CN109836810B - Polyamide resin composition for producing film, preparation and application thereof - Google Patents
Polyamide resin composition for producing film, preparation and application thereof Download PDFInfo
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- CN109836810B CN109836810B CN201711232159.6A CN201711232159A CN109836810B CN 109836810 B CN109836810 B CN 109836810B CN 201711232159 A CN201711232159 A CN 201711232159A CN 109836810 B CN109836810 B CN 109836810B
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Abstract
The invention belongs to the field of film preparation, and particularly discloses a polyamide resin composition for producing a film, which comprises a polyamide resin, fatty acid bisamide with a chemical formula 1, substituted fatty acid amide with a chemical formula 2 and fatty acid amide with a chemical formula 3. The inventor breaks away from the technical constraint that inorganic particles need to be added to solve the problem of film blocking in the prior art, and provides a completely new solution that the fatty acid bisamide, the substituted fatty acid amide and the fatty acid amide are cooperated to be used as an additive component for improving the performance of polyamide, so that a film with good performance, especially good anti-blocking performance can be obtained without adding the inorganic particles.
Description
Technical Field
The invention belongs to the field of film preparation, and particularly relates to a polymer composition with anti-blocking property.
Background
The polyamide film has excellent strength and toughness, freezing resistance, high temperature resistance, good oxygen barrier property, puncture resistance, tearing resistance, good transparency and glossiness and low haze. Is especially suitable for steaming, freezing and vacuum packaging, and can be widely applied to food, chemical products and electronic product packaging.
In addition to the basic performance indicators of strength, stretchability, barrier properties, etc., the antiblocking properties of polyamide films have a large impact on downstream processing. The polyamide films without any additives adhere to each other and are difficult to separate from each other. This can make subsequent printing, bag making difficult. Therefore, an antiblocking agent needs to be added during the film production process to make the film easily separable.
In the production of polyamide films, an anti-blocking agent master batch is generally used to improve the opening property of the film, and the anti-blocking agent master batch contains inorganic additives such as silicon dioxide and the like, so that the adhesion tendency of the film is reduced by forming micro-scale unevenness on the surface of the film. For example, chinese patent publication No. CN101031617 discloses a polyamide resin molding material for films, which is obtained by mixing, based on 100 parts by weight of the total of (a) and (B), the following components: (A) 90-99 parts by weight of polyamide resin granules; (B) 10 to 1 part by weight of a master batch obtained by blending 2 to 8% by weight of inorganic particles and 1 to 5% by weight of a bisamide compound with a polyamide resin; and (C) 0.005 to 0.1 part by weight of a bisamide compound powder.
Further, as disclosed in chinese patent publication No. CN1775858, a processing master batch for nylon packaging films is characterized in that: it comprises 60 to 94 weight percent of polyamide carrier resin, 2 to 20 weight percent of lubricant, 1.5 to 10 weight percent of antiblocking agent, 1.5 to 10 weight percent of nucleating agent and 0.1 to 1.0 weight percent of coupling agent.
In the conventional methods, the anti-blocking property is generally achieved by adding an inorganic additive such as silica to a resin composition for producing a film; although the existing anti-blocking agent master batch has excellent effect, the addition of the master batch increases the mixing process and the production cost, and has certain influence on the transparency.
Disclosure of Invention
In order to solve the technical defects caused by the need of adding inorganic materials such as silicon dioxide in the existing compositions for producing films, the invention aims to provide a polyamide resin composition for producing films, which aims to ensure that the obtained films still have good anti-blocking property without adding anti-blocking master batches.
A polyamide resin composition for producing a film, comprising a polyamide resin, a fatty acid bisamide having a formula of formula 1, a substituted fatty acid amide having a formula of formula 2, and a fatty acid amide having a formula of formula 3;
R1、R2、R3、R4、R5independently is C6～C30Alkyl of (A), C1～C15Alkenyl-substituted C of3～C30An alkyl group of (a);
n is an integer of 2 to 6.
The inventor breaks away from the technical constraint that inorganic particles need to be added to solve the problem of film blocking in the prior art, and provides a completely new solution that the fatty acid bisamide, the substituted fatty acid amide and the fatty acid amide are cooperated to be used as an additive component for improving the performance of polyamide, so that a film with good performance, especially good anti-blocking performance can be obtained without adding the inorganic particles.
The polyamide resin of the present invention is a polymer having amide-based repeating units in a polymer chain.
The polyamide resin of the present invention is preferably a polyamide resin chip.
Preferably, the polyamide resin is at least one of polyamide 6, polyamide 66, polyamide 612, polyamide 1010, polyamide 11, and polyamide 12.
For example, the polyamide resin is polyamide 6, polyamide 66, polyamide 612, polyamide 1010, polyamide 11, polyamide 12, a polyamide 6/polyamide 66 mixture, or a polyamide 6/polyamide 12 mixture.
The polyamide resin preferably has a relative viscosity of 3.0 to 4.5 (measured with 96% sulfuric acid), more preferably 3.2 to 4.2. At this viscosity, the film-forming property is good and the processability is strong.
R1、R2、R3、R4、R5Is C15～C25An alkyl radical of (A), or C1～～C15Alkenyl-substituted C of6～C25Alkyl group of (1).
Further preferably, R is1、R2、R3、R4、R5The alkyl group may be a linear or branched alkyl group having 15 to 25 carbon atoms or an alkyl group having an alkenyl group.
Preferably, n is 2.
Further preferably, the fatty acid bisamide is ethylene bisstearamide and/or ethylene bisoleamide. Studies have shown that the use of the preferred fatty acid bisamides helps to further enhance the properties of the resulting film, such as heat resistance and blocking resistance.
Still more preferably, the fatty acid bisamide is ethylene bisstearamide.
The substituted fatty acid amide is octadecyl stearic acid amide and/or octadecyl erucyl amide. The material and other components have better synergistic effect, and are helpful for further improving the anti-blocking property.
More preferably, the substituted fatty acid is stearyl stearamide.
Preferably, the fatty acid amide comprises at least one of stearic acid amide, erucic acid amide, oleic acid amide and behenic acid amide. The preferred fatty acid amides provide better synergy with other ingredients in the composition, better blocking resistance, and better film performance.
More preferably, the fatty acid amide is erucamide.
Preferably, in the polyamide resin composition, the weight parts of the components are as follows:
studies have shown that controlling the ratio of the components within this range can further enhance the synergistic effect with each other, for example, further enhance the blocking resistance and enhance the overall performance of the film. It has also been found that an excess of fatty acid amides, substituted fatty acid amides, results in excessive lubrication, surface deposits, affects film integrity, and also increases cost.
More preferably, in the polyamide resin composition, the weight parts of the components are as follows:
the invention discloses a preparation method of a polyamide resin composition for producing a film, which comprises the step of treating the polyamide resin at 80-100 ℃ and then uniformly mixing the treated polyamide resin with other components to obtain the polyamide resin composition.
The preparation method comprises the steps of putting polyamide resin slices into a low-speed mixer, heating to 80-100 ℃, then adding other components, fully mixing, and cooling to normal temperature to obtain the composition.
The invention also comprises the use of said polyamide resin composition for the production of films, for the production of polyamide films.
In the present invention, a polyamide film can be produced by a conventional method using the polyamide resin composition of the present invention. For example, the production of a film is carried out by using a single screw film blowing machine.
Advantageous effects
The polyamide resin composition of the invention does not need to add anti-blocking master batches in the process of producing films, and the obtained films have good anti-blocking property (opening property).
Detailed Description
The blocking resistance of the film was evaluated by measuring the coefficient of friction of the film according to the national standard GB 10006-88. The yellowness index YI of the film was measured by a color difference meter according to GB 2913, and the degree of yellowing of the film was evaluated.
Example 1
100 parts of polyamide 6 chips with the relative viscosity of 3.2 are heated to 80 ℃, put into a conical double-screw mixer, then 0.06 part of ethylene bis stearamide, 0.06 part of octadecyl stearamide and 0.03 part of erucamide are added, mixed for 30min and cooled to obtain the polyamide resin composition.
The polyamide resin composition was prepared into a film using a phi 20mm single screw film blowing machine. The temperature of each section of the screw is 205-245 ℃ and the die temperature is 250 ℃ from the feeding section. The cylindrical film obtained by adopting the film blowing process is flattened by a pressing roller to form a double-layer film structure which is attached together. Whether the laminated film can be untwisted is manually tried, and the film friction coefficient is measured according to the national standard GB 10006-88 to evaluate the blocking resistance of the film. The yellowness index YI of the film was measured by a color difference meter according to GB 2913, and the degree of yellowing of the film was evaluated.
Example 2
100 parts of polyamide 6 slices with the relative viscosity of 4.0 are heated to 80 ℃, put into a conical double-screw mixer, then 0.06 part of ethylene bis stearamide, 0.06 part of octadecyl erucamide and 0.03 part of erucamide are added, mixed for 30min and cooled to obtain the polyamide resin composition.
The polyamide resin composition was prepared into a film using a phi 20mm single screw film blowing machine. The temperature of each section of the screw is 205-260-255 ℃ and the die temperature is 255 ℃ from the feeding section. The cylindrical film obtained by adopting the film blowing process is flattened by a pressing roller to form a double-layer film structure which is attached together. The blocking resistance and yellowness index YI test were carried out in the same manner as in example 1.
Example 3
100 parts of polyamide 6 slices with the relative viscosity of 4.0 are heated to 80 ℃, put into a conical double-screw mixer, then 0.06 part of ethylene bis-oleamide, 0.06 part of octadecyl erucamide and 0.03 part of erucamide are added, mixed for 30min and cooled to obtain the polyamide resin composition.
The polyamide resin composition was prepared into a film using a phi 20mm single screw film blowing machine. The temperature of each section of the screw is 205-260-255 ℃ and the die temperature is 255 ℃ from the feeding section. The cylindrical film obtained by adopting the film blowing process is flattened by a pressing roller to form a double-layer film structure which is attached together. The blocking resistance and yellowness index YI test were carried out in the same manner as in example 1.
Example 4
100 parts of polyamide 6/66 copolymer chips having a relative viscosity of 4.0, heating to 80 ℃, feeding into a conical twin-screw mixer, adding 0.06 part of ethylene bis stearamide, 0.06 part of stearyl stearamide and 0.03 part of oleamide, mixing for 30min, and cooling to obtain the polyamide resin composition.
The polyamide resin composition was prepared into a film using a phi 20mm single screw film blowing machine. The temperature of each section of the screw is 190-240 ℃ and the die head temperature is 240 ℃ from the feeding section. The cylindrical film obtained by adopting the film blowing process is flattened by a pressing roller to form a double-layer film structure which is attached together. The blocking resistance and yellowness index YI test were carried out in the same manner as in example 1.
Example 5
100 parts of polyamide 6 slices with the relative viscosity of 4.0 are heated to 80 ℃, put into a conical double-screw mixer, then 0.06 part of ethylene bis stearamide, 0.1 part of octadecyl erucamide and 0.05 part of erucamide are added, mixed for 30min and cooled to obtain the polyamide resin composition.
The polyamide resin composition was prepared into a film using a phi 20mm single screw film blowing machine. The temperature of each section of the screw is 205-260-255 ℃ and the die temperature is 255 ℃ from the feeding section. The cylindrical film obtained by adopting the film blowing process is flattened by a pressing roller to form a double-layer film structure which is attached together. The blocking resistance and yellowness index YI test were carried out in the same manner as in example 1.
Comparative example 1
100 parts of polyamide 6 chips having a relative viscosity of 3.2 were mixed with 2 parts of an antiblocking processing master batch MB3361 (product of Eimers Co., Ltd., Switzerland) to prepare a film using a phi 20mm single screw film blowing machine. The temperature of each section of the screw is 205-245 ℃ and the die temperature is 250 ℃ from the feeding section. The cylindrical film obtained by adopting the film blowing process is flattened by a pressing roller to form a double-layer film structure which is attached together. The blocking resistance test was carried out in the same manner as in example 1.
Comparative example 2
Polyamide 6 chips having a relative viscosity of 3.2 were prepared into films from polyamide resins using a single-screw inflation film former having a diameter of 20 mm. The temperature of each section of the screw is 205-245 ℃ and the die temperature is 250 ℃ from the feeding section. The cylindrical film obtained by adopting the film blowing process is flattened by a pressing roller to form a double-layer film structure which is attached together. The blocking resistance test was carried out in the same manner as in example 1.
Comparative example 3
100 parts of polyamide 6 slices with the relative viscosity of 3.2 are heated to 80 ℃, put into a conical double-screw mixer, then 0.06 part of ethylene bis stearamide is added, mixed for 30min, cooled and prepared into a film by using a single screw film blowing machine with the diameter of 20 mm. The temperature of each section of the screw is 205-245 ℃ and the die temperature is 250 ℃ from the feeding section. The cylindrical film obtained by adopting the film blowing process is flattened by a pressing roller to form a double-layer film structure which is attached together. The blocking resistance test was carried out in the same manner as in example 1.
Comparative example 4
100 parts of polyamide 6 slices with the relative viscosity of 3.2 are heated to 80 ℃, put into a conical double-screw mixer, then 0.06 part of ethylene bis stearamide and 0.06 part of octadecyl stearamide are added, mixed for 30min, cooled and prepared into a film by using a single-screw film blowing machine with the diameter of 20 mm. The temperature of each section of the screw is 205-245 ℃ and the die temperature is 250 ℃ from the feeding section. The cylindrical film obtained by adopting the film blowing process is flattened by a pressing roller to form a double-layer film structure which is attached together. The blocking resistance test was carried out in the same manner as in example 1.
Comparative example 5
100 parts of polyamide 6 slices with the relative viscosity of 3.2 are heated to 80 ℃, put into a conical double-screw mixer, then 0.06 part of ethylene bis-stearamide and 0.06 part of erucamide are added, mixed for 30min, cooled and prepared into a film by using a single-screw film blowing machine with the diameter of 20 mm. The temperature of each section of the screw is 205-245 ℃ and the die temperature is 250 ℃ from the feeding section. The cylindrical film obtained by adopting the film blowing process is flattened by a pressing roller to form a double-layer film structure which is attached together. The blocking resistance test was carried out in the same manner as in example 1.
Comparative example 6
100 parts of polyamide 6 slices with the relative viscosity of 3.2 are heated to 80 ℃, put into a conical double-screw mixer, then 0.06 part of octadecyl stearamide and 0.06 part of erucamide are added, mixed for 30min, cooled and prepared into a film by using a single-screw film blowing machine with the diameter of 20 mm. The temperature of each section of the screw is 205-245 ℃ and the die temperature is 250 ℃ from the feeding section. The blown film process is unstable, and the section skids in the inflation film manufacturing machine feed inlet, and the feeding phenomenon of cutting off.
The evaluation data are shown in the following table:
evaluation comparison of film prepared by examples and comparative examples
As can be seen from the comparison of the data in the above table, the film prepared in the example has the blocking resistance basically same as that of the film prepared in the comparative example 1 by using the special processing master batch, and is more convenient to use and cost-saving. The anti-blocking effect is not ideal when a certain kind of amide additives are singly used in the comparative example.
Claims (17)
1. A polyamide resin composition for producing a film, characterized by consisting of a polyamide resin, a fatty acid bisamide having a chemical formula of formula 1, a substituted fatty acid amide having a chemical formula of formula 2, and a fatty acid amide having a chemical formula of formula 3;
R1、R2、R3、R4、R5independently is C6～C30Alkyl of (A), C1～C15Alkenyl-substituted C of3～C30An alkyl group of (a);
n is an integer of 2-6;
in the polyamide resin composition, the weight parts of the components are as follows:
2. the polyamide resin composition for producing a film as claimed in claim 1, wherein the polyamide resin is at least one of polyamide 6, polyamide 66, polyamide 612, polyamide 1010, polyamide 11 and polyamide 12.
3. The polyamide resin composition for producing films as claimed in claim 2, wherein the polyamide resin is polyamide 6, polyamide 66, polyamide 612, polyamide 1010, polyamide 11, polyamide 12, a polyamide 6/polyamide 66 mixture or a polyamide 6/polyamide 12 mixture.
4. The polyamide resin composition for producing films as claimed in claim 1, wherein the polyamide resin has a relative viscosity of 3.0 to 4.5.
5. The polyamide resin composition for producing films as claimed in claim 4, wherein the polyamide resin has a relative viscosity of 3.2 to 4.2.
6. The polyamide resin composition for producing films as claimed in claim 1, wherein R is1、R2、R3、R4、R5Is C15～C25An alkyl radical of (A), or C1～C15Alkenyl-substituted C of6～C25Alkyl group of (1).
7. The polyamide resin composition for producing films as claimed in claim 1, wherein n is 2.
8. The polyamide resin composition for producing films as claimed in claim 1, wherein the fatty acid bisamide is ethylene bisstearamide and/or ethylene bisoleamide.
9. The polyamide resin composition for producing films as claimed in claim 1, wherein the fatty acid bisamide is ethylene bisstearamide.
10. The polyamide resin composition for the production of films of claim 1 wherein the substituted fatty acid amide is stearyl stearamide and/or stearyl erucamide.
11. The polyamide resin composition for producing films as claimed in claim 1, wherein the substituted fatty acid amide is stearyl stearic acid amide.
12. The polyamide resin composition for producing a film as claimed in claim 1, wherein the fatty acid amide comprises at least one of stearic acid amide, erucic acid amide, oleic acid amide, and behenic acid amide.
13. The polyamide resin composition for the production of films of claim 1 wherein the fatty acid amide is erucamide.
14. The polyamide resin composition for producing a film as claimed in claim 1, wherein the polyamide resin composition comprises the following components in parts by weight:
15. the polyamide resin composition for producing films according to claim 1, wherein the polyamide resin composition comprises 100 parts by weight of polyamide 6, 0.06 parts by weight of ethylene bis stearamide, 0.06 parts by weight of stearyl stearamide, and 0.03 parts by weight of erucamide;
or 100 parts by weight of polyamide, 0.06 part by weight of ethylene bis stearamide, 0.1 part by weight of octadecyl erucamide and 0.05 part by weight of erucamide.
16. A method for preparing a polyamide resin composition for producing a film according to any one of claims 1 to 15, characterized in that the polyamide resin is treated at 80 to 100 ℃ and then mixed with other components to obtain the polyamide resin composition.
17. Use of the polyamide resin composition for producing films according to any one of claims 1 to 15 for producing polyamide films.
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| CN1288907A (en) * | 1999-09-17 | 2001-03-28 | 淮阴市春宇塑料制品有限公司 | Formula of ternary copolymer film |
| CN101029173A (en) * | 2007-03-16 | 2007-09-05 | 许波 | Modified resin material for producing flexible film and shrinkaged film and its production |
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| CN103214843A (en) * | 2013-04-28 | 2013-07-24 | 安特普工程塑料（苏州）有限公司 | Macrofiber-reinforced long carbon chain nylon and preparation method thereof |
-
2017
- 2017-11-29 CN CN201711232159.6A patent/CN109836810B/en active Active
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| US4490324A (en) * | 1982-06-29 | 1984-12-25 | Du Pont Canada Inc. | Nylon film with improved slip characteristics and process therefor |
| CN1288907A (en) * | 1999-09-17 | 2001-03-28 | 淮阴市春宇塑料制品有限公司 | Formula of ternary copolymer film |
| CN101029173A (en) * | 2007-03-16 | 2007-09-05 | 许波 | Modified resin material for producing flexible film and shrinkaged film and its production |
| CN103131151A (en) * | 2013-03-29 | 2013-06-05 | 威海联桥新材料科技股份有限公司 | Polyamide (PA) 6/ polyethylene terephthalate (PET) material for two-direction stretching composite film and production method thereof |
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