JPS6253322A - Polyurethane elastomer composition - Google Patents

Abstract

PURPOSE:The titled composition, obtained by curing a prepolymer having terminal NCO groups with aminobenzylamine and having increased flexibility. CONSTITUTION:A polyurethane elastomer composition obtained by curing a prepolymer having terminal aliphatic or alicyclic NCO groups with one or a mixture of two or more of o-, m- and p-aminobenzylamine as a curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to polyurethane distomers, particularly polyurethane distomer compositions with increased flexibility using aliphatic or cycloaliphatic polyisocyanates.

(Prior art) Polyurethane elastomers have good elasticity, excellent mechanical properties, abrasion resistance, and durability, so they are used in molded products, paints, coatings, sealants, adhesives, binders, printing inks, etc. Among these, polyisocyanates and polyols are used first because they have low reactivity toward hydroxyl groups, especially when aliphatic or alicyclic polyisocyanates are used as raw materials. A prepolymer having an NCO group at the end is synthesized by heating and reacting with a polyamine, and then this prepolymer is reacted with a polyamine curing agent to produce a polyurethane elastomer. (Problem to be solved by the invention) Polyamine As a curing agent, 3.3'-cyclo-4.4
7-Diamidiphenylmethane (MOCA), (imphorondiamine (IPDA), etc.) are used, but the properties of the obtained polyurethane disstomer are constant.If a polyurethane elastomer having all the properties of further flexibility is required. To achieve this, the composition of the polyol in the prepolymer must be changed, but this is an extremely troublesome operation and difficult to perform during molding and construction of polyurethane.Additionally, the amount of amine curing agent must be increased to increase the amount of NCO and NH2 groups. A method of lowering the equivalent ratio of is considered, but it is difficult to implement because the mechanical properties of the obtained polyurethane elastomer are completely deteriorated.

(Means for Solving the Problems) The present inventors conducted various studies aimed at increasing the flexibility of the obtained polyurethane elastomer in the curing stage of the prepolymer without degrading the properties of the obtained polyurethane elastomer. , discovered that aminobenzylamine is effective, and arrived at the present invention.

That is, in the present invention, when curing a prepolymer having an aliphatic or alicyclic NCO group at the end,
A polyurethane composition with increased flexibility characterized by the use of one or a mixture of two or more aminobenzylamines.

The benzylamine used in the present invention is 0-aminobenzylamine, m-aminobenzylamine, p-aminobenzylamine or a mixture of two or three thereof.

Aminobenzylamine can be used with other polyamines, such as I P
Can be used in combination with DA, MOCA, etc. 1. Especially when p-aminobenzylamine, which is liquid at room temperature, as well as mixtures of aminobenzylamines or mixtures of aminobenzylamine and other polyamines, are liquid at room temperature. This is extremely advantageous because it can be mixed with a prepolymer at room temperature and immediately molded or constructed. The organic polyisocyanate used in the production of the prepolymer in the present invention is, for example, hexamethylene di, incyane (HDI).
, isophorone diincyanate (IPDI), dicyclohexylmethane diincyanate (HMDI), methylcyclohexyl diisocyanate ()iTDI),
These aliphatic or alicyclic polyisocyanates include xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (HXDI), dimers, trimers, carbodiimide-modified products, and belet-modified products thereof. Can be used alone or in combination of two or more, and aromatic polyisocyanates such as tolylene diisocyanate (TDI), crude tolylene diisocyanate, diphenylmethane diisocyanate (MDI), polymethylene poly7enylbolyinocyanate It can be used in combination with etc.

Polyol l:jJ+' used in the production of prepolymer in the present invention, polyhydric alcohol such as ethylene glycol, propylene gellicol, glycerin, trimethylolpropane, and pentaerythritol, and alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide. polyether polyol obtained by addition polymerization of one or more of the following, polytetramethylene ether glycol, polyester polyol obtained by reacting a polycarboxylic acid such as adipic acid with a low molecular weight 41 polyol such as butanediol; caprolact 7'f
: A polyester polyol obtained by combining ffi, an OH group-containing higher fatty acid ester such as castor oil.

Furthermore, a polymer polyol obtained by graft polymerizing an ethylenically unsaturated compound of acrylonitrile, styrene, and methyl methacrylate to the above-mentioned known polyether polyol-based polyester polyol, and a 1,2-
Alternatively, 1,4-polybutadiene polyols or hydrogenated products thereof can also be used.1 The average molecular weight of these polyols is usually 200 to 10,000, especially 300.
~7. Q OO is preferred O In addition, if necessary, low-molecular polyhydric alcohols such as ethylene glycol, diethylene glycol, furopylene gellicol, cyfropylene glycol, tripropylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, hexane It is also possible to use a triol or the like mixed with the polyol.

Prepolymer 1! When producing a polyisocyanate, a polyol and, if necessary, a polyhydric alcohol are mixed and reacted at, for example, 30 to 120°C to form a prepolymer. At that time, the equivalent ratio of the NCO group in the polyisocyanate to the OH group in the polyol and polyhydric alcohol (NCOloH)
is suitably from 1.3 to 10, and the free NCO groups contained in the prepolymer are from 0.5 to 15% by weight (in the present invention, % means % by weight, except in specific cases). -! To adjust the viscosity, plasticizers,
A solvent may also be added.

Plasticizers used in the present invention as required include, for example, dioctyl phthalate (DOP) and dibutyl phthalate (DBP).
), dilauryl phthalate (DLP), butylbenzyl 7-thale 1- (BBP), dioctyl adipate (
DOA), diindecyl adipate (DIDA), trioc fk phosphate (TOP), trischloroethyl phosphate (TCEP), )! J-dichloroglobyl phosphate (CTDCPP), propylene glycol divicate polyester, butylene glycol adipate polyester, alkyl epoxy stearate, epoxidized soybean oil, etc. may be used alone or in combination. The amount used is preferably 5 to 100 parts by weight per 100 parts by weight of the prepolymer (in the present invention, parts indicate heavy weight parts).

Examples of fillers that can be used in the present invention if necessary include carbon black, carbonate, talc, clay, zeolite, diatomaceous earth, perlite, vermiculite,
Use titanium dioxide etc. alone or in combination. The amount used is preferably 20-100 parts per 100 parts of prepolymer.

Other auxiliary agents used as necessary in the present invention include solvents, catalysts, thixotropic agents, stabilizers, adhesion promoters, and the like.

Examples of solvents include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, and octane, petroleum solvents ranging from gasoline to kerosene fractions, esters such as ethyl acetate, and methyl ethyl ketone. Ketones: Ether esters such as selonorp acetate and -t are used.

As the catalyst, any catalyst commonly used in the production of polyurethane can be used.

For example, N-methylmorpholine, triethylamine, N
, N, N', N'-tetramethylpropanediamine, tertiary amines such as bis(2-dimethylaminoethyl) ether, and organic compounds such as lead octoate, lead naphthenate, tin octoate, and dibutyltin dilaurate. Use metal compounds alone or in mixtures.

As the thixotropic agent, for example, colloidal silica, hydrogenated castor oil, organic bentonite, tribenzylidene sorbitol, surface-treated precipitated cal/rum carbonate, etc. are used.

In addition, as a stabilizer, for example, the product name Irganox 10
10 and 1.076 (manufactured by Ciba Geigy), Yoshinox BHT%BB and GSY-930 (manufactured by Yoimiya Pharmaceutical)
positionally hindered phenols such as Tinuvin P, 327 and 328 (manufactured by Ciba Geigy); benzophenones such as Tominpu 800 (manufactured by Yoimiya Pharmaceutical Co., Ltd.); Sanol LS-770 and 744% Tinuvin 144 (manufactured by Ciba Geigy); Use positionally hindered amines such as

In carrying out the present invention, aminobenzylamine is mixed with a solvent, a plasticizer, a filler, a catalyst, etc. as necessary to form a curing agent.

After the curing agent is mixed with the prepolymer, it is injected into the mold.

The mixing ratio of prepolymer and curing agent is determined by the N in the prepolymer.
The equivalent ratio of CO groups to NH2 groups in the curing agent is 0.9 to 1.
Make it 1.

The mold is left at room temperature or heated, and then the cured polyurethane molded product is removed.

It is also possible to spray paint the object at the same time as mixing by using an e-tray sprayer. Furthermore, a thermoplastic polyurethane solution can be prepared by reacting the prepolymer with aminobenzylamine and used as a binder, printing ink, etc.

(Function) By using aminobenzylamine as a curing agent, the flexibility of the polyurethane elastomer can be increased.

(Example) The present invention will be specifically explained with reference to Examples below. The flexibility of the cured polyurethane nidistomers was measured by measuring tensile modulus and hardness according to JIS K6301 and comparing them.

Example 1 Polyester diol 3642 with a molecular weight of i and ooo obtained by reacting adipic acid and 1,4-butanediol was reacted with inphorone diincyanate (IPDI) 130.52 at 80°C for 2 hours to obtain NCO group-containing t3 % prepolymer was synthesized.

p-aminobenzylamine 18°32, inphorondiamine (IPDA) 7.8re methyl ethyl ketone 520
2, and then reacted with the prepolymer at 70° C. for 1 hour.

The resulting polyurethane polymer solution was poured onto a glass plate and the methyl ethyl ketone was evaporated, and the physical properties of the film obtained were as shown in Table 1.

Comparative Example 1 Inphorondiamine 29.7r'i was dissolved in methyl ethyl ketone 5201 and reacted with the prepolymer of Example 1 at 70° C. for 1 hour.

This was treated in the same manner as in Example, and the physical properties of the film obtained were as shown in Table 1.

Table 1 Example 2 Polytetramethylene ether glycol 5279, butanediol 472, inphorone diincyane (IPDI) 240F, and tolylene diisocyanate (TDI) 1869 with a molecule i of 1,000 were reacted at 80°C for 3 hours to form an NCO group. Base content: 8%, viscosity: 61.000 cp
s/25° C., and added the aminobenzylamine mixture 122f, which is liquid at room temperature, to the above prepolymer 1.
00of at room temperature, immediately poured into a mold, and heated and cured at 80° C. for 1 hour. After demolding, post-curing was further performed at 80° C. for 24 hours, and the physical properties of the polyurethane disstomer obtained were as shown in Table 2.

Comparative Example 2 In Example 2, the gravolimer-1,0OOP was heated to 800℃. Curing agent: 266 ml of 3'-dichloro-4,47-diamitiphenylmethane (MOCA) was heated and melted at 120°C. Mix both and preheat to 80°C.
It was poured into a mold and cured by heating at the same temperature for 1 hour. After demolding, the polyurethane elastomer was further post-cured for 24 hours at 80°C, and the physical properties of the polyurethane elastomer were as shown in Table 2.

Table 2 (Effects of the Invention) As is clear from Table 1, the addition of p-aminobenzylamine lowers the 100% and 2002 modulus, but there is no significant difference in tensile strength and elongation. Also, as is clear from Table 2, when using the aminobenzylamine mixture, the hardness, 100% and 200% modulus decrease, but the tensile strength and elongation do not decrease.

That is, the present invention makes it possible to increase the flexibility of polyurethane elastomers without deteriorating their mechanical properties.

Claims (1)

[Claims] (1) When curing a prepolymer having an aliphatic or alicyclic NCO group at the end, one type or a mixture of two or more of o-, m-, and p-aminobenzylamine is used. Polyurethane elastomer composition with increased flexibility.