JP2010006936A - Curable resin composition which is thickened through mixing and method for thickening curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition which is cured through mixing and comprises liquid compositions that show low viscosity before mixing but are thickened when mixed so as to yield a good workability and hardly affect physical properties of a coating film formed after curing. <P>SOLUTION: The curable resin composition which is thickened through mixing comprises an epoxy resin, an epoxy resin hardener, water and a liquid composition containing an alkyl silicate compound of the formula. The curable resin composition is cured by mixing at least two liquid compositions, wherein the liquid compositions preferably comprises (A) a liquid composition containing the epoxy resin and the silicate compound of the formula and a liquid composition (B) containing the epoxy resin hardener and water. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable resin composition that is cured by mixing at least two liquid compositions. Although the liquid compositions before mixing each have a low viscosity, they increase rapidly when these liquid compositions are mixed. The present invention relates to a mixed thickening type curable resin composition that gives good workability (thixotropy) by sticking, and hardly affects the physical properties of the film after curing, and a thickening method in the curable resin composition.

Various types of curable resin compositions that are reactively cured by mixing at least two liquid compositions have been known in the past. In the fields of adhesives, paints, sealing materials, potting agents, resin molding materials, etc. It has been used since ancient times.
As such a curable resin composition of mixed curable type, there are many known generally composed of two components called a main agent and a curing agent. For example, the chemical composition thereof is an epoxy type (main agent; epoxy resin / curing). Agents: Curing agents for epoxy resins such as amines and ketimines / for example, Patent Document 1), Modified silicone-epoxy systems (first liquid; Curing agents for epoxy resins such as modified silicone polymers and amines and ketimines / second liquid; epoxy Modification catalysts of modified silicone polymers such as resins and tin compounds / for example, Patent Document 2), urethane systems (main agent; isocyanate compound / curing agent; amine compounds, polyol compounds, etc./for example, Patent Document 3), etc. are known. ing.

  These mixed curable resin compositions are adjusted in advance so as to obtain an appropriate mixture viscosity according to the application application. However, for example, in order to obtain a viscosity of a mixture having a relatively high viscosity and excellent workability (having thixotropy) in order to obtain application workability on a vertical surface, each liquid composition before mixing is naturally. In some cases, the viscosity of the ink may increase, and as a result, the workability during mixing may be deteriorated or a mixing defect may be caused. On the other hand, if the viscosity of each liquid component before mixing is kept low and priority is given to workability during mixing, a dilemma that a desired mixture viscosity cannot be obtained may occur.

JP 2006-219624 A JP 2002-265922 A JP 2005-89527 A

Therefore, in order to solve these problems, it is generally called a mixed thickening type, and the liquid compositions before mixing each have a low viscosity, but when these liquid compositions are mixed, they increase the viscosity and work well. A mixed curable resin composition that imparts properties has been studied.
However, the thickener used as a thickening method at the time of mixing is a component not involved in the curing of the curable resin composition. Therefore, in the conventional mixed thickening type curable resin composition, even if workability by mixed thickening is obtained, there are components that do not participate in curing, so these components are coated after curing. There is a problem in that physical properties are adversely affected (specifically, a plasticizing effect of the film).

Therefore, it has been desired to develop a mixed thickening system which is a simpler system and at the same time hardly affects the physical properties of the cured film after curing.
In the present invention, the liquid compositions before mixing each have a low viscosity, but when these liquid compositions are mixed, the liquid composition is thickened to give good workability, and it is difficult to affect the film properties after curing. An object of the present invention is to provide a mixed curable resin composition.

  Therefore, as a result of intensive studies to realize the novel mixed thickening system as described above, the present inventor has focused on the fact that when the liquid silicate compound and water are mixed, they react rapidly to produce silica fine particles. The present invention has been completed. The present invention is composed of the following first to seventh inventions.

・・・（１）
但し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は炭素数１〜４のアルキル基であり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は同じであっても異なっていてもよく、ｎは１以上の整数である。 That is, the first invention consists of an epoxy resin, an epoxy resin curing agent, water and a liquid composition containing a silicate compound represented by the chemical formula (1), and a mixed thickening type curable resin composition It is about things.

... (1)
^{However, R 1, R 2, R} 3, R 4 is an alkyl group having 1 to 4 carbon ^{atoms, R 1, R 2, R} 3, R 4 may be different even in the same, n represents It is an integer of 1 or more.

  The second invention is a curable resin composition that cures by mixing at least two liquid compositions, and these liquid compositions contain (A) an epoxy resin and a silicate compound represented by the chemical formula (1). The present invention relates to a mixed thickening curable resin composition according to the first invention, characterized by comprising a liquid composition and a liquid composition containing (B) an epoxy resin curing agent and water.

A third invention, R ^1, R 2, ^{R 3,} R ⁴ in the chemical formula (1) is characterized in that it is a methyl group, mixed thickening curing of the first or second one of invention The present invention relates to a conductive resin composition.

  The fourth invention relates to the mixed thickening curable resin composition according to any one of the first to third inventions, wherein n in the chemical formula (1) is an integer of 2 or more.

  The fifth invention relates to a mixed thickening adhesive composition mainly comprising the curable resin composition according to any one of the first to fourth inventions.

6th invention is a curable resin composition which hardens | cures by mixing at least 2 liquid composition, It comprises the process of the following (X) (Y) (Z), At the time of mixing Relates to a method for thickening a mixture of the liquid composition.
(X) Step of mixing at least one liquid composition containing water and another liquid composition containing a silicate compound represented by chemical formula (1) (Y) Water and silicate in the mixed liquid composition Step of generating silica fine particles by reacting with the compound (Z) Step of thickening the mixture of the liquid composition by the generated silica fine particles

  A seventh invention is characterized in that the liquid composition uses a curable resin composition comprising at least (A) a liquid composition containing an epoxy resin and (B) a liquid composition containing a curing agent for the epoxy resin. The invention relates to a method for thickening a mixture of the liquid composition during mixing according to the sixth invention.

  The thickening method in the mixed thickening type curable resin composition and the curable composition according to the present invention increases the viscosity when these liquid compositions are mixed, although the liquid compositions before mixing each have low viscosity. It has the effect of giving good workability and hardly affecting the physical properties of the film after curing.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited only to these illustrations, Of course, a various change can be added in the range which does not deviate from the summary of this invention.

[About curable resin composition]
The curable resin composition in the present invention refers to a resin composition that is reactively cured by mixing at least two liquid compositions.
The curable resin composition of the present invention is composed of a plurality of liquid compositions containing an epoxy resin, an epoxy resin curing agent, water, and a silicate compound represented by the chemical formula (1) as essential components.
Specifically, the first liquid composition (A) is a liquid composition containing at least an epoxy resin and a silicate compound represented by the above chemical formula (1), and the other liquid composition (B) is a cured epoxy resin. A liquid composition containing an agent and water is preferred. The first liquid composition may be combined with an epoxy resin and water, and the second liquid composition may be combined with an epoxy resin curing agent and the silicate compound represented by the above chemical formula (1), but the epoxy resin and water are compatible. The above combination is more preferable because it is difficult to do.
Examples of such curing systems include epoxy systems exemplified in the prior art section (main agent, epoxy resin / curing agent, curing agent for epoxy resins such as amines and ketimines), and modified silicone-epoxy systems (first liquid, This includes a modified silicone polymer and a curing agent / second liquid for epoxy resins such as amines and ketimines; a curing catalyst for modified silicone polymers such as epoxy resins and tin compounds). Further, the liquid composition is not necessarily limited to the two-pack type, and a liquid composition of three or more liquids (for example, water as a third liquid) may be mixed.

  The essence of the present invention focuses on the fact that when mixing a liquid silicate compound and water, it reacts quickly to produce silica fine particles, and this is applied to a curable resin composition to establish a new mixed thickening system. It should be understood that there is a point. In any of these embodiments, when the silicate compound and water are mixed, they react rapidly to produce silica fine particles, thereby exhibiting a thickening action. The silica fine particles produced by the reaction can thicken the system and impart workability (thixotropic properties) even with a small amount. In addition, since the amount of the silica is small, or the silica fine particles act as a filler in the cured film, it acts in the direction of reinforcement rather than plasticizing the film. Such a problem does not occur.

  The mixed curable resin composition of the present invention can be used as an adhesive, a paint, a sealing material, a potting agent, a resin molding material, and the like.

[Epoxy resin]
A conventionally well-known thing can be used for the epoxy resin in this invention, and what kind of thing may be used as long as it has an epoxy group. For example, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type obtained by reacting biphenyl, bisphenol A, bisphenol F, bisphenol AD, bisphenol S and the like with epichlorohydrin Epoxy resins and the like, hydrogenated or brominated epoxy resins, glycidyl ester type epoxy resins, novolac type epoxy resins, urethane-modified epoxy resins having urethane bonds, nitrogen-containing epoxy resins epoxidized with metaxylenediamine, hydantoin, etc. And rubber-modified epoxy resin containing polybutadiene or NBR. It is not limited to these, You may use combining two or more types of epoxy resins.
A commercial item can also be used for the epoxy resin of this invention. Examples of commercially available products include bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin / product name Epicoat 828), bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin / product name Epicoat 830), and the like.

[Epoxy resin curing agent]
As the curing agent for the epoxy resin in the present invention, conventionally known ones can be used, and amine compounds, tertiary amine compounds, mercaptan compounds and the like can be used. Among these, amine compounds are preferable because they promote the reaction between water and silicate. In addition, aliphatic polyamines, alicyclic polyamines, norbornanediamine-epoxy adducts (JP-A-8-253556), a mixture of a Mannich base compound and an aliphatic polyetherdiamine (JP-A-10-339040) Hydrophilic ketimines or hydrophobic ketimines can also be used.
Specifically, compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,3-bisaminomethylcyclohexane, norbornanediamine, metaxylylenediamine, amine compounds having an oxyalkylene skeleton, and these amine compounds Various modified amines obtained by urethane modification, amide modification, Mannich modification, epoxy modification, and the like can be suitably used.

・・・（１）
但し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は炭素数１〜４のアルキル基であり、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は同じであっても異なっていてもよく、ｎは１以上の整数である。 [About silicate compounds]
The silicate compound in the present invention is a compound represented by the following chemical formula (1). Specific examples include monomers and multimers such as tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. It is needless to say that the present invention is not limited to these, and two or more types may be used in combination.
A commercial item can also be used for the silicate compound of this invention. Commercially available products include silicate monomers such as ethyl silicate (manufactured by Colcoat / product name: ethyl silicate 28), N-propyl silicate (manufactured by Colcoat / product name: N-propyl silicate), and N-butyl silicate (colcoat company). Manufactured / product name: N-butyl silicate). Examples of the silicate oligomer include methyl silicate oligomer (manufactured by Colcoat / product name: methyl silicate 51, methyl silicate 53A), ethyl silicate oligomer (manufactured by Colcoat / product name: ethyl silicate 40, ethyl silicate 48), and the like. .

... (1)
^{However, R 1, R 2, R} 3, R 4 is an alkyl group having 1 to 4 carbon ^{atoms, R 1, R 2, R} 3, R 4 may be different even in the same, n represents It is an integer of 1 or more.

R ¹ , R ² , R ³ , and R ⁴ in chemical formula (1) are preferably methyl groups because of their high reactivity and a thickening action that appears immediately after mixing. Further, it is preferable that n in the chemical formula (1) is an integer of 2 or more because the high molecular weight can be increased in a short time, so that silica fine particles can grow and thicken in a short time.

[About the amount of each component]
The compounding quantity of a silicate compound is 1-50 mass parts with respect to 100 mass parts of epoxy resins, Preferably, it is 5-20 mass parts. If the amount is less than 1 part by mass, a problem tends to occur in that thixotropy cannot be achieved. If the amount exceeds 50 parts by mass, the shrinkage of the cured product due to the volatilization of the alcohol compound that occurs during the formation of silica increases and the physical properties deteriorate significantly. In this respect, problems are likely to occur.
About the water which reacts with a silicate compound, it is 1-100 mass parts per 100 mass parts of silicate compounds, Preferably it is 2-50 mass parts, More preferably, it is 2-25 mass parts. If the amount is less than 1 part by mass, the silicate compound does not become a sufficient amount of silica, so that there is no problem in that thixotropic property is not applied. If the amount exceeds 100 parts by mass, water is mixed in the cured product, Problems are likely to occur in terms of reducing adhesiveness.

[Other ingredients]
In the mixed curable resin composition of the present invention, conventionally known fillers and other additives (phenolic resin tackifiers, dehydrating agents such as calcium oxide, etc. are used within the range not impairing the effects of the present invention. , Anti-aging agents such as diluents, plasticizers, flame retardants, hindered amine compounds, hindered phenol compounds, UV absorbers, pigments, various silane coupling agents, various titanate coupling agents, various aluminum coupling agents, Dry oil etc.) can be blended.

[About thickening method]
The thickening method according to the present invention is a thickening method at the time of mixing for a curable resin composition that is cured by mixing at least two liquid compositions, that is, a thickening method for a mixture of liquid compositions. The following steps (X), (Y), and (Z) are provided.
(X) Step of mixing at least one liquid composition containing water and another liquid composition containing a silicate compound represented by chemical formula (1) (Y) Water and silicate in the mixed liquid composition Step of generating silica fine particles by reaction with compound (Z) Step of thickening the mixture (curable resin composition) of the liquid composition by the generated silica fine particles

  The liquid silicate compound and water mixed in the step (X) react rapidly in the step (Y) to produce silica fine particles. And the produced | generated silica microparticles express a thickening effect | action ((Z) process). The silica fine particles produced by the reaction can thicken the system and impart workability (thixotropic properties) even with a small amount. In addition, since the amount of the silica is small, or the silica fine particles act as a filler in the cured film, it acts in the direction of reinforcing rather than plasticizing the film. Such a problem (specifically, plasticization of the cured film) does not occur.

  In the above thickening method, it is preferable to use a curable resin composition in which the liquid composition comprises at least (A) a liquid composition containing an epoxy resin and (B) a liquid composition containing a curing agent for the epoxy resin.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not necessarily limited to an Example.

[Raw materials]
Epoxy resin Epicoat 828 (Liquid bisphenol A type epoxy resin / Japan Epoxy Resin Co., Ltd./trade name)
・ Epoxy resin curing agent tomide 235A (polyaminoamide resin having amide bond and many amino groups in the molecule / Fuji Kasei Kogyo Co., Ltd./trade name)
Silicate Compound MKC Silicate MS51 (Oligomer of tetramethyl silicate having a weight average molecular weight of 500 to 700 (n = about 4 to 6) / Mitsubishi Chemical Corporation / trade name)
TSL8114 (Tetramethoxysilane (n = 1) / Momentive Performance Materials Japan GK / Brand name)
Ethyl silicate 40 (average pentamer ethyl polysilicate (n = about 5) / manufactured by Colcoat Co., Ltd./trade name)
Ethyl silicate 48 (average 10-mer ethyl polysilicate (n = about 10) / manufactured by Colcoat Co., Ltd./trade name)

[Viscosity measurement]
Using a BH type rotational viscometer, the viscosity of the liquid composition (A) alone, the viscosity of the liquid composition (B) alone, and the liquid composition (A ) And (B) were measured for viscosity after 5 minutes of mixing.
Further, a value obtained by dividing the viscosity value of 2 revolutions / minute by the viscosity value of 20 revolutions / minute (TI value) was used as an evaluation index of workability (thixotropy). When the TI value was 1.5 or more, it was judged that workability was good (workability was indicated as “◯” in Table 2 described later).

[Measurement of adhesion strength]
After mixing liquid composition (A) and (B), it apply | coated to the concrete which grind | polished the surface by the application quantity of about 200 g / m < ² >, and it cured at 23 degreeC50% RH for one week. Thereafter, a cut of 4 cm × 4 cm was made in this cured coating film, a jig for tensile measurement test was attached, and a plane tensile test was performed to measure the adhesion strength of the coating film.

[Preparation of Liquid Composition (A) Containing Epoxy Resin and Silicate Compound]
(Preparation Example A1)
100 mass parts of Epicoat 828 as an epoxy resin and 20 mass parts of MKC silicate MS51 as a silicate compound were charged into an airtight container equipped with a stirring blade, and mixed in a nitrogen atmosphere to obtain a liquid composition A1.
(Preparation Example A2)
Except having changed the compounding quantity of the silicate compound into 10 mass parts, it carried out similarly to preparation example A1, and obtained liquid composition A2.
(Preparation Example A3)
Except having changed the compounding quantity of the silicate compound into 5 mass parts, it carried out similarly to preparation example A1, and obtained liquid composition A3.
(Preparation Example A4)
A liquid composition A4 was obtained in the same manner as in Preparation Example A1, except that the silicate compound was changed to TSL8114.
(Preparation Example A5)
A liquid composition A5 was obtained in the same manner as in Preparation Example A1, except that the silicate compound was changed to ethyl silicate 40.
(Preparation Example A6)
A liquid composition A6 was obtained in the same manner as in Preparation Example A1, except that the silicate compound was changed to ethyl silicate 48.
(Preparation Example A7)
A silicate compound was not blended, and only Epicoat 828 was used as an epoxy resin as Liquid Composition A7.

[Preparation of Liquid Composition (B) Containing Epoxy Resin Curing Agent and Water]
(Preparation Example B1)
In a sealed container with a stirring blade, 50 parts by mass of tomide 235A and 0.5 parts by mass of water were charged as an epoxy resin curing agent and mixed in a nitrogen atmosphere to obtain a liquid composition B1.
(Preparation Example B2)
Except having changed the compounding quantity of water into 1 mass part, it carried out similarly to preparation example B1, and obtained liquid composition B2.
(Preparation Example B3)
Except having changed the compounding quantity of water into 5 mass parts, it carried out similarly to preparation example B1, and obtained liquid composition B3.
(Preparation Example B4)
Water was not blended, and only tomide 235A was used as a liquid composition B4 as an epoxy resin curing agent.

Table 1 shows the composition of the preparation examples for the above liquid compositions (A) and (B), the viscosity of the liquid composition (A) or (B) alone , and the TI value .

[Example 1]
Liquid composition A1 (120 parts by mass) and liquid composition B2 (51 parts by mass) were mixed, and the viscosity and adhesion strength after 5 minutes of mixing were measured.
[Example 2]
Liquid composition A2 (110 parts by mass) and liquid composition B2 (51 parts by mass) were mixed and tested in the same manner as in Example 1.
[Example 3]
Liquid composition A3 (105 parts by mass) and liquid composition B2 (51 parts by mass) were mixed and tested in the same manner as in Example 1.
[Example 4]
Liquid composition A4 (120 parts by mass) and liquid composition B3 (55 parts by mass) were mixed and tested in the same manner as in Example 1.
[Example 5]
Liquid composition A3 (105 parts by mass) and liquid composition B3 (55 parts by mass) were mixed and tested in the same manner as in Example 1.
[Example 6]
Liquid composition A1 (120 parts by mass) and liquid composition B1 (50.5 parts by mass) were mixed and tested in the same manner as in Example 1.
[Example 7]
Liquid composition A4 (120 parts by mass) and liquid composition B2 (51 parts by mass) were mixed and tested in the same manner as in Example 1.
[Example 8]
Liquid composition A5 (120 parts by mass) and liquid composition B2 (51 parts by mass) were mixed and tested in the same manner as in Example 1.
[Example 9]
Liquid composition A6 (120 parts by mass) and liquid composition B2 (51 parts by mass) were mixed and tested in the same manner as in Example 1.
[Comparative Example 1]
Liquid composition A7 (100 parts by mass) and liquid composition B4 (50 parts by mass) were mixed and tested in the same manner as in Example 1.

Table 2 shows the formulation details and measurement results of Examples 1 to 9 and Comparative Example 1.

  As is clear from the results of Tables 1 and 2, the liquid composition (A) or (B) before mixing according to the present invention has a low viscosity, but when these are mixed, the viscosity increases at the point of 5 minutes after mixing. In addition, it can be seen that good workability (thixotropy) is expressed. On the other hand, it can be seen that there is neither thickening nor thixotropy in the system of the comparative example in which the silicate compound and water are not blended. Moreover, about the adhesion strength of a coating film, it turns out that it is material destruction of concrete in an Example and a comparative example, and sufficient adhesiveness is expressing like the system which does not mix | blend a silicate compound and water.

  From the above results, the mixed curable curable resin composition according to the present invention has a low viscosity, and the liquid composition before mixing is thickened when these liquid compositions are mixed. It can be seen that the film properties are hard to be affected and the film physical properties after curing are hardly affected.

The mixed curable resin composition according to the present invention has a low viscosity in each of the liquid compositions before mixing, but thickens to give good workability when these liquid compositions are mixed, and Since it has the characteristic of hardly affecting the physical properties of the film after curing, it can be used for applications such as adhesives, paints, sealing materials, potting agents, and resin molding materials that require such performance.

Claims (7)

A mixed thickening type curable resin composition comprising an epoxy resin, an epoxy resin curing agent, water, and a liquid composition containing a silicate compound represented by the chemical formula (1).

... (1)
^{However, R 1, R 2, R} 3, R 4 is an alkyl group having 1 to 4 carbon ^{atoms, R 1, R 2, R} 3, R 4 may be different even in the same, n represents It is an integer of 1 or more. A curable resin composition that cures by mixing at least two liquid compositions,
These liquid compositions comprise (A) a liquid composition containing an epoxy resin and a silicate compound represented by chemical formula (1), and (B) a liquid composition containing an epoxy resin curing agent and water. The mixed thickened curable resin composition according to claim 1. The mixed thickening curable resin composition according to claim ¹ , wherein R ¹ , R ² , R ³ and R ⁴ in the chemical formula (1) are methyl groups.   The mixed thickening curable resin composition according to any one of claims 1 to 3, wherein n in the chemical formula (1) is an integer of 2 or more.   A mixed thickened adhesive composition mainly comprising the curable resin composition according to any one of claims 1 to 4. A curable resin composition that is cured by mixing at least two liquid compositions, comprising the following steps (X), (Y), and (Z): Method of thickening the mixture.
(X) Step of mixing at least one liquid composition containing water and another liquid composition containing a silicate compound represented by chemical formula (1) (Y) Water and silicate in the mixed liquid composition Step of generating silica fine particles by reacting with the compound (Z) Step of thickening the mixture of the liquid composition by the generated silica fine particles

... (1)
^{However, R 1, R 2, R} 3, R 4 is an alkyl group having 1 to 4 carbon ^{atoms, R 1, R 2, R} 3, R 4 may be different even in the same, n represents It is an integer of 1 or more. The curable resin composition comprising a liquid composition containing at least (A) an epoxy resin and (B) a liquid composition containing a curing agent for an epoxy resin is used as the liquid composition. Method of thickening the mixture of the liquid composition during mixing.