to 0.9/1, most preferably 0.7/1 to 0.85/1.

The number average molecular weights of (a3) and (a4) are 1,500 to 100, from the viewpoint of substrate adhesion after curing of the curable urethane composition and dispersibility of the inorganic filler in the curable urethane composition. 000, more preferably 2,000 to 50,000.

The hydroxyl values of (a3) and (a4) are preferably 1 to 75 mgKOH/g, more preferably 2 to 60 mgKOH/g, from the viewpoint of substrate adhesion of the cured product.

In the present invention, the molar average functional group number of the hydroxyl group component (A) is preferably 2 to 6 or more, more preferably 2 to 5, particularly preferably 2 to 4, and most preferably 2 to 4, from the viewpoint of curability. 3.

<Isocyanate component (B)>
The isocyanate component (B) in the present invention includes an aliphatic isocyanate (b1) having 2 to 18 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), an araliphatic isocyanate (b2) having 8 to 15 carbon atoms, Aromatic isocyanates having 6 to 20 carbon atoms (b3), these isocyanurate groups, uretimine groups, allophanate groups, biuret groups, uretimine groups, carbodiimide groups and / or isocyanate modified products having uretdione groups (b4), the above (iii) ) “a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a hydroxyl group component containing the compound (S) with an isocyanate component” (b5), a urethane prepolymer having an isocyanate group other than the above (b5) (b6 ) and the like. The isocyanate component (B) may be used alone or in combination of two or more.

Aliphatic isocyanates having 2 to 18 carbon atoms (b1) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4 - or 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis(2-isocyanatoethyl) fumarate, bis( 2-isocyanatoethyl) carbonate, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexyl silene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and the like.

Examples of the araliphatic isocyanate (b2) having 8 to 15 carbon atoms include m- or p-xylylene diisocyanate (XDI), diethylbenzene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI). is mentioned.

The aromatic isocyanate (b3) having 6 to 20 carbon atoms includes 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'- or 2 , 4′-diphenylmethane diisocyanate (MDI), m- or p-isocyanatophenylsulfonyl isocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, and the like.

The isocyanate modified product (b4) having an isocyanurate group, uretimine group, allophanate group, biuret group, uretimine group, carbodiimide group and/or uretdione group includes a modified product of MDI having a uretimine group and a modified product of HDI having a biuret group. and isocyanurate group-containing modified forms of HDI.

The above (iii) "a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a hydroxyl group component containing the compound (S) and an isocyanate component" (b5) is used with the compound (S) if necessary. at least one selected from the group consisting of low-molecular-weight polyols (a1) and high-molecular-weight polyols (a2); urethane prepolymers having terminal isocyanate groups obtained by reacting with at least one of

The urethane prepolymer (b6) having an isocyanate group other than (b5) includes at least one selected from the group consisting of low-molecular-weight polyols (a1) and high-molecular-weight polyols (a2), excess isocyanate (b1), ( Urethane prepolymers having terminal isocyanate groups obtained by reacting with at least one selected from the group consisting of b2), (b3) and isocyanate modified products (b4).

In (b6), (a1) and (a2) preferably have a hydroxyl equivalent (molecular weight per hydroxyl group, hereinafter the same) of 1 from the viewpoint of the productivity of the urethane prepolymer and the adhesion of the cured product to the substrate. ,000 or less, more preferably from 30 to 500.

Specific examples of the urethane prepolymer (b6) include, for example, a hydrogenated MDI (2 mol) adduct of glycerin mono(meth)acrylate (1 mol), a TDI (4 mol) adduct of pentaerythritol (1 mol), tri HDI (3 mol) or TDI (3 mol) adduct of methylolpropane (1 mol), hydrogenated MDI (2 mol) adduct of bisphenol A AO 2 mol adduct (1 mol) and poly(oxypropylene) glycol ( 1 mol) MDI (2 mol) adducts, and the like.

In the present invention, the isocyanate component (B) is selected from the group consisting of tri- to octahydric polyhydric alcohols and isocyanates (b1), (b2) and (b3) from the viewpoint of the cohesion of the curable urethane composition. It preferably contains a urethane prepolymer having an isocyanate group which is a reactant with at least one species.
A curable urethane containing a urethane prepolymer having an isocyanate group, which is a reaction product of a tri- to octahydric polyhydric alcohol and at least one selected from the group consisting of isocyanates (b1), (b2) and (b3). Since the degree of cross-linking of the composition after curing increases and the cohesion of the cured product tends to increase, the adhesive strength after coating on the substrate tends to improve.

As the method for producing the urethane prepolymers (a3) and (a4) having hydroxyl groups at the ends and the urethane prepolymers (b5) and (b6) having isocyanate groups at the ends, known methods for producing urethane can be used. (toluene, xylene, ethyl acetate, butyl acetate, dimethylformamide, acetone, methyl ethyl ketone, tetrahydrofuran, etc.) or in the presence or absence of a reaction between the necessary hydroxyl group component and isocyanate component.

For the reaction, a known reaction apparatus (mixing vessel equipped with a stirrer, static mixer, etc.) can be used, and the reaction temperature is preferably 10 to 160° C., more preferably 25 to 160° C., from the viewpoint of reactivity and suppression of thermal deterioration. It is 120° C., and from the viewpoint of stability, it is preferable to replace the gas phase with nitrogen.

In the present invention, the molar average functional group number of the isocyanate component (B) is preferably 2 to 6 or more, more preferably 2 to 5, particularly preferably 2 to 4, from the viewpoint of curability.

The NCO equivalent weight (molecular weight per NCO group, hereinafter the same) of the isocyanate component (B) is preferably 1000 or less, more preferably 500 or less, and particularly preferably 300 or less, from the viewpoint of substrate adhesion of the cured product. be.
In addition, the isocyanate group content in the isocyanate component (B) (the weight ratio of the isocyanate groups contained in the isocyanate component (B), hereinafter the same) is preferably 0.5 to 50% by weight, more preferably 1 to 35% by weight, particularly preferably 3 to 30% by weight, particularly preferably 4 to 25% by weight, most preferably 12 to 24% by weight.

<Curable urethane composition>
The curable urethane composition of the present invention is a curable urethane composition containing a hydroxyl group component (A) and an isocyanate component (B), wherein at least one of the following (i) to (iii) is satisfied: It is a flexible urethane composition.
(i) The above (A) contains a compound (S) represented by the following general formula (1).
(ii) The hydroxyl group component (A) contains a urethane prepolymer having terminal hydroxyl groups obtained by reacting a hydroxyl group component containing the compound (S) with an isocyanate component.
(iii) The isocyanate component (B) contains a urethane prepolymer having terminal isocyanate groups obtained by reacting a hydroxyl group component containing the compound (S) with an isocyanate component.
The curable urethane composition of the present invention, from the viewpoint of substrate adhesion after curing of the curable urethane composition, is composed of a main agent containing the hydroxyl group component (A) and a curing agent containing the isocyanate component (B). It is preferable that it is a two-liquid curable urethane composition consisting of.

The curable urethane composition of the present invention contains the compound (S) as a hydroxyl group component (A) and/or a constituent monomer.
The content of the compound (S) in the curable urethane composition (including those contained as constituent monomers in the cases of (ii) and (iii)) is determined by the hydroxyl group component (A) and the isocyanate component (B ) based on the total weight of the curable urethane composition, preferably 0.1 to 60% by weight, from the viewpoint of the substrate adhesion after curing of the curable urethane composition and the dispersibility of the inorganic filler in the curable urethane composition, and further It is preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.
The content of the compound (S) in the hydroxyl group component (A) (including that contained as a constituent monomer in the case of (ii) above) is, based on the weight of the hydroxyl group component (A), curable urethane From the viewpoints of substrate adhesion after curing of the composition and dispersibility of the inorganic filler in the curable urethane composition, the content is preferably 1 to 99% by weight, more preferably 5 to 70% by weight, and particularly preferably 10 to 99% by weight. 60% by weight.

The concentration of the sulfonate group of the compound (S) based on the total weight of the hydroxyl group component (A) and the isocyanate component (B) is determined by the substrate adhesion and the curable urethane composition after curing. From the viewpoint of dispersibility of the inorganic filler in the composition, it is preferably 0.01 to 0.9 mmol/g, more preferably 0.02 to 0.85 mmol/g.
The concentration of the sulfonate group includes the concentration of the sulfonate group in the compound (S), and the content of the compound (S) in the hydroxyl group component (A) and the isocyanate component (B) ((ii) and ( (including the compound (S) as a constituent monomer of the urethane prepolymer in iii)).

In the curable urethane composition, the molar ratio (NCO group/hydroxyl group) between the isocyanate group in the isocyanate component (B) and the hydroxyl group in the hydroxyl group component (A) is preferably 0.7/1 to 2/1, and further Preferably 0.8/1 to 1.5/1, particularly preferably 0.9/1 to 1.3/1, most preferably 1/1 to 1.2/1.

The curable urethane composition of the present invention may contain an inorganic filler (C).
Further, when the curable urethane composition is a two-part curable urethane composition, from the viewpoint of the dispersibility of the inorganic filler (C), the compound (S) is included (including those contained as constituent monomers). It is preferable that the inorganic filler (C) is contained in the component. That is, in the case of (i) and/or (ii), it is preferable to contain the inorganic filler (C) in the main agent, and in the case of (iii), it is preferable to contain the inorganic filler (C) in the curing agent. preferable.
When the curable urethane composition of the present invention contains an inorganic filler, the inorganic filler is excellent in dispersibility in the curable urethane composition. This is because inorganic fillers generally have a high polarity, and thus have a high affinity with highly polar sulfonate groups. It is presumed that the inclusion of an acid base increases the affinity between (A) and/or (B) and the inorganic filler and improves the dispersibility of the inorganic filler (C) in the curable urethane composition. In addition, since the dispersibility of the inorganic filler (C) in the curable urethane composition is improved, the secondary aggregates of the inorganic filler (C) are reduced, the smoothness of the adhesion surface with the substrate is improved, and the adhesion area is increased. It is presumed that the larger the size, the better the adhesion to the substrate.

<Inorganic filler (C)>
Examples of inorganic fillers (C) include calcium carbonate, magnesium carbonate, fly ash, dehydrated sludge, natural silica, synthetic silica, kaolin, clay, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, barium sulfate, and calcium hydroxide. , aluminum hydroxide, alumina, magnesium hydroxide, talc, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite , xonolite, aluminum borate, silica balloons, glass flakes, glass balloons, silica, steel slag, copper, iron, iron oxide, carbon black, sendust, alnico magnets, magnetic powders such as various ferrites, cement, glass powder, diatomaceous earth, Antimony trioxide, magnesium oxysulfate, hydrated aluminum, hydrated gypsum, alum, inorganic pigments (alumina white, graphite, zinc white, lead white, white carbon, molybdenum white, litharge, lithopone, barite, cadmium red, cadmium mercury Red, red iron oxide, molybdenum red, red lead, yellow lead, cadmium yellow, barium yellow, strontium yellow, titanium yellow, titanium black, chrome oxide green, cobalt oxide, cobalt green, cobalt chrome green, ultramarine blue, dark blue, cobalt blue, cerulean blue, manganese purple, cobalt purple, etc.).
The inorganic filler (C) preferably has a volume average particle size of 0.01 to 20 μm.
These may be used alone or in combination of two or more.
Among these, calcium carbonate, magnesium oxide, alumina, talc, wollastonite, silica and iron oxide are preferred from the viewpoint of curability of the curable urethane composition.

The content of the inorganic filler (C) in the curable urethane composition is preferably 50 to 95, based on the weight of the curable urethane composition, from the viewpoint of coating properties of the curable urethane composition on a substrate. % by weight, more preferably 55 to 90% by weight, particularly preferably 60 to 85% by weight.
Weight ratio of the weight of the inorganic filler (C) in the curable urethane composition to the weight of the compound (S) (including those contained as constituent monomers in the cases of (ii) and (iii)) ( The inorganic filler/compound (S)) is preferably 2 to 90, more preferably 3 to 85, from the viewpoint of dispersibility of the inorganic filler (C) in the curable urethane composition.
When the inorganic filler (C) is included, the concentration of the sulfonate of the compound (S) in the curable urethane composition is the curable urethane from the viewpoint of the dispersibility of the inorganic filler (C) in the curable urethane composition. It is preferably 0.005 to 0.5 mmol/g, more preferably 0.01 to 0.45 mmol/g, based on the weight of the composition.
The sulfonic acid concentration of the compound (S) in the curable urethane composition is determined by the concentration of the sulfonic acid group in the compound (S) and the content of the compound (S) in the curable urethane composition ((ii ) and (iii) including the compound (S) as a constituent monomer of the urethane prepolymer.
The weight of the curable urethane composition does not include the weight of the solvent described later.

The curable urethane composition of the present invention can be prepared from solvents [e.g. aromatic solvents (toluene, xylene, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), amide solvents (dimethylformamide, etc.), ketone solvents (acetone and methyl ethyl ketone, etc.) and an ether solvent (tetrahydrofuran, etc.)].

Containing a solvent improves the handleability of the curable urethane composition.
The amount of solvent used is preferably based on the total weight of the hydroxyl group component (A), the isocyanate component (B) and the inorganic filler (C) optionally contained, from the viewpoint of handling and leveling of the curable urethane composition. 80% by weight or less, more preferably 10 to 50% by weight.

The curable urethane composition of the present invention may further contain a tackifier (E) in order to improve the substrate adhesiveness of the cured product.

Examples of the tackifier (E) include terpene resins, terpene phenol resins, phenol resins, aromatic hydrocarbon-modified terpene resins, rosin resins, modified rosin resins, synthetic petroleum resins (aliphatic, aromatic or alicyclic synthetic petroleum resins, etc.), coumarone-indene resins, xylene resins, styrene resins, dicyclopentadiene resins, and hydrogenated products of these having hydrogenatable unsaturated double bonds. The tackifier may be used alone or in combination of two or more.
Among these, those having an acid value and/or a hydroxyl value are preferable from the viewpoint of adhesiveness, and rosin resins, phenol resins, terpene phenol resins, xylene resins and hydrogenated products thereof are more preferable, and terpene phenol resins and their hydrogen Additives are particularly preferred.

The acid value or hydroxyl value of the tackifier (E) (the total value of the acid value and the hydroxyl value when both the acid group and the hydroxyl group are present in the molecule) is different from other polyol components used in the curable urethane composition. From the viewpoint of compatibility, it is preferably 10 to 400 mgKOH/g, more preferably 20 to 300 mgKOH/g, particularly preferably 50 to 250 mgKOH/g, most preferably 100 to 220 mgKOH/g.

The amount of the tackifier (E) used is based on the total weight of the hydroxyl group component (A), the isocyanate component (B) and the inorganic filler (C) in the case of a curable urethane composition. From the viewpoint of resistance and heat resistance, preferably 100% by weight or less, more preferably 1 to 50% by weight, particularly preferably 3 to 40% by weight, particularly preferably 5 to 35% by weight, most preferably 10 to 30% by weight. is.

The curable urethane composition of the present invention can contain a catalyst generally used for urethanization reaction if necessary to promote the curing reaction. Specific examples of catalysts include organometallic compounds [dibutyltin dilaurate, dioctyltin laurate, bismuth carboxylate, bismuth alkoxide, chelate compounds of bismuth with compounds having a dicarbonyl group, etc.], inorganic metal compounds [bismuth oxide, water bismuth oxide, bismuth halide, etc.]; amines [triethylamine, triethylenediamine, diazabicycloundecene, etc.] and combinations of two or more thereof.
Although the amount of the catalyst used is not particularly limited, it is preferably 0.0001 to 0.3% by weight, more preferably 0.001 to 0.3% by weight, based on the total weight of the hydroxyl group component (A) and the isocyanate component (B). 2% by weight, particularly preferably 0.01 to 0.1% by weight.

The curable urethane composition of the present invention may further contain additives such as antioxidants, ultraviolet absorbers, plasticizers, fillers and pigments within a range that does not impair the effects of the present invention.

Antioxidants include hindered phenol compounds [triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythrityl-tetrakis[3-(3,5 -di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc.] and phosphorous acid Ester compounds [tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, bis (2,6-di-t- butylphenyl)pentaerythritol-di-phosphite, tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylene-di-phosphonite, etc.]. These antioxidants may be used alone or in combination of two or more.
The amount of the antioxidant used is preferably 5 based on the total weight of the hydroxyl group component (A), the isocyanate component (B) and the inorganic filler (C), from the viewpoint of the antioxidant effect and the substrate adhesiveness of the cured product. % by weight or less, more preferably 0.05 to 1% by weight.

Examples of UV absorbers include salicylic acid derivatives (phenyl salicylate, -P-octylphenyl salicylate, -P-tert-butylphenyl salicylate, etc.), benzophenone compounds [2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 , 2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4 -Methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-(2-hydroxy-3-methacryloxy)propoxybenzophenone, bis(2-methoxy-4-hydroxy-5- benzoylphenyl)methane, etc.], benzotriazole compounds {2-(2'-hydroxy-5'-methyl-phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butyl-phenyl ) benzotriazole, 2-(2′-hydroxy-3′-t-butyl-5′-methyl-phenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5′- Di-t-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-4'-n-octoxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl ) benzotriazole, 2-(2′-hydroxy-3′,5′-di-t-amylphenyl)benzotriazole, 2-[2′-hydroxy-3′-(3″,4″,5″, 6″-tetrahydrophthalimidomethyl)-5′-methylphenyl]benzotriazole, 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl ) phenol], etc.}, cyanoacrylate compounds (2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, etc.), and the like. The ultraviolet absorbers may be used singly or in combination of two or more.
The amount of the ultraviolet absorber used is preferably 5 based on the total weight of the hydroxyl group component (A), the isocyanate component (B) and the inorganic filler (C), from the viewpoint of the ultraviolet absorption effect and the adhesiveness of the cured product to the substrate. % by weight or less, more preferably 0.1 to 1% by weight.

Examples of plasticizers include hydrocarbons [process oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, chlorinated paraffin, paraffin wax, copolymerization of ethylene and α-olefin (having 3 to 20 carbon atoms) (weight ratio 99.9/0.1 to 0.1/99.9) oligomer (Mw 5,000 to 100,000), copolymerized oligomer of propylene and α-olefin other than ethylene (4 to 20 carbon atoms) (weight ratio 99 .9/0.1 to 0.1/99.9) oligomers (Mw 5,000 to 100,000)]; chlorinated paraffins; esters [phthalates [diethyl phthalate (DEP), dibutyl phthalate (DBP), -2-ethylhexyl phthalate (DOP), didecyl phthalate, dilauryl phthalate, distearyl phthalate, diisononyl phthalate, etc.], adipates [di(2-ethylhexyl) adipate (DOA), dioctyl adipate, etc.] and sebacate esters ( dioctyl sebacate, etc.)]; animal and vegetable oils and fats (linoleic acid, linolenic acid, etc.); and hydrogenated products of these having hydrogenatable unsaturated double bonds. A plasticizer may be used individually by 1 type, or may use 2 or more types together.
The amount of the plasticizer used is preferably 100% by weight or less, based on the total weight of the hydroxyl group component (A), the isocyanate component (B), and the inorganic filler (C), from the viewpoint of substrate adhesion and cohesive strength of the cured product. , more preferably 0.5 to 30% by weight.

Pigments include organic pigments (shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, dye lakes, etc.). The above pigments are fine particles having a volume average particle diameter of preferably about 0.01 to 5 μm, and may be used alone or in combination of two or more.
The amount of the pigment used is preferably 250% by weight or less, more preferably 0.1 to 250% by weight, based on the total weight of the hydroxyl group component (A), the isocyanate component (B) and the inorganic filler (C), from the viewpoint of cohesion. 50% by weight.

Additives such as the solvent, tackifier (E), catalyst, antioxidant, UV absorber, plasticizer, filler and pigment may be added to either the main agent or the curing agent. and the inorganic filler (C) may be added at the time of blending, but it is preferable to add it to the main agent in advance.

<Cured product>
The cured product of the curable urethane composition of the present invention is a cured product obtained by subjecting the curable urethane composition of the present invention to a urethanization reaction.
The urethane group concentration of the cured product of the curable urethane composition of the present invention is based on the total weight of the hydroxyl group component (A) and the isocyanate component (B) contained in the curable urethane composition. From the viewpoint of material adhesion and mechanical properties of the cured product, preferably 0.02 to 4.5 mmol/g, more preferably 0.03 to 4.3 mmol/g, particularly preferably 0.04 to 4.0 mmol/g. is.
When the curable urethane composition of the present invention contains the inorganic filler (C), the concentration of urethane groups in the cured product is based on the weight of the cured product from the viewpoint of adhesion to the substrate of the cured product and mechanical properties of the cured product. , preferably 0.01 to 1.0 mmol/g, more preferably 0.02 to 0.95 mmol/g, particularly preferably 0.03 to 0.90 mmol/g.

The urea group concentration of the cured product of the curable urethane composition of the present invention is based on the total weight of the hydroxyl group component (A) and the isocyanate component (B) contained in the curable urethane composition. From the viewpoint of material adhesion and mechanical properties of the cured product, preferably 0.02 to 1.6 mmol/g, more preferably 0.03 to 1.5 mmol/g, particularly preferably 0.04 to 1.4 mmol/g. is.
When the curable urethane composition of the present invention contains the inorganic filler (C), the urea group concentration of the cured product is based on the weight of the cured product from the viewpoint of the substrate adhesion of the cured product and the mechanical properties of the cured product. , preferably 0.01 to 0.40 mmol/g, more preferably 0.03 to 0.37 mmol/g, particularly preferably 0.05 to 0.35 mmol/g.

The total concentration of urethane groups and urea groups in the cured product of the curable urethane composition of the present invention is based on the total weight of the hydroxyl group component (A) and the isocyanate component (B) contained in the curable urethane composition. , From the viewpoint of adhesion to the substrate of the cured product and mechanical properties of the cured product, preferably 0.04 to 6.1 mmol / g, more preferably 0.06 to 5.8 mmol / g, particularly preferably 0.08 to 5.4 mmol/g.
When the curable urethane composition of the present invention contains the inorganic filler (C), the total concentration of urethane groups and urea groups in the cured product is It is preferably 0.02 to 1.2 mmol/g, more preferably 0.05 to 1.07 mmol/g, particularly preferably 0.08 to 1.00 mmol/g, based on the weight of the product.

In the present invention, the cross-linking point density of the urethane resin in the cured product of the curable urethane composition (based on the total weight of the hydroxyl group component (A) and the isocyanate component (B) contained in the curable urethane composition) The number of moles of cross-linking points) is preferably 0.05 to 1.0 mmol/g, more preferably 0.1 to 0.9 mmol/g, from the viewpoint of adhesion to the substrate and mechanical properties of the cured product. be.
The cross-linking point density means the molar concentration of cross-linking points in the urethane resin. It can be adjusted by setting the concentration (mmol/g) to an appropriate range.
The cross-linking point density can be obtained from the following formula (1).
Crosslinking point density (mmol / g) = {Σ (fa-2) × wa / ma} / W × 1000 (1)

fa: Functional group number of compound a used as raw material for urethane resin wa: Weight (g) of compound a used as raw material for urethane resin
ma: Molecular weight (g/mol) of compound a used as raw material for urethane resin
W: total weight (g) of the hydroxyl group component (A) and the isocyanate component (B)

The curing temperature is preferably 10 to 160°C, more preferably 25 to 120°C, from the viewpoint of the curability and heat resistance of the curable urethane composition.
The viscosity of the curable urethane composition at the curing temperature (the viscosity of the mixture of the main agent and the curing agent) is determined from the viewpoint of moldability (thick coating is possible and there is no appearance defect such as warping or sink marks after curing) and coating properties. Therefore, it is preferably 0.01 to 100 Pa·s, more preferably 0.02 to 50 Pa·s, and particularly preferably 0.03 to 10 Pa·s.

The curable urethane composition of the present invention can be molded into various forms according to the application using methods such as cast molding, roll coating, and slit coating. As for the form, a sheet is preferred from the standpoint of ease of processing and wide range of applications.
The preferred thickness of the sheet varies depending on the properties and applications, but in the case of a member that is strongly desired to be made smaller and thinner, it is preferably as thin as 10 to 500 μm, more preferably 10 to 300 μm.

As a method for forming the sheet, after kneading the curable urethane composition, a method of directly extruding from a T-die, a method of rolling with a roll, a method of stretching, a method of filling a mold with a curable urethane composition and then pressurizing. a method in which the curable urethane composition is made into a solution and then cast, or a method in which another resin or a metal sheet is coated with the composition can be used.
A sheet comprising a cured product of the curable urethane composition of the present invention can be provided with an adhesive layer by coating an adhesive or attaching a double-sided tape to the sheet itself.

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited thereto.

Production Example 1 [Production of compound (S0-1)]
250 parts by weight of poly(oxytetramethylene) glycol ["PTMG250" manufactured by Mitsubishi Chemical Corporation: Mn = 250] and 49 parts by weight of maleic anhydride were charged into a reaction vessel, stirred and mixed under a nitrogen atmosphere, and then under normal pressure. , and reacted at 120±10° C. for 1 hour to half-esterify the acid anhydride group portion, and further reacted under reduced pressure at 120±10° C. for 3 hours to esterify the remaining carboxyl group, maleic anhydride. A compound (S0-1) was obtained by esterifying 1 mol of poly(oxytetramethylene)glycol with 2 mol of poly(oxytetramethylene)glycol.

Production Example 2 [Production of compound (S0-2)]
Compound (S0-2) in the same manner as in Production Example 1 except that 250 parts by weight of poly(oxytetramethylene) glycol is changed to 650 parts by weight of poly(oxytetramethylene) glycol [BASF "PolyTHF650": Mn = 650] got

Production Example 3 [Production of compound (S0-3)]
Compound ( S0-3) was obtained.

Production Example 4 [Production of compound (S0-4)]
Compound ( S0-4) was obtained.

Production Example 5 [Production of compound (S0-5)]
Compound (S0-5) in the same manner as in Production Example 1 except that 250 parts by weight of poly(oxytetramethylene) glycol was changed to 400 parts by weight of polyethylene glycol [manufactured by Sanyo Chemical Industries, Ltd. "PEG400": Mn = 400] got

Production Example 6 [Production of compound (S0-6)]
Compound (SO- 6) was obtained.

Production Example 7 [Production of compound (S0-7)]
The procedure was the same as in Production Example 1 except that 250 parts by weight of poly(oxytetramethylene) glycol was changed to 1070 parts by weight of polyester diol ["Sanester 4610" (polyethylene butylene adipate) manufactured by Sanyo Chemical Industries, Ltd.: Mn = 1070]. to obtain compound (S0-7).

Production Example 8 [Production of compound (S0-8)]
Production Example 1 except that 250 parts by weight of poly(oxytetramethylene) glycol was changed to 410 parts by weight of an ethylene oxide adduct of bisphenol A [“Newpol BPE-40” manufactured by Sanyo Chemical Industries, Ltd.: Mn = 410]. Compound (S0-8) was obtained in the same manner.

Comparative Production Example 1 [Production of compound (ratio S0-1)]
In the same manner as in Production Example 1, except that 250 parts by weight of poly(oxytetramethylene) glycol was changed to 582 parts by weight of an ethylene oxide adduct of oleyl alcohol ["Emalmin NL90" manufactured by Sanyo Chemical Industries, Ltd.: Mn = 582]. A compound (ratio S0-1) was obtained.

Production Example 9 [Production of compound (S-1)]
580 parts by weight of compound (S0-1), 95 parts by weight of sodium pyrosulfite, 300 parts by weight of water, and 100 parts by weight of isopropanol were charged into a reaction vessel, stirred and mixed under a nitrogen atmosphere, and A sulfonate is added to the unsaturated carbon-carbon double bond portion of the unsaturated dicarboxylic acid diester of compound (S0-1), and unreacted water and isopropanol are removed under reduced pressure at 100°C ± 10°C. ℃ for 3 hours to obtain a compound (S-1).

Production Example 10 [Production of compound (S-2)]
Compound (S-2) was obtained in the same manner as in Production Example 9 except that 580 parts by weight of compound (S0-1) was changed to 1380 parts by weight of compound (S0-2).

Production Example 11 [Production of compound (S-3)]
Compound (S-3) was obtained in the same manner as in Production Example 9 except that 580 parts by weight of compound (S0-1) was changed to 2080 parts by weight of compound (S0-3).

Production Example 12 [Production of compound (S-4)]
Compound (S-4) was obtained in the same manner as in Production Example 9 except that 580 parts by weight of compound (S0-1) was changed to 4080 parts by weight of compound (S0-4).

Production Example 13 [Production of compound (S-5)]
Compound (S-5) was obtained in the same manner as in Production Example 9 except that 580 parts by weight of compound (S0-1) was changed to 480 parts by weight of compound (S0-5).

Production Example 14 [Production of compound (S-6)]
Compound (S-6) was obtained in the same manner as in Production Example 9 except that 580 parts by weight of compound (S0-1) was changed to 1280 parts by weight of compound (S0-6).

Production Example 15 [Production of compound (S-7)]
Compound (S-7) was obtained in the same manner as in Production Example 9 except that 580 parts by weight of compound (S0-1) was changed to 2220 parts by weight of compound (S0-7).

Production Example 16 [Production of compound (S-8)]
Compound (S-8) was obtained in the same manner as in Production Example 9 except that 580 parts by weight of compound (S0-1) was changed to 900 parts by weight of compound (S0-8).

Production Example 17 [Production of compound (S-9)]
Compound (S-9) was obtained in the same manner as in Production Example 9 except that 95 parts by weight of sodium pyrosulfite was changed to 111 parts by weight of potassium pyrosulfite.

Production Example 18 [Production of compound (S-10)]
2080 parts by weight of compound (S0-3), 111 parts by weight of potassium pyrosulfite, 300 parts by weight of water, and 100 parts by weight of isopropanol were charged into a reaction vessel, stirred and mixed under a nitrogen atmosphere, and A sulfonate is added to the unsaturated carbon-carbon double bond portion of the unsaturated dicarboxylic acid diester of compound (S0-3), and unreacted water and isopropanol are removed under reduced pressure at 100°C ± 10°C. °C for 3 hours to obtain a compound (S-10).

Production Example 19 [Production of compound (S-11)]
580 parts by weight of compound (S0-1) in a reaction vessel, 304 parts by weight of ammonium hydrogen sulfite aqueous solution [manufactured by Daito Chemical Co., Ltd. "ammonium bisulfite solution": 65% by weight aqueous solution], ammonium sulfite monohydrate [Nacalai "Ammonium sulfite monohydrate" manufactured by Tesque Co., Ltd.] 214 parts by weight and 660 parts by weight of water are charged, stirred and mixed in an air atmosphere, reacted at 60 ° C. ± 10 ° C. for 6 hours, and compound (S0 A sulfonate is added to the unsaturated carbon-carbon double bond portion of the unsaturated dicarboxylic acid diester of -1), 470 parts by weight of methanol is charged to precipitate the reaction adduct, and the compound (S-11) is filtered. ).

Production Example 20 [Production of compound (S-12)]
Compound (S-12) was obtained in the same manner as in Production Example 19 except that 580 parts by weight of compound (S0-1) in the reaction vessel was changed to 2080 parts by weight of compound (S0-3).

Comparative Production Example 2 [Production of compound (ratio S-1)]
A compound (ratio S-1) was obtained in the same manner as in Production Example 1 except that 580 parts by weight of the compound (S0-1) in the reaction vessel was changed to 1244 parts by weight of the compound (ratio S0-1).

Table 1 shows the physical properties of compounds (S-1) to (S-12) and (ratio S-1) obtained in Production Examples 9 to 20 and Comparative Production Example 2.

Production Example 21 [Production of hydroxyl group component (a-1)]
300 parts by weight of bisphenol A ethylene oxide ["Newpol BPE-20T" manufactured by Sanyo Chemical Industries, Ltd.: Mn = 320] and polytetramethylene glycol ["PTMG250" manufactured by Mitsubishi Chemical Corporation: Mn = 300 parts by weight in a reaction vessel. 250] 100 parts by weight, polytetramethylene glycol ["PTMG1000" manufactured by Mitsubishi Chemical Corporation: Mn = 1000] 80 parts by weight, compound (S-1) 240 parts by weight, hexamethylene diisocyanate [manufactured by Asahi Kasei Corporation "Duranate 50 M", NCO content 50.0% by weight] 280 parts by weight of methyl ethyl ketone and 2000 parts by weight of methyl ethyl ketone are charged, stirred and mixed under a nitrogen stream, and reacted at 60 to 70°C for 10 hours to obtain a urethane prepolymer having terminal hydroxyl groups. (a-1) was obtained.

Production Examples 22 to 46 [Production of hydroxyl group components (a-2) to (a-26)]
Urethane prepolymers (a-2) to (a-26) having terminal hydroxyl groups were obtained in the same manner as in Production Example 21, except that the starting materials shown in Tables 2 and 3 were used.

Production Example 47 [Production of isocyanate component (b-1)]
In a reaction vessel, 170 parts by weight of bisphenol A/ethylene oxide adduct ["Newpol BPE-40" manufactured by Sanyo Chemical Industries, Ltd.: Mn = 410] and 4,4'-diphenylmethane diisocyanate ["Millionate" manufactured by Tosoh Corporation. MT", NCO content 33.6% by weight] was charged, stirred and mixed under a nitrogen stream, reacted at 70 to 80°C for 3 hours, and then carbodiimide-modified 4,4'-diphenylmethane diisocyanate [BASF 510 parts by weight of "Luplanate MM-103" manufactured by INOAC Polyurethane Co., Ltd., NCO content 29.5% by weight] were charged, stirred and mixed under a nitrogen stream to obtain a urethane prepolymer having an isocyanate group at its end (b- 1) was obtained.

Production Examples 48 to 50 [Production of isocyanate components (b-2) to (b-4)]
Urethane prepolymers (b-2) to (b-4) having terminal isocyanate groups were obtained in the same manner as in Production Example 47, except that the raw materials shown in Table 3 were used.

The isocyanate content, hydroxyl value, sulfonic acid group concentration, molar average functional group number and Mn of the urethane prepolymers (a-1) to (a-26) and (b-1) to (b-4) are shown in the table below. 2.

なお、表２及び３中の各原料は下記である。
・ビスフェノールＡ・ＥＯ付加物 Ｍｎ＝４１０：三洋化成工業（株）製「ニューポールＢＰＥ－４０」
・ビスフェノールＡ・ＥＯ付加物 Ｍｎ＝３２０：三洋化成工業（株）製「ニューポールＢＰＥ－２０Ｔ」
・ポリテトラメチレングリコール Ｍｎ＝２５０：三菱化学（株）製「ＰＴＭＧ２５０」
・ポリテトラメチレングリコール Ｍｎ＝１０００：三菱化学（株）製「ＰＴＭＧ１０００」
・ポリ（オキシプロピレン）グリコール Ｍｎ＝１０００：三洋化成工業（株）製「ＰＰ－１０００」
・ポリエステルジオール Ｍｎ＝１０７０：三洋化成工業（株）製「サンエスター４６１０」
・ビスフェノールＡ・ＰＯ付加物 Ｍｎ＝１０００：三洋化成工業（株）製「ＢＰ－１３Ｐ」
・ポリ（オキシプロピレン）グリコール Ｍｎ＝２５０：三洋化成工業（株）製「サンニックス ＧＰ－２５０」
・トリシクロデカンジメタノール：ＯＱケミカルズジャパン（株）製「ＴＣＤ ａｌｃｏｈｏｌ ＤＭ」
・化合物Ｓ－１～Ｓ－１２：製造例９～２０で得られた化合物
・４，４’－ジフェニルメタンジイソシアネート：東ソー（株）製「ミリオネートＭＴ」、ＮＣＯ含有量３３．６重量％
・カルボジイミド変性ＭＤＩ：カルボジイミド変性４，４’－ジフェニルメタンジイソシアネート［ＢＡＳＦ ＩＮＯＡＣポリウレタン（株）製「ルプラネートＭＭ－１０３」、ＮＣＯ含有量２９．５重量％］
・モノメリックＭＤＩ－ＭＩ：４、４’－ジフェニルメタンジイソシアネートと４、２－ジフェニルメタンジイソシアネートの混合物［ＢＡＳＦ ＩＮＯＡＣ ポリウレタン（株）製「モノメリックＭＤＩ－ＭＩ」、ＮＣＯ含有量３３．６重量％］
・ヘキサメチレンジイソシアネート：旭化成（株）製「デュラネート５０Ｍ」、ＮＣＯ含有量５０．０重量％
・イソホロンジイソシアネート：住化コベストロウレタン（株）「ＤＥＳＭＯＤＵＲ Ｉ」、ＮＣＯ含有量３７．８重量％

In addition, each raw material in Tables 2 and 3 is as follows.
・ Bisphenol A EO adduct Mn = 410: "Newpol BPE-40" manufactured by Sanyo Chemical Industries, Ltd.
・ Bisphenol A EO adduct Mn = 320: "Newpol BPE-20T" manufactured by Sanyo Chemical Industries, Ltd.
- Polytetramethylene glycol Mn = 250: "PTMG250" manufactured by Mitsubishi Chemical Corporation
- Polytetramethylene glycol Mn = 1000: "PTMG1000" manufactured by Mitsubishi Chemical Corporation
· Poly (oxypropylene) glycol Mn = 1000: "PP-1000" manufactured by Sanyo Chemical Industries, Ltd.
· Polyester diol Mn = 1070: Sanyo Chemical Industries, Ltd. "San Estar 4610"
· Bisphenol A · PO adduct Mn = 1000: Sanyo Chemical Industries, Ltd. "BP-13P"
・ Poly (oxypropylene) glycol Mn = 250: Sanyo Chemical Industries, Ltd. "Sannics GP-250"
・ Tricyclodecanedimethanol: OQ Chemicals Japan Co., Ltd. "TCD alcohol DM"
- Compounds S-1 to S-12: compounds obtained in Production Examples 9 to 20 - 4,4'-diphenylmethane diisocyanate: "Millionate MT" manufactured by Tosoh Corporation, NCO content 33.6% by weight
Carbodiimide-modified MDI: carbodiimide-modified 4,4'-diphenylmethane diisocyanate [BASF INOAC Polyurethane Co., Ltd. "Lupranate MM-103", NCO content 29.5% by weight]
Monomeric MDI-MI: a mixture of 4,4′-diphenylmethane diisocyanate and 4,2-diphenylmethane diisocyanate [BASF INOAC Polyurethanes Co., Ltd. “Monomeric MDI-MI”, NCO content 33.6% by weight]
・Hexamethylene diisocyanate: “Duranate 50M” manufactured by Asahi Kasei Co., Ltd., NCO content 50.0% by weight
・Isophorone diisocyanate: Sumika Covestro Urethane Co., Ltd. "DESMODUR I", NCO content 37.8% by weight

Examples 1-51 and Comparative Examples 1-2
Using each component in the number of parts shown in Tables 4 and 5, using the hydroxyl group component (A) as the main component and the isocyanate component (B) as the curing agent, two-component curable urethane compositions (Y1) to (Y51) and (comparative Y1) to (ratio Y2) were obtained. The resulting two-part curable urethane compositions (Y1) to (Y51) and (ratio Y1) to (ratio Y2) were mixed with the main agent, curing agent, and organic solvent in the amounts shown in Tables 4 and 5 in a planetary mixer. and mixed to obtain a curable urethane composition.

Examples 52-93, 95-98 and Comparative Examples 3-4
Using each component in the number of parts shown in Tables 6 and 7, a hydroxyl group component (A) and an inorganic filler (C) are mixed as a main component, and an isocyanate component (B) is used as a curing agent to prepare a two-pack curable urethane composition. (Y52) to (Y93), (Y95) to (Y98) and (ratio Y3) to (ratio Y4) were obtained. The main agents, curing agents and organic solvents of the obtained two-component curable urethane compositions (Y52) to (Y93), (Y95) to (Y98) and (ratio Y3) to (ratio Y4) are shown in Tables 6 and 7. The indicated amounts were mixed using a planetary mixer to obtain a curable urethane composition.

Example 94
Using each component in the number of parts shown in Table 7, the isocyanate component (B) and the inorganic filler (C) are mixed to form a curing agent, and the hydroxyl group component (A) is used as the main component to prepare a two-pack curable urethane composition (Y94 ). The main component and curing agent of the obtained two-component curable urethane composition (Y94) were mixed in the amounts shown in Table 3 using a planetary mixer to obtain a curable urethane composition.

The details of each component in Tables 4 to 7 are as follows.
(S-1) to (S-12) and (ratio S-1): compounds obtained in Production Examples 9 to 20 and Comparative Production Example 2 (a-1) to (a-26): Production Examples Urethane prepolymer having a terminal hydroxyl group obtained in 21 to 46 (a-27): polyether diol ["Sannics PP-1000" manufactured by Sanyo Chemical Industries, Ltd.: Mn = 1000]
(a-28): polytetramethylene glycol [manufactured by BASF "PolyTHF650": Mn = 650]
(a-29): polyester diol [Sanyo Chemical Industries, Ltd. "Sanester 4610": Mn = 1070]
(a-30): Ethylene oxide adduct of bisphenol A ["Newpol BPE-40" manufactured by Sanyo Chemical Industries, Ltd.: Mn = 410]
(a-31): polyether polyol [Sanyo Chemical Industries, Ltd. "Sannics GP-250": Mn = 250, hydroxyl group average trifunctional]
(a-32): polyether polyol ["Newpol NP-300" manufactured by Sanyo Chemical Industries, Ltd.: Mn = 300, hydroxyl group average tetrafunctional]
・ (a-33): Polyether polyol [Sanyo Chemical Industries, Ltd. “Sannics SP-750”: Mn = 750, hydroxyl group average 6 functional]
- (b-1) to (b-4): urethane prepolymer having an isocyanate group at the end obtained in Production Examples 47 to 50 - (b-5): isocyanurate (hexamethylene diisocyanate trimer compound) [ Asahi Kasei Co., Ltd. "Duranate TPA-100", isocyanate group average trifunctional]
・ (C-1): Calcium carbonate [“Ryton A” manufactured by Bihoku Funka Kogyo Co., Ltd. Average particle size: 1.8 μm]
・ (C-2): Alumina ["Admafine AO-502" manufactured by Admatechs, particle size: 0.2 to 0.3 μm]
・ (C-3): Iron oxide ["Iron oxide (III)" manufactured by Nacalai Tesque Co., Ltd.]

(1) Mechanical properties of cured product of curable urethane composition The curable urethane composition obtained in Examples or Comparative Examples is placed in a release box (length 20 cm x width 10 cm x depth 2.5 cm) after curing. The mixture was poured to a thickness of 2 mm, dried in a circulating air dryer at 100°C for 10 hours, cured in an incubator at 50°C for 3 days, and dumbbells were prepared.
Using the prepared dumbbell, the tensile strength (MPa) was measured according to the tensile test method of JIS K7311, and the values are shown in Tables 4-7.
In Tables 6 and 7, the larger the numerical value of the tensile strength, the better the dispersibility of the inorganic filler, which means that the interface adhesion between the cured products of (A) and (B) and the inorganic filler (C) is high. do.

(2) Method for measuring substrate adhesive strength The curable urethane composition obtained in Examples or Comparative Examples was applied to a PET film (thickness: 50 µm) using an applicator so that the thickness after curing was 50 µm. After drying for 5 minutes in a circulating air dryer at 100°C, a PET film was laminated using a roll and cured in an incubator at 50°C for 3 days to obtain a laminate film.
The laminate film was cut into a size of 200 mm×25 mm, and the T-peel strength (unit: N/25 mm) was measured using a tensile tester at 23° C. and a tensile speed of 300 mm/min. Five samples were measured, and the average values are shown in Tables 4-7.

(3) Moisture and heat resistance evaluation method Each of the curable urethane compositions obtained in Examples or Comparative Examples was applied to a PET film (thickness: 50 µm) using an applicator so that the thickness after curing was 50 µm. After drying for 5 minutes in a circulating air dryer at 100°C, the PET film was laminated using a roll, cured in an incubator at 50°C for 3 days, and then placed in a constant temperature and humidity machine at 85°C and 85% RH for 1 week. It was allowed to stand still to obtain a laminate film.
The laminate film was cut into a size of 200 mm×25 mm, and the T-peel strength (unit: N/25 mm) was measured using a tensile tester at 23° C. and a tensile speed of 300 mm/min. Five samples were measured, the average value was calculated, and compared with the substrate adhesive strength measured in (2), the wet heat resistance was evaluated according to the following evaluation criteria. The results are shown in Tables 4-7.
◎: 95% or more of the numerical value of the substrate adhesive strength ○: 90% or more and less than 95% of the numerical value of the substrate adhesive strength △: 85% or more and less than 90% of the numerical value of the substrate adhesive strength ×: Numerical value of the substrate adhesive strength less than 85% of

(4) Evaluation Method of Dispersibility of Inorganic Filler In Tables 6 and 7, the dispersibility of the inorganic filler was evaluated. Specifically, in (2) above, the appearance after coating on a PET film (thickness 50 μm) using an applicator so that the thickness after curing is 50 μm is observed, and the dispersibility of the inorganic filler is evaluated as follows. was evaluated by the evaluation level of The results are shown in Tables 6-7.
<Evaluation level>
⊚: No blurring occurred on the coated surface, and no lifting of the inorganic filler.
◯: Although the coating surface is not scratched, a slight floating of the inorganic filler can be confirmed.
Δ: The coated surface is slightly scratched, and the inorganic filler is lifted.
x: Scratches occurred on the coated surface, and floating of the inorganic filler was conspicuous.

From the results in Tables 4 to 7, the cured products of the curable urethane compositions of Examples containing the compound (S) as a constituent monomer in the cured products of the curable urethane compositions exhibited substrate adhesiveness after curing. It turns out that it is good. Furthermore, the cured product has high mechanical properties and good moisture and heat resistance, and it can be seen that the cured product of the curable urethane composition containing the inorganic filler has high dispersibility of the inorganic filler.
On the other hand, in Comparative Examples 1 to 4, in which the cured product of the curable urethane composition did not contain the compound (S) as a constituent monomer, the mechanical properties of the cured product and the adhesive strength to the substrate of the cured product were low. It can be seen that 4 also has low filler dispersibility. In particular, when Example 36 containing the compound (S) as a constituent monomer is compared with Comparative Example 1, which is otherwise substantially the same, it can be seen that Comparative Example 1 is inferior in mechanical properties and substrate adhesion. . In addition, when comparing Examples 24 to 35 containing the compound (S) as a constituent monomer and Comparative Example 2 under almost the same conditions other than that, Comparative Example 2 has all of mechanical properties, substrate adhesion and moist heat resistance. It can be seen that it is inferior in Further, when Example 85 containing the compound (S) as a constituent monomer is compared with Comparative Example 3 under almost the same conditions other than that, Comparative Example 3 is inferior in filler dispersibility, mechanical properties and substrate adhesiveness. I know there is. Furthermore, from a comparison between Examples 73 to 84 and Comparative Example 4 using a compound having no hydroxyl value (ratio S-1), it was observed that filler dispersibility tended to improve by using the compound (ratio S-1). However, it can be seen that the mechanical properties, substrate adhesion and moist heat resistance of the cured product are extremely low.

The curable urethane composition of the present invention has excellent adhesiveness to substrates and good dispersibility of inorganic fillers. (for example, sealing materials, binders for electromagnetic wave shields, binders for electromagnetic wave absorbing sheets, heat dissipation gap fillers, heat dissipation adhesives, heat shield paints, conductive paints, etc.).

Claims (8)

A curable urethane composition containing a hydroxyl group component (A) and an isocyanate component (B) and satisfying at least one of the following (i) to (iii).
(i) the hydroxyl group component (A) contains a compound (S) represented by the following general formula (1); (ii) the hydroxyl group component (A) contains the compound (S); a hydroxyl group component and an isocyanate component; (iii) the isocyanate component (B) containing a urethane prepolymer having a hydroxyl group at the end obtained by reacting an isocyanate group at the end obtained by reacting a hydroxyl group component containing the compound (S) and an isocyanate component contains a urethane prepolymer having

[In general formula (1), X ¹ and X ² represent a residue obtained by removing one hydroxyl group from a compound having two hydroxyl groups, and X ¹ and X ² may be the same or different; SO 3 Z represents a trivalent chain saturated hydrocarbon group having 2 to 10 carbon atoms; SO ₃ Z represents a sulfonate group. ] 2. Curability according to claim 1, wherein the curable urethane composition is a two-part curable urethane composition comprising a main component containing the hydroxyl group component (A) and a curing agent containing the isocyanate component (B). Urethane composition. 3. The curable urethane composition according to claim 1, wherein the compound (S) has a hydroxyl value of 25 to 190 mgKOH/g. The concentration of the sulfonate group in the compound (S) based on the total weight of the hydroxyl group component (A) and the isocyanate component (B) is 0.01 to 0.9 mmol/g. A curable urethane composition according to any one of the preceding items. The curable urethane composition according to any one of claims 1 to 4, further comprising an inorganic filler (C). The curable urethane composition according to Claim 5, wherein the content of the inorganic filler (C) in the curable urethane composition is 50 to 95% by weight based on the weight of the curable urethane composition. A cured product of the curable urethane composition according to any one of claims 1 to 6. The urethane group concentration of the cured product of the curable urethane composition is 0.02 to 4.0, based on the total weight of the hydroxyl group component (A) and the isocyanate component (B) contained in the curable urethane composition. The cured product according to claim 7, which is 5 mmol/g.