JPS61254616A - Polyurethane resin having improved abrasion resistance and tear resistance - Google Patents

Abstract

PURPOSE:To obtain the titled resin for artificial leather, by adding a specific amount of an alkylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane to an aliphatic polyol having high molecular weight, and reacting the mixture with a polyurethane. CONSTITUTION:(A) 100pts.wt. of an aliphatic polyol having high molecular weight (preferably a polyalkylene polyol having a molecular weight of 3,000-7,000 and containing 2-3 functional groups) is added with (B) 5-30pts.wt. of an alkylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane (e.g. a propylene oxide adduct of the above propane) and if necessary, (C) a catalyst, a foaming agent, etc., and stirred by a propeller stirrer. The mixture is mixed further with (D) a polyisocyanate (e.g. tolylenediisocyanate) and cured to obtain the objective resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane resin with improved abrasion and tear resistance, either as a foamed polyurethane Y7 ohm or as an unfoamed elastomer.

For example, it is applicable to the field of polyurethane leather such as artificial leather 1 or synthetic leather, or to products that require wear resistance and tear resistance, such as rolls for OA equipment.

The main raw materials for Yuijitsu polyurethane of "Juu" L are polyol and polyisocyanate, and catalyst,! ! ! ! It is produced by blending a foaming agent, water, a blowing agent, a filler, etc., and causing an exothermic reaction between the hydroxyl groups and isocyanate groups in the main raw material components.

Regarding improvement of wear resistance, see 2, JP-A-60-53520.
"Abrasion-resistant, abrasion-resistant hard polyurethane" is the prior art, which consists of (1) 40 to 801 parts of a propylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] and (1) OH value 200
It is characterized in that a mixed polyol consisting of 20 to 60 parts by weight of an aromatic amine-based polyoxyalkylene polyol of 1 to 700 is used, and an aliphatic or aromatic oil component is further added.

That is, based on 100 parts of an aromatic amine-based polyoxyalkylene polyol with an OH value of 200 to 700, 67 to 400 parts by weight of a propylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane is used in combination. , further requires the addition of an aliphatic or aromatic oil component.

The purpose of the present invention is to provide a polyurethane resin with improved abrasion and tear resistance based on commonly used aliphatic polyols.

Composition of the invention. The polyurethane resin with improved wear resistance and tear resistance according to the present invention is a polyurethane produced using a high molecular weight aliphatic polyol and a polyisocyanate as main raw materials. 2,2 parts by weight
- It is characterized in that 5 to 30 parts by weight of an alkylene oxide adduct of bis(4-hydroxyphenyl)propane is added.

That is, compared to the prior art, although a fullylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane is used as a chain extender, the amount added is 5 to 5 parts by weight per 100 parts by weight of high molecular weight polyol. Advantages include that a very small amount of 30 parts by weight is required, that commonly used high molecular weight aliphatic polyols can be used, and that there is no need to add aliphatic or aromatic oil components.

The high molecular weight aliphatic polyol used in the present invention has a molecular weight in the range of 500 to 12,000, and its type is not particularly limited, but preferably has a molecular weight in the range of 3.000 to 12,000.
Polyalkylene polyols, polymer polyols, etc. having a molecular weight of 7.000 and having 2 to 3 functional groups are used.

As the polyisocyanate, those commonly used in polyurethane production can be used, such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), MDI prepolymer, carbodiimide-modified MDI, and the like.

The amount of polyisocyanate used relative to the high molecular weight aliphatic polyol is 100 as the isocyanate index.
A range of 150 to 150 is appropriate.

2,2 based on 100 parts by weight of high molecular weight aliphatic polyol
- It is appropriate that the amount of the fullylene oxide adduct of bis(4-hydroxyphenyl)propane, specifically the propylene oxide or ethylene oxide adduct, be 5 to 30 parts by weight; Even if it is added, no improvement in effectiveness is observed.

Conventionally known technical means can be used to produce polyurethane from these raw materials.

- Examples include high molecular weight aliphatic polyols and 2,2-bis(
A necessary amount of a catalyst, blowing agent, etc. is added to a mixture of 4-hydroxyphenyl)propane and a 7-rukylene oxide adduct to make one batch, and the polysisocyanate component is stirred and mixed or collision-mixed with the mixture. The one-shot method is one in which the polymer is cured by a reaction, but a prepolymer method may also be used.
Moreover, either a foamed material or a non-foamed material may be used.

Typical catalysts are amine compounds and organic tin compounds, and amine compounds include triethylenediamine and N-
Methylmorpholine, N-ethylmorpholine, triethanolamine, N-methyl-getanolamine, N-ethyl-getanolamine can be used. Further, as the organic tin compound, dibutyltin dilaurate, dibutyltin diacetate, etc. can be used.

In addition, additives commonly used in the production of polyurethane may be optionally used as required.

Although the details of the mechanism by which the abrasion resistance and tear strength are improved by the addition of the fullylene oxide adduct of 2.2-bis(4-hydroxyphenyl)propane are still unclear, the improvement in strength properties is 22.2- Screw(
It is thought that the rigid structure of 4-hydroxyphenyl)propane, in which two phenyl groups and two methyl groups are bonded to the central carbon, may have contributed.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way.

Regarding the physical property evaluation of the obtained polyurethane, hardness, tensile strength, elongation and tear strength were measured according to JIS-6301. Regarding wear resistance, JIS-7
204, a taper set wear tester manufactured by Toyo Seiki Co., Ltd. was used.

Example 1.2 First, polyol 10 was prepared according to the formulation shown in Table 1.
Weigh 0gr into a paper cup and add a predetermined amount of BA-P to it.
2 (2,2-bis(4-hydroxyphenyl)propane adduct of 2 moles of propylene oxide), chain extender,
The catalyst and water were added and stirred for about 20 seconds using a propeller type stirrer. When a predetermined amount of polyisocyanate is added to this uniform mixture and stirred for about 20 seconds, the reaction starts.
It became creamy. This was quickly heated to 50°C and poured into a 200 x 200 x 4 mm metal mold, then the lid was tightened and fixed with a clamp. This was heated in an open air at 50° C. for about 5 minutes and then demolded. The molded sample obtained was left at room temperature for one week and then subjected to a physical property evaluation test, and the results shown in Table 1 were obtained.

Comparative Examples 1 to 3 Polyurethane molded products were made according to the formulation shown in Table $1 using the same molding method as in the example except that BA-P2 was not added. Physical property measurement results were obtained.

Table 1 *l:l: Efcenol 82 Mongzi lees; OH value = 33~
35 * 2: GL-5000 (OH value of E-asu-kuna =
33-35 *3: Manufactured by Nikki Emulsifier Mai Wood 4: Manufactured by Sankyo Air Products *5: Manufactured by Nitto Im Jin Book 6: Manufactured by Nippon Polyureta Ikkan Examples 3-5 First, according to the formulation in Table 2, polyol After weighing 20 kg, add a chain extender such as BA-P2 or BA-P8 (8 mol propylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane), a crosslinking agent, a catalyst, and a blowing agent. , mix thoroughly with stirring to form a single component.
Next, polyisocyanate was used as another component, and the mixture was rapidly impinged and mixed at a discharge rate such that one component had the weight ratio shown in Table 2, and was injection molded into a mold heated to 60°C. The mold was removed 3 minutes after injection, and after being left at room temperature for one week, it was subjected to a physical property evaluation test, and the results shown in Table 2 were obtained.

Comparative Example 4 A polyurethane molded product was produced according to the formulation shown in Table 2 using the same molding method as in Examples 3 to 5 except that BA-P2 or BA-P8 was not added. The physical property measurement results shown in are obtained.

Table 2 Zero l: EXCENOL 821C LiF extension; OH value = 33
~ 35 one book 2: Japan a (tJJII! 1 book 3: Sankyo z7) Cf Taku) abbreviation book 4: Niszuka (b Kyoto)
Tree 5: Asahi Glass Binding 6: Toray Sirico 1
Book 7: Effects of the invention made by Nippon Polyurethane 2 As is clear from the test results shown in Tables 1 and 2, the samples of the examples of the present invention had less wear mass than the samples of the comparative examples, and Excellent abrasion resistance. It can also be seen that the tear strength is excellent.

Claims (1)

[Claims] A polyurethane produced using high molecular weight aliphatic polyol and polyisocyanate as main raw materials, 2,2-bis(4-
A polyurethane resin with improved abrasion resistance and tear resistance, characterized in that 5 to 30 parts by weight of an alkylene oxide adduct of (hydroxyphenyl)propane is added.