JP2975533B2 - Polyurethane sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane sheet having excellent oleic acid resistance, light discoloration resistance and light deterioration resistance. More specifically, the present invention relates to a polyurethane sheet suitable for use in fields requiring durability, such as clothing, furniture, and vehicles.

[0002]

2. Description of the Related Art When a polyurethane resin product is used for clothing, furniture, vehicles, and the like, durability such as light deterioration resistance and light discoloration resistance is required. Further, in the use of polyurethane resin products in these fields, there is a problem that particularly abnormal deterioration occurs particularly at a portion in contact with human skin, and durability against the abnormal deterioration has been required. According to the study of the present inventor, the abnormal deterioration is attributed to the fact that oily substances contained in human sweat, especially oleic acid, repeatedly adhere to specific areas of artificial leather products and plasticize the polyurethane resin. I found it.
Therefore, in the use of polyurethane resin products for clothing, furniture, vehicles, etc., oleic acid resistance is required especially in the area where human skin touches, in addition to light deterioration resistance and light discoloration resistance.

However, conventional polyurethane resins having excellent light discoloration resistance have poor oleic acid resistance, and polyurethane resins having excellent oleic acid resistance have poor light discoloration resistance and poor light deterioration resistance. There is nothing that combines. Therefore, the performance of a sheet made of a conventional polyurethane resin is insufficient for use in clothing, furniture, vehicles, and the like, and improvements are required.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a performance which can be used in the fields of clothing, furniture, vehicles and the like, and furthermore, it has an oleic acid resistance, light discoloration resistance and light deterioration resistance. An object of the present invention is to provide a polyurethane sheet having the same. The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a polyurethane resin having the above properties can be obtained by using a specific isocyanate and a specific chain extender, and completed the present invention. Was.

[0005]

According to the present invention, in order to solve the problems], a polyol component, it consisting of linear alkylene diisocyanates at least 50 wt% including a polyisocyanate component and a polyurethane resin obtained by a dihydrazide compound alone is reacted as a chain extender There is provided a sheet made of polyurethane characterized by the following.

[0006]

The polyurethane resin using a linear alkylene diisocyanate as a polyisocyanate and a dihydrazide compound as a chain extender is more effective than a polyurethane resin using other isocyanates and a chain extender.
Oleic acid resistance, light discoloration resistance, and light deterioration resistance are improved.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to preferred embodiments. The polyurethane resin used in the present invention is a polyurethane resin synthesized using a polyisocyanate containing at least 50% by weight of a polyol and a linear alkylene diisocyanate and a chain extender containing at least 10% by weight of a dihydrazide compound.

The polyol used as the active hydrogen component used in the present invention usually has a molecular weight of 500 to 200.
About 0 or more known polyester polyols, polyether polyols, polycarbonate polyols and derivatives thereof, or mixtures and copolymers thereof, and long-chain diols are not particularly limited. Examples of the polyester polyols include, for example, condensed polyester polyols of dicarboxylic acids such as adipic acid and phthalic acid and glycols such as ethylene glycol, diethylene glycol and tetramethylene glycol and triols such as hexanetriol, and ε-caprolactam and the like. The lactone-based polyester polyol obtained by ring-opening polymerization is a polyether polyol, for example, polytetramethylene ether glycol, tetrahydrofuran-ethylene oxide copolymer polyol, polyoxypropylene ether polyol, polyoxyethylene-propylene ether polyol, and the like, polycarbonate Examples of the polyol include 1,6-hexane carbonate diol and the like. In addition, these long-chain polyols may have an aromatic or alicyclic ring structure in the molecular chain.

In the present invention, a short-chain diol may be used in combination with the above-mentioned polyol within a range not to impair the gist of the present invention. Short-chain diols include linear methylene glycol such as ethylene glycol and 1,4-butanediol, cyclohexylene such as cyclohexanediol and spiroglycol, a spiro ring and a methylene chain, and an ether bond for linking them.
Those containing various bonds such as ester bonds and derivatives containing various substituents can be used.

As the linear alkylene diisocyanate used in the present invention, a known linear aliphatic diisocyanate having a methylene number of 1 or more can be used and is not particularly limited. For example, methylene diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, dodeca Methylene diisocyanate and the like can be mentioned. The content of the linear alkylene diisocyanate in the polyisocyanate is at least 50% by weight, and if it is less than 50% by weight, the oleic acid resistance of the polyurethane resin is not sufficient.

As other components of the polyisocyanate, known polyisocyanates other than those described above can be used and are not particularly limited. For example, aromatic isocyanates such as MDI (4,4'-diphenylmethane diisocyanate) and TDI (toluene diisocyanate); Hydrogenation 4,
Alicyclic isocyanates, such as 4'-diphenylmethane diisocyanate and isophorone diisocyanate, are mentioned.

[0012] Chain extenders used in the present invention is a dihydrazide compound. As the dihydrazide compound, alkyl dihydrazide such as carbodihydrazide and adipic dihydrazide, alicyclic dihydrazide, aromatic dihydrazide and derivatives thereof can be used alone or as a mixture .

The polyurethane sheet of the present invention is produced using a polyurethane resin synthesized according to a conventional method using the above-mentioned components. The method for producing the polyurethane resin is not particularly limited. Polyurethane sheet material is
It can be manufactured by a conventionally known method according to the purpose of use, and the manufacturing method is not particularly limited. For example, a sheet-like material provided on or without a base material by a wet film forming method manufactured from a polyurethane resin solution, a polyurethane resin film bonded by a dry film forming method on a variety of base materials, or without a base material Sheet-like material, a sheet-like material such as calendered by softening the polyurethane resin by heating, or a sheet-like material created by various methods, a polyurethane resin solution applied by gravure printing, spraying, or the like, or It is obtained by laminating a sheet produced from the polyurethane resin with a sheet produced by various other methods. As the polyurethane resin film, both microporous and nonporous can be used.

[0014]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. Unless otherwise specified, parts and percentages in Examples, Comparative Examples, Synthesis Examples and Comparative Synthesis Examples are by weight. Synthesis Example 1 In a reaction vessel, 150 parts of poly 1,6-hexane carbonate diol (average molecular weight: 2,000), 14 parts of 1,3-butanediol, and hexamethylene diisocyanate 7
0 parts were added and reacted at 80 ° C. for 2 hours with stirring. Next, 621 parts of dimethylformamide (DMF) and 32 parts of adipic dihydrazide were added and reacted to obtain a solid matter of 30%.
%, And a polyurethane resin solution having a viscosity of 1000 dPa · s.

Synthesis Example 2 150 parts of poly 1,6-hexane carbonate diol (average molecular weight: 1000), 14 parts of 1,4-butanediol and 92 parts of hexamethylene diisocyanate were placed in a reaction vessel.
Then, the mixture was reacted at 80 ° C. for 2 hours with stirring. Next, 698 parts of DMF and 43 parts of adipic dihydrazide were added and reacted, and the solid content was 30% and the viscosity was 500 dPa · s.
Was obtained.

Comparative Synthesis Example 1 150 parts of poly-1,6-hexane carbonate diol (average molecular weight: 2,000) and 40 parts of hydrogenated 4,4-diphenylmethane diisocyanate were added to a reaction vessel and reacted at 100 ° C. for 4 hours with stirring. . Then 474 parts of DM
F and 13 parts of isophoronediamine were added and reacted to obtain a polyurethane resin solution having a solid content of 30% and a viscosity of 500 dPa · s.

Comparative Synthesis Example 2 150 parts of poly-1,6-hexane carbonate diol (average molecular weight: 2,000), 47 parts of ethylene glycol and 47 parts of DMF were added to a reaction vessel and 47 parts of 4,4-diphenylmethane diisocyanate were added and reacted at 80 ° C. for 2 hours. Thus, a polyurethane resin solution having a solid content of 30% and a viscosity of 500 dPa · s was obtained.

Example 1 The polyurethane resin solution obtained in Synthesis Example 1 was applied on a polyester film with a clearance of 150 μm.
A transparent film having a thickness of 40 μm was obtained.

Example 2 The polyurethane resin solution obtained in Synthesis Example 2 was applied onto a polyester film with a clearance of 150 μm.
A transparent film having a thickness of 40 μm was obtained.

Comparative Example 1 The polyurethane resin solution obtained in Comparative Synthesis Example 1 was applied on a polyester film with a clearance of 150 μm to obtain a transparent film having a thickness of 40 μm.

Comparative Example 2 The polyurethane resin solution obtained in Comparative Synthesis Example 2 was applied on a polyester film with a clearance of 150 μm to obtain a transparent film having a thickness of 40 μm.

Example 3 100 parts of the polyurethane resin solution obtained in Synthesis Example 1, D
A mixed solution consisting of 50 parts of MF, 2 parts of resamine CUT-30 and 1 part of resamine CUT-250 (revised) was applied on a fibrous base material with a clearance of 1.3 mm, and 10% D
It was immersed in an MF aqueous solution, washed and dried to obtain a 2.1 mm thick sheet having a porous film on the surface.

Comparative Example 3 100 parts of the polyurethane resin solution obtained in Comparative Example 2, D
A mixed solution consisting of 50 parts of MF, 2 parts of resamine CUT-30 and 1 part of resamine CUT-250 (revised) was applied on a fibrous base material with a clearance of 1.3 mm, and 10% D
It was immersed in an MF aqueous solution, washed and dried to obtain a 2.1 mm thick sheet having a porous film on the surface.

Evaluation Results The sheet materials of the above Examples and Comparative Examples were evaluated for oleic acid resistance, light deterioration resistance and light discoloration resistance by the following methods. The results are shown in Tables 1 and 2. (1) Oleic acid resistance After immersion in oleic acid at 70 ° C. for 24 hours, the breaking strength or peel strength was measured. (2) Light deterioration resistance Sunshine fade meter (black panel, 83
C.) for 600 hours, and then the breaking strength or peel strength was measured. (3) Light discoloration resistance Sunshine fade meter (black panel, 63
C)), the discoloration was determined by JIS L0805.
Judge according to.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

The polyurethane resin sheet of the present invention is excellent in oleic acid resistance, light discoloration resistance and light deterioration resistance. Therefore, the sheet-like material can be applied to fields requiring durability, such as clothing, furniture, and vehicles.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Isao Kondo 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (56) References JP-A-7-10948 (JP, A) JP-A-59-100778 (JP, A) JP-A-59-100779 (JP, A) JP-A-58-214590 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 18 / 00-18/87 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A polyol component, only the polyisocyanate component and the dihydrazide compound a linear alkylene diisocyanates containing at least 50 wt% and a chain extender
A sheet made of polyurethane, comprising a polyurethane resin obtained by reacting with a sheet. 2. The polyurethane sheet according to claim 1, wherein the polyol component is a polyester polyol, a polyether polyol, a polycarbonate polyol, or a mixture thereof.