JP6630416B2 - Curable composition - Google Patents

Description

  The present invention is a curable composition which gives a cured product having excellent surface appearance without foaming of a molded article or a coating film upon curing, and is particularly excellent in defoaming property and leveling property, and thus has excellent surface appearance. The present invention relates to a curable urethane composition that gives a product.

  Curable urethane resins are widely used in thermosetting moldings, paints, cold-curing moldings, injections, paints and coating materials. In addition, cured products obtained by curing epoxy resins are widely used as electrical and electronic insulating materials, paints, adhesives, casting materials, etc. because of their excellent heat resistance, electrical properties, mechanical properties, etc. ing. In these applications, at the time of molding or coating of paint, foams on the cured surface, cissing, various defects such as craters may occur and the finish of the cured surface may be impaired, and as a countermeasure, an antifoaming agent is used. Often. These defoaming agents have either the effect of improving the surface activity or the effect of making the compatibility worse, that is, the effect of incompatibility. An antifoaming agent or an antifoaming agent composed of a modified butadiene polymer has been used. As the defoaming agent containing a vinyl polymer as a component, for example, Patent Document 1 discloses an antifoaming agent composed of an acrylic / vinyl ether copolymer, and Patent Document 2 discloses a defoaming agent composed of a vinyl ether polymer. (Patent Documents 1 and 2).

  However, silicone-based defoaming agents with high surface-active effects exhibit good defoaming effects when added in a small amount, but they become the main cause of repelling and crater phenomena in the coatings industry, and greatly impair the aesthetics of the cured surface. was there. An acrylic / vinyl ether copolymer-based antifoaming agent, a modified butadiene-based polymer antifoaming agent, or a vinyl ether polymer antifoaming agent may not have a sufficient antifoaming effect depending on the viscosity of the system and the presence or absence of a solvent. Was. In addition, since the antifoaming agent utilizing the incompatibility effect is not compatible with the composition, it inhibits the glossiness of the cured surface, and in extreme cases, the entire surface becomes cloudy or causes a bleeding phenomenon. There was a case.

JP-A-61-141772 JP-A-2-232271

  An object of the present invention is to provide a curable composition which does not foam a molded article or a coating film during curing and provides a cured product having excellent surface appearance.

The present invention relates to the following [1] to [10].
[1] at least one curable resin (X) selected from a curable urethane resin and a curable epoxy resin;
A curable composition containing an anti-foaming agent (Y) composed of an α-olefin (co) polymer satisfying the following requirements (y-1) to (y-2):
(Y-1) The methyl group index measured from ¹ H-NMR is 25 to 60% (here, the methyl group index is obtained by dissolving the α-olefin (co) polymer in heavy chloroform. ¹ H-NMR was measured, and when the solvent peak based on CHCl ₃ in deuterated chloroform was used as a reference (7.24 ppm), 0 was defined as the integrated value of the peak within the range of 0.50 to 2.20 ppm. .50 to 1.15 ppm).
(Y-2) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is from 1,500 to 11,000.

[2] The antifoaming agent (Y) is curable group composition as described in [1], wherein the melting point as measured by differential scanning calorimetry (DSC) not observed.
[3] The curable resin (X) is a curable urethane resin, curable group composition as described in [1] or [2].

[4] The curing according to any one of [1] to [3], wherein the amount of the antifoaming agent (Y) used is 0.001 to 20 parts by weight per 100 parts by weight of the curable resin (X). Composition.
[5] The method according to any one of [1] to [4], wherein the methyl group index of the α-olefin (co) polymer constituting the antifoaming agent (Y) is 25 to 40%. The curable composition according to the above.

  [6] The method according to any one of [1] to [4], wherein the methyl group index of the α-olefin (co) polymer constituting the antifoaming agent (Y) is 40 to 60%. The curable composition according to the above.

[7] A molded article formed from the curable composition according to any one of [1] to [6].
[8] A paint containing the curable composition according to any one of [1] to [6].
[9] A waterproof material formed from the curable composition according to any one of [1] to [6].
[10] A coating film formed from the curable composition according to any one of [1] to [6].

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition which does not foam a molded object or a coating film at the time of hardening, and which gives the hardened | cured material which is excellent in surface appearance, especially glossiness (glossiness) can be provided.

FIG. 1 is a graph showing a change in gloss (%) in a cured product obtained from the curable composition with respect to the content (% by weight) of the antifoaming agent (Y) in the curable composition.

Hereinafter, the present invention will be described specifically. In the following description, “to” indicating a numerical range, for example, when described as “A to B”, means “not less than A and not more than B” unless otherwise specified. Further, in this specification, the term “(co) polymer” is used as a concept including both homopolymers and copolymers.
Curable group composition as the present invention, moldings, coatings, elastic coating material, can be used in various applications such as waterproof material.

<Curable composition>
The curable composition of the present invention contains the following curable resin (X) and defoamer (Y).
(X) at least one curable resin selected from a curable urethane resin and a curable epoxy resin The curable resin (X) constituting the curable composition according to the present invention is (X-1) a curable urethane resin. And (X-2) at least one curable resin selected from the group consisting of curable epoxy resins.

(X-1) Curable urethane resin In the present invention, a curable urethane resin (X-1) is one of the components that can be the curable resin (X). Here, in the present invention, a curable urethane resin (X-1) is suitably adopted as the curable resin (X). The curable urethane resin used in the present invention may be any of various curable urethane resins including conventionally known ones. Generally, an active hydrogen group-containing compound and an excessive amount of an organic polyisocyanate contain water in the atmosphere. It consists of a one-part curing type that reacts and cures below, and a liquid A containing an organic polyisocyanate and a liquid B containing an active hydrogen group-containing compound. It is roughly classified into a two-pack curing type that is subjected to curing by measuring and mixing. In the present invention, the curable urethane resin (X-1) may be used in any one of a one-part curing type and a two-part curing type. A two-part curing type in which the curing speed can be easily adjusted is preferable.

Here, the organic polyisocyanate contained in the liquid A has an average of two or more isocyanate groups in one molecule. Such organic polyisocyanate is not particularly limited, but, for example,
m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate Aromatic diisocyanates such as isocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate;
Aromatic ring-containing aliphatic diisocyanate such as 1,3- or 1,4-xylylene diisocyanate;
Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- Or aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, norbornane diisocyanate, and 2,6-diisocyanatomethyl caproate;
1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methyl-2 Alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane; and carbodiimide-modified, biuret-modified, allophanate-modified diisocyanates Examples thereof include organic polyisocyanates used in the production of ordinary polyurethane resins, such as monomers and trimers. These organic polyisocyanates may be used alone or in a combination of two or more.

  Among the above organic polyisocyanates, aromatic diisocyanates are preferable, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate or a mixture thereof, 4,4′-diphenylmethane diisocyanate, carbodiimide-modified 4,4′-diphenylmethane Diisocyanate and polymethylene polyphenyl polyisocyanate (hereinafter referred to as "crude MDI") are preferred.

  On the other hand, the active hydrogen group-containing compound contained in the solution B is not particularly limited, and examples thereof include a polyamine and a polyol. Here, in general, among the curable urethane resins used in the present invention, a polyamine is mainly used as the active hydrogen group-containing compound, and the bond between the active hydrogen group-containing compound and the organic polyisocyanate is mainly formed by a urea bond. The resulting curable resin is mainly referred to as a urea resin, and a polyol is mainly used as an active hydrogen group-containing compound, and a curable resin in which an active hydrogen group-containing compound and an organic polyisocyanate are mainly bonded through a urethane bond is referred to as a urethane resin. Although they may be separated, in the present application, they are collectively referred to as a curable urethane resin without distinction.

Here, as the polyamine, for example,
Aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, polyoxyalkylenepolyamine;
Alicyclic polyamines such as isophoronediamine, norbornenediamine, hydrogenated xylylenediamine;
Aromatic ring-containing aliphatic polyamines such as xylylenediamine;
3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 4,4′-diaminodiphenylmethane, 2,4-tolylenediamine, 2,6-tolylenediamine, 1,1'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4.4'-diaminodiphenylmethane, 1,1 ', 2,2'-tetrachloro-4,4'-diaminodiphenylmethane , 1,3,5-triethyl-2,6-diaminobenzene, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenyl-methane, N, N'-bis (t-butyl)- Aromatic polyamines having an amine value of 180 to 700, such as 4,4'-diaminodiphenyl-methane and di (methylthio) toluenediamine.

On the other hand, as the polyol, for example,
Ethylene glycol, propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,6-hexanediol, neopentyl glycol, alkanediol (carbon number: 7 to 22), diethylene glycol , Triethylene glycol, dipropylene glycol, cyclohexane dimethanol, alkane-1,2-diol (carbon number: 17 to 20), hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl- Low molecular weight diols such as 1-octene-3,8-diol, bishydroxyethoxybenzene, xylene glycol, bishydroxyethylene terephthalate, bisphenol A, bisphenol F;
Glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) Low molecular weight triols such as propane, 2,2-bis (hydroxymethyl) -3-butanol, and aliphatic triols having 8 to 24 carbon atoms;
Low molecular weight polyols having four or more hydroxyl groups in one molecule, such as pentaerythritol;
Corresponding polyolefins obtained by dehydration-condensation of the low-molecular-weight diol, the low-molecular-weight triol, and the low-molecular-weight polyol having four or more hydroxyl groups in one molecule, such as diethylene glycol, dipentaerythritol, and ditrimethylolpropane. Dihydric alcohol ether;
Polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran;
Natural fat polyols such as castor oil;
Examples thereof include polyolefin polyols such as polybutadiene polyol and polyisoprene polyol, and hydrogenated products thereof.

In addition, as other polyols which can be the active hydrogen group-containing compound, the low molecular weight diol, low molecular weight triol, diamine or triamine or higher polyamine is obtained by an addition reaction with an alkylene oxide such as ethylene oxide and propylene oxide. Polyoxyalkylene polyol;
A polyester polyol obtained by ring-opening polymerization of a lactone such as ε-caprolactone or γ-valerolactone using the low-molecular diol or low-molecular triol as a starting material;
A polycarbonate polyol obtained by ring-opening polymerization of ethylene carbonate using the low molecular diol and the low molecular triol as starting materials;
At least one polyol selected from the group consisting of low-molecular diols and low-molecular triols; oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3- At least one selected from the group consisting of dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (carbon numbers: 11 to 13), hetic acid and derivatives thereof And polyester polyols obtained by reaction with certain compounds. Here, as the carboxylic acid derivative, acid anhydrides such as oxalic anhydride, succinic anhydride, 2-alkyl anhydride (carbon number: 12 to 18) succinic acid, oxalic acid dichloride, adipic acid chloride, sebacic acid chloride And the like.

  These active hydrogen group-containing compounds may be used alone or in combination of two or more. As the active hydrogen group-containing compound, preferably, polyoxyethylene polyol, polyoxyethylene propylene polyol, polyoxypropylene polyol, bisphenol-based polyol having 2 to 4 active hydrogen groups per molecule and an average molecular weight of 200 to 6000 And castor oil polyols.

  Among these active hydrogen group-containing compounds, polyols are preferred from the viewpoint of obtaining a cured product having excellent flexibility. Among them, those in which two or more compounds selected from polyols having 2 to 4 active hydrogen groups in one molecule are used.

  On the other hand, polyamines are preferred from the viewpoints of particularly excellent curing reaction rates at low temperatures and excellent chemical stability of cured products. Here, preferred examples of the polyamine include polyoxyalkylenediamines having an average molecular weight of at least one amino group in one molecule and a molecular weight of 200 to 6000, and polyoxyalkylene triamines. Diamine having a structure in which a terminal hydroxyl group is substituted by an amino group, and triamine having a structure in which a terminal hydroxyl group of a polyol is obtained by dehydrating and condensing polypropylene glycol with a trihydric alcohol such as glycerin, and the like, is exemplified. Can be Further, such polyoxyalkylene diamine or polyoxyalkylene triamine can be used in combination with the above-mentioned polyamine.

When the polyol and the polyamine are used in combination, a cured product having both characteristics is obtained, which is preferable.
In the present invention, as described above, a two-part curable urethane resin can be suitably used as the curable urethane resin (X-1).

  Here, as the liquid A of the two-part curable curable urethane resin, an excess of the organic polyisocyanate can be used without limitation, and at least one of the organic polyisocyanates in one molecule obtained by the reaction with the active hydrogen group-containing compound is used. It is preferred to use a prepolymer having two free isocyanate groups. Specifically, under a nitrogen gas atmosphere, the organic polyisocyanate and the active hydrogen group-containing compound are mixed with each other at a ratio of one to one active hydrogen group in the active hydrogen group-containing compound to one isocyanate group of the organic polyisocyanate. It is prepared by reacting at a rate of 2.0 at a temperature of 40 to 120 ° C. for 4 to 8 hours with stirring. The urethane prepolymer thus obtained preferably has an isocyanate group content of 1 to 20% by weight, preferably 2 to 10% by weight.

  As the active hydrogen group-containing compound used in the liquid B of the two-part curable urethane resin, the above-mentioned active hydrogen group-containing compounds, such as polyamine and polyol, can be used without any particular limitation. It is preferable to use a prepolymer having at least one active hydrogen group-containing compound in one molecule obtained by reacting the organic polyisocyanate with an excess of the active hydrogen group-containing compound.

  In the curable urethane resin used in the present invention, the active hydrogen group (hydroxyl group and / or amino group) in the active hydrogen group-containing compound is preferably 0.1 to 2 per one isocyanate group in the organic polyisocyanate. , More preferably 0.5 to 1.5, and even more preferably 0.8 to 1.2.

(X-2) Liquid epoxy resin As the liquid epoxy resin (X-2) used in the present invention, a known epoxy resin can be used without any particular limitation as long as it is a liquid epoxy resin at room temperature. Specifically, glycidyl ether type epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, hydrogenated bisphenol A type liquid epoxy resin; glycidyl ester type epoxy resin, for example, hexahydro Glycidyl phthalate, glycidyl dimer; glycidylamine type epoxy resin, for example, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane; linear aliphatic epoxide, for example, epoxidized polybutadiene, epoxidized soybean oil; alicyclic epoxy side For example, 3,4-epoxy-6-methylcyclohexylmethyl carboxylate, 3,4-epoxycyclohexylmethyl carboxylate and the like can be mentioned. It may be used as a mixture of two or more. Among these, it is preferable to contain a bisphenol-type epoxy resin from the viewpoint that the obtained cured product has excellent mechanical properties and heat resistance and is easily available industrially.

  As the liquid epoxy resin (X-2) used in the present invention, various solid epoxy resins or the like may be used in combination and liquefied by heating and mixing as long as the effects of the present invention are not impaired. good.

The liquid epoxy resin (X-2) used in the present invention may be added with a low-viscosity aliphatic epoxy compound to reduce the viscosity of the liquid epoxy resin, and may be adjusted to have a desired viscosity. As such a low-viscosity aliphatic epoxy compound, specifically, a glycidyl ether of a polyhydric alcohol or a glycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to a polyhydric alcohol, For example,
Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and pentaerythritol poly Glycidyl ethers of aliphatic polyhydric alcohols such as glycidyl ether and hydrogenated bisphenol A diglycidyl ether;
Examples thereof include glycidyl ethers of aliphatic polyether polyols such as diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polyoxyethylene polyoxypropylene glycol diglycidyl ether. Preferably, it is a glycidyl ether of a polyhydric alcohol or a glycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to a polyhydric alcohol, having a viscosity of 100 mPa · s or less at room temperature. Further, the epoxy compound used for the purpose of reducing the viscosity of the liquid epoxy resin in the present invention is not limited to the low-viscosity aliphatic epoxy compound, for example, such as resorcinol diglycidyl ether, a relatively high viscosity of aromatic glycidyl ethers. It may be a low one or an aromatic glycidylamine such as diglycidylaniline, which has a relatively low viscosity.
These epoxy compounds may be used alone or as a mixture of two or more.

(Y) Antifoaming agent As the antifoaming agent (Y) constituting the curable composition according to the present invention, an α-olefin (co) polymer is used. The α-olefin (co) polymer serving as the antifoaming agent (Y) in the present invention is specifically a (co) polymer of an α-olefin having 2 to 20 carbon atoms.

Examples of the α-olefin having 2 to 20 carbon atoms constituting the α-olefin (co) polymer used as the antifoaming agent (Y) in the present invention include ethylene, propylene, 1-butene, 1-pentene and 1-pentene. -Hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tricene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene , 1-nonadecene, 1-eicosene linear α-olefin, 3-methyl-1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6- Examples thereof include branched α-olefins such as methyl-1-undecene and 6,8-dimethyl-1-decene.
These α-olefins can be used alone or in combination of two or more.

The α-olefin (co) polymer used in the present invention is characterized in that the proportion of methyl groups in all protons is within a certain range. It is generally known that a peak of a proton of a methyl group is observed on the high magnetic field side in ¹ H-NMR measurement (“Polymer Analysis Handbook” (P. 163-170, published by Asakura Shoten)). For this reason, in the present application, the ratio of the peak on the high magnetic field side observed when measured by ¹ H-NMR was used as an index of a methyl group (hereinafter, referred to as “methyl group index”). Specifically, an α-olefin (co) polymer was dissolved in deuterated chloroform and ¹ H-NMR was measured. When the solvent peak based on CHCl ₃ in deuterated chloroform was used as a reference (7.24 ppm), The ratio of the integrated value of the peak within the range of 0.50 to 1.15 ppm to the integrated value of the peak within the range of 0.50 to 2.20 ppm was defined as a methyl group index. Here, the peak based on the α-olefin (co) polymer is almost included in the range of 0.50 to 2.20 ppm. In this range, the peak based on the methyl group is likely to be included in the range of 0.50 to 1.15 ppm.

  The α-olefin (co) polymer used in the present invention has a methyl group index of 25 to 60%, a preferred embodiment is 25 to 35%, and another preferred embodiment is 45 to 55%. In general, in order to exhibit defoaming properties, it is important that a component that is incompatible with a liquid (a curable resin in the present application) that generates foam is taken into the foam film and destabilizes the foam film. It is said that. However, if the compatibility is too poor, bleed out occurs on the surface, and the appearance deteriorates. Therefore, in order to achieve both defoaming properties and appearance, it is important to appropriately control the compatibility with the curable resin. When the methyl group index is in the range of 25% to 60%, the compatibility with the curable resin is optimal, the defoaming property can be effectively exhibited, and the appearance can be maintained.

  The methyl group index can be controlled by selecting an appropriate monomer and polymerizing it. For example, a homopolymer of an α-olefin having 3 to 5 carbon atoms such as propylene, butene, and isobutene has an excessively high ratio of a methyl group to a monomer. In this case, it is necessary to select an α-olefin having 6 to 20 carbon atoms as a monomer. A polymer satisfying such requirements is a higher α-olefin (co) polymer (PAO), which is a preferred embodiment of the α-olefin (co) polymer in the present invention. Details will be described later. Also, for example, since a homopolymer of ethylene does not have a methyl group, it is necessary to appropriately copolymerize an α-olefin having 3 to 20 carbon atoms to increase the ratio of the methyl group. A polymer satisfying such requirements is an ethylene / α-olefin copolymer which is another preferred embodiment of the α-olefin (co) polymer in the present invention. Details will be described later.

  The α-olefin (co) polymer used in the present invention is preferably liquid at room temperature. It is preferable to be liquid at normal temperature, since it is excellent in mixing with a curable resin which is often liquid, and easily exhibits defoaming with a small amount.

  The α-olefin (co) polymer used in the present invention preferably has no observed melting point as measured by differential scanning calorimetry (DSC). Here, that the melting point (Tm) is not observed means that the heat of fusion (ΔH) (unit: J / g) measured by the differential scanning calorimetry (DSC) is not substantially measured. The fact that the heat of fusion (ΔH) is not substantially measured means that no peak is observed in the differential scanning calorimeter (DSC) measurement or the observed heat of fusion is 1 J / g or less. The melting point (Tm) and heat of fusion (ΔH) of the α-olefin (co) polymer are measured by a differential scanning calorimeter (DSC), cooled to −100 ° C., and then heated to 150 ° C. at a rate of 10 ° C./min. When the temperature was raised to, the DSC curve was analyzed and determined with reference to JIS K7121. If the melting point is not observed, it tends to be liquid at normal temperature, and the defoaming property is easily developed as described above.

  The weight average molecular weight (Mw) of the α-olefin (co) polymer used in the present invention is preferably in the range of 1,500 to 11,000, preferably 1,500 to 10,000, more preferably 2,500. The range is from 000 to 6,000. Since the compatibility with the curable resin is improved by the contribution of the entropy term as the molecular weight is smaller, the control of the average molecular weight is important for appropriately controlling the compatibility. When the weight average molecular weight is smaller than the above lower limit, particularly 1,500, the compatibility may be too high to exhibit the defoaming property, and bleed-out is likely to occur due to the low molecular weight component. On the other hand, if the weight average molecular weight is larger than the above upper limit, particularly 11,000, the compatibility with the curable resin may be too low, which may cause bleed out. On the other hand, if the weight average molecular weight is more than the above upper limit, especially 11,000, the viscosity becomes too high, the dispersibility decreases, and it is difficult to be taken into the foam film, and the defoaming property may be impaired.

  The molecular weight distribution (Mw / Mn) of the α-olefin (co) polymer used in the present invention measured by gel permeation chromatography is not particularly limited, but the upper limit is usually 3 or less, Preferably it is 2.5 or less, more preferably 2 or less. The lower limit is usually 1.0 or more, preferably 1.2 or more. If the molecular weight distribution is wide (Mw / Mn is large), defoaming properties are hardly exhibited, and a large amount of high molecular weight or low molecular weight components that bleed out to the surface and impair the appearance are included, which is not preferable.

  The weight average molecular weight and the molecular weight distribution can be measured by gel permeation chromatography (GPC) calibrated using a standard substance having a known molecular weight (monodisperse polystyrene).

The kinematic viscosity at 100 ° C. of the α-olefin (co) polymer used in the present invention is preferably in the range of 1 to 1,500 mm ² / s, more preferably in the range of 4 to 1,000 mm ² / s. Yes, more preferably in the range of 10 to 800 mm ² / s, still more preferably in the range of 15 to 600 mm ² / s, and particularly preferably in the range of ^{20 to} 300 mm ² / s. When the kinematic viscosity at 100 ° C. of the α-olefin copolymer is smaller than the above lower limit, particularly 1 mm ² / s, the defoaming property is not exhibited, and bleeding out to the surface may impair the appearance. On the other hand, if the kinematic viscosity at 100 ° C. of the α-olefin copolymer is higher than the above upper limit, especially 1,500 mm ² / s, the viscosity becomes too high, dispersibility in the curable resin is lowered, and the Since it is difficult to be taken in, the defoaming property may be impaired. In other words, when the kinematic viscosity at 100 ° C. of the α-olefin (co) polymer is within the above numerical range, the dispersibility of the α-olefin (co) polymer in the curable resin is sufficiently maintained. In this form, sufficient defoaming properties can be exhibited.
The α-olefin (co) polymer according to the present invention may be used singly, or two or more α-olefin (co) polymers may be used in combination.

(Higher α-olefin (co) polymer)
In the present invention, one preferred embodiment of the α-olefin (co) polymer constituting the antifoaming agent (Y) is a (co) polymer of a monomer comprising one or more α-olefins having 6 to 20 carbon atoms. It is united. Here, the (co) polymer of a monomer comprising one or more α-olefins having 6 to 20 carbon atoms refers to an α-olefin homopolymer having 6 to 20 carbon atoms or a carbon atom An α-olefin copolymer having 6 to 20 carbon atoms and containing at least one structural unit corresponding to α-olefins having 6 to 20 carbon atoms. In the present specification, such an α-olefin (co) polymer may be referred to as “higher α-olefin (co) polymer” for convenience. Further, if necessary, ethylene and / or an α-olefin having 3 to 5 carbon atoms can be introduced as a copolymer component within a range not exceeding 50 mol%. Such higher α-olefin (co) polymers are generally referred to as PAOs.

  In the present specification, when an olefin constituting a certain (co) polymer is represented by X, the expression “structural unit derived from X” may be used. Unit ", that is, a structural unit having a pair of bonds, formed by opening a π bond constituting a double bond of X.

  Examples of the α-olefin having 6 to 20 carbon atoms used in the higher α-olefin (co) polymer (PAO) include 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-hexene. Linear α-olefins of dodecene, 1-tricene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and 3-methyl-1 Α having a branch such as -pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, 6,8-dimethyl-1-decene, etc. Examples thereof include olefins, preferably linear α-olefins having 8 to 12 carbon atoms, and particularly preferably 1-octene and 1-decene.

  In the present invention, the content of the structural unit derived from the monomer composed of the α-olefin having 6 to 20 carbon atoms constituting the higher α-olefin (co) polymer (PAO) is in the range of 50 to 100 mol%. And preferably 55 to 100 mol%, more preferably 60 to 100 mol%.

  In the present invention, the content of the constituent unit derived from ethylene constituting the higher α-olefin (co) polymer (PAO) is in the range of 0 to 50 mol%, preferably 0 to 45 mol%, more preferably. Ranges from 0 to 40 mol%.

  Further, if necessary, an α-olefin having 3 to 5 carbon atoms can be contained at a ratio of 0 to 30 mol%. Examples of such α-olefins having 3 to 5 carbon atoms include linear α-olefins such as propylene, 1-butene and 1-pentene, and branched α-olefins such as 3-methyl-1-butene. be able to. These α-olefins having 3 to 5 carbon atoms can be used alone or in combination of two or more.

The methyl group index of the higher α-olefin (co) polymer (PAO) is not particularly limited, but is preferably 25% to 40%, more preferably 25% to 35% in order to maintain a liquid state.
These α-olefins can be used alone or in combination of two or more.

  Since the higher α-olefin (co) polymer (PAO) has a small composition distribution in the molecule when having a low regular structure, it is easy to appropriately control the compatibility with the curable composition. preferable.

  The above-mentioned higher α-olefin (co) polymer (PAO) is disclosed in U.S. Pat. No. 3,382,291, U.S. Pat. No. 3,763,244, and U.S. Pat. No. 5,171,908. U.S. Pat. No. 3,780,128; U.S. Pat. No. 4,032,591; JP-A-1-163136; U.S. Pat. No. 4,967,032; U.S. Pat. No. 4,926,004. As described in the gazette, it can be obtained by oligomerization using an acid catalyst such as boron trifluoride or a chromic acid catalyst. Further, a metallocene compound as described in JP-A-63-037102, JP-A-2005-200447, JP-A-2005-200448, JP-A-2009-503147, and JP-A-2009-501836 is used. It can also be obtained by a method using a catalyst system using a transition metal complex such as zirconium, titanium, hafnium or the like. Oligomerization with an acid catalyst is preferred from the viewpoint of versatility of the production method and availability of the obtained α-olefin (co) polymer (PAO). Among these acid catalysts, boron trifluoride is particularly preferred in that a low-ordered structure is obtained.

  Such PAOs are commercially available and are available from ExxonMobil Chemical Company, Inc., "SpectraSyn (registered trademark)", "SpectraSyn (registered trademark) Plus", "SpectraSyn (registered trademark) Elite", "SpectraSyn (registered trademark) Ultra", Ineos (urs) "Duras" (Trademark) and Chemtura (Synton (trademark)).

(Ethylene / α-olefin copolymer)
In the present invention, another preferred embodiment of the α-olefin (co) polymer is an α-olefin copolymer having 3 or more carbon atoms of ethylene (hereinafter, also referred to as “ethylene / α-olefin copolymer”). is there. Examples of the α-olefin constituting the ethylene / α-olefin copolymer include α-olefins other than ethylene, and typical examples include propylene, butene-1, pentene-1, hexene-1, heptene-1, and octene. -1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eicosene-1, etc. And 3 to 20 α-olefins. In the ethylene / α-olefin copolymer, one kind of these α-olefins may be used alone, or two or more kinds may be used in combination. However, in the present invention, in order to distinguish from the above “higher α-olefin (co) polymer”, in the ethylene / α-olefin copolymer, the structural unit corresponding to the α-olefin having 6 to 20 carbon atoms is used. The content is less than 50 mol%. Among these α-olefins, the point that the crystallinity is effectively reduced to make the sample liquid, the compatibility with the curable resin is controlled, and the balance between the defoaming property and the appearance of the curable composition is improved. And an α-olefin having 3 to 10 carbon atoms is preferable, and propylene is particularly preferable.

  The ethylene / α-olefin copolymer has an ethylene structural unit content of 30 to 80 mol%, preferably 40 to 75 mol%, more preferably 40 to 60 mol%. If the ethylene content is too large or too small, the crystallinity becomes high, the liquid crystal is not liquid, and it becomes difficult to mix with the curable resin, and the defoaming effect may be reduced.

The ethylene content of the ethylene / α-olefin copolymer can be measured by ¹³ C-NMR method. For example, the peak is determined according to the method described later and the method described in “Polymer Analysis Handbook” (published by Asakura Shoten, pages 163-170). Can be identified and quantified.

  The ethylene / α-olefin copolymer according to the present invention has a blockiness (B value) measured by NMR of usually 0.9 or more, preferably 1.0 or more. The B value is a parameter indicating the randomness of the copolymerization monomer chain distribution. When the B value is small, the crystallinity is high, the liquid is not liquid, and it is difficult to mix with the curable resin, and the defoaming effect is reduced. .

  The methyl group index of the ethylene / α-olefin copolymer according to the present invention is not particularly limited, but is preferably 40 to 60%, more preferably 40 to 55%, and still more preferably 45 to 50% in order to maintain a liquid state. Is more preferred.

  The ethylene / α-olefin copolymer according to the present invention can be produced using a known method without limitation. For example, ethylene and an α-olefin are copolymerized in the presence of a catalyst comprising a transition metal compound such as vanadium, zirconium, titanium, or hafnium, and an organic aluminum compound (organic aluminum oxy compound) and / or an ionized ionic compound. Method. A metallocene catalyst using a transition metal compound such as zirconium, titanium, or hafnium has a reduced 2,1-bond amount (inversion) of two or more continuous propylene monomers, and improves the low-temperature characteristics of the curable composition. Therefore, it is preferable. Such a method is described in, for example, WO 2000/34420 pamphlet, JP-A-62-121710, WO 2004/29062 pamphlet, JP-A 2004-175707, WO 2001/27124 pamphlet and the like. Have been.

(Other aspects)
In the present invention, the α-olefin (co) polymer used as the antifoaming agent (Y) may be in the form as it is, or may have been given a polar group by graft modification. Good. Vinyl compounds having a polar group used for modification include acids, acid anhydrides, esters, alcohols, epoxies, vinyl compounds having an oxygen-containing group such as ether, isocyanates, vinyl compounds having a nitrogen-containing group such as amide, A vinyl compound having a silicon-containing group such as vinyl silane can be used.

Among these, a vinyl compound having an oxygen-containing group is preferable, and specific examples thereof include an unsaturated epoxy monomer, an unsaturated carboxylic acid, and derivatives thereof. Examples of the unsaturated epoxy monomer include unsaturated glycidyl ether and unsaturated glycidyl ester (for example, glycidyl methacrylate). Examples of the unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid ^TM (endocis-bicyclo [2,2,1] hept-5). -Ene-2,3-dicarboxylic acid).

  In addition, examples of the derivative of the unsaturated carboxylic acid include an acid halide compound, an amide compound, an imide compound, an acid anhydride, and an ester compound of the unsaturated carboxylic acid. Specific examples include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

Among these, unsaturated dicarboxylic acids and acid anhydrides thereof are more preferable, and maleic acid, nadic acid ^TM and acid anhydrides thereof are particularly preferably used.
The position at which the vinyl compound having a polar group or a derivative thereof is grafted to the α-olefin (co) polymer is not particularly limited, and an unsaturated carbon atom at any carbon atom of the α-olefin (co) polymer may be used. A carboxylic acid or a derivative thereof may be bonded.

The modified α-olefin (co) polymer as described above can be prepared using various conventionally known methods, for example, the following methods.
(1) A method in which the unmodified olefin polymer is mixed in an extruder, a batch reactor, or the like, and a vinyl compound having a polar group or a derivative thereof is added thereto, followed by graft copolymerization.

(2) A method in which the unmodified olefin polymer is dissolved in a solvent, and a vinyl compound having a polar group or a derivative thereof is added, followed by graft copolymerization.
In any method, it is preferable to carry out the graft reaction in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer of the vinyl compound having a polar group or a derivative thereof.

  As the radical initiator, for example, organic peroxides, azo compounds and the like are used. Examples of the organic peroxide include benzoyl peroxide, dichlorobenzoyl peroxide, and dicumyl peroxide. Examples of the azo compound include azobisisobutylnitrile and dimethylazoisobutyrate.

  As such a radical initiator, specifically, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5- Dialkyl peroxides such as dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.

  These radical initiators are usually used in an amount of 0.001 to 1 part by weight, preferably 0.003 to 0.5 part by weight, and more preferably 100 parts by weight of the unmodified α-olefin (co) polymer. It is used in an amount of 0.05 to 0.3 parts by weight.

  The reaction temperature in the graft reaction using a radical initiator as described above or the graft reaction performed without using a radical initiator is usually set in the range of 60 to 350 ° C, preferably 120 to 300 ° C.

  The graft amount of the vinyl compound having a polar group in the modified α-olefin (co) polymer thus obtained is usually 0.01 to 15 when the mass of the modified olefin polymer is 100% by weight. %, Preferably 0.05 to 10% by weight.

(Amount of defoamer (Y) used)
The amount of the antifoaming agent (Y) used in the curable composition of the present invention is preferably 0.001 to 20 parts by weight, more preferably 0.002 to 15 parts by weight, based on 100 parts by weight of the curable resin (X). Parts by weight, more preferably 0.002 to 10 parts by weight, more preferably 0.002 to 3 parts by weight, further preferably 0.01 to 1 part by weight, more preferably 0.01 to 0.4 part by weight, Preferably it is 0.01 to 0.09 parts by weight, more preferably 0.01 to 0.049 parts by weight. On the other hand, the content of the antifoaming agent (Y) in the entire curable composition of the present invention is preferably 0.0005 to 12% by weight or less, more preferably 0.001 to 10% by weight, and more preferably 0.001 to 10% by weight. 2% by weight, more preferably 0.005 to 1% by weight, more preferably 0.005 to 0.4% by weight, more preferably 0.005 to 0.2% by weight, and still more preferably 0.005 to 0. 06% by weight, more preferably 0.005 to 0.03% by weight. When the ratio of the antifoaming agent (Y) to the curable resin (X) and the content of the antifoaming agent (Y) in the entire curable composition are respectively equal to or more than the above lower limits, the defoaming agent (Y) is used. The action of the foam is fully exhibited. On the other hand, when the ratio of the antifoaming agent (Y) to the curable resin (X) and the content of the antifoaming agent (Y) in the entire curable composition are respectively equal to or less than the upper limit, the curable composition to be obtained is obtained. This is preferable because the gross decrease or bleed-out hardly occurs.

Other components In addition to the curable resin (X) and the defoaming agent (Y), the curable composition of the present invention may further comprise, as necessary, other components such as a catalyst (curing agent), a solvent, and a plasticizer. Agents, fillers, coloring agents, additives and the like. Here, when a two-component curable urethane resin (that is, a two-component curable urethane resin among (X-1) curable urethane resins) is used as the curable resin (X), these "others" It is preferable that the “components” are prepared by previously mixing with the liquid B.

(catalyst)
The curable composition of the present invention may contain a catalyst for the purpose of accelerating the curing of the curable resin (X).

  Examples of the catalyst include, but are not particularly limited to, a catalyst that is liquid at room temperature and a solid catalyst. A catalyst that is liquid at room temperature is preferable, and a room temperature-curable catalyst is more preferable. A solid catalyst may be used in combination with a liquid catalyst as long as the effects of the present invention are not impaired.

  For example, aliphatic polyamines, alicyclic polyamines, amine compounds such as polyamide polyamines or polymercaptans, and modified compounds thereof, tin, bismuth, lead, nickel, compounds such as cobalt, and even when used alone, You may mix and use two or more types.

  Specifically, triethylamine, tripropylamine, N-methylmorpholine, triethanolamine, triethylenediamine, 1,1′-dichloro-4,4′-diaminodiphenylmethane, 1,1 ′, 2,2′-tetrachloromethane -4,4'-diaminodiphenylmethane, di (methylthio) toluenediamine, dimorpholinodiethylene glycol, tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth octylate, neodecanoic acid Bismuth, lead octylate, lead naphthenate, nickel naphthenate, cobalt octylate and the like can be mentioned.

  The reactivity of the curable composition can be controlled by adding the catalyst. Regarding the reactivity of the curable composition, the touch drying time specified in JIS K5400 is preferably from 2 to 3600 seconds, more preferably from 2 to 1800 seconds.

(solvent)
The curable composition of the present invention may contain a solvent, if necessary.
Examples of the solvent include, but are not particularly limited to, aromatic hydrocarbons such as xylene, toluene, and ethylbenzene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; and alicyclic hydrocarbons such as cyclohexane, cyclohexene, and methylcyclohexane. , Ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, diethylene glycol monoethyl acetate, Ester esters such as diethylene glycol monomethyl ether acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, acetone, Rahidorofuran, and the like. Among them, aromatic hydrocarbons can be preferably used.

(Plasticizer)
The curable composition of the present invention may contain a filler as needed.
Although it does not specifically limit as a plasticizer, For example, dibutyl phthalate (abbreviation: DBP), dioctyl phthalate (alias: bis 2-ethylhexyl phthalate, abbreviation: DEHP, DOP, DEHA), diisononyl phthalate (abbreviation: DINP) Esters of phthalic anhydride and alcohols, esters of adipic acid and alcohols such as dioctyl adipate (also known as bis-2-ethylhexyl adipate, abbreviated as DEHA, DOA), tricresyl phosphate, trioctyl phosphate, epoxidized soybean oil And modified castor oil. Among these, a phthalic acid plasticizer hardly causes bleed-out, and can be suitably used. The content of the plasticizer in the present invention is 100 parts by weight or less, preferably 1 to 80 parts by weight, more preferably 5 to 5 parts by weight, based on 100 parts by weight of the curable resin (X) contained in the curable composition of the present invention. Desirably, it is about 50 parts by weight. On the other hand, the content in the entire curable composition is 50% by weight or less, preferably 1 to 40% by weight, and more preferably 1 to 30% by weight.

(filler)
The curable composition of the present invention may contain a filler as needed.
As the filler, an inorganic filler is preferable, and a powder filler such as mica, carbon black, silica, calcium carbonate, talc, graphite, stainless steel, aluminum, aluminum hydroxide, calcium sulfate, barium sulfate, zinc white; glass fiber or Examples thereof include fibrous fillers such as metal fibers. The content of the filler in the present invention is 150 parts by weight or less, preferably 10 to 120 parts by weight, more preferably 30 to 100 parts by weight, based on 100 parts by weight of the curable resin (X) contained in the composition of the present invention. Parts. On the other hand, the content in the entire curable composition is 60% by weight or less, preferably 10 to 55% by weight, and 20 to 50% by weight.

(Colorant)
The curable composition of the present invention may optionally contain a colorant as needed.
Although it does not specifically limit as a coloring agent, For example, titanium dioxide, carbon black, red iron oxide, chromium oxide, ultramarine, phthalocyanine green, and phthalocyanine blue are mentioned.

(Other additives)
Other additives include conventionally known defoaming agents, leveling agents, anti-separation agents, stabilizers, silane coupling agents, organic and inorganic compound-based lubricants, light stabilizers, antioxidants, and phosphorus-based processing. Examples include a heat stabilizer and an antistatic agent. In particular, it is preferable that the antioxidant and the light stabilizer are appropriately added depending on the use of the composition thereafter. Other resins, elastomers and the like may be added as long as the object of the present invention is not impaired.

  Examples of the antioxidant optionally used in the present invention include Asahi Denka Kogyo Co., Ltd., trade names of Irganox 1010, 1076, 1135, 245, 3114, and 3790 manufactured by Ciba Specialty Chemicals. Trade name: ADK STAB AO-60, AO-70, AO-80 and the like. When the antioxidant is added, it is added in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the curable resin (X) contained in the curable composition of the present invention. preferable.

  As the phosphorus-based processing heat stabilizer optionally used in the present invention, for example, trade names of Ciba Specialty Chemicals: Irgafos 38, 126, P-EPQ, etc., trade names of Asahi Denka Kogyo KK: Adekastab PEP-4C, 11C, 24, 36 and the like. When the phosphorus-based heat stabilizer is added, it is added in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the curable resin (X) contained in the curable composition of the present invention. Is preferred.

  Examples of the light stabilizer optionally used in the present invention include, for example, trade names of Tinuvin P, 234, 326, 327, 328, 329, 213, and 571 manufactured by Ciba Specialty Chemicals. 1577, 622LD, 144, 765, 770, B75, B88, etc., trade names manufactured by Sankyo LS-770, 765, 2626, 944, etc., and Asahi Denka Kogyo Co., Ltd. Trade names: LA-32, 36, 1413, 52, 62, 77, 601, T-940, etc. or hindered amine light stabilizers. When a light stabilizer is added in the present invention, it is preferable to use a combination of an ultraviolet absorber and a hindered amine-based light stabilizer. On the other hand, it is preferable to add in the range of 0.05 part by weight or more and 3 parts by weight or less.

  In the present invention, an organic compound-based or inorganic compound-based lubricant can be optionally added. Examples of organic compound-based lubricants include fatty acid amides, and commercially available products manufactured by Nippon Kasei Co., Ltd .: Nikka Amide, trade name: bisamide, trade name: Slipax, etc., or Clariant Co., Ltd. Trade name: licowax, trade name: recolbu, and the like. In addition, examples of the inorganic compound-based lubricant include talc and silica. When an organic compound-based lubricant is added in the present invention, it is in the range of 0.05 to 2 parts by weight based on 100 parts by weight of the curable resin (X) contained in the curable composition of the present invention. It is preferable to add in.

  In some cases, a conventionally known antifoaming agent which does not correspond to the antifoaming agent (Y) can be added separately from the above-described antifoaming agent (Y). Examples of such conventionally known antifoaming agents include ethylene / α-olefin copolymers, silicone-based, acrylic-based, butadiene-based and the like.

Method for Producing Curable Composition The curable composition of the present invention is a composition containing the above-mentioned curable resin (X) and the above-described antifoaming agent (Y) as essential components.

  Such a curable composition of the present invention is obtained by mixing the above-mentioned curable resin (X), the above-described antifoaming agent (Y), and the above-mentioned “other components” by a known method. Can be obtained.

  Here, the curable resin (X) may be added in the process of producing the curable composition of the present invention, and immediately before the curable composition of the present invention is to be cured, the curable resin (X) may be added. ) May be added to the composition containing all the components other than the above.

  Further, in the present invention, as described above, the two-component curable urethane resin is preferable as the curable resin (X) because the curable resin (X) can easily adjust the curing speed. Adopted. Therefore, the curable resin (X) may be formed in the process of preparing the curable composition of the present invention by mixing the liquid A containing the organic polyisocyanate with the liquid B containing the active hydrogen group-containing compound. .

  On the other hand, the antifoaming agent (Y) may be added in the process of producing the curable composition, or all the other than the antifoaming agent (Y) may be added immediately before the curable composition is to be cured. It may be added to the composition containing the components. Here, for example, when a two-component curable curable urethane resin is used as the curable resin (X), it is preferable that the defoaming agent (Y) is previously mixed with the B liquid.

  Further, the above-mentioned “other components” such as the above-mentioned catalyst (curing agent), solvent, plasticizer, filler, colorant, and additive may be added in the process of producing the curable composition, or Immediately before the curable composition is to be cured, it may be added to the curable composition. In addition, in the process of manufacturing the curable composition, while adding some components of the “other components”, and immediately before trying to cure the curable composition, the remaining components of the “other components” May be added to the curable composition. However, when a two-component curable urethane resin is used as the curable resin (X), it is preferable that the “other constituents” are previously mixed with the B liquid.

  That is, in one particularly preferred embodiment of the present invention, the curable composition of the present invention comprises a liquid B containing the active hydrogen group-containing compound and the optional “other constituents”, It can be obtained by mixing the liquid A containing isocyanate and the defoaming agent (Y). In this case, a curable composition containing the curable resin (X) and the antifoaming agent (Y) is formed through the reaction between the liquid A and the liquid B due to the mixing.

  In another aspect, the curable composition of the present invention comprises a liquid B containing the active hydrogen group-containing compound, the antifoaming agent (Y), and the optional “other constituents”, It can also be obtained by mixing solution A containing polyisocyanate. Also in this case, the curable composition containing the curable resin (X) and the antifoaming agent (Y) is similarly formed through the reaction between the liquid A and the liquid B by this mixing.

The conditions for curing the curable composition of the present invention may be room temperature or heat curing.
In addition, a known method can be used, regardless of a means for producing (curing means) the cured product.
For example, a cured product having a desired shape can be obtained by applying or casting the curable composition of the present invention and curing it as it is. That is, the present invention also provides a molded article formed from the curable composition of the present invention.

  The curable composition of the present invention, the defoaming property of the composition is significantly improved, and when used for forming a cast product, the curable composition or the curable composition is in the process of being transformed into a cured product. Bubble and gas inside the curing reaction intermediate resulting from the above process are degassed, and a molded article having excellent smoothness and excellent mechanical properties can be obtained without impairing the surface gloss. In addition, when used as a coating agent, not only does air bubbles remain inside the coating film, but also the surface of the coating film which is rich in smoothness without impairing the gloss of the surface and excellent in mechanical properties is obtained. That is, in the present invention, a paint containing the curable composition of the present invention is also provided, and a coating film formed from the curable composition is also provided.

  The polyurethane composition of the present invention having improved cured surface finish can be used as a thermosetting molded article as an industrial product, or as a coating material as a coating agent, as a cold-curable molded product as an industrial product, an injection product, or as a coating agent. Can be used as a coating material such as a paint, a waterproof coating material, and a floor material. That is, the present invention also provides a waterproof material formed from the curable composition of the present invention.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
In the following Examples, Reference Examples and Comparative Examples, each physical property was measured or evaluated by the following methods.

(Kinematic viscosity)
Based on ASTM D445, the measurement was performed using a fully automatic viscometer CAV-4 manufactured by Canon Inc.

[Methyl group index, regularity of higher α-olefin (co) polymer]
Using EX270 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., chloroform deuterium as solvent, 55 mg / 0.6 mL as sample concentration, room temperature as measurement temperature, ¹ H (270 MHz) as observation nucleus, single pulse as sequence, pulse width 6.5 μs (45 ° pulse), 5.5 seconds as the repetition time, 16 times as the number of times of integration, and 7.24 ppm of the solvent peak based on CHCl ₃ in deuterated chloroform as the reference value for the chemical shift. did.

It is in the range of 0.50 to 1.15 ppm with respect to the integrated value of the peak in the range of 0.50 to 2.20 ppm in the spectrum obtained from the ¹ H-NMR spectrum measured as described above. The ratio of the integrated value of the peak was used as a methyl group index. Here, the peak based on the α-olefin (co) polymer is almost included in the range of 0.50 to 2.20 ppm. In this range, the peak based on the methyl group is likely to be included in the range of 0.50 to 1.15 ppm.

The regularity of the higher α-olefin (co) polymer (PAO) is determined by measuring the integral of the peak at 0.50 to 0.77 ppm in the ¹ H-NMR spectrum measured as described above. The ratio of the peak of 20 ppm to the integrated value was determined, and when it was 1% or more, it was determined to be low. As described above, the peak due to the α-olefin (co) polymer is almost included in the range of 0.50 to 2.20 ppm. In this range, a minor peak indicating low stereoregularity is observed in the range of 0.50 to 0.77 ppm.

[Ethylene content, B value]
Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of orthodichlorobenzene / deuterated benzene (80/20% by volume) as a solvent, a sample concentration of 55 mg / 0.6 mL, a measurement temperature of 120 ° C., and an observation core ¹³ C (125 MHz), single pulse proton decoupling as a sequence, 4.7 μs (45 ° pulse) as a pulse width, 5.5 seconds as a repetition time, 10,000 times or more as the number of times of integration, reference value of chemical shift Was measured using 27.50 ppm.

The ethylene content of the ethylene / α-olefin copolymer was determined from the ¹³ C-NMR spectrum measured as described above, based on “Polymer Analysis Handbook” (published by Asakura Shoten, P163-170); J. Ray (Macromolecules, 10, 773 (1977)); C. Randall (Macro-molecules, 15, 353 (1982)); It was determined based on the report of Kimura (Polymer, 25, 4418 (1984)).

The B value of the ethylene / α-olefin random copolymer was calculated by the following equation.
B value = POE / (2PO · PE)
(Wherein PE and PO are the mole fraction of the ethylene component and the mole fraction of the α-olefin component, respectively, contained in the ethylene / α-olefin copolymer, and POE is the total dyad) It is the ratio of the number of alternating ethylene / α-olefin chains to the number of chains.)
The PE, PO and POE values were determined from the ¹³ C-NMR spectrum measured as described above, based on the method described in the above-mentioned known literature.

[Molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
It was determined by the following high-speed GPC measuring device.
High-speed GPC measuring device: HLC8320GPC manufactured by Tosoh Corporation
Mobile phase: THF (manufactured by Wako Pure Chemical Industries, Ltd., without stabilizer, grade for liquid chromatography)
Column: Two TSKgel Super Multipore HZ-M manufactured by Tosoh Corporation were connected in series.
Sample concentration: 5mg / mL
Mobile phase flow rate: 0.35 mL / min Measurement temperature: 40 ° C
Standard sample for calibration curve: Tosoh PStQuick MP-M

(Melting point)
The melting points of the higher α-olefin (co) polymer and the liquid ethylene / propylene copolymer used as the defoaming agent were measured using X-DSC-7000 manufactured by Seiko Instruments. Approximately 8 mg of a sample is placed in an easily sealable aluminum sample pan and placed in a DSC cell. The DSC cell is heated from room temperature to 150 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere, and then at 150 ° C. for 5 minutes. After the temperature was kept, the temperature was lowered at a rate of 10 ° C./min, and the DSC cell was cooled to −100 ° C. (temperature decreasing process). Next, after holding at −100 ° C. for 5 minutes, the temperature was raised to 150 ° C. at 10 ° C./min, and the temperature at which the enthalpy curve obtained during the temperature increase showed the maximum value was taken as the melting point (Tm), and the endothermic amount accompanying melting Was defined as the heat of fusion (ΔH). When no peak was observed or the value of the heat of fusion (ΔH) was 1 J / g or less, it was considered that no melting point (Tm) was observed. The melting point (Tm) and the heat of fusion (ΔH) were determined based on JIS K7121.

(Surface smoothness)
The resulting curable composition was visually observed, and evaluated according to the number of bubbles remaining on the surface as follows.
：: No bubbles are observed. Δ: Slight bubbles are observed. X: One side is covered with bubbles.

〔gross〕
The cured product obtained in each of Examples, Reference Examples, and Comparative Examples was measured for 60 ° surface gloss using Gloss Meter VG7000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in a manner conforming to JIS Z8741.

Note that the 60 ° surface gloss measured here corresponds to the specular gloss when the specular gloss at the incident angle of 60 ° defined on the glass surface having a refractive index of 1.567 of 0.1001 is 100%.

[Production Example 1] (Production of liquid ethylene / propylene copolymer)
Ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl _1.5 ) was charged with 1 liter of dehydrated and purified hexane in a continuous polymerization reactor equipped with a stirring blade having a capacity of 2 liters and sufficiently purged with nitrogen and adjusted to 96 mmol / L. Of VO (OC ₂ H ₅ ) Cl ₂ adjusted to 16 mmol / L as a catalyst, and hexane was added in an amount of 500 mL / h. It was continuously supplied at a rate of 500 mL / h. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization vessel such that the polymerization liquid in the polymerization liquid vessel was always 1 liter. Next, ethylene gas was supplied at a rate of 35 L / h, propylene gas was supplied at a rate of 35 L / h, and hydrogen gas was supplied at a rate of 80 L / h using a bubbling tube. The copolymerization reaction was carried out at 35 ° C. by circulating a refrigerant through a jacket attached outside the polymerization vessel.

  As a result, a polymerization solution containing the ethylene / propylene copolymer was obtained. The resulting polymerization solution was decalcified with hydrochloric acid, poured into a large amount of methanol to precipitate an ethylene / propylene copolymer, and then dried under reduced pressure at 130 ° C. for 24 hours to obtain a liquid ethylene / propylene copolymer. A compound (y-3) was obtained. Table 1 shows the analysis results of the obtained liquid ethylene / propylene copolymer (y-3).

[Production Examples 2 to 6]
In Production Example 3, the ethylene-propylene copolymers (y-1) shown in Tables 1 and 2 were adjusted by appropriately adjusting the supply amounts of ethylene gas, propylene gas, and hydrogen gas. y-2) and (y-4) to (y'-6) were obtained. Table 1 shows the analysis results of the obtained ethylene / propylene copolymers.

[Production Example 7]
Ethylene / propylene copolymerization with [diphenylsilylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)] zirconium dichloride (50 ° C)
Heptane (250 mL) was charged into a 1 L glass polymerization reactor which had been sufficiently purged with nitrogen, and the temperature in the system was raised to 50 ° C., followed by ethylene at 35 L / hr, propylene at 65 L / hr, and hydrogen at 100 L / hr. The mixture was continuously supplied into the polymerization vessel at a flow rate of hr, and stirred at a stirring rotation speed of 600 rpm. Next was charged triisobutylaluminum 0.2mmol the polymerization vessel, followed MMAO 0.868 mmol and [diphenylsilylene (eta ⁵ - cyclopentadienyl) (eta ^5-2,7-di -t- butyl-fluorenyl)] Polymerization was started by charging a premix of 0.00288 mmol of zirconium dichloride in toluene for 15 minutes or more into a polymerization vessel. Thereafter, continuous supply of ethylene, propylene, and hydrogen was continued, and polymerization was performed at 50 ° C. for 15 minutes. After terminating the polymerization by adding a small amount of isobutyl alcohol to the system, unreacted monomers were purged. The obtained polymer solution was washed three times with 100 mL of 0.2 mol / L hydrochloric acid and then three times with 100 mL of distilled water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained polymer was dried under reduced pressure at 80 ° C. overnight. As a result, 2.31 g of an ethylene / propylene copolymer (y-7) was obtained. Table 1 shows the analysis results of the obtained ethylene / propylene copolymers.

[Production Example 8]
[Methylphenylmethylene (eta ⁵ - cyclopentadienyl) (eta ^5-2,7-di -t- butyl-fluorenyl)] zirconium dichloride with ethylene / propylene copolymer sufficiently stainless steel having an inner volume of 2L was purged with nitrogen After 850 mL of heptane and 75 g of propylene were charged into the autoclave, the temperature in the system was raised to 150 ° C., and 1.56 MPa of hydrogen and 0.11 MPa of ethylene were supplied to adjust the total pressure to 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, 0.00015 mmol of [methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)] zirconium dichloride and N, N-dimethylanilyl The polymerization was initiated by introducing 0.0015 mmol of nitrogen tetrakis (pentafluorophenyl) borate with nitrogen and setting the stirring rotation speed to 400 rpm. Thereafter, the total pressure was maintained at 3 MPaG by continuously supplying only ethylene, and polymerization was carried out at 110 ° C. for 8 minutes. After terminating the polymerization by adding a small amount of ethanol into the system, unreacted ethylene, propylene and hydrogen were purged. The obtained polymer solution was washed three times with 1000 mL of 0.2 mol / L hydrochloric acid and then three times with 1000 mL of distilled water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained polymer was dried under reduced pressure at 80 ° C. overnight. As a result, 25.1 g of an ethylene / propylene copolymer (y-8) was obtained. Table 1 shows the analysis results of the obtained ethylene / propylene copolymers.

[Production Example 9] (Production of liquid octene homopolymer)
350 mL of n-heptane and 150 mL of 1-octene were charged into a 1 L stainless steel autoclave sufficiently purged with nitrogen, the temperature of the system was increased to 89 ° C. while stirring, and then hydrogen was supplied. The pressure was 0.9 MPa-G. Next, an n-heptane solution of triisobutylaluminum is 0.4 mmol in Al concentration, 0.005 mmol of a racemic solution of racemic-dimethylsilylenebis (indenyl) hafnium dichloride in toluene and N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate are used. 0.05 mmol of a toluene slurry was injected under pressure with nitrogen, and polymerization was performed at 90 ° C. for 60 minutes at a stirring rotation speed of 350 rpm. The polymerization was stopped by adding a small amount of methanol to the system. After depressurization, n-heptane was added to the solution taken out, then transferred to a separating funnel, added with 100 mL of 0.1N hydrochloric acid, shaken, allowed to stand for about 10 minutes, and then subjected to oil-water separation. After this operation was repeated three times, the organic layer was separated and then washed three times with water. A small amount of sodium sulfate was added to the organic layer, and the organic layer was left standing for about 10 minutes to dehydrate. Then, after filtering to remove sodium sulfate, n-heptane, toluene, methanol and unreacted 1-octene were distilled off at 135 ° C. under reduced pressure (5 mmHg). The weight of the obtained transparent liquid polymer was 26.8 g. Table 2 shows the analysis results of the obtained octene homopolymer (y-15).

[Production Example 10]
In Production Example 9, the octene homopolymer (y-16) shown in Table 2 was obtained by appropriately adjusting the charged amount of octene and the supplied amount of hydrogen gas. Table 2 shows the analysis results of the obtained octene homopolymer.

[Other (co) polymers]
Higher poly-α-olefins (y-9) to (y-14), liquid polybutenes (y′-17) to (y′-19) and paraffinic process oils (y′-20) to (y′-21) )), The following commercially available products were used.

y-9: higher poly-α-olefin, acid catalyst product (ExxonMobil Chemical, Spectra Syn (trademark) 40, having a low regular structure)
y-10: higher poly-α-olefin, acid catalyst product (ExxonMobil Chemical, Spectra Syn (trademark) 100, having a low regular structure)
y-11: Higher poly-α-olefin, metallocene catalyst product (Spectra Syn Elite (trademark) 150, manufactured by ExxonMobil Chemical)
y-12: Higher poly-α-olefin, chromic acid catalyst (Spectra Syn Ultra (trademark) 150, manufactured by ExxonMobil Chemical)
y-13: higher poly-α-olefin, acid catalyst product (Durasyn ™ 184, manufactured by Ineos, having a low regular structure)
y-14: higher poly-α-olefin, metallocene catalyst product (Durasyn (trademark) 184R, manufactured by Ineos)
y'-17: Liquid polybutene (Nisseki Polybutene (trademark) HV-35, manufactured by JX Nippon Oil & Energy)
y'-18: Liquid polybutene (JX Nippon Oil & Energy Corporation, Nisseki Polybutene (trademark) HV-100)
y'-19: Liquid polybutene (JX Nippon Oil & Energy Corporation, Nisseki Polybutene (trademark) HV-300)
y'-20: Paraffin-based process oil (Diana Process Oil PW-100 manufactured by Idemitsu Kosan Co., Ltd.)
y'-21: Paraffin-based process oil (Diana Process Oil PW-380, manufactured by Idemitsu Kosan Co., Ltd.)
Table 2 shows the physical properties of these higher poly-α-olefins, liquid polybutenes, and paraffinic process oils.

[Reference Example 1]
(About liquid A)
As the liquid A, an isocyanate-containing prepolymer (Hyprene P-306A, manufactured by Mitsui Chemicals, Inc .; viscosity: 6,000 cps / 25 ° C.) was used.
Here, the NCO group content in this isocyanate-containing prepolymer is 0.69 milliequivalent (2.9% by weight).

(Solution B)
105 g of polyether polyol (MC-506, manufactured by Mitsui Chemicals, Inc .; viscosity 1,400 cps / 25 ° C .; containing polyamine) in a round can, 124 g of DINP (manufactured by J-Plus Co.) as a softening agent, and bismuth octylate (catalyst) 4.3 g of Nitto Kasei Co., Ltd., Neostan U-600) is inserted into a round can, and 345 g of calcium carbonate (NS-200, Nitto Powder Chemical Industry Co., Ltd.) is gradually charged while stirring with a turbine blade stirrer. Then, the mixture was stirred at 600 rpm for 20 minutes to prepare a curing agent to be a liquid B.

  The above-mentioned MC-506 used as the polyether polyol is, specifically, 24% by weight of 3,3′-dichloro-4.4′-diaminodiphenylmethane, aniline and 2-chloroaniline in the presence of a mineral acid. Is a liquid amine composed of 24% by weight of an aromatic polyamine obtained by condensing the compound with formaldehyde, and 52% by weight of a polyether polyol, and has an active hydrogen content of 3.7 meq.

(Resin curing)
129 mg of liquid ethylene / propylene copolymer (y-1) as an antifoaming agent was added to 24.2 g of Solution B prepared as described above, and the mixture was stirred at 600 rpm for 1 minute. 25.8 g of the above solution A was added to the mixture thus obtained, and the mixture was stirred at 600 rpm for 3 minutes to obtain a curable composition.

  Table 3 below shows the amounts of the constituent materials in the curable composition obtained in Reference Example 1. Here, in the curable composition, the ratio of the number of active hydrogen groups in the active hydrogen group-containing compound to one isocyanate group of the isocyanate-containing prepolymer was 0.9 (≒ ( 3.7 × 8.8) / (0.69 × 51.5)).

この硬化性組成物を、７ｃｍφのＰＰカップに２０ｇ流し込み、１晩室温で静置して硬化物を得た。硬化物の外観を観察した結果、およびグロス測定結果を表４−１〜４−２に示す。

20 g of this curable composition was poured into a 7 cmφ PP cup, and allowed to stand at room temperature overnight to obtain a cured product. The results of observing the appearance of the cured product and the results of gloss measurement are shown in Tables 4-1 to 4-2.

[Examples 2 , 6 , 7 , 15 ; Reference Examples 3 to 5 , 8 to 14, 16 to 19 , 20 to 31, and Comparative Examples 1 to 9]
The resin was cured in the same manner as in Reference Example 1 except that the type and amount of the defoaming agent to be blended were changed as shown in Tables 4-1 and 4-2 to obtain a cured product. The contents of the components other than the antifoaming agent were adjusted according to the amount of the antifoaming agent added, while keeping the ratio of each other constant. That is, the ratio of the sum of the liquid A and the liquid B and the ratio of the defoaming agent was adjusted while the ratio of the liquid A and the liquid B was kept constant.
The results of observing the appearance of the obtained cured product are shown in Tables 4-1 and 4-2.

  In Comparative Example 1 in which no defoaming agent was used, the foam did not come off from the cured product, the surface smoothness was not obtained, and the gloss remained low. In Comparative Examples 2 and 3 using an ethylene / α-olefin copolymer having an Mw of more than 11,000, bubbles did not come off, surface smoothness was not obtained, and gloss was poor.

  In Comparative Examples 4 to 6 in which liquid polybutene was used as an antifoaming agent, bubbles were not removed, surface smoothness was not obtained, and gloss was poor. Here, the liquid probutenes of Comparative Examples 4 to 6 are mainly obtained by polymerizing isobutene (2-methylpropylene), and have a methyl group index of more than 60% because of having many methyl groups in side chains. .

  In addition, even when a saturated hydrocarbon having a structure similar to that of the α-olefin (co) polymer constituting the curable composition of the present invention, a paraffin-based process oil having a Mw of less than 1,500 is used. In Examples 7 to 9, the bubbles did not come off, the surface smoothness was not obtained, and the gloss was poor.

  The curable composition of the present invention having improved cured surface finish can be used as a thermosetting molded article for industrial products or a coating material as a coating agent, and as a room temperature curable molded product for an industrial product, an injection product, or a coating agent. As a coating material such as a paint, a waterproof coating material, a floor material and the like.

Claims (7)

One kind of curable resin (X) which is a curable urethane resin;
An anti-foaming agent (Y) comprising an α-olefin (co) polymer satisfying the following requirements (y-1) to (y-2),
The α-olefin (co) polymer,
An α-olefin copolymer having 3 or more ethylene-carbon atoms, and
Contains less than 50 mol% of structural units corresponding to monomers composed of an α-olefin having 6 to 20 carbon atoms, and
Curable composition wherein the amount of the defoaming agent (Y) used is 0.01 to 0.049 parts by weight per 100 parts by weight of the curable resin (X):
(Y-1) The methyl group index measured from ¹ H-NMR is 25 to 60% (here, the methyl group index is obtained by dissolving the α-olefin (co) polymer in heavy chloroform. ¹ H-NMR was measured, and when the solvent peak based on CHCl ₃ in deuterated chloroform was used as a reference (7.24 ppm), 0 was defined as the integrated value of the peak within the range of 0.50 to 2.20 ppm. .50 to 1.15 ppm).
(Y-2) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is from 1,500 to 11,000. The antifoaming agent (Y) is curable group composition as claimed in claim 1, wherein a melting point as measured by differential scanning calorimetry (DSC) not observed.   The curable composition according to any one of claims 1 to 2, wherein the methyl group index of the α-olefin (co) polymer constituting the antifoaming agent (Y) is 40 to 60%. Composition.   A molded article formed from the curable composition according to claim 1.   A paint containing the curable composition according to claim 1.   A waterproof material formed from the curable composition according to claim 1.   A coating film formed from the curable composition according to claim 1.

Images