JP2007070591A - Curable resin/polyurethane mixture and curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition to be a cured product having a high glass transition temperature and to provide a mixture of a curable resin with the cured product in which the curable resin is hardly compatible with the cured product of another curable resin dispersed in the curable resin and can be uniformized. <P>SOLUTION: The curable resin/polyurethane mixture comprises the curable resin containing ≥2 epoxy groups and/or ≥2 hydrolyzable silyl groups and a cross-linked particulate polyurethane dispersed in the curable resin. The curable resin composition comprises the curable resin/polyurethane mixture and a curing agent reactive with the curable resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a curable resin / polyurethane mixture and a curable resin composition.

  As a method for imparting or improving mechanical properties such as toughness to the cured product of the curable resin, for example, there is a method of curing a composition of two or more curable resins. Examples of such a composition include a composition containing an epoxy resin and a rubber-modified epoxy resin (as rubber, for example, NBR, CTBN), a composition containing an epoxy resin and a urethane resin, a modified silicone and a thermoplastic. The composition containing a urethane resin is mentioned.

  Moreover, the method of using the mixture which hardened | cured a part of composition containing 2 or more types of curable resin as another method is mentioned. For example, Patent Document 1 includes (A) urethane (meth) acrylate having at least three (meth) acrylic groups in the molecule, glycol-based or glycerol-based dimethacrylate, bisphenol-type epoxy resin, and a specific structure. A main agent liquid mainly composed of a compound, and (B) 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane and / or a modified product thereof. It is described that a two-component mixed curable resin composition composed of a curing agent liquid as a main component is temporarily cured by light irradiation, and is further cured at room temperature or by heating.

  Patent Document 2 states that “a polymer of a polymerizable unsaturated group-containing monomer by polymerizing a polymerizable unsaturated group-containing monomer in a silyl group-containing polyether containing at least one reactive silyl group in the molecule”. In the method for producing a composition in which fine particles are dispersed in a silyl group-containing polyether, the majority of the polymerizable unsaturated group-containing monomer is a highly flocculating monomer, and the highly flocculating monomer is a homopolymer of a silyl group. It is a monomer that can form polymer fine particles that do not dissolve in the contained polyether, and at least a part of the highly cohesive monomer or at least a part of the other polymerizable unsaturated group-containing monomer is an epoxy group-containing monomer Is a production method of a composition in which polymer fine particles are dispersed in a silyl group-containing polyether.

  Patent Document 3 states that “having at least two hydroxyl groups, mercapto groups or mono-substituted or unsubstituted amino groups as functional groups capable of reacting with isocyanate groups, and via urethane bonds or urea bonds with the functional groups. Copolymerization of an acrylic monomer having one polymerizable unsaturated group and an acrylic monomer having two or more (meth) acryloyloxy groups in a polymer having at least two hydrolyzable silyl groups introduced in the molecule A moisture curable polymer composition characterized by comprising uniformly dispersed acrylic polymer fine particles made of a polymer. "

JP-A-6-83050 Japanese Patent Laid-Open No. 5-194777 Japanese Patent Laid-Open No. 8-253681

However, when an epoxy resin is used in a method for curing a composition containing two or more kinds of curable resins as described above, the epoxy resin is cured in a state in which it is completely compatible with a resin other than the epoxy resin. It is known that the glass transition temperature of the cured product is lower than that of the cured product containing only the epoxy resin.
In addition, when curing a composition in which a cured product of a curable resin other than an epoxy resin is dispersed in an epoxy resin, the cured product is cured in a state in which the cured product is partially or completely dissolved in the epoxy resin. It is known that the glass transition temperature of a product will be lower than that of a cured product containing only an epoxy resin.
Furthermore, in the case of a composition containing a modified silicone and particles in which a curable resin other than the modified silicone is polymerized in the modified silicone, it is known that the particles are separated from the modified silicone.

Accordingly, a first object of the present invention is to provide a curable resin composition that can be a cured product having a high glass transition temperature.
The present invention also provides a mixture of a curable resin and a cured product that is difficult to be compatible with a curable resin and a cured product of another curable resin dispersed in the curable resin and can be uniform. The purpose.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups and a crosslinked particulate polyurethane are hardly compatible, It has been found that crosslinked polyurethane particles can be dispersed in a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups to form a uniform mixture.
In addition, the inventor contains the curable resin and a polyurethane dispersed in the curable resin, and the polyurethane is a polyurethane produced in the curable resin. It has been found that the polyurethane is dispersed in a curable resin which is hardly compatible with the polyurethane and contains two or more epoxy groups and / or hydrolyzable silyl groups to form a uniform mixture.
Moreover, this inventor discovered that the hardened | cured material with a high glass transition temperature was obtained from the curable resin composition containing the above mixture and a hardening | curing agent, and came to complete this invention.

That is, the present invention provides the following (1) to (11).
(1) A curable resin / polyurethane mixture containing crosslinked particulate polyurethane dispersed in a curable resin.
(2) containing a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups, and polyurethane dispersed in the curable resin,
A curable resin / polyurethane mixture, wherein the polyurethane is a polyurethane produced in the curable resin.
(3) The curable resin / polyurethane mixture according to (2) above, wherein the polyurethane is a crosslinked particulate polyurethane.
(4) The curable resin / polyurethane mixture according to any one of (1) to (3), wherein the polyurethane is obtained by a reaction between a urethane prepolymer and a curing agent capable of reacting with the urethane prepolymer.
(5) The curable resin / polyurethane mixture according to the above (4), wherein the urethane prepolymer has a functional group equivalent of 3000 g / equivalent or less.
(6) The curable resin / polyurethane mixture according to the above (4) or (5), wherein the curing agent is an aromatic diamine.
(7) Curable resin / polyurethane mixture in any one of said (1)-(6) whose content of the said polyurethane is 1-40 mass parts with respect to 100 mass parts of said curable resins.
(8) A curable resin composition comprising the curable resin / polyurethane mixture according to any one of (1) to (7) above and a curing agent capable of reacting with the curable resin.
(9) A revolution drive motor, a rotation shaft extending vertically from the revolution drive motor and transmitting the rotation of the revolution drive motor, a revolution body mounted horizontally on the rotation shaft, and the revolution A rotating bearing arranged on an axis inclined from the axis of the rotating shaft at a position deviated from the extension of the rotating shaft on the body, a stirred container holder supported by the rotating bearing, and stored in the stirred container holder A stirring vessel, a rotation driving motor, and a transmission device that transmits rotation of the rotation driving motor to the rotation bearing;
The stirring container is revolved by rotating the revolving body, and is rotated by an axis inclined with respect to the axis of the rotating shaft by rotating the stirring holder. ,
While the curable resin A, the curable resin B, and the curing agent and / or the curing catalyst capable of reacting with the curable resin B are charged into the stirring vessel and stirred, the curable resin B and the curing agent and / or A curable resin in which a mixture containing the curable resin A and the crosslinked compound dispersed in the curable resin A can be obtained by reacting with a curing catalyst to form a particulate crosslinked compound. / Method for producing cross-linking compound mixture.
(10) The revolution speed of the stirring container is 100 to 10,000 rpm, and the rotation speed of the stirring container is 0.05 to 1 times the revolution speed of the curable resin / crosslinking compound mixture according to (9) above. Production method.
(11) Curing in which the curable resin A is a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups, and the crosslinking compound is a cured product containing two or more epoxy groups and / or hydrolyzable silyl groups The method for producing a curable resin / crosslinked compound mixture according to the above (9) or (10), which is a crosslinked particulate polyurethane dispersed in a curable resin.

The curable resin composition of the present invention can be a cured product having a high glass transition temperature.
In addition, the curable resin / polyurethane mixture of the present invention is difficult to be compatible with the curable resin and polyurethane, and can be uniform.

Hereinafter, the present invention will be described in detail.
First, the curable resin / polyurethane mixture of the present invention will be described below.
The curable resin / polyurethane mixture of the present invention is a curable resin / polyurethane mixture in which crosslinked particulate polyurethane is dispersed in a curable resin having two or more epoxy groups and / or reactive silyl groups.

The curable resin used in the curable resin / polyurethane mixture of the present invention will be described below.
The curable resin is not particularly limited as long as it has two or more epoxy groups and / or hydrolyzable silyl groups. Examples thereof include an epoxy resin having two or more epoxy groups and a curable resin having two or more hydrolyzable silyl groups.

The epoxy resin will be described below.
The epoxy resin is not particularly limited as long as it has two or more epoxy groups. For example, epoxy compounds having a bisphenyl group such as bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type, polyalkylene glycol type, alkylene glycol Type epoxy compound, epoxy compound having naphthalene ring, bifunctional glycidyl ether type epoxy resin such as epoxy compound having fluorene group; phenol novolak type, orthocresol novolak type, trishydroxyphenylmethane type, trifunctional type, tetra Polyfunctional glycidyl ether type epoxy resin such as phenylolethane type; Glycidyl ester type epoxy resin of synthetic fatty acid such as dimer acid; N, N, N ′, N′-tetraglycidyldiame Aromatic epoxy resins having a glycidylamino group such as diphenylmethane (TGDDM), tetraglycidyl-m-xylylenediamine, triglycidyl-p-aminophenol, N, N-diglycidylaniline; tricyclo [5.2.1. ^0,6 ] epoxy compounds having a decane ring (for example, epoxy compounds which can be obtained by a production method in which dicyclopentadiene and cresols such as m-cresol or phenols are polymerized and then reacted with epichlorohydrin) It is done.

  Examples of the epoxy resin include an epoxy resin having a sulfur atom in an epoxy resin main chain such as Flep 10 manufactured by Toray Fine Chemical Co., Ltd .; a urethane-modified epoxy resin having a urethane bond; polybutadiene, liquid polyacrylonitrile-butadiene rubber, Rubber-modified epoxy resin containing rubber such as acrylonitrile butadiene rubber (NBR); bisphenol A type epoxy resin, bisphenol F type epoxy resin, sorbitol type epoxy resin, polyglycerol type epoxy resin, pentaerythritol type epoxy resin, trimethylolpropane An epoxy resin having an acetoacetate group in the molecule, such as a type epoxy resin.

The said epoxy resin can be used individually or in combination of 2 types or more, respectively.
As the epoxy resin used in the present invention, those which are liquid at room temperature are preferable from the viewpoint of easy handling and mixing.

The curable resin having two or more hydrolyzable silyl groups will be described below.
The curable resin having two or more hydrolyzable silyl groups is not particularly limited, and examples thereof include a modified silicone polymer. The modified silicone-based polymer has a property that a siloxane bond is formed by a hydroxy group and / or a hydrolyzable group bonded to a silicon atom to form a cured product by crosslinking. Examples of the main chain of the modified silicone polymer include a polyether polymer, a polyester polymer, an ether / ester block copolymer, an ethylenically unsaturated compound polymer, and a diene compound polymer. Moreover, the hydrolyzable silyl group should just be couple | bonded with the terminal or side chain of such a principal chain.

Examples of the polyether polymer include those having repeating units of ethylene oxide, propylene oxide, butylene oxide, and polyphenylene oxide.
Examples of the polyester polymer include carboxylic acids such as acetic acid, propionic acid, maleic acid, phthalic acid, citric acid, pyruvic acid, and lactic acid, carboxylic acid anhydrides, their intramolecular and / or intermolecular esters, and substitution thereof. The thing which has a body as a repeating unit is illustrated.
Examples of the ether / ester block copolymer include those having as a repeating unit both the repeating unit used in the above-mentioned polyether polymer and the repeating unit used in the above-mentioned polyester polymer.

  Examples of the ethylenically unsaturated compound polymer and diene compound polymer include homopolymers such as ethylene, propylene, acrylic ester, methacrylic ester, vinyl acetate, acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene, and the like. These 2 or more types of copolymers are mentioned. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer. Polymer, polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylate ester, polymethacrylate ester Can be mentioned.

  The hydrolyzable silyl group is not particularly limited as long as it is a silicon atom-containing group or silanol group having a hydrolyzable group directly bonded to a silicon atom. The hydrolyzable silyl group can cause a condensation reaction such as a dehydration reaction by using a condensation catalyst under conditions where moisture, a crosslinking agent and the like are present. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these, an alkoxy group is preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  The modified silicone polymer is not particularly limited with respect to its production method. For example, it can be produced by a conventionally known method as described in Japanese Patent Publication No. 61-18569. Examples of commercially available products include MS polymer S-203, MS polymer S-303, MS polymer S-903, MS polymer S-911, silyl polymer SAT200, silyl polymer MA430, and silyl polymer manufactured by Kaneka Corporation. MAX447: Exastar ESS-3620, Exester ESS-3430, Exester ESS-2420, Exester ESS-2410, etc. manufactured by Asahi Glass Co., Ltd. may be mentioned.

The molecular weight of the curable resin having two or more hydrolyzable silyl groups is not particularly limited, and the number average molecular weight is preferably 1,000 to 30,000 from the viewpoint of viscosity and workability. More preferably, it is 1,000 to 15,000. In such a range, the viscosity of the curable composition becomes appropriate and handling becomes easy.
The said curable resin which has 2 or more of epoxy groups and / or hydrolysable silyl groups can be used individually or in combination of 2 types or more, respectively.

The polyurethane used in the present invention will be described below.
As said polyurethane, the thing obtained by reaction with the hardening | curing agent which can react with a urethane prepolymer and a urethane prepolymer is mentioned suitably, for example.
In one preferred embodiment, the polyurethane is a crosslinked particulate polyurethane. In order to make the polyurethane cross-linked, one of the preferred embodiments is that any one of the urethane prepolymer and the curing agent used as the raw material of the polyurethane is trifunctional or more. Among them, it is preferable to use a trifunctional or higher functional urethane prepolymer from the viewpoint that the polyurethane and the curable resin are less compatible with each other and the curable resin / polyurethane mixture is likely to be more uniform.

Moreover, it is one of the preferable aspects that the said polyurethane is manufactured in the said curable resin. When polyurethane is produced in the curable resin, the polyurethane dispersed in the curable resin can be easily formed, and the resulting curable resin composition has a low viscosity and can be a cured product having a high glass transition temperature. . The polyurethane produced in the curable resin may not be crosslinked, but may be a crosslinked particulate polyurethane from the viewpoint of obtaining a composition that can be a cured product having a higher glass transition temperature. preferable.
Even when the polyurethane produced in the curable resin is not cross-linked, after the obtained curable resin / polyurethane mixture is cured, the polyurethane is in the form of particles dispersed uniformly in the curable resin. It is thought that it becomes a polyurethane.

  The urethane prepolymer used in the production of the polyurethane is a reaction product that can be obtained by reacting a polyol compound with an excess of a polyisocyanate compound, and is a polymer containing an isocyanate group at the molecular end. .

The polyisocyanate compound is not particularly limited. For example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate ( 4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate ( Aromatic polyisocyanates such as NDI); hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (NBDI), xylylene diisocyanate Cyanate (XDI), aliphatic polyisocyanates such as tetramethyl xylylene diisocyanate (TMXDI); trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (water And alicyclic polyisocyanates such as MDI); carbodiimide-modified polyisocyanates of the above polyisocyanates, or isocyanurate-modified polyisocyanates thereof. A polyisocyanate compound can be used individually or in combination of 2 types or more, respectively.

  The polyol compound is not particularly limited, and examples thereof include polyether polyol, polyester polyol, other polyols, and mixed polyols thereof.

  Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, 1, At least one selected from polyhydric alcohols such as 4-butanediol, 4,4'-dihydroxyphenylmethane, 4,4'-dihydroxyphenylpropane, pentaerythritol, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. Polyols obtained by adding at least one selected from: polyoxytetramethylene oxide and the like.

  Examples of the polyol obtained by adding at least one selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like to at least one selected from the above polyhydric alcohols include, for example, polyethylene glycol, polypropylene glycol, polypropylene Examples include triol, polyglycerin, polytrimethylolpropane, polyhexanetriol, polybutanediol, polydihydroxyphenylmethane, and polydihydroxyphenylpropane.

  Examples of the polyester polyol include one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane, and other low molecular polyols. And a condensation polymer of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, and other low molecular carboxylic acids and oligomeric acids; propionlactone , Ring-opening polymers such as valerolactone and caprolactone.

Other polyols include, for example, polymer polyols; polycarbonate polyols; polybutadiene polyols, hydrogenated polybutadiene polyols; acrylic polyols; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, and hexanediol. A low molecular polyol etc. are mentioned.
These polyol compounds can be used alone or in combination of two or more.

  The combination of a polyol compound and a polyisocyanate compound is not particularly limited. Each of the polyol compounds and each of the polyisocyanate compounds can be used in any combination. Among them, a urethane prepolymer obtained from a trifunctional or higher functional polyol compound and a polyisocyanate compound is preferable, and at least one polyisocyanate compound selected from the group consisting of 1,1,1-trimethylolpropane, IPDI, HDI and XDI. The urethane prepolymer obtained from the above is more preferred. Further, a trifunctional urethane prepolymer in which HDI and / or IPDI are bonded by an isocyanurate bond is preferable.

  The said urethane prepolymer is not specifically limited about the manufacturing method. For example, a method in which the reaction temperature is set to about 50 to 100 ° C. and a polyol compound and a polyisocyanate compound are reacted under normal pressure to obtain a urethane prepolymer. Further, a urethanization catalyst such as an organic tin compound or an organic bismuth compound can be used.

  In the production of the urethane prepolymer, the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate compound to the hydroxy group of the polyol compound is preferably 1.2 to 3.0, and preferably 1.4 to 2.5. Is more preferable. When NCO / OH is in such a range, there is no foaming due to the remaining polyisocyanate compound, and there is no increase in the viscosity of the urethane prepolymer due to the extension of the molecular chain, and the physical properties of the resulting cured product are good.

  The urethane prepolymer preferably has a functional group equivalent of 3000 g / equivalent or less. In such a range, the polyurethane and the curable resin are less likely to be compatible, and the curable resin / polyurethane mixture tends to be more uniform. Since it is excellent by such an effect, it is more preferable that the functional group equivalent of a urethane prepolymer is 50-2000 g / equivalent.

  The urethane prepolymer is preferably trifunctional or higher from the viewpoint that the polyurethane and the curable resin are less compatible with each other and the curable resin / polyurethane mixture tends to be more uniform.

  It is preferable that the usage-amount of a urethane prepolymer is 1-38 mass parts with respect to 100 mass parts of said curable resins, and it is more preferable that it is 2-28 mass parts. In such a range, the fluidity is excellent, and the heat resistance and physical properties after curing are excellent.

The curing agent will be described below.
The curing agent used in the production of the polyurethane is not particularly limited as long as it is a compound that can react with the urethane prepolymer. For example, a polyamine compound having two or more amino groups in the molecule, or a hydroxy group in the molecule. Examples thereof include a polyol compound having two or more, a polymercaptan-based curing agent, and a phenol resin. Of these, polyamine compounds are preferred because of their fast reaction with isocyanate groups.
When the polyurethane is produced in the thermosetting resin, the curing agent is inert to the thermosetting resin, or more reactive to the urethane prepolymer than the reactivity to the thermosetting resin. A larger curing agent is preferred. Specific examples of such a curing agent include polyol compounds and aromatic polyamines.

Examples of the polyamine compound include amine compounds having two amino groups in the molecule (aliphatic diamine, aromatic diamine, etc.), amine compounds having three or more amino groups in the molecule, and the like.
Examples of the aliphatic diamine include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and 1,7-heptane. Diamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, hexamethylenediamine, trimethylhexamethylene Diamine, iminobispropylamine, methyliminobispropylamine, 1,5-diamino-2-methylpentane, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl -3,3,5-tri Chill - cyclohexylamine, dimethylene amines norbornane skeleton, such as meta-xylylenediamine (MXDA) and the like.

  Examples of the aromatic diamine include 3,3′-dichloro-4,4′-diaminodiphenylmethane (MOCA), 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, p- Examples include phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine, and the like.

Examples of the amine compound having three or more amino groups in the molecule include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
Further, ketimines in which the amino group of the polyamine compound is blocked with a ketone or aldimine blocked with an aldehyde can also be used. In such a case, it is preferable to use water necessary for hydrolyzing ketimine or aldimine.

  Examples of the polyol compound having two or more hydroxy groups in the molecule include those similar to the polyol compound used as a raw material for the urethane prepolymer.

Above all, when mixed with urethane prepolymer, the curing agent can be ensured adequately until it is uniformly dispersed in the system, and the polyurethane reaction proceeds uniformly in the system. The agent is preferably an aromatic diamine.
Curing agents that can react with the urethane prepolymer can be used alone or in combination of two or more.

  The amount of the curing agent capable of reacting with the urethane prepolymer is preferably such that the functional group in the curing agent is 0.3 to 1.5 times equivalent to the NCO group in the urethane prepolymer, 0.9 It is more preferable that it is -1.1 times equivalent. When the amount of the curing agent is within such a range, polyurethane is easily dispersed in the curable resin as a crosslinked body.

The curable resin / polyurethane mixture of the present invention may further contain a urethane prepolymer curing catalyst.
Examples of the curing catalyst for the urethane prepolymer include a metal catalyst and an amine catalyst. Examples of the metal catalyst include dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin dimethoxide, diphenyltin diacetate, dibutylbis (triethoxysiloxy) tin, dibutylbis (acetylacetonato) tin, dioctyltin dilaurate Organotin compounds such as: tetrabutyl titanate, titanates such as tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium Chelate compounds such as tetraacetylacetonate and titanium tetraacetylacetonate; octanoic acid , Octanoic acid metal salts such as bismuth octoate and the like.

  Examples of the amine catalyst include monoamines such as butylamine, octylamine, dibutylamine, triethylamine, N, N-dimethylcyclohexylamine; N, N, N ′, N′-tetramethylethylenediamine, N, N, N Diamines such as', N'-tetramethylpropane-1,3-diamine, N, N, N ', N'-tetramethylhexane-1,6-diamine; N, N, N', N ", Triamines such as N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine; N-methylmorpholine, N, N′-dimethylpiperazine, N-methyl-N ′ Cyclic amines such as-(2-dimethylamino) -ethylpiperazine, 1,4-diazabicyclo [2.2.2] octane; Alcohol amines such as aminoethanol, dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethylethanolamine; bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethyl) aminopropylether And ether amines or their salt compounds.

Among these, an organic tin compound such as dibutyltin laurate is preferable from the viewpoint that sufficient curability can be obtained with a small amount of use.
The above curing catalysts can be used alone or in combination of two or more.

  The urethane prepolymer curing catalyst is preferably 0.1 to 10000 ppm, more preferably 0.5 to 1000 ppm with respect to 100 parts by mass of the urethane prepolymer, from the viewpoint of curing speed and storage stability. .

  The curable resin / polyurethane mixture of the present invention uses a curable resin having two or more epoxy groups and / or hydrolyzable silyl groups, a urethane prepolymer, a curing agent capable of reacting with the urethane prepolymer, and if necessary. In addition to the urethane prepolymer curing catalyst that can be used, in the range that does not impair the purpose of the present invention, for example, fillers, plasticizers, antioxidants, anti-aging agents, inorganic pigments, organic pigments, adhesion-imparting agents, Additives such as flame retardants, dehydrating agents, solvents, silane coupling agents, thixotropic agents, antistatic agents, and fillers can be blended. The amount of the additive used is not particularly limited as long as it can be used in the curable resin composition.

  Examples of the filler include fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate Waxy clay, kaolin clay, calcined clay; carbon black; or a treated product obtained by treating these with a fatty acid, a resin acid, a fatty acid ester, a urethane compound, or the like.

  Examples of the plasticizer include diisononyl adipate dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dioctyl adipate, isodecyl succinate, diethylene glycol dibenzoate, pentaerythritol ester, butyl oleate, methyl acetylricinoleate, tricresyl phosphate, phosphate Examples include trioctyl, propylene glycol adipate polyester, butylene glycol adipate polyester, and the like.

Examples of the antioxidant include butylhydroxytoluene, butylhydroxyanisole, triphenyl phosphite and the like.
Examples of the anti-aging agent include hindered phenol-based, benzotriazole-based, hindered amine-based compounds, and the like.

Examples of the inorganic pigment include titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and the like.
Examples of organic pigments include azo pigments and copper phthalocyanine pigments.
Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins and the like.
Examples of the flame retardant include chloroalkyl phosphate, dimethylmethylphosphonate, bromine atom and / or phosphorus atom-containing compound, ammonium polyphosphate, diethyl bishydroxyethylaminoethyl phosphate, neopentyl bromide polyether, brominated polyether, etc. Is mentioned.
Examples of the dehydrating agent include acyloxysilyl group-containing polysiloxane.

  The method for producing the curable resin / polyurethane mixture of the present invention is not particularly limited. For example, first, a curable resin having two or more epoxy groups and / or hydrolyzable silyl groups, a urethane prepolymer, a curing agent capable of reacting with the urethane prepolymer, and a curing catalyst that can be used as necessary. It can be produced by putting it into a stirring apparatus and reacting a urethane prepolymer and a curing agent capable of reacting with the urethane prepolymer in an environment where the reaction temperature is room temperature to 80 ° C. while stirring.

  Examples of the stirring device used in the production of the curable resin / polyurethane mixture of the present invention include a stirring device that stirs the content by rotating and revolving the stirring container, and the content by rotating the stirring blade. A stirring device (for example, a single screw mixer, a twin screw mixer, a concentric twin screw mixer, a planetary mixer) can be used. Since the reaction between the urethane prepolymer and the curing agent is fast, it is necessary to mix uniformly in a short time, and in order to stir the highly viscous mixture efficiently, the stirring container rotates and revolves to stir the contents. A stirring apparatus is preferred. A stirring device that stirs the contents by rotating and revolving the stirring container will be described later.

  In the case of using a stirring device that stirs the contents by rotating and revolving the stirring container, the mixing of the urethane prepolymer and the curing agent that are quickly reacted is made uniform, and the particle size of the polyurethane is constant and small. The revolution speed of the stirring container is preferably 100 to 10,000 rpm, more preferably 200 to 5000 rpm. In addition, the rotation speed of the stirring container is 0.05 to 1 times the revolution speed of the stirring container from the viewpoint of uniform mixing of the urethane prepolymer and the curing agent having a fast reaction, and a uniform particle size of the polyurethane. It is preferable that it is 0.2 to 1.0 times.

  Of the stirring devices in which the stirring blades rotate, stirring devices that stir the contents while the stirring blades rotate and revolve are preferable.

  In the production of the curable resin / polyurethane mixture of the present invention, a stirrer is used to react with a curable resin having two or more epoxy groups and / or hydrolyzable silyl groups, a urethane prepolymer, and a urethane prepolymer. The curing agent is stirred and the reaction temperature is room temperature to 80 ° C., and the urethane prepolymer and the curing agent capable of reacting with the urethane prepolymer are reacted. By reacting in this manner, the urethane prepolymer and the curing agent become polyurethane and can be uniformly dispersed in the curable resin having two or more epoxy groups and / or hydrolyzable silyl groups. In the curable resin / polyurethane mixture of the present invention, the polyurethane and the curable resin having two or more epoxy groups and / or hydrolyzable silyl groups are hardly compatible.

  In the curable resin / polyurethane mixture of the present invention, the content of polyurethane is preferably 1 to 40 parts by mass and more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the curable resin. In such a range, the fluidity is excellent, and the heat resistance and physical properties after curing are excellent.

  In the curable resin / polyurethane mixture of the present invention, the average particle size of the crosslinked particulate polyurethane is preferably 5 to 300 nm from the viewpoint that the polyurethane is less compatible with the curable resin, More preferably, it is 5-100 nm.

Conventionally, when a part of a composition containing two or more curable resins is cured to form a mixture containing a curable resin and a particulate resin, the phase separation form differs depending on the curing temperature, It is known that the resin dissolves in the curable resin.
On the other hand, the curable resin / polyurethane mixture of the present invention is less compatible with the curable resin and polyurethane and can be uniform.
The inventors speculate that this is due to the fact that the polyurethane is an aggregate of certain strong urea bonds and urethane bonds, and the hydrogen bonding force is very strong. Further, the curable resin / polyurethane mixture of the present invention is observed to be in a water tank shape and has high thixotropy. This indicates that hydrogen bonding between the polyurethanes is strong.
Examples of the use of the curable resin / polyurethane mixture of the present invention include an adhesive, a coating material, a primer, and a sealing material.

Next, the curable resin composition of the present invention will be described.
The curable resin composition of the present invention contains the curable resin / polyurethane mixture of the present invention and a curing agent capable of reacting with the curable resin.

The curable resin / polyurethane mixture used in the curable resin composition of the present invention is not particularly limited as long as it is the curable resin / polyurethane mixture of the present invention described above.
The curing agent used in the curable resin composition of the present invention will be described below.
The curing agent is particularly a curable resin contained in the curable resin / polyurethane mixture of the present invention, as long as it can react with a curable resin having two or more epoxy groups and / or hydrolyzable silyl groups. Not limited. The curing agent capable of reacting with the curable resin may be one capable of reacting with polyurethane or a urethane prepolymer that is a raw material of polyurethane.

  Examples of the curing agent capable of reacting with the curable resin include a silicon compound having a hydrolyzable group and / or a partial hydrolysis condensate thereof, a polyol, an amine curing agent, an acid or acid anhydride curing agent, and a basic compound. Examples include active hydrogen compounds, imidazoles, polymercaptan curing agents, and phenol resins. A hardening | curing agent can be selected according to the kind of curable resin.

As a hardening | curing agent of curable resin which has 2 or more of epoxy groups, the thing similar to the hardening | curing agent which can react with said urethane prepolymer is mentioned, for example. Among these, aromatic diamines are preferable from the viewpoint that the obtained cured product has a higher glass transition temperature and excellent heat resistance.
The curing agents capable of reacting with the curable resin can be used alone or in combination of two or more.

The content of the curing agent capable of reacting with the curable resin is not particularly limited, and is not particularly limited as long as it is an amount capable of curing the curable resin, for example.
When the curable resin contains two or more epoxy groups, the content of the curing agent is excellent in physical properties after curing, so that the functional group of the curing agent is 0.3 to 1.2 times equivalent to the epoxy group Is preferably an amount corresponding to 0.5 to 1.1 equivalents.

The curable resin composition of the present invention can further contain a curing catalyst.
The curing catalyst that can be used in the curable resin composition of the present invention is not particularly limited as long as it can react with the curable resin. The curing catalyst may react with the urethane prepolymer.
Examples of the curing catalyst include metal catalysts, amine catalysts, imidazoles (eg, 2-methylimidazole), phosphorus catalysts (eg, triphenylphosphine, tetraphenylphosphonium tetraphenylborate), and tin catalysts. The curing catalyst can be selected according to the curable resin.

  Examples of a curing catalyst that can be used for a curable resin having two or more epoxy groups include carboxylic acids such as 2-ethylhexanoic acid and oleic acid; phosphorus such as polyphosphoric acid, ethyl acid phosphate, and butyl acid phosphate. Acids; organic metals such as dibutyltin dilaurate and dioctyltin dilaurate; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol (for example, DMP-30) and the like.

  Examples of a curing catalyst that can be used for a curable resin having two or more hydrolyzable silyl groups include, for example, cobalt octoate, manganese octoate, iron octoate, zinc octoate, tin octoate, tin naphthenate, Carboxylic acid metal salts such as tin caprylate and tin oleate; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin dimethoxide, diphenyltin diacetate, dibutylbis (triethoxysiloxy) tin, dibutylbis (acetyl) Acetonato) tin, organotin compounds such as dioctyltin dilaurate; tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, 1,3-propanedioxytitanium bis (ethylacetylacetate) Alkoxy titaniums such as: aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate, triethoxyaluminum and other organic aluminum; zirconium tetraacetylacetonate, tetraisopropoxyzirconium, tetrabutoxyzirconium, Organic zirconium compounds such as tributoxyzirconium acetylacetonate and tributoxyzirconium stearate; titanium chelate compounds such as diisopropoxybis (ethylacetylacetato) titanium; amine compounds; quaternary ammonium compounds. Organotin compounds and alkoxy titanium compounds having a large amount of catalytic ability are preferable. From the viewpoint of curability, a tin-based catalyst is preferable.

  The curable resin composition of the present invention includes the curable resin / polyurethane mixture of the present invention, a curing agent capable of reacting with the curable resin, and a curing catalyst that can be used as necessary. Additives can be blended within a range that does not impair the purpose. The additives are the same as described above.

  The manufacturing method of the curable resin composition of the present invention is not particularly limited. For example, a first liquid containing the curable resin / polyurethane mixture of the present invention and a second liquid containing a curing agent capable of reacting with the curable resin and a curing catalyst that can be used as necessary are prepared separately. Examples thereof include a method in which these are mixed and cured in an environment where the reaction temperature is room temperature to 250 ° C. to obtain a cured product. The additive can be added to the first liquid and / or the second liquid. The first liquid and the second liquid can be stored in separate containers replaced with an inert gas such as nitrogen gas.

Further, for example, in the production of the curable resin / polyurethane mixture of the present invention, a curable resin having two or more epoxy groups and / or hydrolyzable silyl groups, a urethane prepolymer, a urethane prepolymer, and a curable resin. A curing agent that can react with the catalyst, a curing catalyst that can be used as needed, and additives are added to the stirring device, and at this time, the amount of curing agent used is an excess amount relative to the urethane prepolymer. can do. While stirring these with a stirrer, the urethane prepolymer and the curing agent are reacted in an environment having a reaction temperature of room temperature to 80 ° C. to form polyurethane, thereby providing two epoxy groups and / or hydrolyzable silyl groups. A curable resin composition containing the curable resin having the above, the curing agent remaining without reacting with the urethane prepolymer, and the polyurethane dispersed in the curable resin and the curing agent can be produced.
In such a case, the conditions of the stirring device and the stirring device are the same as described above.
The curable resin composition thus obtained is heated to room temperature to 250 ° C., and the curable resin having two or more epoxy groups and / or hydrolyzable silyl groups and the curing agent are cured to obtain a cured product. can do.

Conventionally, when a part of a composition containing two or more kinds of curable resins is cured to form a mixture containing a curable resin and a particulate resin and then cured to obtain a cured product, the resulting cured product is obtained. The glass transition temperature is lower than that of a cured product obtained from one kind of curable resin. Such a decrease in glass transition temperature leads to a decrease in toughness.
On the other hand, the cured product obtained from the curable resin composition of the present invention has a higher glass transition temperature than the cured product obtained from one kind of curable resin, and the cured product has excellent toughness. Show.
Thus, the reason why the cured product obtained from the curable resin composition of the present invention exhibits a high glass transition temperature is a certain strong urea bond or urethane bond agglomerate in which the polyurethane contained in the composition is, The inventor speculates that the hydrogen bonding force is very strong. That is, the heat resistance is improved by the strong interaction between the hydroxy group generated when the curable resin having two or more epoxy groups and / or reactive silyl groups is cured and the polyurethane.
In addition, the curable resin composition of the present invention is observed to be in a water tank shape and has high thixotropy. This indicates that hydrogen bonding between the polyurethanes is strong.

Applications of the curable resin composition of the present invention include, for example, structural adhesive seals, sealing materials, adhesives, coating materials, primers, paints, and the like.
The adherend in which the curable resin composition of the present invention can be used is not particularly limited, and examples thereof include metals, plastics, glass, and coated plates.

Next, the manufacturing method of the curable resin / crosslinking compound mixture of the present invention will be described below.
The method for producing the curable resin composition / crosslinking compound mixture of the present invention includes a revolution drive motor, a rotary shaft that extends vertically from the revolution drive motor, and transmits the rotation of the revolution drive motor, and A revolution body mounted horizontally on the rotation shaft, a rotation bearing arranged on an axis inclined with respect to the axis of the rotation shaft at a position deviated from the extension of the rotation shaft on the revolution body, and the rotation bearing A stirring container holder supported; a stirring container housed in the stirring container holder; a rotation driving motor; and a transmission device for transmitting rotation of the rotation driving motor to the rotation bearing. However, the revolving body rotates and the stirring holder rotates so that the rotating body rotates on an axis inclined with respect to the axis of the rotating shaft. Using a stirrer, the curable resin A, the curable resin B, and a curing agent and / or a curing catalyst capable of reacting with the curable resin B are charged into the agitated container and stirred. A mixture containing the curable resin A and the crosslinked compound dispersed in the curable resin A by reacting the curing agent and / or a curing catalyst to form a particulate crosslinked compound is obtained. This is a method for producing a curable resin / crosslinking compound mixture that can be obtained.

  The stirring apparatus used in the method for producing a curable resin composition / crosslinking compound mixture of the present invention will be described with reference to the accompanying drawings. In addition, the stirring apparatus used is not limited to what is shown in drawing.

FIG. 1 is a schematic view schematically showing the interior of an example of a stirring apparatus used in the method for producing a curable resin composition / crosslinking compound mixture of the present invention.
In FIG. 1, reference numeral 1 denotes a container body (housing body) having an open end, and 2 denotes a detachable container lid (sealing body) that hermetically seals the opening of the container body 1. Here, the container main body 1 and the container lid body 2 are provided with a resin or rubber sealing material (not shown) on the sealing surface so that airtightness is maintained when a vacuum pressure is applied to the inside. Yes. In addition, the container body 1 and the container lid 2 have a structure and strength that can withstand vacuum pressure. At least one of the container body 1 and the container lid 2 is provided with an air port (not shown) for returning the vacuum pressure to normal pressure.

  Further, a support plate 3 is mounted and disposed in the container body 1 via a vibration absorber 4. The vibration absorber 4 is, for example, a spring or rubber, and functions to absorb the vibration of the support plate 3 caused by the rotation of the revolution drive motor 5 and to block the vibration to other members. A rotating shaft 5 a that transmits the rotation of the revolution driving motor 5 extends vertically upward from the revolution driving motor 5, and the rotating shaft 5 a is mounted on the support plate 3. Moreover, the revolution body 6 is mounted horizontally at the tip of the rotating shaft 5a. Rotational transmission of the revolution drive motor 5 that contributes to the revolution of the revolution body 6 can be performed by interposing a transmission mechanism such as a gear instead of directly by the rotation shaft 5a.

At a position outside the extension of the rotating shaft 5a on the revolution body 6, the rotation bearing 12 is arranged with an axis inclined with respect to the axis of the rotating shaft 5a. The rotation bearing 12 supports the stirring container holder 7. The stirring vessel holder 7 is arranged with an axis inclined with respect to the axis of the rotary shaft 5 a in the same manner as the rotation bearing 12. The stirring container holder 7 accommodates the stirring container 8 therein.
A vacuum pump 9 for evacuating the inside of the hermetically sealed container (housing) to a predetermined pressure is installed outside the container body 1. A pipe 10 c is connected to the vacuum pump 9, and the pipe 10 c is connected to a vacuum suction hole 10 provided in at least one of the container main body 1 and the container lid 2. An exhaust hole 11 is provided in the lid 8 a of the stirring vessel 8.

  The stirring container holder 7 and the stirring container 8 revolve by the rotation of the rotating shaft (revolving shaft) 5 a accompanying the driving of the revolving drive motor 5. Further, the stirring container holder 7 is configured to rotate by a rotation driving mechanism and a rotation transmission mechanism (not shown). When the stirring container holder 7 rotates, the stirring container 8 stored in the stirring container holder 7 rotates. The stirring container holder 7 is agitated in order to easily stir the agitated material 14 (the curable resin A, the curable resin B, and the curing agent and / or curing catalyst of the curable resin B) in the stirred container 8. The container holder 7 is set so that the axis of the container holder 7 is inclined at a fixed or variable angle with respect to the axis of the rotation axis (revolution axis) 5a. In addition, a cooling mechanism 13 can be provided in order to suppress a temperature rise in the container body 1 caused by driving of the revolution drive motor 5.

  The rotating bearing 12 of the stirring vessel holder 7 and the bearing (not shown) of the rotating shaft (revolving shaft) 5a are hermetically sealed so that the built-in lubricating oil does not evaporate under vacuum pressure or scatter by rotating centrifugal force. It has a formula structure. In addition, the electronic circuit board constituting the control mechanism of the stirring device may be installed outside the container body 1 to avoid the influence of the vacuum pressure because the mounted and mounted capacitors may puncture under vacuum pressure. It is desirable to do.

A method for producing a curable resin composition / crosslinking compound mixture using the stirring apparatus shown in FIG. 1 will be described below.
First, inside the stirring vessel 8, the curable resin A, the curable resin B, and the curing agent and / or the curing catalyst of the curable resin B are accommodated, the lid 8a is attached, and the stirred vessel 8 is closed. It is attached to a stirring vessel holder 7 that is attached to the revolution body 6 in the main body 1. Next, the container lid body 2 is attached to seal the opening, while an air port (not shown) and the like are hermetically sealed. Then, depending on the type and amount of the curing agent and / or curing catalyst of the curable resin A, the curable resin B, the curable resin B accommodated in the stirring vessel 8, the rotation speed, the revolution speed, and the timing for applying the vacuum pressure Then, set the operating conditions such as stirring time and vacuum pressure, and start the driving operation.

  By this operation and driving, the stirring vessel 8 rotates while revolving, and the curing agent and / or curing catalyst of the curable resin A, curable resin B, curable resin B contained in the stirring vessel 8 is stirred. The Further, the inside of the container formed by the container main body 1 and the container lid 2 is evacuated at a required timing, and the bubbles in the stirring container 8 are eliminated while the vacuum pressure is applied for at least a certain time. When the necessary stirring operation is completed, air is introduced into the main body container 1 to release the vacuum pressure. Thereafter, the container lid 2 is opened, the stirring container 8 is removed from the stirring container holder 7, and the lid 8a of the stirring container 8 is opened to obtain a curable resin / crosslinked compound mixture.

  When the stirring apparatus shown in FIG. 1 is used, the revolving speed of the stirring vessel 8 from the viewpoint that the cross-linking compound is less compatible with the curable resin A, the mixture becomes uniform, and the particle size of the cross-linking compound is constant and small. Is preferably 100 to 10,000 rpm, and more preferably 200 to 5000 rpm. In addition, the rotation speed of the stirring vessel 8 is set to 0. The revolution speed of the stirring vessel 8 from the viewpoint that the crosslinking compound is less compatible with the curable resin, the mixture becomes uniform, and the particle size of the polyurethane is constant and small. It is preferable that it is 05-1 times, and it is more preferable that it is 0.2-1.0 times.

The temperature at the time of stirring is preferably room temperature to 100 ° C, more preferably room temperature to 60 ° C.
The pressure at the time of stirring is preferably normal pressure to 0.1 Torr, and more preferably 1.0 to 400 Torr.

The curable resin A used in the production of the curable resin / crosslinking compound mixture of the present invention will be described below.
The curable resin A used in the production of the curable resin / crosslinking compound mixture of the present invention is not particularly limited. For example, the curing includes two or more polyisocyanates, epoxy groups and / or hydrolyzable silyl groups. Resin and acrylic resin.
The polyisocyanate is not particularly limited as long as it contains two or more isocyanate groups, and examples thereof include the above polyisocyanate compounds and urethane prepolymers. The curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups is the same as described above. The acrylic resin is not particularly limited, and examples thereof include conventionally known ones.
Among these, the curable resin A is preferably an epoxy resin or a modified silicone polymer. The epoxy resin and the modified silicone polymer are the same as described above.

The curable resin B used in the production of the curable resin / crosslinking compound mixture of the present invention will be described below.
The curable resin B used in the production of the curable resin / crosslinked compound mixture of the present invention is particularly limited as long as it can react with a curing agent and / or a curing catalyst to form a particulate crosslinked compound. For example, the same thing as said curable resin A is mentioned. Especially, it is mentioned as one of the aspects with preferable curable resin B that it is a urethane prepolymer. The urethane prepolymer is the same as described above.

  The amount of the curable resin B used is preferably 1 to 38 parts by mass, more preferably 2 to 28 parts by mass with respect to 100 parts by mass of the curable resin A. In such a range, the fluidity is excellent, and the cured product obtained after curing is excellent in heat resistance and physical properties.

  The combination of the curable resin A and the curable resin B is not particularly limited as long as the reactivity is different. For example, when both curable resin A and curable resin B are urethane prepolymers, they may be urethane prepolymers obtained from different isocyanate compounds.

The curing agent and / or curing catalyst that can react with the curable resin B used in the production of the curable resin / crosslinking compound mixture of the present invention will be described below.
The curing agent and / or curing catalyst is not particularly limited as long as it can react with the curable resin B. For example, examples of the curing agent and / or curing catalyst for the curable resin containing two or more polyisocyanates, epoxy groups and / or hydrolyzable silyl groups are the same as those described above. Examples of the curing agent and / or curing catalyst for the acrylic resin include conventionally known ones.
When the curable resin B is a urethane prepolymer, the curing agent is preferably an aromatic diamine. Specific examples of the aromatic diamine are the same as those described above.

The amount of the curing agent that can react with the curable resin B is such that the functional group of the curing agent is 0.3 to 1.2 times the functional group of the curable resin B from the viewpoint of the crosslinking density of the crosslinking compound. Equivalent weight is preferred.
The amount of the curing catalyst that can react with the curable resin B is not particularly limited.

  Further, when the curing agent capable of reacting with the curable resin B is capable of reacting with the curable resin A, the curing agent capable of reacting with the curable resin A and the curable resin B is used with respect to the curable resin B. Can be used excessively. Specifically, the functional group of the curing agent is preferably 0.3 to 1.2 times equivalent to the total amount of the functional group of the curable resin A and the functional group of the curable resin B. In such a case, the curing agent that did not react with the curable resin B remains in the resulting mixture, and as a result, the curable resin / polyurethane mixture includes the curable resin A, the crosslinking compound, and the curable resin. And a curing agent that did not react with B. Such a mixture containing a curing agent remaining without reacting with the curable resin B (this curing agent can react with the curable resin A) can be used as it is as a curable resin composition.

  It is preferable that it is 1-40 mass parts with respect to 100 mass parts of curable resin A, and, as for content of a crosslinking compound, it is more preferable that it is 2-30 mass parts. In such a range, excellent fluidity and excellent heat resistance and physical properties can be imparted to the curable resin A.

  In the curable resin / crosslinking compound mixture of the present invention, the average particle size of the crosslinking compound is preferably 5 to 300 nm from the viewpoint that the crosslinking compound is less compatible with the curable resin A. More preferably, it is ˜100 nm.

  According to the method for producing a curable resin / crosslinking compound mixture of the present invention, a mixture containing the curable resin A and the particulate crosslinking compound dispersed in the curable resin A can be produced. The curable resin A and the cross-linking compound are hardly compatible, and the mixture can be uniform. Among these, from the viewpoint that the curable resin A and the crosslinking compound are more difficult to be compatible, the curable resin A is a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups, and the crosslinking compound is an epoxy. Preferred is a curable resin / crosslinked compound mixture which is a crosslinked particulate polyurethane dispersed in a curable resin containing two or more groups and / or hydrolyzable silyl groups. A crosslinked particulate form dispersed in a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups and a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups. Examples of the curable resin / polyurethane mixture containing polyurethane are the same as described above.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

1. Examples and Comparative Examples (1) Example 1
Into the stirring vessel 8 of the stirring apparatus shown in FIG. 1, the epoxy resin, the urethane prepolymer 1 and the aromatic diamine 1 are charged in the quantitative ratio shown in Table 1 and the rotation speed is 1000 rpm and the revolution speed is 2000 rpm for 10 minutes at 25 ° C. The urethane prepolymer 1 and the aromatic diamine 1 were reacted with stirring at a pressure of 10 Torr. Next, the product is taken out from the stirring vessel 8, and the aromatic diamine 2 is added thereto in the quantitative ratio shown in Table 1 and cured at 100 ° C. for 2 hours, 130 ° C. for 1 hour, and 180 ° C. for 1 hour. A cured product was obtained. This cured product is referred to as cured product 1.

(2) Example 2
A cured product was obtained in the same manner as in Example 1 except that the amounts of the urethane prepolymer 1 and the aromatic diamine 1 were changed to the amounts shown in Table 1. This cured product is designated as cured product 2.

(3) Example 3
In the stirring container 8 of the stirring apparatus shown in FIG. 1, the epoxy resin, the urethane prepolymer 1 and the aromatic diamine 2 are charged in the quantitative ratio shown in Table 1, and at room temperature for 10 minutes, the rotation speed is 1000 rpm, the revolution speed is 2000 rpm, The urethane prepolymer 1 and the aromatic diamine 2 were reacted with stirring at a pressure of 10 Torr. Subsequently, the product was taken out from the stirring vessel 8, and the product was cured at 100 ° C. for 2 hours, 130 ° C. for 1 hour, and 180 ° C. for 1 hour to obtain a cured product. This cured product is referred to as cured product 3.

(4) Example 4
A cured product was obtained in the same manner as in Example 1 except that the amounts of the urethane prepolymer 1 and the aromatic diamine 1 were changed to the amounts shown in Table 1. This cured product is referred to as cured product 4.

(5) Example 5
In the stirring container 8 of the stirring apparatus shown in FIG. 1, the modified silicone, the urethane prepolymer 1 and the aromatic diamine 1 are charged in the quantitative ratio shown in Table 1, and at room temperature for 10 minutes, the rotation speed is 1000 rpm, the revolution speed is 2000 rpm, The stirred urethane prepolymer 1 and the aromatic diamine 1 were reacted at a pressure of 10 Torr. Thereafter, a tin catalyst and water were added at a quantitative ratio shown in Table 1, mixed, and cured at 80 ° C. for 3 hours to obtain a cured product. This cured product is referred to as cured product 5.

(6) Comparative Example 1
1 is charged into the stirring container 8 of the stirring apparatus shown in FIG. 1 in the quantitative ratio shown in Table 1, and stirred at 150 ° C. for 3 hours at a rotation speed of 1000 rpm, a revolution speed of 2000 rpm, and a pressure of 10 Torr. To make them compatible. Aromatic diamine 2 (23.4 parts by mass) was added thereto and mixed, and cured at 100 ° C. for 2 hours, 130 ° C. for 1 hour, and 180 ° C. for 1 hour to obtain a cured product. This cured product is referred to as cured product 6.

(7) Comparative Example 2
A cured product was obtained in the same manner as in Comparative Example 1 except that 10 parts by mass of NBR-modified epoxy was used in place of thermoplastic urethane, and the amount of aromatic diamine 2 was 24.8 parts by mass. This cured product is referred to as cured product 7.

(8) Comparative Example 3
A cured product was obtained in the same manner as in Example 5 except that 10 parts by mass of thermoplastic urethane was used in place of the urethane prepolymer 1 and the aromatic diamine 1 was not used. This cured product is referred to as cured product 8.

(9) Reference example 1
A cured product was obtained in the same manner as in Example 3 except that the urethane prepolymer 1 was not used and the amount of the aromatic diamine 2 was changed to 23.4 parts by mass. This cured product is referred to as cured product 9.

2. Evaluation method About the obtained hardened | cured material, the glass transition temperature and bending elongation were evaluated in accordance with the following evaluation method. The results are shown in Table 1.
(1) Glass transition temperature Cured products 1 to 4 and cured products obtained with a viscoelasticity measuring device (DMA) (TA Instruments, RDS-II) under the conditions of a frequency of 1 Hz and a strain of 0.01%. About 6-7 and the hardened | cured material 9, it heated from room temperature to 250 degreeC with the temperature increase rate of 5 degree-C / min, and measured glass transition temperature (degreeC) and tan-delta. The higher the glass transition temperature (Tg), the better the toughness and heat resistance. The glass transition temperature (° C.) and tan δ DMA charts measured for cured product 1, cured product 6, cured product 7 and cured product 9 are shown in FIG.

(2) Bending elongation Test pieces having a length of 85 mm, a width of 10 mm, and a thickness of 4 mm were prepared from the cured products 1 to 4, the cured products 6 to 7, and the cured product 9. A three-point bending test was performed under the condition of 2 mm / min. Bending elongation is
Bending elongation (%) = deflection × [thickness of test piece (mm)] × 6 / [distance between fulcrums (mm)] ²
It was calculated by applying the following formula. The higher the bending elongation, the better the toughness.
In the above formula, “deflection” represents a stroke (mm) until the test piece breaks.

(3) Tensile properties A sample having a thickness of 1 mm punched from the cured product 5 and the cured product 8 into a No. 3 dumbbell shape (according to JIS K6251-1993) was prepared, and the test speed was 2 mm / min using an autograph. Tensile tests were conducted to measure tensile elongation and tensile strength.

The details of each component in Table 1 are as follows.
Epoxy resin: bisphenol A type epoxy resin (EP4100E, manufactured by Asahi Denka Co.)
Modified silicone: Cycle SAT200, manufactured by Kaneka Corp. Urethane prepolymer 1: Urethane prepolymer / butyl acetate solution containing 75% of solid content of trifunctional isocyanate compound terminated with isophorone diisocyanate in butyl acetate (Takenate D140) (Mitsui Takeda Chemical Co., Ltd.). In addition, the numerical value outside parentheses in the column of urethane prepolymer 1 in Table 1 is the mass part of the urethane prepolymer contained in the butyl acetate solution, and the numerical value in parentheses is the total mass of the urethane prepolymer and butyl acetate. Part.
・ Aromatic diamine 1: Liquid aromatic diamine (Epicure W, manufactured by Japan Epoxy Resin Co., Ltd.)
-Thermoplastic urethane: Pelecene 90AE, manufactured by DOW-NBR-modified epoxy: EPR1309, manufactured by Asahi Denka Kogyo Co., Ltd.-Aromatic diamine 2: Liquid aromatic diamine (Epicure W, manufactured by Japan Epoxy Resin Co., Ltd.)
・ Tin catalyst: Dibutyltin laurate, manufactured by Kanto Chemical Co., Inc.

As is apparent from the results shown in Table 1, the glass transition temperature and the bending elongation of Examples 1 to 4 are higher than those of the reference example although they contain a crosslinked particulate polyurethane. In addition, Example 5 is superior in tensile properties to Comparative Example 3 in spite of containing crosslinked particulate polyurethane. Such a high glass transition temperature, bending elongation and tensile physical properties indicate that the cured product is excellent in toughness.
The reason why the cured products of Examples 1 to 4 exhibit such a high glass transition temperature and bending elongation, and the cured product of Example 5 exhibits such a high tensile physical property is that there are specific particulate polyurethanes that are crosslinked. The inventor speculates that it is an aggregate of strong urea bonds and urethane bonds and has a very strong hydrogen bonding force. That is, the heat resistance is improved by the interaction between the crosslinked polyurethane and the hydroxy group produced during curing from a curable resin having two or more epoxy groups and / or reactive silyl groups.
Moreover, in the Examples, the obtained curable resin / polyurethane mixture is observed to be uniform and syrupy and has high thixotropy. This indicates that hydrogen bonds between crosslinked polyurethane particles are strong.
In contrast, Comparative Examples 1 and 2 have a lower glass transition temperature and bending elongation than the reference examples. Further, Comparative Example 3 has lower tensile physical properties than Example 5.

(Examples 6 to 8)
Each component of Table 2 below (excluding aromatic diamine 2) is mixed in the composition (parts by mass) shown in Table 2, and using a stirrer (Three-One Motor, Shinto Kagaku Co., Ltd., the same shall apply hereinafter) The urethane prepolymer and the aromatic diamine 1 were reacted by stirring at 30 ° C. for 30 minutes at a stirring speed of 150 rpm. Next, the amount of aromatic diamine 2 shown in Table 2 was added to this mixture and sufficiently dispersed to obtain each composition shown in Table 2. Each composition obtained was cured at 100 ° C. for 2 hours, 130 ° C. for 1 hour, and 180 ° C. for 1 hour to obtain each cured product.
About each obtained hardened | cured material, the glass transition temperature and bending elongation were measured by the method similar to Examples 1-5.
The results are shown in Table 2.

The details of each component in Table 2 are as follows. In Table 2, the epoxy resin, urethane prepolymer 1, aromatic diamine 1, and aromatic diamine 2 are the same as those shown in Table 1.
Urethane prepolymer 2: Trifunctional isocyanate compound based on HDI (100% solid content) (Takenate D170, manufactured by Mitsui Takeda Chemical Co., Ltd.)

  As is apparent from the results shown in Table 2, compositions containing polyurethane obtained by reacting a urethane prepolymer and an aromatic diamine in an epoxy resin using an ordinary agitator (Examples 6 to 6) As in Examples 1 to 4, 8) had a glass transition temperature and a bending elongation higher than those of the reference example, although it contained a crosslinked particulate polyurethane.

(Examples 9 to 11)
Each component of Table 3 below (excluding aromatic diamine 2) was mixed using the stirrer with the composition (parts by mass) shown in Table 3 and stirred at 60 ° C. for 5 hours. Next, the aromatic diamine 2 was mixed in the amount shown in Table 3 to obtain each composition shown in Table 3. Each composition obtained was cured at 100 ° C. for 2 hours, 130 ° C. for 1 hour, and 180 ° C. for 1 hour to obtain each cured product.
About each obtained hardened | cured material, the glass transition temperature and bending elongation were measured by the method similar to Examples 1-5.
The results are shown in Table 3.

(Reference Example 2)
The bisphenol F-type resin and aromatic diamine 2 shown in Table 3 below were mixed using a stirrer with the composition (parts by mass) shown in Table 3 to obtain the composition shown in Table 3. The obtained composition was cured at 100 ° C. for 2 hours, at 130 ° C. for 1 hour, and at 180 ° C. for 1 hour to obtain each cured product.
About the obtained hardened | cured material, the glass transition temperature and bending elongation were measured by the method similar to Examples 1-5.
The results are shown in Table 3.

Details of each component in Table 3 are as follows. In Table 3, aromatic diamine 1 and aromatic diamine 2 are the same as those shown in Table 1.
Urethane prepolymer dispersed epoxy resin 1: 170 g of bifunctional polypropylene glycol (Exenol 2020, manufactured by Asahi Glass Co., Ltd., molecular weight 2000, hereinafter the same) in 900 g of bisphenol A type epoxy resin (DER332, manufactured by Dow Chemical Co., hereinafter the same) and 25 g of TDI (Cosmonate T80, manufactured by Mitsui Takeda Chemical Co., Ltd., the same applies hereinafter) was added, and a urethane prepolymer was produced by heating and stirring at 80 ° C. for 15 hours at a stirring speed of 100 rpm using a stirrer. A polymer-dispersed epoxy resin 1 was obtained.
-Urethane prepolymer dispersed epoxy resin 2: 170 g of bifunctional polypropylene glycol and 25 g of TDI were added to 600 g of bisphenol A type epoxy resin, and the mixture was stirred with a stirrer at 100 rpm with a stirring speed of 100 rpm for 15 hours. A prepolymer was produced to obtain a urethane prepolymer-dispersed epoxy resin 2.
-Urethane prepolymer dispersed epoxy resin 3: Bisphenol F type epoxy resin (Epicoat 806, manufactured by Japan Epoxy Resin Co., Ltd.) in 600 g, bifunctional polypropylene glycol 170 g and TDI 25 g were added, and the stirring speed was 100 rpm using a stirrer. A urethane prepolymer was produced by stirring at 80 ° C. for 15 hours to obtain a urethane prepolymer-dispersed epoxy resin 3.
Bisphenol F type epoxy resin: Epicoat 806, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 165

  As is apparent from the results shown in Table 3, the compositions (Examples 9 to 11) containing an epoxy resin in which a bifunctional urethane prepolymer is dispersed have a glass transition temperature and a bending elongation as compared with Reference Example 1 or 2. it was high. Further, when Examples 9 to 10 were compared with Comparative Example 1 containing an epoxy resin and thermoplastic urethane, the bending elongation was the same, but Examples 9 to 10 had a glass transition temperature of 20 ° C. or higher. it was high. Furthermore, when the composition immediately after manufacture of the composition of Examples 9-10 and the comparative example 1 was compared, the viscosity of the composition of Examples 9-10 was clearly lower.

FIG. 1 is a schematic view schematically showing the interior of an example of a stirring apparatus used in the method for producing a curable resin composition of the present invention. FIG. 2 is a DMA chart of glass transition temperature and tan δ measured for cured product 1, cured product 6, cured product 7 and cured product 9.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Container body 2 Container lid 3 Support plate 4 Vibration absorber 5 Revolution drive motor 5a Rotating shaft (revolving shaft)
6 Revolving body 7 Stirred container holder 8 Stirred container 8a Lid 9 Vacuum pump 10 Vacuum suction hole 10c Pipe 11 Exhaust hole 12 Rotating bearing 13 Cooling mechanism 14 Stirred material

Claims (11)

  A curable resin / polyurethane mixture containing a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups, and a crosslinked particulate polyurethane dispersed in the curable resin. Containing a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups, and polyurethane dispersed in the curable resin,
A curable resin / polyurethane mixture, wherein the polyurethane is a polyurethane produced in the curable resin.   The curable resin / polyurethane mixture according to claim 2, wherein the polyurethane is a crosslinked particulate polyurethane.   The curable resin / polyurethane mixture according to claim 1, wherein the polyurethane is obtained by a reaction between a urethane prepolymer and a curing agent capable of reacting with the urethane prepolymer.   The curable resin / polyurethane mixture according to claim 4, wherein the urethane prepolymer has a functional group equivalent of 3000 g / equivalent or less.   The curable resin / polyurethane mixture according to claim 4 or 5, wherein the curing agent is an aromatic diamine.   Content of the said polyurethane is 1-40 mass parts with respect to 100 mass parts of said curable resins, The curable resin / polyurethane mixture in any one of Claims 1-6.   A curable resin composition comprising the curable resin / polyurethane mixture according to claim 1 and a curing agent capable of reacting with the curable resin. A revolving drive motor, a revolving shaft extending vertically from the revolving drive motor and transmitting the rotation of the revolving drive motor, a revolving body mounted horizontally on the revolving shaft, and the revolving body A rotation bearing arranged at an axis inclined with respect to the axis of the rotation shaft at a position deviated from the extension of the rotation shaft, a stirring container holder supported by the rotation bearing, and a stirring container accommodated in the stirring container holder A container, a rotation drive motor, and a transmission device that transmits rotation of the rotation drive motor to the rotation bearing;
The stirring container is revolved by rotating the revolving body, and is rotated by an axis inclined with respect to the axis of the rotating shaft by rotating the stirring holder. ,
While the curable resin A, the curable resin B, and the curing agent and / or curing catalyst capable of reacting with the curable resin B are charged into the stirring vessel and stirred, the curable resin B and the curing agent and / or A curable resin in which a mixture containing the curable resin A and the crosslinked compound dispersed in the curable resin A can be obtained by reacting with a curing catalyst to form a particulate crosslinked compound. / Method for producing cross-linking compound mixture.   The method for producing a curable resin / crosslinking compound mixture according to claim 9, wherein the revolution speed of the stirring container is 100 to 10,000 rpm, and the rotation speed of the stirring container is 0.05 to 1 times the revolution speed.   The curable resin A is a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups, and the cross-linking compound is a curable resin containing two or more epoxy groups and / or hydrolyzable silyl groups. The method for producing a curable resin / crosslinked compound mixture according to claim 9 or 10, wherein the polyurethane is a crosslinked particulate polyurethane dispersed in the polymer.

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