JP5710856B2 - Urea urethane resin composition - Google Patents

Description

    The present invention relates to a urea urethane resin composition that can be handled manually.

  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.

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)
When the temperature is low (5 ° C.), the curing time is delayed. When the curing time is accelerated using a catalyst, problems such as foaming may occur.
JP 2005-213842 A JP-A-6-271640 JP 63-202612 A Japanese Patent Laid-Open No. 1-1121380

  The present invention provides a urea urea urethane resin composition that ensures a pot life that can be handled manually and has good curability and workability at low temperatures.

上記式で ｍ＝１〜２、ｎ＝２〜３、Ｒがポリエーテルである。 The invention of claim 1 is a urea urethane resin composition comprising a terminal isocyanate prepolymer and an aromatic amine represented by the following chemical formula, wherein all polyols used for the synthesis of the terminal isocyanate prepolymer have a molecular weight of 1000 to 3000. Yes , it is a urea urethane resin composition characterized in that polyester polyol or polycarbonate diol is blended in an amount of 50 to 80% by weight with 100% by weight of all polyols . You can speed up the time .

In the above formula, m = 1 to 2, n = 2 to 3, and R is a polyether.

  In the urea urethane resin composition according to the present invention, workability that can be hand-painted and workable time are ensured, and the finger-curing curing time at a low temperature is increased, so that the working time can be shortened.

  The present invention is the result of intensive studies to eliminate the deterioration of curability and workability so that the pot life can be within the range that can be hand-painted.

Aromatic amine resin The present invention uses an aromatic amine of the following chemical formula 1 in order to secure the pot life in order to handle it manually. Therefore, the aromatic amine has an aromatic ring in the molecule, and in particular, a molecule in which the aromatic ring and the amino group are directly bonded is used. Moreover, it has two or more amines in the same molecule.
With the amine described in Patent Document 4, the pot life can be secured and the physical properties are good, but improvement in low-temperature curability has been a problem to be overcome.

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
上記芳香族アミンの内、ｍ＝１、ｎ＝２で、Ｒがポリエーテルの市販製品としてエラスマー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 = 1-2, n = 2-3, R is a polyether Among the above aromatic amines, m = 1, n = 2, and R is a polyether product, Elastomer 1000P (Ihara Chemical Co., Ltd., product) Name, amine value 80-90), VERSALINKP-1000 (Air Products Japan Ltd., trade name, amine value 80-90).

Terminal isocyanate prepolymer The terminal isocyanate prepolymer of the present invention is prepared from a polyol having a molecular weight of 1000 to 3000, in which 50 to 80% by weight, preferably 60 to 70% by weight of polyester polyol or polycarbonate diol is blended. It can be obtained by the reaction with an arbitrary polyisocyanate by the method described above.
In the range of 50 to 80% by weight, curability at a low temperature is good and workability is also good.
The terminal isocyanate prepolymer has a viscosity of 10 Pa · s or less, preferably 3 to 10 Pa · s. Within this range, handling of manual work such as mixing can be easily performed.

  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).

Urea urethane resin The ratio of the isocyanate group functional group of the terminal isocyanate prepolymer to the amino group of the aromatic amine is within the range of 1.0: 0.5 to 0.99. Blend. More preferably, 1.0: 0.6 to 0.8 is preferable. At this time, the strength and the elongation rate are the most excellent.

Other blends Fillers, diluents, and the like can be blended for improving the physical properties of the resin and adjusting workability, adjusting the viscosity of the adhesive, and imparting thixotropy.
As the filler, heavy calcium carbonate, light calcium carbonate, kaolin, talc, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, carbon black, fine powder titanium, silica sand, clay, talc, fine powder silica and the like can be blended.
Diluents such as phthalic acid esters, aliphatic dibasic acid esters, and phosphoric acid esters can be used. Among these, a diluent containing an ester in the structure itself is useful because it may act as an accelerator. 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, additives such as general-purpose antifoaming agents, adhesion assistants, anti-aging agents and stabilizers are blended as necessary.
Next, examples and comparative examples are given, and the results are shown in Table 1 and described in detail.

  48 parts by weight of Kuraray polyol P-2010 (Kuraray Co., Ltd., trade name, polyester polyol (molecular weight 2000, bifunctional)), Exenol 903 (Asahi Glass Co., Ltd., trade name, polyether polyol (molecular weight 1500, trifunctional) ) Was mixed, 40 parts by weight of Millionate MT (Nippon Polyurethane Co., Ltd., trade name, 4,4′-diphenylmethane diisocyanate, NCO 33.6% by weight) was added and reacted at 80 ° C. for 3 hours. Example 1 was prepared by blending 50 parts by weight of an isocyanate prepolymer and 50 parts by weight of Elastomer 1000P.

  42 parts by weight of Kuraray polyol P-2050 (Kuraray Co., Ltd., trade name, polyester polyol (molecular weight 2000, bifunctional)), URIC H-56 (Ito Oil Co., Ltd.), trade name, castor oil modified polyol (molecular weight 1500, Example of blending 18 parts by weight of trifunctional)), 40 parts by weight of Millionate MT, and 50 parts by weight of terminal isocyanate prepolymer obtained by reacting at 80 ° C. for 3 hours and 50 parts by weight of Elastomer 1000P 2.

36 parts by weight of T4671 (Asahi Kasei Chemicals Corporation, trade name, polycarbonate diol, molecular weight 1000, bifunctional), 24 ADEKA polyether P3000 (ADEKA, trade name, polyether polyol, molecular weight 3000, bifunctional) 24 Example 3 was prepared by blending 50 parts by weight of a terminal isocyanate prepolymer obtained by mixing 40 parts by weight of Millionate MT and reacting at 80 ° C. for 3 hours, and 50 parts by weight of VERSALINKP-1000.

36 parts by weight of T5651 (Asahi Kasei Chemicals Co., Ltd., trade name, polycarbonate diol, molecular weight 1000, bifunctional), 24 parts by weight of URIC H-56, 40 parts by weight of Millionate MT were added and reacted at 80 ° C. for 3 hours. Example 4 was prepared by blending 50 parts by weight of the obtained terminal isocyanate prepolymer and 50 parts by weight of Elastomer 1000P.

30 parts by weight of Maximol FSK-1200 (Kawasaki Kasei Kogyo Co., Ltd., trade name, polyester polyol (molecular weight 1200, bifunctional)) and 30 parts by weight of Adeka Polyether P3000 were added, and 40 parts by weight of Millionate MT was added. Example 5 was prepared by blending 50 parts by weight of the terminal isocyanate prepolymer obtained by reacting at 80 ° C. for 3 hours and 50 parts by weight of VERSALINKP-1000.

Comparative Example 1
30 parts by weight of Preminol PML-4002 (Asahi Glass Co., Ltd., trade name, polyether polyol (molecular weight 4000, bifunctional)), 30 parts by weight of URIC H-56, 40 parts by weight of Millionate MT and 80 ° C. for 3 hours Comparative Example 1 was prepared by blending 50 parts by weight of the terminal isocyanate prepolymer obtained by the reaction and 50 parts by weight of Elastomer 1000P.

Comparative Example 2
25 parts by weight of Kuraray polyol P-2050, 25 parts by weight of HS2G-270B (Toyoku Oil Co., Ltd., trade name, castor oil-modified polyol (molecular weight 430, bifunctional)), 50 parts by weight of Millionate MT were added, and 80 ° C. Comparative Example 2 was prepared by blending 50 parts by weight of the terminal isocyanate prepolymer obtained by reacting for 3 hours and 50 parts by weight of Elastomer 1000P.

Comparative Example 3
T4671 (Asahi Kasei Chemicals Co., Ltd., trade name, polycarbonate diol (molecular weight 1000, bifunctional)) 54 parts by weight, Adeka Polyether P3000 6 parts by weight, Millionate MT 40 parts by weight was added and reacted at 80 ° C. for 3 hours. Comparative Example 3 was prepared by blending 50 parts by weight of the terminal isocyanate prepolymer obtained and 50 parts by weight of VERSALINKP-1000.

Comparative Example 4
18 parts by weight of Kuraray Polyol P-1010 (Kuraray Co., Ltd., trade name, polyester polyol, molecular weight 1000, bifunctional), Adeka Polyether P2000 (ADEKA, Co., Ltd., trade name, polyether polyol, molecular weight 2000, bifunctional) ) Was mixed and 50 parts by weight of the terminal isocyanate prepolymer obtained by adding 40 parts by weight of Millionate MT and reacting at 80 ° C. for 3 hours, and 50 parts by weight of VERSALINKP-1000, Comparative Example 4 It was.

Comparative Example 5
A terminal isocyanate prepolymer obtained by adding 60 parts by weight of Kuraray Polyol P-1010 (Kuraray Co., Ltd., trade name, polyester polyol, molecular weight 1000, bifunctional) and 40 parts by weight of Millionate MT and reacting at 80 ° C. for 3 hours. 50 parts by weight and 50 parts by weight of Elastomer 1000P were used as Comparative Example 5.

Comparative Example 6
Comparative Example 6 containing 60 parts by weight of Adeka Polyether P2000, 40 parts by weight of Millionate MT and 50 parts by weight of a terminal isocyanate prepolymer obtained by reacting at 80 ° C. for 3 hours and 50 parts by weight of VERSALINKP-1000 It was.

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 at a film thickness of 1 mm under conditions of a low temperature of 5 ° C., and those having a finger erosion curing time of 5 hours or less were evaluated as “x”.

Viscosity: The viscosity of the terminal isocyanate prepolymer was measured with a B-type viscometer (20 rpm for BH rotor number No. 6 or 60 rpm for BM type rotor number No. 4) at 23 ° C. and 50% RH.

Workability: The above viscosity of 10 Pa · s or less is indicated by ◯, and the others are indicated by ×.

Claims (1)

A urea urethane resin composition containing a terminal isocyanate prepolymer and an aromatic amine represented by the following chemical formula, wherein all polyols used for the synthesis of the terminal isocyanate prepolymer have a molecular weight of 1000 to 3000 , and are polyester polyols or polycarbonate diols There urea-urethane resin composition characterized in that it is 50 to 80 wt% blended polyol entire hand as 100 wt%.

In the above formula, m = 1 to 2, n = 2 to 3, and R is a polyether.