JP2000007780A - Antistatic polyamide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high molecular weight antistatic agent having a long- lasting effect by specifying the molecular structure of a resin obtained by reacting a polyether compound having an amino group on its terminal with a dibasic acid. SOLUTION: An antistatic polyamide resin is shown in formula I. In the formula, R1 is hydrogen, methyl or a 2-20C hydrocarbon molecular chain; a+b is 0-45; Ra is phenylene or a 1-20C hydrocarbon molecular chain; Rb is formula II (wherein c is 1-45) or a 2-50C hydrocarbon molecular chain. The polyamide resin is obtained by reacting a polyamino compound of a polyether having an amino group on its terminal with a dibasic acid or its derivative such as terephthalic acid, dimethyl terephthalate or the like in an inert gas atmosphere at 180-250 deg.C for 2-3 hr. This resin has a longer effect than an additive type of an antistatic agent and is useful for preparing an antistatic thin board, an antistatic bag, a cover tape for ICs when the resin is added to general polymer materials.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic polyamide resin, and more particularly to a polyether compound having a terminal amino group and a dibasic acid, which has a long-lasting effect. It relates to a polyamide resin which is an antistatic agent.

[0002]

2. Description of the Related Art A polymer material generally imparts an antistatic property by adding an antistatic agent, and the antistatic agent is a conventional surfactant type low molecular weight type. When,
It can be roughly classified into other high molecular weight types. Generally, in the case of a low molecular weight type antistatic agent, since it has low compatibility with a polymer material, it is likely to migrate to the surface of the polymer material and cause a deterioration in surface characteristics. In addition, the surface is easily detached by wiping, washing, or the like, which causes deterioration or even loss of the antistatic properties of the polymer material. On the other hand, in the case of a high molecular weight type antistatic agent, since the antistatic agent itself is a polymer, compatibility with a polymer material is large, and problems such as migration do not occur. Further, the antistatic properties hardly deteriorate due to wiping, washing, and the like, and therefore, the durability is excellent.

[0003] High molecular weight antistatic agents often used in polyester polymer materials can be roughly classified into two types. The first is a method of applying or adding a high molecular weight sulfonate or polyethylene oxide to a polyester to obtain an antistatic polyester. For example, U.S. Patent Nos. 5,194,327 and 5,182,
No. 169, the application of a high molecular weight antistatic agent of a sulfonate to the polyester surface improves the disadvantages such as opacity or clumping of the surface which are observed when using a low molecular weight antistatic agent, The antistatic property is improved. In U.S. Pat. No. 5,262,460, an antistatic resin is obtained by kneading polyethylene oxide having a molecular weight of 5,000 to 16,000 (g / mol) with PET. , 193,
By kneading a polyethylene oxide copolymer having a molecular weight of 2,000 to 50,000 (g / mol) with PET, compatibility and antistatic properties are enhanced.

Another method is to modify the hydrophilicity of the polyester with ethylene oxide or a sulfonate to obtain an antistatic polyester. For example, US Pat. Nos. 5,130,073 and 5,064,70
Nos. 4,713,194 and 4,506.
In No. 070, poly (ethylene oxide) and polyester are copolymerized to improve the hydrophilicity of polyester.
Since the reaction between poly (ethylene oxide) and the dibasic acid is incomplete, there is a disadvantage that it is difficult to form a high molecular weight antistatic agent. Also, U.S. Pat. No. 4,943,510,
Nos. 5,051,475 and 4,468,433
In JP-A No. 195/1995, phthalic acid containing sulfonic acid salts is copolymerized with polyester to improve the hydrophilicity of polyester, but the antistatic agent obtained in this way has not only excellent antistatic properties but also high It causes the deterioration of the physical properties of the molecular material.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a polyamide resin which is a long-acting high molecular weight antistatic agent, and has as its object to improve the drawbacks of known antistatic agents. Purpose.

[0006]

That is, according to the present invention, the molecular structure is

[0007]

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(Where R ¹ is hydrogen, methyl, or a molecular chain of a hydrocarbon having 2 to 20 carbon atoms, the sum of a and b is 0 to 45, and ^Ra is phenylene or carbon number. Is a hydrocarbon molecular chain of 1 to 20, and R ^b is

[0009]

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(Where c is a numerical value from 1 to 45),
Or a hydrocarbon chain having 2 to 50 carbon atoms).

[0011]

DETAILED DESCRIPTION OF THE INVENTION

[0012]

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There is provided a polyamide resin represented by the formula: Here, R ¹ is hydrogen, methyl, or having 2 to 2 carbon atoms.
20 hydrocarbon chains, and the sum of a and b is 0 to 45
R ^a is phenylene or a hydrocarbon chain having 1 to 20 carbon atoms, and R ^b is

[0014]

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(Where c is a numerical value of about 1 to 45), or a hydrocarbon chain having 2 to 50 carbon atoms.

A first feature of the present invention is that when ^Ra in the antistatic polyamide resin is phenylene, R ¹ is methyl,
R ^b is

[0017]

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(Where c is a numerical value from 1 to 45).

A second feature of the present invention is that when ^Ra in the antistatic polyamide resin is butylene, R ¹ is methyl, R
^b is

[0020]

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(Where c is a numerical value of about 1 to 45).

A third feature of the present invention is that when ^Ra in the antistatic polyamide resin is octamethylene, R ¹ is methyl and R ^b is

[0023]

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(Where c is a numerical value of about 1 to 45).

A typical method for producing a polyamide resin according to the present invention is to prepare a polyamino compound having an amino group at a terminal and a dibasic acid or a derivative of a dibasic acid at 180 to 250 ° C. under an inert gas. The reaction is carried out at a temperature for 2 to 3 hours to obtain a polyamide resin having antistatic properties. Here, the reaction temperature is particularly preferably from 200 to 230 ° C.

The molecular structure of the polyamino compound having an amino group at the terminal is

[0027]

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Containing, or

[0029]

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It is also possible to further contain NH ₂ —R ² —NH ₂ or a mixture of both. Where R ¹
Is a molecular chain of hydrogen, methyl, or a hydrocarbon having 2 to 20 carbon atoms, the sum of a and b is 0 to 45, and c is 1 to
Taking a numerical value of 45, R ² is a hydrocarbon molecular chain having 2 to 50 carbon atoms.

The molecular structure of the dibasic acid or the derivative of the dibasic acid used in the present invention is as follows: A—R ^a —A (where R ^a is phenylene or a carbon number of 1 to 20).
Wherein A is a carboxyl group or a carboxyester group). Specifically, terephthalic acid, dimethyl terephthalate, isophthalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, and naphthalic acid
d) and the like.

The above and other objects and features of the present invention,
In order to further clarify the advantages and advantages, the following six preferred embodiments are provided as a source of analysis. The structural formula of the polyamino compound used in the examples is shown below.

[0033]

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[0034]

EXAMPLES Example 1 200 g (1.03 mol) of dimethyl terephthalate, Hu
About 99 g (0.67 mol) of a polyamino compound EDR148 (weight average molecular weight 148, amino equivalent 37) containing amino group at the terminal manufactured by ntsman Company, and ED2003 (weight average molecular weight 2000, amino equivalent 5)
00) About 720 g (0.36 mol) was placed in a reactor and reacted at 200 to 230 ° C. for 3 hours under nitrogen gas. As a result, the surface resistance was about 5 × 10 ⁷ Ω / □ (□: (Representing a unit area). Here, the equivalent ratio of the polyamino compound having an amino group at the terminal to dimethyl terephthalate is 1: 1, and EDR148 and ED2003 occupy 65 mol% and 35 mol%, respectively.

Example 2 100 g (0.52 mol) of dimethyl terephthalate, E
About 38 g of DR148 and about 520 g of ED2003 were put into a reactor and reacted at a temperature of 200 to 230 ° C. for 2.5 hours under a nitrogen gas. As a result, the surface resistance was about 1.3 ×
A 10 ⁸ Ω / □ polyamide resin was obtained. Here, the equivalent ratio of the polyamino compound having an amino group at the terminal to dimethyl terephthalate is 1: 1 and EDR148 and ED2003 each occupy 50 mol%.

Example 3 73 g (0.5 mol) of adipic acid, EDR148 about 4
8.8 g (0.33 mol) and about 34 ED2003
0 g (0.17 mol) was placed in a reactor and reacted under a nitrogen gas at a temperature of 200 to 230 ° C. for 2.5 hours. As a result, a polyamide having a surface resistance of about 1.6 × 10 ⁶ Ω / □ was obtained. A resin was obtained. Here, the equivalent ratio of the polyamino compound having an amino group at the terminal to adipic acid is 1: 1 and EDR
148 and ED2003 account for 66 mol% and 34 mol%, respectively.

Example 4 73 g (0.5 mol) of adipic acid, EDR148 about 1
7.7 g (0.12 mol), and ED 2003 about 76
0 g (0.38 mol) was placed in a reactor and reacted under a nitrogen gas at a temperature of 200 to 230 ° C. for 2.5 hours. As a result, a polyamide resin having a surface resistance of about 4 × 10 ⁹ Ω / □ was obtained. Obtained. Here, the equivalent ratio of the polyamino compound having an amino group at the terminal to adipic acid is 1: 1 and EDR14
8 and ED2003 were 24 mole% and 76
Account for mole%.

Example 5 Sebacic acid 101 g (0.5 mol), EDR148 about 4
8.8 g (0.33 mol) and about 34 ED2003
0 g (0.17 mol) was placed in a reactor and reacted at a temperature of 200 to 230 ° C. for 3 hours under nitrogen gas.
A polyamide resin having a surface resistance of about 6 × 10 ⁸ Ω / □ was obtained. Here, the equivalent ratio of the polyamino compound having an amino group at the terminal to sebacic acid is 1: 1 and EDR148
And ED2003 account for 66 mol% and 34 mol%, respectively.

Example 6 Sebacic acid 101 g (0.5 mol), EDR148 about 1
7.7 g (0.12 mol), and ED 2003 about 76
0 g (0.38 mol) was placed in a reactor and reacted under a nitrogen gas at a temperature of 200 to 230 ° C. for 2.5 hours. As a result, a polyamide resin having a surface resistance of about 4 × 10 ⁹ Ω / □ was obtained. Obtained. Here, the equivalent ratio of the polyamino compound having an amino group at the terminal to sebacic acid is 1: 1 and EDR14
8 and ED2003 were 24 mole% and 76
Account for mole%.

Table 1 summarizes the composition of the reactants used and the surface resistance of the obtained polyamide resin in each of the six examples described above. From the table, it is found that the polyamide compounds obtained as a result of mixing various polyamino compounds in various ratios and further reacting with an acid or an acid derivative have very excellent surface resistance characteristics (10 ⁷ to 10 ⁷ ).
10 ⁹ Ω / □).

[0041]

[Table 1]

According to the above examples, the molecular structure of the polyamide resin provided by the present invention is as follows:

[0043]

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Is represented by Here, R ¹ is a molecular chain of hydrogen, methyl, or a hydrocarbon having 2 to 20 carbon atoms, the sum of a and b is 0 to 45, R ^a is phenylene,
Or a hydrocarbon chain having 1 to 20 carbon atoms,
^b is

[0045]

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(Where c is a number from 1 to 45),
Alternatively, it is a hydrocarbon chain having 2 to 50 carbon atoms.

A first feature of the present invention is that when ^Ra in the antistatic polyamide resin is phenylene, R ¹ is methyl,
R ^b is

[0048]

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(Where c is a numerical value from 1 to 45).

A second feature of the present invention is that when ^Ra in the antistatic polyamide resin is butylene, R ¹ is methyl, R
^b is

[0051]

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(Where c is a numerical value of about 1 to 45).

A third feature of the present invention is that when ^Ra in the antistatic polyamide resin is octamethylene, R ¹ is methyl and R ^b is

[0054]

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(Where c is a numerical value from 1 to 45).

Therefore, the polyamide resin obtained in the present invention is a high-molecular-weight antistatic agent having a long-lasting effect,
By kneading with a general polymer material, the antistatic property of the polymer material can be improved. The polyamide resin obtained in the present invention has a better antistatic effect than a general antistatic agent modified with PEO, and is more excellent than a product obtained by reacting PEO with an acid or an acid derivative. Shows reactivity. The polyamide resin obtained in the present invention is kneaded with a general polymer material, and is used for various applications such as an antistatic thin plate, an antistatic bag, an IC cover tape, an antistatic garment, and a sterile garment. Antistatic products can be manufactured, and thus can be widely applied to various industrial fields such as electronic information, semiconductors, and photoelectrics.

While the preferred embodiments have been disclosed above, they do not limit the scope of the invention in any way, and anyone skilled in the art will be able to make the same without departing from the spirit and scope of the invention. Various variations and additions should be made, and accordingly, the protection scope of the present invention is based on the contents specified in the claims.

[0058]

The polyamide resin obtained by the present invention has the following advantages. (1) A long-lasting antistatic agent. (2) It has better antistatic properties than general antistatic agents of polyester or polyethers containing no amino group, and has a longer effect than general antistatic agents of the addition type. (3) Than the polyester modified hydrophilicity by PEO,
Excellent reactivity. (4) By being added to the resin, it is possible to manufacture antistatic products for various uses such as antistatic thin plates, antistatic bags, IC cover tapes, and the like. It can be widely applied to various industrial fields such as.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Lin Dong-Yu, No. 34, No. 34, 131, Yanji Street, Taipei City, Taiwan

Claims (15)

[Claims] The molecular structure is as follows: (Where R ¹ is hydrogen, methyl, or a compound having 2 to 2 carbon atoms)
0 is the molecular chain of a hydrocarbon, the sum of a and b is 0 to 45, ^Ra is phenylene, or a molecular chain of a hydrocarbon having 1 to 20 carbon atoms, and R ^b is (Where c is a numerical value of 1 to 45) or a hydrocarbon chain having 2 to 50 carbon atoms). 2. The antistatic polyamide resin according to claim 1, which is obtained by polymerizing a dibasic acid or a derivative of a dibasic acid with a polyamino compound having an amino group at a terminal. 3. The method according to claim 1, wherein the dibasic acid or a derivative of the dibasic acid is A- ^Ra- A (where ^Ra is phenylene, or has 1 to 20 carbon atoms).
Wherein A is a carboxyl group or a carboxyester group). 4. The polyamino compound having an amino group at the terminal, (Where R ¹ is hydrogen, methyl, or a compound having 2 to 2 carbon atoms)
The antistatic polyamide resin according to claim 2, wherein the hydrocarbon chain is 0 and the sum of a and b is 0 to 45). 5. The polyamino compound having an amino group at its terminal, (Where c is a numerical value from 1 to 45).
An antistatic polyamide resin as described. 6. The polyamino compound having an amino group at a terminal thereof is NH ₂ —R ² —NH ₂ (where R ² is a hydrocarbon molecular chain having 2 to 50 carbon atoms). Item 6. An antistatic polyamide resin according to item 4. 7. The antistatic polyamide resin according to claim 1, wherein said ^Ra is phenylene. 8. The antistatic polyamide resin according to claim 7, wherein said R ¹ is methyl. 9. The method according to claim 9, wherein R ^b is (Where c is a numerical value from 1 to 45).
An antistatic polyamide resin as described. 10. The antistatic polyamide resin according to claim 1, wherein said ^Ra is butylene. 11. The antistatic polyamide resin according to claim 10, wherein said R ¹ is methyl. 12. The method according to claim 12, wherein R ^b is The antistatic polyamide resin according to claim 10, wherein (c is a numerical value of about 1 to 45). 13. The antistatic polyamide resin according to claim 1, wherein said ^Ra is octamethylene. 14. The antistatic polyamide resin according to claim 13, wherein said R ¹ is methyl. 15. The method according to claim 14, wherein R ^b is (1) where c is a numerical value from 1 to 45.
3. The antistatic polyamide resin according to 3.