JP2009091414A - Urea resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a urea resin composition with which hand-painting can be performed and which has normal strength, is excellent in water resistance, acid resistance, and alkali resistance, and can maintain mechanical strength. <P>SOLUTION: This urea resin composition comprises: a prepolymer with isocyanate terminals made of polyol and isocyanate compounds made by mixing 60-90 parts by weight of bifunctional polyol of the molecular weight of 1000-4000 and 40-10 parts by weight of trifunctional polyol of the molecular weight of 500-3000; and aromatic amine. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a urea resin composition that can be applied by hand, has good water resistance, and can be applied to an anti-peeling coating material.

The urea resin and urea urethane resin in the conventional anti-peeling method are obtained by the reaction of a low molecular weight amine compound and polyisocyanate. The reaction rate is fast, the mechanical strength is fast, the coating thickness is easy to increase, and the epoxy resin is used. Unlike the peeling prevention method used, there were advantages such as not using a sheet.
In order to withstand these environments, such as the effects of water, acid rain, acidity such as acid rain, alkalinity of the underlying concrete, heat from the influence of direct sunlight, etc. Alkali and water resistance are essential conditions.
The conventional urea resin-based exfoliation preventing method is generally performed by collision-mixing type mechanical spraying because of its high reaction speed, and the water resistance is not a difficult problem. On the other hand, there is a urea resin using an aromatic amine for manual application because it cannot be applied by a machine, etc., but there is a problem that water resistance, strength development is slow or does not develop due to slow reaction rate .

A layer of an epoxy resin primer containing a silane coupling agent is provided on the surface of the concrete structure, and a tensile strength of 7 N / mm ² or more and a tensile elongation at break of 50 to 800% made of polyurethane or polyurea 0.8 to A surface structure for preventing flaking that can be applied even in a wet state by providing a layer of 4 mm, can be formed without using a fiber sheet in a short time, and a construction method thereof are disclosed. . (Patent Document 1)

A polyalkylene ether polyamine obtained from a random copolymer of tetrahydrofuran and 3-methyltetrahydrofuran in which the polyalkylene group that is part of the polyalkylene ether aminobenzoate is reacted with a polyisocyanate compound or a terminal isocyanate prepolymer, Polyurethane urea resins are manufactured, and these are low temperature liquidity polyalkylene ether polyamines, which can be mixed at low temperature and cured at room temperature. Polyurea with improved workability and resin properties, or polyurethane urea A method for producing an elastomer is disclosed. (Patent Document 2)
JP 2005-213842 A JP-A-6-271640 JP 63-202612 A Japanese Patent Laid-Open No. 1-1121380

  The problem to be solved by the present invention is to provide a urea resin composition having water resistance, acid resistance and alkali resistance of a cured product in a urea resin composition for hand coating.

  The invention of claim 1 is directed to a terminal isocyanate prepolymer comprising a polyol and an isocyanate compound in which 60 to 90 parts by weight of a bifunctional polyol having a molecular weight of 1000 to 4000 and 40 to 10 parts by weight of a trifunctional polyol having a molecular weight of 500 to 3000 are mixed. It is a urea resin composition characterized by containing a group amine, can be applied by hand, and the cured product has good water resistance, acid resistance, and alkali resistance.

  The invention according to claim 2 is the urea resin composition according to claim 1, wherein the cured product of the urea resin has a strength retention of 80% or more after 30 days of immersion in water at 50 ° C. Can be applied and has good water resistance.

  The invention according to claim 3 is characterized in that the cured product of the urea resin has a strength retention of 80% or more after 30 days of immersion in sulfuric acid at 40 ° C. and 10%. It is a urea resin composition, can be applied by hand, and the acid resistance of the cured product is good.

  The invention of claim 4 is characterized in that the cured product of the urea resin has a strength retention of 80% or more after 30 days of immersion in an aqueous 10% sodium hydroxide solution at 40 ° C. And can be applied by hand, and the cured product has good alkali resistance.

  The present invention relates to a terminal isocyanate prepolymer comprising a polyol and an isocyanate compound obtained by mixing 60 to 90 parts by weight of a bifunctional polyol having a molecular weight of 1000 to 4000 and 10 to 40 parts by weight of a trifunctional polyol having a molecular weight of 500 to 3000, an aromatic amine, By making the urea resin composition characterized by containing, it becomes possible to apply by hand, the cured product has good water resistance, acid resistance and alkali resistance, and can maintain mechanical strength.

  The present invention is a urea resin composition that can be applied by hand, and has water resistance, acid resistance, and alkali resistance, which can be applied to prevent peeling and prevent deterioration over time.

Urea resin The urea resin of the present invention can be obtained by mixing the following terminal isocyanate prepolymer and aromatic amine in an equivalent ratio of amine: isocyanate = 0.5 to 0.99: 1.0. Preferably, 0.6 to 0.8: 1.0 provides good mechanical strength.

It is obtained by a reaction of a mixture of a terminal isocyanate prepolymer difunctional and trifunctional polyol with a polyisocyanate usually used for producing a polyurethane elastomer.
Examples of polyols include polyether polyols, polyester polyols, polycarbonate diols, castor oil-modified polyols and the like, and any type may be used by mixing two or more types so long as they have molecular weights within the range.
A bifunctional polyol having a molecular weight of 1000 to 4000, preferably 1500 to 2500, and a trifunctional polyol having a molecular weight of 500 to 3000, preferably 700 to 2000 are mixed in a bifunctional: trifunctional = 60-90: 40-10. A terminal isocyanate prepolymer is obtained by reacting with an isocyanate compound having two or more isocyanate groups. If the polyol is difunctional or trifunctional, if the molecular weight is smaller than the predetermined molecular weight, the viscosity increases, making it difficult to perform a manual coating operation, and if it is larger, it takes time to cure.

  The isocyanate compound used in the terminal isocyanate prepolymer may be an isocyanate compound usually used in the production of polyurethane elastomers, such as hexamethylene diisocyanate (HMDI), 2,2,4-trimethylhexamethylene diisocyanate, 1,3,6-hexamethylene. Triisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate, tris (6-isocyanatohexyl) isocyanurate, adduct of trimethylolpropane and hexamethylene diisocyanate, 2,4-tri Diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI) and these 2,4-TDI 2,6-TDI mixture, dimer 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), dianisidine diisocyanate (DADI), 4,4'-diphenylmethane diisocyanate (MDI), 3,3 Examples include '-dimethyl-4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate (TTI), and the like.

Aromatic amine The aromatic amine used in the present invention is characterized in that it has an aromatic ring in the molecule. In particular, an amine in which an aromatic ring and an amino group are directly bonded can increase the pot life. And diaminodiphenyl ether aromatic polyamines described in (1). Commercially available products include elastomer 1000P (Ihara Chemical Co., Ltd., trade name), VERSALINKP-1000 (Air Products Japan Co., Ltd., trade name), Porea SL100A (Ihara Chemical Co., Ltd., trade name) and the like. Further, the one shown in Patent Document 4 is preferable in terms of work because it is difficult to crystallize.

Diluents diluents which may be used to improve the workability.
Examples of the diluent include phthalate plasticizers such as benzyl alcohol, dioctyl phthalate, and butyl benzyl phthalate.

Fillers may be used for improving physical properties such as fillers, adjusting workability, adjusting adhesive viscosity, imparting thixotropic properties, and the like. Examples include heavy calcium carbonate, light calcium carbonate, kaolin, talc, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, carbon black, fine powder titanium, cinnabar sand, clay, talc, fine powder silica and the like.
Further, generally used additives such as an antifoaming agent, an adhesion assistant, an anti-aging agent, and a stabilizer can be used as required.
Next, an Example and a comparative example are given and a detail is shown.

The synthesis examples of terminal isocyanate prepolymers and comparative examples are shown in Table 1 below.
Hereinafter, the terminal isocyanate prepolymer is referred to as a prepolymer.

Prepolymer 1
50 parts by weight of Exenol 2020 (Asahi Glass Co., Ltd., trade name, polypropylene glycol, molecular weight 2000, bifunctional, hydroxyl value 56), Exenol 903 (Asahi Glass Co., Ltd., trade name, glycerin polyol, molecular weight 1500, trifunctional, 10 parts by weight of hydroxyl value 109) was added, 40 parts of Millionate MT (Nippon Polyurethane Co., Ltd., trade name, 4,4′-MDI, NCO content 33.6%) was added and mixed at 60 ° C. for 3 hours. The prepolymer 1 was synthesized by stirring.

Prepolymer 2
Preminol PML-4002 (Asahi Glass Co., Ltd., trade name, polyether polyol, molecular weight 4000, bifunctional, hydroxyl value 45) 52 parts by weight, ADEKA polyether G1500 (ADEKA, trade name, polypropylene glycol, molecular weight 1500) 13 parts by weight of trifunctional and hydroxyl value 109) were mixed, 35 parts of Millionate MT was added and mixed and stirred at 60 ° C. for 3 hours to synthesize Prepolymer 2.

Prepolymer 3
36 parts by weight of ADEKA polyether P1000 (trade name, ADEKA, trade name, polypropylene polyol, molecular weight 1000, bifunctional, hydroxyl value 110), ADEKA polyether G3000B (trade name, ADEKA, trade name, polypropylene glycol, molecular weight 3000, 24 parts by weight of trifunctional, hydroxyl value 56) was mixed, 40 parts of Millionate MT was added and mixed and stirred at 60 ° C. for 3 hours to synthesize Prepolymer 3.

Prepolymer 4
55 parts by weight of ADEKA polyether P2000 (ADEKA, trade name, molecular weight 2000, bifunctional, hydroxyl value 56), ADEKA polyether G700 (ADEKA, trade name, molecular weight 700, trifunctional, hydroxyl value 225) 5 parts by weight, 40 parts of Millionate MT was added and mixed and stirred at 60 ° C. for 3 hours to synthesize Prepolymer 4.

Prepolymer 5
Kuraray polyol P1010 (Kuraray Co., Ltd., trade name, polyester polyol, molecular weight 1000, bifunctional, hydroxyl value 110) 44 parts by weight, URIC H-30 (Ito Oil Co., Ltd., trade name, castor oil modified polyol, molecular weight about 500 Prepolymer 5 was synthesized by adding 11 parts by weight of 2.7 functional, hydroxyl value 161) and 45 parts of Millionate MT and mixing and stirring at 60 ° C. for 3 hours.

Prepolymer 6
60 parts by weight of Adeka Polyether P2000 and 40 parts of Millionate MT were added and mixed and stirred at 60 ° C. for 3 hours to synthesize Prepolymer 6.

Prepolymer 7
65 parts by weight of Exenol 4030 (Asahi Glass Co., Ltd., trade name, polypropylene glycol, molecular weight 4000, trifunctional, hydroxyl value 42) and 35 parts of Millionate MT were added and mixed and stirred at 60 ° C. for 3 hours to synthesize Prepolymer 7. .

Prepolymer 8
30 parts by weight of Adeka Polyether P2000 and 30 parts by weight of Kuraray Polyol P2010 (Kuraray Co., Ltd., trade name, polyester polyol, bifunctional, hydroxyl value 56) are mixed, 40 parts of Millionate MT are added and mixed at 60 ° C. for 3 hours. The prepolymer 8 was synthesized by stirring.

  50 parts by weight of prepolymer 1 and 50 parts by weight of elastomer 1000P (Ihara Chemical Co., Ltd., trade name, amine value 90.6) were mixed to obtain a urea resin composition of Example 1.

  The urea resin composition of Example 2 was prepared by mixing 50 parts by weight of prepolymer 2 and 50 parts by weight of VERSALINKP-1000 (Air Products Japan Ltd., trade name, amine value 90.6) and reacting them. .

The urea resin composition of Example 3 was prepared by mixing 50 parts by weight of Prepolymer 3 and 50 parts by weight of Porea SL100A (Ihara Chemical Co., Ltd., trade name, amine number 90.6).

  A urea resin composition of Example 4 was obtained in the same manner as in Example 1 except that Prepolymer 1 was changed to Prepolymer 4.

  A urea resin composition of Example 5 was obtained in the same manner as in Example 1 except that Prepolymer 1 was changed to Prepolymer 5.

Comparative Example 1
A urea resin composition of Comparative Example 1 was prepared in the same manner as Example 1 except that Prepolymer 1 was changed to Prepolymer 6.

Comparative Example 2
A urea resin composition of Comparative Example 2 was prepared in the same manner as in Example 1 except that Prepolymer 1 was changed to Prepolymer 7.
Comparative Example 3

A urea resin composition of Comparative Example 3 was obtained in the same manner as Example 1 except that Prepolymer 1 was changed to Prepolymer 8.
Comparative Example 4

When 40 parts by weight of Millionate MT was added to 60 parts by weight of TLM (Toyoku Oil Co., Ltd., trade name, castor oil polyol, trifunctional), and the mixture was stirred at 60 ° C. for 3 hours, it gelled in the reaction vessel and was not used. It was possible.
Comparative Example 5

JUX-33 (Aika Industry Co., Ltd., urea resin for machine application for spraying) was used as a test sample, and Comparative Example 5 was obtained.

Normal strength evaluation Examples / comparative examples of urea resin compositions produced a No. 2 dumbbell-type tensile test body after 1 day, and left to stand at 23 ° C. for 7 days to conduct a tensile test according to JISK6251. went. A sample having an elongation of 5 MPa or more and 200% was rated as ◯, and a value less than that was rated as ×.

Warm water evaluation, alkali evaluation, acid evaluation Urea resin compositions of Examples and Comparative Examples 1 day later, No. 2 dumbbell-type tensile test specimens were prepared and left standing at 23 ° C. for 7 days. After curing for 7 days with% RH, immerse in 50 ° C warm water, 40 ° C 10% sulfuric acid solution, 40 ° C 10% sodium hydroxide aqueous solution, take out after 30 days, and use JISK6251 using a universal physical property tester. A tensile test was conducted according to the above.
The normal strength before the start of the immersion test was compared, and the case where the strength was maintained at 80% or more under each condition was rated as ◯, and the others were marked as x.

Pot life The time for increasing the viscosity from the initial viscosity by a factor of 2 was taken as the pot life.

Final evaluation: All the above evaluations were evaluated as “good”, and one item with “×” was evaluated as “poor”.

Claims (4)

  It contains a terminal isocyanate prepolymer comprising a polyol and an isocyanate compound obtained by mixing 60 to 90 parts by weight of a bifunctional polyol having a molecular weight of 1000 to 4000 and 40 to 10 parts by weight of a trifunctional polyol having a molecular weight of 500 to 3000, and an aromatic amine. Characteristic urea resin composition   The urea resin composition according to claim 1, wherein the cured product of the urea resin has a strength retention of 80% or more after 30 days of immersion in water at 50 ° C.   The urea resin composition according to any one of claims 1 and 2, wherein the cured product of the urea resin has a strength retention of 80% or more after 30 days of immersion in sulfuric acid at 40 ° C and 10%.   The urea resin composition according to any one of claims 1 to 3, wherein the cured product of the urea resin has a strength retention of 80% or more after 30 days of immersion in an aqueous 10% sodium hydroxide solution at 40 ° C.