CN113861638A - Preparation method of modified polyester and application of modified polyester in polyester film for dry film resist - Google Patents
Preparation method of modified polyester and application of modified polyester in polyester film for dry film resist Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/21—Anti-static
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B32—LAYERED PRODUCTS
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/54—Yield strength; Tensile strength
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- B32B2307/00—Properties of the layers or laminate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a preparation method of modified polyester and application thereof in a polyester film for a dry film resist, which comprises the preparation of polyester modified nano silicon dioxide, the preparation of polyester prepolymer and the preparation of modified PET resin slices. Reacting silicon dioxide powder obtained by neutralizing titanate coupling agent ZJ-38S with silica sol, phenoxyethanol, hydroxyl-terminated hyperbranched polyester and p-toluenesulfonic acid to obtain polyester modified nano silicon dioxide; dibutyl oleamide, hexamethylphosphoric triamide, trimethylolpropane, ethylene glycol, isophorone diisocyanate, butanone oxime, ethylene glycol monoethyl ether solvent and a catalyst zinc octoate react to obtain a polyester prepolymer; terephthalic acid, ethylene glycol, polyester modified nano silicon dioxide and polyester prepolymer are subjected to conventional esterification dehydration reaction to obtain modified polyester chips. The modified resin prepared by the invention has mechanical and optical properties, and meets the application requirements of the polyester film for the dry film resist.
Description
Technical Field
The invention relates to a preparation method of modified polyester and application of the modified polyester in a polyester film for a dry film resist, belonging to the technical field of polyester modification.
Background
Dry Film resists, called Dry films (Dry films) for short, are used mainly in the electronic industry for the manufacture of circuit boards (PCBs). The dry film is composed of three layers of polyester film as support film, photoresist layer (photoresist), and protective film, when the dry film is used in the manufacturing process of circuit board, the protective film of the dry film is removed first, the exposed photoresist layer is tightly adhered on the conductive substrate, then, a glass plate or film (called a photomask) on which a circuit is printed is closely attached to the surface of the polyester film on the other side of the photoresist layer, and, upon exposure, the light firstly penetrates through the transparent part printed on the photomask, then penetrates through the polyester film layer to irradiate the photoresist layer, the photoresist is subjected to exposure reaction, the photomask and the polyester film are removed after the reaction is finished, the unexposed part in the photoresist layer is dissolved and removed by using a proper solvent, then etching or electroplating treatment is carried out to form a pattern, finally, a remover is used for stripping off a cured product generated by the exposure reaction of the photosensitive resin, thus realizing pattern transfer, and obtaining a circuit printed on the photomask on the conductive base material. In the exposure process, the main function of the polyester film is to prevent oxygen from diffusing to the photoresist layer during exposure on the premise of ensuring that light can be fully transmitted, and the oxygen diffusion can damage free radicals generated in the exposure reaction to cause insufficient exposure reaction.
The circuit board manufactured by relying on the dry film has the remarkable advantages of high resolution, capability of manufacturing graphs with the line width smaller than 0.1 mm, capability of obtaining lines with vertical edges within the thickness range of the dry film and capability of ensuring line precision. With the rapid development of electronic products toward miniaturization and high functional integration, the resolution of ultra-fine circuit printing has been increased from millimeter level to micrometer level, which is very strict for the requirements of haze and transparency of polyester film. The haze is one of the main differences between the high-transparency polyester film and the general polyester film, and the smaller the haze of the polyester film, the higher the transparency thereof. Polyethylene terephthalate is a linear macromolecule with a symmetrical aromatic ring structure, with a high degree of stereoregularity, with all the aromatic rings lying in almost the same plane. This makes it easy for the concave-convex parts of adjacent macromolecules to inlay each other, thus having close packing ability and crystallization tendency, so that the polyethylene terephthalate has strong crystallinity, and the crystallization degree has the greatest influence on the transparency of the film. When the crystalline phase, the amorphous phase and the auxiliary agent in the polyester film coexist, because the two phases have different refractive indexes, light rays are refracted and reflected on the interface of the two phases when passing through, and then are milky and opaque. When producing polyester film, some additives and auxiliary materials are often added in order to adjust the surface structure of the film, improve some physical properties (such as surface static electricity, surface friction coefficient, flame retardance, mechanical properties and the like) of the film and facilitate the post-processing of the film, but the additives and auxiliary materials have an inevitable influence on the transparency of the subsequent polyester film. In order to find a method for thoroughly improving the light transmittance of the polyester film, practitioners in the polyester film industry put emphasis on the synthesis and modification of polyester resin as a film raw material so as to obtain the polyester resin film with excellent mechanical, optical and processing properties, reduce the addition of additives in the manufacturing process of the polyester film as much as possible, and fundamentally improve the light transmittance of the polyester film.
Chinese patent CN104448736A discloses a high-transparency modified polyester and a preparation method thereof, wherein a nucleating agent and a nucleating accelerator are added into polyethylene terephthalate, and a finished product is prepared after melting granulation is carried out by a double-screw extruder; the nucleating agent is long-chain linear saturated carboxylate, the length of a carbon chain is C28-C32, and the content of the nucleating agent in the whole material is 0.05-5 wt%; the nucleating accelerant is polyethylene glycol, the molecular weight of the polyethylene glycol is 200-4000, and the content of the nucleating accelerant in the whole material is 0.1-0.5 wt%. The invention also relates to a preparation method of the high-transparency modified polyester. The invention has the advantages that: can be used for producing products with high transparency and high glossiness, simultaneously has the toughness, tensile strength, impact strength, high glossiness, high transparency and hardness of polyester and moderate cost, and is beneficial to large-scale industrial production. The transparency of the high-transparency modified polyester prepared by the patent is only suitable for polyester films in the general packaging field, and the patent adopts a resin melt blending method to prepare the modified polyester, the added nucleating agent and nucleating accelerant are long-chain linear saturated carboxylate and polyethylene glycol, the two substances are difficult to uniformly disperse into a viscous polyester melt, and the good uniform dispersion degree is difficult to achieve only by double-screw blending extrusion.
Chinese patent CN106674509A discloses an optical polyester film with high surface tension and hardness, which adopts 4,4 '-dihydroxy diphenyl sulfone, dihydric alcohol of 4,4' -dihydroxy benzophenone and modified polyester of polynary compounds such as trimesic acid, pyromellitic acid, isophthalic acid, 2, 6-dicarboxylic naphthalene-4-sulfonic acid and the like, adopts the prior stretching process, is simple and easy to operate, improves the surface performance of the polyester film surface, and improves the bonding fastness and the adhesive force with a functional layer. The modification of the polyester in the patent is mainly focused on the improvement of the surface performance, the improvement of other performances is still based on the addition of an auxiliary agent or the surface coating of a functional coating, and the modified polyester resin film with excellent performances in all aspects of mechanics, optics, processability and the like is not obtained fundamentally.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of modified polyester and application thereof in a polyester film for a dry film resist, which realizes the following purposes: the prepared modified polyester resin has excellent mechanical and optical properties and meets the application requirements of dry film resists, has high light transmittance, good mechanical strength and excellent antistatic property, and can be biaxially stretched to prepare the polyester film for the dry film resists, which has high light transmittance, low haze, flexibility, stretch resistance, antistatic surface and good sliding property, without adding functional additives.
In order to realize the purpose, the invention adopts the following technical scheme:
the preparation method of modified polyester mainly comprises three steps of preparation of polyester modified nano silicon dioxide, preparation of polyester prepolymer and preparation of modified PET resin slices, and the obtained modified PET resin slices are subjected to a conventional biaxial stretching process to prepare the polyester film for the three-layer dry film resist.
The following is a further improvement of the above technical solution:
step (1) preparation of polyester modified nano silicon dioxide
Adding a titanate coupling agent ZJ-38S with the mass of 7-11% into silica sol, heating to 50-65 ℃ under constant temperature reaction for 2-3 hours under high-speed stirring at 15000-20000 rpm, generating white precipitate, separating by using a high-speed centrifuge, washing for 3 times by using absolute ethyl alcohol, drying in vacuum at 50 ℃ and grinding into 600-800 mesh white powder, slowly adding the white powder into phenoxyethanol at the stirring speed of 20000-25000 rpm, stirring for 30-45 minutes to uniformly disperse the powder, adding hydroxyl hyperbranched polyester and p-toluenesulfonic acid, heating to 100-120 ℃ and reacting for 1-1.5 hours under constant temperature, performing high-speed centrifugal separation after the reaction is completed to obtain the white precipitate, washing for 3 times, and drying in vacuum at 80 ℃ for 2 hours to obtain a solid, namely polyester modified nano-silica;
the mass fraction of silicon dioxide in the silica sol is 30%, the particle size is 15-18 nm, and the pH is = 8.5;
the titanate coupling agent ZJ-38S is a chelate solution of bis (dioctyloxy pyrophosphate) ethylene titanate and triethanolamine;
the dosage of the phenoxyethanol is 1.6-2 times of the mass of the white powder;
the hydroxyl-terminated hyperbranched polyester has the model number of HyPer H103, the hydroxyl value of 560mg KOH/g, the molecular weight of 2400g/mol, and the adding amount is 60-80% of the mass of white powder;
the adding amount of the p-toluenesulfonic acid is 30-45% of the mass of the white powder.
Step (2) preparation of polyester prepolymer
Adding dibutyl oleamide, hexamethyl phosphoric triamide, trimethylolpropane and ethylene glycol into a reaction kettle according to a certain mass ratio, heating to 100 ℃, vacuumizing to remove water in the raw materials, then cooling, keeping the temperature at 70-85 ℃, adding a certain amount of isophorone diisocyanate at 2000-3000 r/min, stirring for reacting for 2-4 hours, adding a certain amount of end-capping reagent butanone oxime, ethylene glycol monoethyl ether solvent and catalyst zinc octoate, heating to 90-110 ℃, increasing the stirring rate to 3500-4000 r/min, stirring for reacting until the viscosity of the system at the reaction temperature is unchanged, and cooling to room temperature to obtain a polyester prepolymer;
the mass ratio of the dibutyl oleamide to the hexamethyl phosphoric triamide to the trimethylolpropane to the ethylene glycol is 8-10: 10-15: 18-22: 53-64;
the adding amount of the isophorone diisocyanate is 50-65% of the mass of ethylene glycol;
the addition amount of the butanone oxime is 40-50% of the mass of isophorone diisocyanate;
the addition amount of the ethylene glycol monoethyl ether is 70-85% of the mass of the ethylene glycol;
the adding amount of the zinc octoate is 3-5% of the mass of the isophorone diisocyanate.
Preparation of modified PET resin slice in step (3)
Adding terephthalic acid and ethylene glycol into a stainless steel reaction kettle with a fractionating column according to a molar ratio of 1: 1.2-1.4, adding polyester modified nano-silica and polyester prepolymer, introducing nitrogen to displace all air in the kettle, maintaining the pressure in the kettle at 0.1MPa by using nitrogen, raising the temperature to 220-250 ℃ at a speed of 3-5 ℃/min and keeping the temperature constant at a stirring speed of 1500-2000 rpm, adjusting an adjusting valve at the top of the fractionating column to stabilize the pressure in the kettle at about 0.4MPa, carrying out constant-temperature reaction until the pressure in the kettle obviously begins to drop, obviously reducing the amount of distilled water in the fractionating column, unloading the pressure in the kettle to normal pressure, raising the temperature to 270-290 ℃, stirring and reacting for 3-4 hours at 2500-3000 rpm, pressing a polyester melt into a cooling water tank by using nitrogen, and slicing to obtain modified PET resin slices;
the addition amount of the polyester modified nano silicon dioxide and the polyester prepolymer is 5-9% and 8-13% of the total mass of terephthalic acid and ethylene glycol respectively.
The modified PET resin slice prepared by the method is processed by the conventional process steps of slice pre-crystallization, drying, melting, co-extrusion, die head casting, longitudinal stretching, transverse stretching, traction edge cutting and rolling, slitting, finished product warehousing and the like to obtain the polyester film for the three-layer dry film resist.
The preferable technical scheme is as follows:
the preparation of the polyester modified nano silicon dioxide in the step (1)
Adding a titanate coupling agent ZJ-38S with the mass of 9 percent into silica sol, heating to 55 ℃ under high-speed stirring at 18000 r/min, reacting for 2.5 hours at constant temperature, generating white precipitate, separating by using a high-speed centrifuge, washing for 3 times by using absolute ethyl alcohol, drying in vacuum at 50 ℃, grinding into 700-mesh white powder, slowly adding the white powder into phenoxyethanol at 23000 r/min stirring speed, stirring for 40 minutes to uniformly disperse the powder, adding hydroxyl hyperbranched polyester and p-toluenesulfonic acid, heating to 110 ℃ and reacting for 1.2 hours at constant temperature, performing high-speed centrifugal separation after the reaction is finished to obtain white precipitate, washing for 3 times, and drying in vacuum at 80 ℃ for 2 hours to obtain a solid, namely polyester modified nano-silicon dioxide;
the dosage of the phenoxyethanol is 1.8 times of the mass of the white powder;
the adding amount of the hydroxyl-terminated hyperbranched polyester is 70 percent of the mass of the white powder;
the p-toluenesulfonic acid is added in an amount of 37% by mass of the white powder.
Step (2) preparation of polyester prepolymer:
adding dibutyl oleamide, hexamethyl phosphoric triamide, trimethylolpropane and glycol into a reaction kettle according to a certain mass ratio, heating to 100 ℃, vacuumizing to remove moisture in the raw materials, then cooling, keeping the temperature at 80 ℃, adding a certain amount of isophorone diisocyanate at 2500 rpm, stirring for reacting for 3 hours, adding a certain amount of end-capping reagent butanone oxime, ethylene glycol monoethyl ether solvent and catalyst zinc octoate, heating to 100 ℃, increasing the stirring speed to 3800 rpm, stirring for reacting until the viscosity of the system at the reaction temperature is not changed, and cooling to room temperature to obtain a polyester prepolymer;
the mass ratio of the dibutyl oleamide to the hexamethyl phosphoric triamide to the trimethylolpropane to the ethylene glycol is 9:13:20: 58;
the adding amount of the isophorone diisocyanate is 60% of the mass of the ethylene glycol;
the addition amount of the butanone oxime is 45 percent of the mass of the isophorone diisocyanate;
the addition amount of the ethylene glycol monoethyl ether is 80 percent of the mass of the ethylene glycol;
the adding amount of the zinc octoate is 4 percent of the mass of the isophorone diisocyanate.
Preparing the modified PET resin slice in the step (3):
adding terephthalic acid and ethylene glycol into a stainless steel reaction kettle with a fractionating column according to a molar ratio of 1:1.3, adding polyester modified nano silicon dioxide and polyester prepolymer, introducing nitrogen to displace all air in the kettle, maintaining the pressure in the kettle at 0.1MPa by using nitrogen, raising the temperature to 240 ℃ at a speed of 4 ℃/min and keeping the temperature constant at a stirring speed of 1700 rpm, adjusting an adjusting valve at the top of the fractionating column to stabilize the pressure in the kettle at about 0.4MPa, carrying out a constant-temperature reaction until the pressure in the kettle obviously begins to drop, obviously reducing the amount of distilled water in the fractionating column, unloading the pressure in the kettle to normal pressure, raising the temperature to 280 ℃, carrying out a stirring reaction at 2800 rpm for 3.5 hours, pressing a polyester melt into a cooling water tank by using nitrogen, and slicing to obtain modified PET resin slices;
the addition amount of the polyester modified nano silicon dioxide and the polyester prepolymer is respectively 7 percent and 10 percent of the total mass of terephthalic acid and ethylene glycol.
Compared with the prior art, the invention has the following beneficial effects:
1. the modified polyester resin which has excellent mechanical and optical properties and meets the application requirement of a dry film resist is prepared, and the resin has high light transmittance, good mechanical strength and excellent antistatic property;
2. the modified PET resin prepared by the invention can be used for obtaining the polyester film for the three-layer dry film resist with high light transmittance, low haze, high mechanical strength, good surface sliding property and excellent antistatic property by a biaxial stretching process under the condition of not adding a functional auxiliary agent, and the obtained polyester film has the light transmittance of 91.79-91.96%, the haze of 1.52-1.62%, and the surface inherent resistance of 0.92 multiplied by 1011~1.16×1011Ω, static friction coefficient: 0.52-0.55 mu s of inner surface layer, 0.40-0.45 mu s of outer surface layer,tensile strength MD 234-248N/mm2、TD254~267N/mm2Elastic modulus MD 4292-4346N/mm2、TD4592~4753 N/mm2Elongation at break MD 128-139%, TD 122-132%, thermal shrinkage ratio MD 1.6-2.1%, and TD 0.7-1.1%.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1: preparation method of modified polyester and application of modified polyester in polyester film for dry film resist
The method comprises the following steps:
1. preparation of polyester modified nano silicon dioxide
Adding 90 kg of titanate coupling agent ZJ-38S into 1000 kg of silica sol, heating to 55 ℃ under high-speed stirring at 18000 r/min, reacting for 2.5 hours at constant temperature, generating white precipitate, separating by using a high-speed centrifuge, washing for 3 times by using absolute ethyl alcohol, drying in vacuum at 50 ℃, grinding into 700-mesh white powder, slowly adding 900 kg of white powder into 1620 kg of phenoxyethanol at 23000 r/min, stirring for 40 minutes to uniformly disperse the powder, adding 630 kg of hydroxyl-terminated hyperbranched polyester and 333 kg of p-toluenesulfonic acid, heating to 110 ℃ and reacting for 1.2 hours at constant temperature, performing high-speed centrifugal separation after the reaction is finished to obtain white precipitate, washing for 3 times, and drying in vacuum at 80 ℃ for 2 hours to obtain solid, namely polyester modified nano silicon dioxide;
the mass fraction of silicon dioxide in the silica sol is 30%, the particle size is 15-18 nm, and the pH is = 8.5;
the titanate coupling agent ZJ-38S is a chelate solution of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine.
2. Preparation of polyester prepolymer
90 kg of dibutyl oleamide, 130 kg of hexamethylphosphoric triamide, 200 kg of trimethylolpropane and 580 kg of ethylene glycol are added into a reaction kettle, the temperature is raised to 100 ℃, the vacuum pumping is carried out to remove the moisture in the raw materials, then the temperature is lowered and the constant temperature is 80 ℃, 348 kg of isophorone diisocyanate is added at 2500 r/min, the stirring reaction is carried out for 3 hours, 156.6 kg of end-capping reagent butanone oxime, 464 kg of ethylene glycol monoethyl ether solvent and 14 kg of catalyst zinc octoate are added, the temperature is raised to 100 ℃, the stirring speed is raised to 3800 r/min, the stirring reaction is carried out until the viscosity of the system at the reaction temperature is not changed, and the temperature is lowered to room temperature to obtain the polyester prepolymer.
3. Preparing modified PET resin slices:
adding 664.5 kg of terephthalic acid and 322.8 kg of ethylene glycol into a stainless steel reaction kettle with a fractionating column, adding 69.1 kg of polyester modified nano silicon dioxide and 98.7 kg of polyester prepolymer, introducing nitrogen to displace all air in the kettle, maintaining the pressure in the kettle at 0.1MPa by using nitrogen, heating to 240 ℃ at the speed of 4 ℃/min at the stirring speed of 1700 rpm, keeping the temperature constant, adjusting an adjusting valve at the top of the fractionating column to stabilize the pressure in the kettle at about 0.4MPa, carrying out constant-temperature reaction until the pressure in the kettle obviously begins to drop, obviously reducing the amount of distilled water in the fractionating column, unloading the pressure in the kettle to the normal pressure, heating to 280 ℃, carrying out stirring reaction at 2800 rpm for 3.5 hours, pressing polyester melt into a cooling water tank by using nitrogen, and slicing to obtain modified PET resin slices.
Example 2: preparation method of modified polyester and application of modified polyester in polyester film for dry film resist
The method comprises the following steps:
1. preparation of polyester modified nano silicon dioxide
Adding 70 kg of titanate coupling agent ZJ-38S into 1000 kg of silica sol, heating to 50 ℃ under high-speed stirring at 15000 r/min, reacting for 2 hours at constant temperature, generating white precipitate, separating by using a high-speed centrifuge, washing for 3 times by using absolute ethyl alcohol, drying in vacuum at 50 ℃ and grinding into 600-mesh white powder, slowly adding 900 kg of white powder into 1440 kg of phenoxyethanol at 20000 r/min stirring speed, stirring for 30 minutes to uniformly disperse the powder, adding 540 kg of hydroxyl-terminated hyperbranched polyester and 270 kg of p-toluenesulfonic acid, heating to 100 ℃ and reacting for 1 hour at constant temperature, performing high-speed centrifugal separation after the reaction is finished to obtain white precipitate, washing for 3 times, and drying in vacuum at 80 ℃ for 2 hours to obtain solid, namely polyester modified nano silicon dioxide;
the mass fraction of silicon dioxide in the silica sol is 30%, the particle size is 15-18 nm, and the pH is = 8.5;
the titanate coupling agent ZJ-38S is a chelate solution of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine.
2. Preparation of polyester prepolymer
80 kg of dibutyl oleamide, 100 kg of hexamethylphosphoric triamide, 180 kg of trimethylolpropane and 530 kg of ethylene glycol are added into a reaction kettle, the temperature is raised to 100 ℃, the vacuum pumping is carried out to remove the moisture in the raw materials, then the temperature is lowered and the constant temperature is kept at 70 ℃, 265 kg of isophorone diisocyanate is added at 2000 r/min, the stirring reaction is carried out for 3 hours, 102.4 kg of end-capping reagent butanone oxime, 371 kg of ethylene glycol monoethyl ether solvent and 8 kg of catalyst zinc octoate are added, the temperature is raised to 90 ℃, the stirring speed is raised to 3500 r/min, the stirring reaction is carried out until the viscosity of the system at the reaction temperature is not changed, and the temperature is lowered to room temperature to obtain the polyester prepolymer.
3. Preparing modified PET resin slices:
adding 664.5 kg of terephthalic acid and 297.9 kg of ethylene glycol into a stainless steel reaction kettle with a fractionating column, adding 48.1 kg of polyester modified nano silicon dioxide and 77 kg of polyester prepolymer, introducing nitrogen to displace all air in the kettle, maintaining the pressure in the kettle at 0.1MPa by using nitrogen, raising the temperature to 220 ℃ at the speed of 3 ℃/min at the stirring speed of 1500 rpm, keeping the temperature constant, adjusting an adjusting valve at the top of the fractionating column to stabilize the pressure in the kettle at about 0.4MPa, carrying out constant-temperature reaction until the pressure in the kettle obviously begins to drop, obviously reducing the amount of distilled water in the fractionating column, unloading the pressure in the kettle to the normal pressure, raising the temperature to 270 ℃, carrying out stirring reaction at 2500 rpm for 3 hours, pressing polyester melt into a cooling water tank by using nitrogen, and slicing to obtain modified PET resin slices.
Example 3: preparation method of modified polyester and application of modified polyester in polyester film for dry film resist
The method comprises the following steps:
1. preparation of polyester modified nano silicon dioxide
Adding 110 kg of titanate coupling agent ZJ-38S into 1000 kg of silica sol, heating to 65 ℃ under high-speed stirring at 20000 rpm, reacting for 3 hours at constant temperature to generate white precipitate, separating by using a high-speed centrifuge, washing for 3 times by using absolute ethyl alcohol, drying in vacuum at 50 ℃, grinding into 800-mesh white powder, slowly adding 900 kg of white powder into 1800 kg of phenoxyethanol at 25000 rpm, stirring for 45 minutes to uniformly disperse the powder, adding 720 kg of hydroxyl-terminated hyperbranched polyester and 405 kg of p-toluenesulfonic acid, heating to 120 ℃ and reacting for 1.5 hours at constant temperature, performing high-speed centrifugal separation after the reaction is finished to obtain white precipitate, washing for 3 times, and drying in vacuum at 80 ℃ for 2 hours to obtain solid, namely polyester modified nano-silicon dioxide;
the mass fraction of silicon dioxide in the silica sol is 30%, the particle size is 15-18 nm, and the pH is = 8.5;
the titanate coupling agent ZJ-38S is a chelate solution of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine.
2. Preparation of polyester prepolymer
100 kg of dibutyl oleamide, 150 kg of hexamethylphosphoric triamide, 220 kg of trimethylolpropane and 640 kg of ethylene glycol are added into a reaction kettle, the temperature is raised to 100 ℃, the vacuum pumping is carried out to remove the moisture in the raw materials, then the temperature is lowered and the constant temperature is 85 ℃, 416 kg of isophorone diisocyanate is added at 3000 r/min, the stirring reaction is carried out for 4 hours, 208 kg of blocking agent butanone oxime, 544 kg of ethylene glycol monoethyl ether solvent and 20.8 kg of catalyst zinc octoate are added, the temperature is raised to 110 ℃, the stirring speed is raised to 4000 r/min, the stirring reaction is carried out until the viscosity of the system at the reaction temperature is not changed, and the temperature is lowered to room temperature to obtain the polyester prepolymer.
3. Preparing modified PET resin slices:
adding 664.5 kg of terephthalic acid and 347.6 kg of ethylene glycol into a stainless steel reaction kettle with a fractionating column, adding 91.1 kg of polyester modified nano silicon dioxide and 131.6 kg of polyester prepolymer, introducing nitrogen to displace all air in the kettle, maintaining the pressure in the kettle at 0.1MPa by using nitrogen, raising the temperature to 250 ℃ at the speed of 5 ℃/min at the stirring speed of 2000 r/min, keeping the temperature constant, adjusting an adjusting valve at the top of the fractionating column to stabilize the pressure in the kettle at about 0.4MPa, carrying out constant-temperature reaction until the pressure in the kettle obviously begins to drop, obviously reducing the amount of distilled water in the fractionating column, unloading the pressure in the kettle to normal pressure, raising the temperature to 290 ℃, stirring and reacting for 4 hours at 3000 r/min, pressing polyester melt into a cooling water tank by using nitrogen, and slicing to obtain modified PET resin slices.
Preparation of three-layer dry film resist with polyester film:
the modified PET resin slices obtained in the embodiments 1, 2 and 3 are prepared into corresponding polyester films by the following processes
(1) Slicing, pre-crystallizing and drying:
pre-crystallizing and drying the modified PET resin slices, wherein the pre-crystallizing temperature is 165 ℃, the pre-crystallizing residence time is 22min, the drying temperature is 175 ℃, and the drying residence time is 3 hours;
(2) melting, co-extrusion and die head casting:
respectively putting the raw materials with an A/B/C three-layer structure into corresponding double-screw extruders, heating the heating zones of the main extruder and the auxiliary extruder to 260 ℃, melting and extruding the raw materials, and cooling and solidifying a melt co-extruded from the three layers of the die heads on the surface of a casting sheet roller to form a thick sheet;
the raw materials of the A/B/C three-layer structure comprise A, B, C three layers which are all modified PET resin slices;
when the A/B/C three-layer structure is extruded, the mass ratio of the A/B/C three-layer extruded melt is 1:4: 1;
(3) and longitudinal stretching:
stretching the film to form a base film on a longitudinal stretcher, wherein the stretching temperature is 120 ℃, the multiplying power is 5:1, and the tensile strength is 320 MPa; carrying out heat setting on the longitudinally stretched base film on the surfaces of a group of cooling rollers, wherein the setting temperature is 185 ℃, and the setting time is 4 seconds;
(4) and transverse stretching:
longitudinally stretching the base film, then feeding the base film into a transverse stretching machine, wherein the stretching temperature is 130 ℃, the transverse stretching multiplying power is 4.5:1, the stretching strength is 290MPa, the stretched base film is cooled after being subjected to heat setting on the surface of a group of cooling rollers, the setting temperature is 180 ℃, and the setting time is 2.5 seconds;
(5) traction trimming and rolling:
the base film at the transverse drawing outlet enters a traction station, an edge device in the traction station carries out edge cutting and trimming on the edge of the base film through an edge cutting knife, and then the base film is drawn to a winding machine to be wound to obtain a large roll of base film;
(6) cutting and warehousing finished products:
the base film is pulled to a cutter from an unreeling frame, the tension and the flattening of the base film are ensured in the process, the base film is cut into required specifications at a cutting roller, then the base film is coiled to obtain an A/B/C three-layer polyester film finished product, and the finished product is packaged, weighed and warehoused;
the total thickness of the A/B/C three-layer polyester film finished product is 15 micrometers, and the thickness ratio of the A/B/C three-layer polyester film to the A/B/C three-layer polyester film finished product is 3:19: 3.
The performance test method of the polyester film comprises the following steps:
1. light transmittance: according to ASTM D1003, using Japanese electrochromic NDH-5000 test;
2. uniformity of thickness: the thickness value of the film was measured according to ASTM D374 using a thickness tester (Millimar 1240) manufactured by Mahr, Germany, and the thickness deviation (2. sigma. value) was calculated from the thickness value;
3. haze value: the haze value of the film was measured according to ASTM D1003 using a haze tester (BS 2782) manufactured by Diffusion System, UK. The haze of the film was evaluated according to the following criteria:
a level: the haze value of the film is not more than 1.0%. the film has excellent haze
B stage: the haze value of the film is more than 1.0 and less than or equal to 1.5
C level: haze value of 1.5 < haze value
4. Coefficient of friction (μ s): the static coefficient of friction (. mu.s) of the film was measured according to ASTM D1894 using a friction coefficient tester manufactured by Blbert Instrument Co.USA. The film was evaluated for slip according to the following criteria:
a level: has a coefficient of friction of not more than 0.6
B stage: a coefficient of friction of more than 0.6 and less than or equal to 0.8
C level: poor sliding properties, 0.8 < coefficient of friction
5. Antistatic property: after sufficient humidity conditioning was performed at 23 ℃ and 50% RH using a high resistance measuring device HP4339B and a measuring electrode HP16008B manufactured by Hewlett packard Co., Japan, an applied voltage of 100V was measured and the applied voltage was continuedThe antistatic property was evaluated based on the intrinsic surface resistance value after 1 minute, which was less than 1X 1011Omega, good antistatic property, more than 1 × 1011Omega is less than 1 x 1013Omega antistatic property of more than 1X 1013Omega antistatic property is poor;
6. mechanical strength: tensile strength, modulus of elasticity, elongation at break, and the like, according to ASTM D882;
7. heat shrinkage ratio: tested according to ASTM D1204.
Test data:
TABLE 1
TABLE 2
Claims (7)
1. A preparation method of modified polyester is characterized by comprising the following steps: the preparation of the modified polyester comprises the preparation of polyester modified nano silicon dioxide, the preparation of polyester prepolymer and the preparation of modified PET resin slices; the preparation method of the polyester modified nano silicon dioxide comprises the steps of adding silicon dioxide powder treated by a titanate coupling agent into phenoxyethanol at 20000-25000 r/min, stirring for 30-45 minutes to uniformly disperse the powder, adding hydroxyl-terminated hyperbranched polyester and p-toluenesulfonic acid, heating to 100-120 ℃, reacting at a constant temperature for 1-1.5 hours, carrying out high-speed centrifugal separation to obtain white precipitate, washing for 3 times by using deionized water, and carrying out vacuum drying at 80 ℃ for 2 hours to obtain the polyester modified nano silicon dioxide; the preparation method comprises the steps of adding dibutyl oleamide, hexamethyl phosphoric triamide, trimethylolpropane and ethylene glycol into a reaction kettle according to a certain mass ratio, heating to 100 ℃, vacuumizing to remove water in raw materials, then cooling, keeping the temperature at 70-85 ℃, adding a certain amount of isophorone diisocyanate at 2000-3000 r/min, stirring and reacting for 2-4 hours, adding a certain amount of end-capping reagent butanone oxime, ethylene glycol monoethyl ether solvent and catalyst zinc octoate, heating to 90-110 ℃, increasing the stirring rate to 3500-4000 r/min, stirring and reacting until the viscosity of the system at the reaction temperature is not changed, and cooling to room temperature to obtain the polyester prepolymer; the preparation method of the modified PET resin slice comprises the steps of adding reactants into a stainless steel reaction kettle with a fractionating column, introducing nitrogen to replace all air, maintaining the pressure in the kettle at 0.1MPa by using the nitrogen, heating to 220-250 ℃ at the speed of 3-5 ℃/min and keeping the temperature constant, adjusting an adjusting valve at the top of the fractionating column to enable the pressure in the kettle to be stable at about 0.4MPa, obviously reducing the pressure in the kettle until the pressure in the kettle obviously decreases, obviously reducing the amount of distilled water in the fractionating column, unloading the pressure in the kettle to normal pressure, heating to 270-290 ℃, stirring and reacting at 2500-3000 rpm for 3-4 hours, then pressing a polyester melt into a cooling water tank by using the nitrogen, and slicing to obtain the modified PET resin slice.
2. The process for producing a modified polyester according to claim 1, wherein: the operation of the silicon dioxide powder treated by the titanate coupling agent is that the titanate coupling agent ZJ-38S is added into silica sol, the mixture is stirred at a high speed of 15000-20000 rpm, the mixture is subjected to constant temperature reaction at 50-65 ℃ for 2-3 hours, then a high-speed centrifuge is used for separating to obtain white precipitate, the white precipitate is washed for 3 times by absolute ethyl alcohol, and the white precipitate is dried in vacuum at 50 ℃ and then ground into 600-800 meshes of powder to obtain the silicon dioxide powder treated by the titanate coupling agent.
3. The process for producing a modified polyester according to claim 1, wherein: the dosage of the phenoxyethanol is 1.6-2 times of the mass of the silicon dioxide powder treated by the titanate coupling agent; the hydroxyl-terminated hyperbranched polyester has the model number of HyPer H103, the hydroxyl value of 560mg KOH/g, the molecular weight of 2400g/mol, and the adding amount is 60-80% of the mass of the silicon dioxide powder treated by the titanate coupling agent; the adding amount of the p-toluenesulfonic acid is 30-45% of the mass of the silicon dioxide powder treated by the titanate coupling agent.
4. The process for producing a modified polyester according to claim 2, wherein: the mass fraction of silicon dioxide in the silica sol is 30%, the particle size is 15-18 nm, and the pH is = 8.5; the titanate coupling agent ZJ-38S is a chelate solution of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine, and the addition amount of the titanate coupling agent ZJ-38S is 7-11% of the mass of the silica sol.
5. The process for producing a modified polyester according to claim 1, wherein: the mass ratio of the dibutyl oleamide to the hexamethyl phosphoric triamide to the trimethylolpropane to the ethylene glycol is 8-10: 10-15: 18-22: 53-64; the adding amount of the isophorone diisocyanate is 50-65% of the mass of ethylene glycol; the addition amount of the butanone oxime is 40-50% of the mass of isophorone diisocyanate; the addition amount of the ethylene glycol monoethyl ether is 70-85% of the mass of the ethylene glycol; the adding amount of the zinc octoate is 3-5% of the mass of the isophorone diisocyanate.
6. The process for producing a modified polyester according to claim 1, wherein: the reactants are terephthalic acid, ethylene glycol, polyester modified nano silicon dioxide and polyester prepolymer; the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.2-1.4; the addition amount of the polyester modified nano silicon dioxide and the polyester prepolymer is 5-9% and 8-13% of the total mass of terephthalic acid and ethylene glycol respectively.
7. The application of the modified polyester in the polyester film for the dry film resist is characterized in that: the modified polyester is subjected to slice pre-crystallization, drying, melting, co-extrusion, die head sheet casting, longitudinal stretching, transverse stretching, traction edge cutting and rolling, slitting and finished product warehousing to obtain a polyester film finished product for the A/B/C three-layer dry film resist, wherein the total thickness is 15 micrometers, and the thickness ratio of the A/B/C three layers is 3:19: 3.
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| US9631069B1 (en) * | 2015-12-27 | 2017-04-25 | Zhejiang Sci-Tech University | Poly (cyclic butylene terephthalate) / silicon dioxide nanocomposite |
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| CN112659691A (en) * | 2021-03-15 | 2021-04-16 | 富维薄膜（山东）有限公司 | Polyester film for fire-resistant dry film resist and preparation method thereof |
| CN112980151A (en) * | 2021-02-04 | 2021-06-18 | 慧智科技（中国）有限公司 | Organic silicon modified polyester resin with tensile toughness and preparation method thereof |
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| US9631069B1 (en) * | 2015-12-27 | 2017-04-25 | Zhejiang Sci-Tech University | Poly (cyclic butylene terephthalate) / silicon dioxide nanocomposite |
| CN106854262A (en) * | 2016-12-29 | 2017-06-16 | 桐乡市中维化纤有限公司 | Moisture absorption can contaminate low melting point polyester chip and preparation method thereof |
| CN109880312A (en) * | 2019-01-29 | 2019-06-14 | 安徽天光传感器有限公司 | A kind of preparation method of sensor outer housing modified butanediol ester poly succinic acid composite material |
| CN112980151A (en) * | 2021-02-04 | 2021-06-18 | 慧智科技（中国）有限公司 | Organic silicon modified polyester resin with tensile toughness and preparation method thereof |
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