JP2009242599A - Urea urethane resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain great thixotropy without shortening a working life, degrading workability and worsening a product quality. <P>SOLUTION: A urea urethane resin composition comprises at least a terminal isocyanate prepolymer, aromatic amine, and hydrophobic silica, wherein the hydrophobic silica is subject to hydrophobic treatment with a trimethylsilyl group or polydimethylsiloxane. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a urea urethane resin composition having thixotropic properties.

  Conventionally, urea resins have been applied to prevent the spraying and peeling off of ceilings and wall surfaces because of their high strength. Since this urea resin is obtained by the reaction of a low molecular amine and a low molecular isocyanate component, it cures in a short time and prevents sagging and the like. However, due to the speed of reactivity, there is no method other than mechanically mixed coating, and the disadvantages are that it can cope with parts where machines can not enter, the coating film thickness is not uniform, and the appearance is bad, so the applicable range is limited. It was.

  On the other hand, urea urethane resins that can be applied manually have been imparted with thixotropic properties by adding a low-molecular amine to a special aromatic amine and increasing the viscosity. This method has problems such as poor workability, short pot life, and uneven thickness.

  Use a mixture of amine polyol and diethyltoluenediamine as the active hydrogen component, use polyisocyanate or its prepolymer as the isocyanate component, and if you want fast curability, use an MDI isocyanate monomer or its high NCO content in the isocyanate component It has been disclosed that, by using a prepolymer, a polyurethane polyurea elastomer-based coating composition has a curing property that is relatively independent of temperature and gives excellent physical properties. (Patent Document 1)

  A surface structure formed by laminating a layer of a solvent-free epoxy resin primer containing a tertiary amine or a derivative thereof and a layer of polyurethane or polyurea on the surface layer of the structure, and a construction method thereof. Curing agent whose main component is a resin liquid whose main component is a resin liquid containing epoxy resin as a main component and 0.1-10 parts by weight of tertiary amine or its derivative with respect to 100 parts by weight of curing agent It is disclosed that it preferably consists of a liquid. (Patent Document 2)

  A thixotropic polyurethane resin composition comprising a polyurethane resin, hydrophobic colloidal silica, and (c) an adduct of an aliphatic or alicyclic polyisocyanate and a monoamine and / or diamine is extremely effective for imparting thixotropy. It is disclosed to be effective. (Patent Document 3)

A thixotropic polyuren resin composition comprising a polyurethane resin, a hydrophobic colloidal silica and a bisalkoxysilyl compound. Is extremely effective in imparting thixotropy. (Patent Document 4)
JP 10-292149 A JP 2006-348707 A Japanese Unexamined Patent Publication No. 64-24851 JP-A-2-167365 JP-A-63-202612

  The problem to be solved by the present invention is to provide a urea urethane resin composition having thixotropic properties and capable of being applied manually.

  The invention of claim 1 is a urea urethane resin composition comprising at least a terminal isocyanate prepolymer, an aromatic amine, and hydrophobic silica, and imparts good workability and great thixotropic properties.

  The invention according to claim 2 is characterized in that the hydrophobic silica is subjected to a hydrophobic treatment with a trimethylsilyl group or polydimethylsiloxane, and imparts great thixotropy even in a small amount, according to the urea urethane resin composition according to claim 1 To do.

  The urea urethane resin composition of the present invention does not have a shortened pot life, can be applied manually, is provided with sufficient thixotropy so that it does not sag, is uniform on the ceiling surface and wall surface, and has a good appearance. A coating layer can be formed.

Terminal isocyanate prepolymer The terminal isocyanate prepolymer of the present invention can be obtained by reacting a polyol with an arbitrary polyisocyanate by a general-purpose technique.
Examples of the polyol include polyether polyol, polyester polyol, polycarbonate diol, castor oil-modified polyol, and the like.
The residual terminal isocyanate is 8 to 16% by weight in terms of NCO weight, and is appropriately selected depending on the physical property life obtained.

  The polyisocyanate is an isocyanate compound having two or more isocyanate groups, and may be any polyisocyanate used for producing a general-purpose polyurethane elastomer. Examples include hexamethylene diisocyanate (HMDI), 2,2,4-trimethylhexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexano. Ate, tris (6-isocyanatohexyl) isocyanurate, adduct of trimethylolpropane and hexamethylene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6- TDI) and mixtures of these 2,4-TDI and 2,6-TDI, dimers of 2,4-tolylene diisocyanate, xylene diisocyanate (XDI), metaxylylene diisocyanate (MXDI), tetramethylxylylene diisocyanate, m-phenylene diisocyanate, 4,4'-biphenyl diisocyanate, diphenyl ether-4,4'-diisocyanate, 3,3'-ditoluene-4,4'-diisocyanate (TODI), diani Shidin diisocyanate (DADI), 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate (TTI) (In the above () is an abbreviation).

Aromatic amines Compositions in which the effects of the present invention are useful include aromatic amines, which can be applied by hand and have a pot life, so that dripping occurs on vertical surfaces, ceilings, and the like. This aromatic amine has an aromatic ring in the molecule, and in particular an amine in which the aromatic ring and an amino group are directly bonded has a longer pot life. Among the amines described in Patent Document 5, those represented by the following chemical formula 1 are representative.

Ｒの構造はポリエーテル、ポリエステル等があげられる。ｍ＝１〜２、ｎ＝２〜３、Ｒがポリエーテル
市販製品として上記芳香族アミンのｍ＝１、ｎ＝２で、Ｒがポリエーテルであるエラストマー１０００Ｐ（イハラケミカル（株）、商品名、アミン価８０〜９０）、ＶＥＲＳＡＬＩＮＫＰ−１０００（エアプロダクツジャパン（株）、商品名、アミン価８０〜９０）がある。

Examples of the structure of R include polyether and polyester. m = 1 to 2, n = 2 to 3, R is a polyether. Elastomer 1000P (Ihara Chemical Co., Ltd., trade name) where m = 1, n = 2 of the above aromatic amine and R is a polyether as a commercial product. , Amine value 80-90), VERSALINKP-1000 (Air Products Japan Ltd., trade name, amine value 80-90).

Hydrophobic silica The hydrophobic silica used in the present invention is a silica which has been subjected to a hydrophobic treatment with fumed silica having a specific surface area of 50 m ² / g or more. Those having a large hydrophobic group, for example, hydrophobic silica modified with polydimethylsiloxane or trimethylsilyl group, can improve the thixotropy with a small addition. As commercial products of this hydrophobic silica, Aerosil RX200 (trimethylsilane chemical modification), Aerosil RY200 (polydimethylsiloxane chemical modification), R812 (trimethylsilyl chemical modification), Aerosil R202 (above, Nippon Aerosil Co., Ltd., trade name), WACKER HDK H18 (Asahi Kasei, trade name) is raised.

Urea urethane resin composition The present invention comprises at least the above-mentioned terminal isocyanate prepolymer, aromatic amine, and hydrophobic silica.
The terminal isocyanate prepolymer and the aromatic amine are blended in a ratio of the isocyanate group functional group of the terminal isocyanate prepolymer and the amino group of the aromatic amine in the range of NCO group: amino group = 1.0: 0.5 to 0.99. To do. More preferably, 1.0: 0.6 to 0.8 is preferable. Within this range, the strength and elongation will be good, but can be changed as appropriate according to the purpose.

In addition to the above, the following formulations can be used.
As the diluent, a non-reactive diluent can be used for adjusting viscosity suitability such as workability. General-purpose products such as phthalic acid esters, aliphatic dibasic acid esters, and phosphoric acid esters can be used. Diisononyl adipate (DINA), diisononyl phthalate (DINP), bis (2-ethylhexyl) phthalate (DOP), bis (2-ethylhexyl) adipate (DOA), triphenyl phosphate (TPP), dimethyl sebacate (DMS), bis ( Butyl diglycol) adipate (BXA) (above abbreviations are abbreviations) and the like are preferable.

  Moreover, a filler can be used for physical property adjustment of a hardened | cured material, workability | operativity adjustment, and viscosity adjustment. Examples include heavy calcium carbonate, light calcium carbonate, kaolin, talc, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, carbon black, finely powdered titanium, cinnabar sand, clay, and talc. Since this filler also imparts thixotropic properties, it is blended as appropriate in accordance with the number of hydrophobic silica added and the thixotropic effect. In addition, generally used additives such as an antifoaming agent, an adhesion assistant, an antiaging agent, and a stabilizer can be used as necessary.

In the present invention, the TI value was used as a thixotropic effect. The larger the numerical value of the viscosity ratio at the time of high shear and the viscosity at the time of low shear, the more difficult it is to sag. When the measurement method of this method has a TI value of 2.5 or more, dripping does not easily occur during the wall surface construction, and when it is 3.5 or more, a better evaluation can be obtained.
In the dispersion system, the viscosity decreases according to the rotational speed. A high viscosity is obtained during low-speed rotation, and a low viscosity is obtained during high-speed rotation. At this time, the value obtained by taking the ratio of the viscosity at the rotational speed is the so-called TI value. The closer this ratio is to 1, the higher the water-like Newtonian viscosity, and the higher the ratio, the higher the thixotropic property and the less dripping.

  Next, the results of Examples and Comparative Examples are shown in Table 1, and details are shown.

Terminal isocyanate prepolymer Examples of terminal isocyanate prepolymers used in Examples and Comparative Examples are 55 parts by weight of Exenol 2020 (Asahi Glass Co., Ltd., trade name, molecular weight 2000, bifunctional), Adeka Polyether G700 (ADEKA Corporation) , Trade name, molecular weight 700, trifunctional) and 5 parts by weight of Millionate MT (Nippon Polyurethane Co., Ltd., trade name, 4,4′-diphenylmethane diisocyanate, NCO 33.6% by weight) was added at 80 ° C. The mixture was stirred for 3 hours. (NCO% is 10.23 wt%)

50 parts by weight of elastomer 1000P and 10 parts by weight of DINA (Daihachi Chemical Industry Co., Ltd., trade name, diisononyl adipate) were mixed and stirred for 5 minutes, 10 parts by weight of Aerosil RX200, Union Clay RC-1
(Takehara Chemical Industry Co., Ltd., Kaolin clay) 30 parts by weight was added and stirred for 10 minutes, and 70 parts by weight of this composition and 30 parts by weight of the above-mentioned terminal isocyanate prepolymer were mixed. It was.

  Example 2 was performed in the same manner as Example 1 except that Aerosil RX200 of Example 1 was changed to Aerosil RY200.

  Example 3 was performed in the same manner as in Example 1 except that Aerosil RX200 in Example 1 was changed to Aerosil R812.

Comparative Example 1
Comparative Example 1 was performed in the same manner as in Example 1 except that Aerosil RX200 of Example 1 was changed to Aerosil 200 (Nippon Aerosil Co., Ltd., trade name, hydrophilic untreated silica).

Comparative Example 2
Comparative Example 2 was performed in the same manner as Example 1 except that Aerosil RX200 of Example 1 was changed to WACKER HDK H15 (Asahi Kasei, trade name, methylchlorosilane treatment).

Comparative Example 3
Comparative Example 3 was performed in the same manner as in Example 1 except that Aerosil RX200 of Example 1 was changed to Aerosil R972 (Nippon Aerosil Co., Ltd., trade name, methyl group chemical modification).

Comparative Example 4
Comparative Example 4 was performed in the same manner as in Example 1 except that Aerosil RX200 of Example 1 was changed to AEROXIDE Alu C (Nippon Aerosil Co., Ltd., trade name, aluminum oxide).

TI value: After blending the examples and comparative examples, the mixture was allowed to stand for 5 minutes, and the Brookfield analog viscometer BH viscometer rotor No. 7, the viscosity at 2 rpm and the viscosity at 20 rpm were measured. The ratio between the low speed and the high speed (2 rpm viscosity (Pa · s) / 20 rpm (Pa · s) viscosity) was defined as the TI value.

Sagability: After blending the examples and comparative examples, let stand for 5 minutes, and apply the resins of the examples and comparative examples to the wall surface at 23 ° C. with a thickness of 3 mm (width 100 mm, length 300 mm) before curing. It was evaluated whether resin dripping occurred. The case where the resin sag of 2 mm or more occurred was indicated as x, and the case where the resin sag occurred was indicated as ◯.

Pot life: Under the condition of 23 ° C., Brookfield analog viscometer BH viscometer rotor No. No. 7 was used and the time until the initial viscosity at 20 rpm was doubled was defined as the pot life. When this time was 15 minutes or more, it was evaluated as ◯, and less than 15 minutes as x.

Curability:
Curing time measurement: The curing time in the present invention was measured using a drying recorder (Taijiki Co., Ltd., trade name, paint drying time measuring device).
The drying recorder takes advantage of the fact that when the needle moves over the paint applied to the glass stage and the paint dries, it will not be damaged by the needle. It is a device that measures time. The resin compositions of Examples and Comparative Examples were applied to a glass plate with a film thickness of 1 mm under a condition of low temperature of 5 ° C. It was evaluated.

Finish: When the resin compositions of Examples and Comparative Examples were applied at 2 kg / m2 on a vertical substrate at 23 ° C. with a scissors, those with no foaming or irregularities were found, and those with defects such as foaming were found X.

Evaluation: In all items of TI characteristics, sagability, pot life, curability, and finish, “good” means “good”, and others indicate “poor”.

Claims (2)

  A urea urethane resin composition comprising at least a terminal isocyanate prepolymer, an aromatic amine, and hydrophobic silica.   The urea urethane resin composition according to claim 1, wherein the hydrophobic silica is subjected to a hydrophobic treatment with a trimethylsilyl group or polydimethylsiloxane.