JPS62101628A - Fine resin powder and its production - Google Patents

Abstract

PURPOSE:To produce a fine resin powder excellent in dispersibility, smoothness, filling property, toughness, etc., by dissolving a specified polyethylene terephthalate resin in a lactam and solid state-polymerizing the crystallized fine resin intermediate powder. CONSTITUTION:A lactam of the formula (wherein R is H or a 1-6C alkyl and n is 1-12) is added to a polyethylene terephthalate resin of intrinsic viscosity <0.3, containing 60mol% or above ethylene terephthalate units, and the obtained mixture is heated at a temperature <=the b.p. of the lactam for 30-40min to form a melt. This melt is added dropwise to a precipitation solvent such as water or methanol to crystallize a fine resin intermediate powder. This fine powder is filtered, washed, dried and solid state-polymerized at a temperature by 5-100 deg.C lower than the m.p. of the fine powder in a vacuum <=5mmHg or in an atmosphere of an inert gas to obtain a smooth-faced spherical fine resin powder having an average particle diameter <=10mum, a maximum particle diameter <=20mum, an intrinsic viscosity <0.7 and a crystallinity >=60%.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to ultrafine polyethylene terephthalate resin powder and a method for producing the same. More specifically, unexploited nA has good dispersibility, smoothness, and smoothness, making it suitable for use as, for example, cosmetic additives, lubricants, lubricants, porous polymer materials, powder coating agents, fillers, and cell culture medium materials. ,
The present invention relates to a novel polyethylene terephthalate resin fine powder that has excellent properties such as feel, fillability, toughness, hardness, abrasion resistance, and weather resistance, and a method for producing the same.

BACKGROUND OF THE INVENTION Polyester resins such as polyethylene terephthalate resins have traditionally been used in various fields of application, such as rutting fibers and films, due to their excellent physical, chemical and thermal properties. It is widely used as a material and as a material for industrial life.

10,000, the polyethylene terephthalate-based fat is used, for example, as an additive to cosmetics, a lubricant, a lubricant, a porous polymer material, a powder coating agent, a filler, a medium material for cell culture, particles for suspensions, etc. In this case, it is necessary to pulverize the polyethylene terephthalate resin in order to obtain a powder with excellent dispersibility, smoothness, smoothness, and texture.

In particular, when used in cosmetics, basic cosmetics such as creams, emulsions, lotions, powders,
The reality is that finished cosmetics (makeup cosmetics) such as lipsticks require different powder properties and are mixed with different types of powder each time depending on the purpose. Therefore, the powder used in such cosmetics is
Depending on the application, it must have either hydrophilicity, oiliness, or both, and in terms of effectiveness, properties such as astringency, sebum absorption, drainage, and skin protection are required. . Generally, when used in cosmetics, fine powder having an average particle size of 20 μm or less, preferably 10 μm or less, and more preferably 1 to 5 μm is suitable.

As the particle size decreases, the specific surface area increases, and properties that depend on surface properties such as adsorption to other substances and light reflectivity increase significantly, as well as extensibility.

As a result of increased caking, it may not stick to the skin during use,
This is manifested in improvements in elongation, smoothness, gloss, burl effect, light shielding effect, etc.

By the way, fine powder of polyethylene terephthalate resin has significantly different shape, physical properties, and chemical properties from conventionally used fine powder such as talc, kaolin, and titanium dioxide, so it is used for various purposes including cosmetics. When used for this purpose, it produces unique effects.

Therefore, various methods have been tried in the past for pulverizing polyester resins, typified by polyethylene terephthalate resins, but polyester resins are generally tough and it is extremely difficult to pulverize them into powder. Due to excessive frictional heat generated during crushing, resin quality inevitably deteriorates. As a method to solve all of these problems in pulverization, there is a method in which JM fat is immersed in an ultra-low temperature liquid such as liquid nitrogen at -147°C or lower, and then powdered in a pulverizer. A method of solid phase polymerization after finely pulverizing a resin having a degree of polymerization (Japanese Unexamined Patent Publication No. 5
4-165439), a method in which a polyester resin with a low degree of polymerization is sprayed in a molten state into an inert gas through pores to form a granular solid, and then solid-state polymerized (Japanese Patent Publication No. 46
(Japanese Patent Publication No. 46-3192, Japanese Patent Publication No. 46-3193), a method of heating and dissolving halogens in aromatic specific solvents, cooling them, precipitating them, and pulverizing them; A method of obtaining a powder by removing the medium, and a method of dissolving it in benzyl alcohol and adding a diluent to precipitate the polyester powder (Japanese Patent Laid-Open No. 73452/1983) have been proposed.

However, depending on these conventional methods, it is difficult to meet all the performance requirements for the above-mentioned applications and to achieve an average particle size of 20 μm.
It was not possible to obtain the following fine powder.

Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to improve dispersibility, smoothness, smoothness, feel, fillability, and toughness, which could not be obtained by conventional methods. The object of the present invention is to provide a polyethylene terephthalate resin fine powder that has excellent properties such as hardness, abrasion resistance, and weather resistance.

Means for Solving the Problems The inventors of the present invention have conducted intensive research to achieve the above-mentioned object. As a result, the present inventors have solved the polyethylene terephthalate resin having a specific solid state viscosity in a lactam solvent, and then crystallized it. It was discovered that polyethylene terephthalate resin fine powder having the desired properties and an average particle size of 20 μm or less could be obtained by solid-phase polymerizing the obtained resin fine powder at a predetermined temperature.Based on this knowledge, this book was developed. The invention was completed.

That is, 1 the present invention has an intrinsic viscosity of less than 0.7 and a crystallinity of 6
The present invention provides a fine resin powder having an average particle size of 20 μm or less and consisting of 0% or more polyethylene terephthalate resin. Such resin fine powder is obtained by converting raw material polyethylene terephthalate resin having an intrinsic viscosity of less than 0.3 into a compound of the general formula % formula % (1) (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
(where n is an integer from 1 to 12) and crystallize the resulting intermediate resin fine powder. It can be easily produced by in-phase polymerization at a temperature in the range of ~100°C.

The resin fine powder of the present invention is made of a polyethylene terephthalate resin having an intrinsic viscosity of less than 0.7 and a crystallinity of 60% or more. If the intrinsic viscosity is 0.7 or more or the crystallinity is less than 60%, it will not have the properties required as an additive for cosmetics and the like.

A polyethylene terephthal resin having an intrinsic viscosity and a degree of crystallinity within the above range usually contains ethylene terephthalate units in an amount of 60 molar or more, preferably J-j7575% or more. Therefore, the polyethylene terephthalate resin may contain units derived from other copolymer components as long as they are 40 molar or less, preferably 25 molar or less. Examples of dicarboxylic acid components in the copolymerization component include phthalic acid, inophthalic acid, adipic acid, oxalic acid, sebacic acid, speric acid, glutaric acid, pimeline acid, fumaric acid, cono-phosphoric acid, and naphthalene-2.
, 6-dicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid, etc., while the glycol component includes, for example, a glycol component having 3 to 10 carbon atoms.
polymethydi/glycol,/chlorhexane-1.4-
At least one selected from dimethatol, pentaerythritol, etc. can be mentioned.

Of course, ester-forming derivatives of dicarboxylic acids, such as lower alkyl esters, aryl esters, carbonic esters, acid chlorides, etc., can be used in place of the dicarboxylic acids, and diols can also be ester-forming derivatives, such as acetyl esters. It can be used in the form of body, alkali metal salt, etc.

Furthermore, as a modifier, dimethyl-5-hydroxyisophthalate, dimethyl-5-hydroxyhexahydroisophthalate, benzene-1,3,5-tricarboxylic acid,
p-carbomethoxyphenyl diethyl phosphate, 3
．． There is no problem even if one or more of 5-dicarboxyphenyldiethyl phosphate, phosphoric acid, tri-p-carbomethoxyphenyl phosphate, tricaprylborate, sorbitan, trimethosic acid, etc. are contained in small amounts. do not have.

If these copolymer components exceed 40 molar ratios, not only will the excellent physical properties of polyethylene terephthalate be impaired, but also the crystallinity will be significantly reduced.

The resin particles of the resin fine powder of the present invention have an average particle size of 20 μm.
It is preferable that the average particle size be 10 μm or less, the maximum particle size be 20 μm or less, have a smooth surface, and be substantially spherical.

Next, to explain the method for manufacturing the resin fine powder of the present invention, first, a raw material polyethylene terephthalate resin having an intrinsic viscosity of less than 0.3 is dissolved in a lactam represented by the general formula (1) and crystallized. Obtain an intermediate fine powder.

Examples of the lactam include ε-caprolactam and β-caprolactam.
Propiolactam, γ-butyrolactam, γ-valerolactam, δ-valerolactam, heptolactam, etc. may be used, and each of these may be used alone or in a mixture of two or more, and may be difficult to operate. Compound 1, such as tetrahydrofurano, which has heat resistance and boiling point that does not cause lactam and is compatible with the lactam, may be used in combination as necessary.

There are no particular restrictions on the method of dissolving the raw material polyethylene terephthalate resin in the lactam, but for example, put the lactam in a sealed container, heat it to a temperature of 170°C or higher and lower than the boiling point of the lactam, and then dissolve the polyethylene while stirring. The terephthalate resin may be added and stirred while maintaining the temperature for 30 to 40 minutes to dissolve it.

After dissolving the raw material polyethylene terephthalate resin in this way, this solution is dropped into a precipitation solvent and cooled to crystallize the resin. At this time, various additives such as known crystal nucleating agents and lubricants are added. , molding aids, anti-aggregation agents, heat resistance and light resistance stabilizers such as known antioxidants and ultraviolet absorbers, hydrolysis resistance improvers, coloring agents such as pigments and dyes, antistatic agents, conductive agents, A flame retardant, a reinforcing agent, a filler, a mold release agent, etc. can be added to the solution as desired and contained in the fine powder.

In particular, the heat aging resistance of fine powder can be improved by adding known heat stabilizers such as amine type and hindered phenol type, and also known crystal nucleating agents.
By adding sodium p-phenolsulfonate or the like, a very fine powder can be obtained. In this case, the amount added is preferably u 0.00 based on the total amount of raw material polyethylene terephthalate resin and lactam.
It is selected in the range of 3 to 6.0 weight coefficient. Furthermore, by adding a known carbodiimide compound or epoxy compound as a hydrolysis resistance improver, a fine powder with significantly improved hydrolysis resistance can be obtained. The amount added is preferably in the range of 0.03 to 10% by weight based on the total amount of raw material polyethylene terephthalate resin and lactam. An alkaline compound or the like may be used in combination.

In the present invention, the inherent viscosity of the raw material polyethylene terephthalate resin is 0.3 in order to obtain fine powder.
It needs to be less than 0.25, preferably less than 0.25. If the intrinsic viscosity is 0.3 or more, the crystallization process will not result in a fine powder, but will instead become a solid fibrous mass, making it difficult to obtain the desired powder. By using a raw material polyethylene terephthalate resin with an intrinsic viscosity of less than 0.3, preferably less than 0.25, crystallization becomes easy without being greatly limited by the type of precipitation solvent, and high crystallization is achieved. It is possible to obtain fine powder with high yield.

Crystallization of the intermediate fine powder in the present invention is carried out, for example, by dropping a lactam solution in which raw material polyethylene terephthalate fruit wood @ is dissolved into a precipitation solvent such as water, methanol, ethanol, or tetrahydrofuran while stirring, and cooling the solution. The shape of the fine powder varies depending on the crystallization conditions.For example, if a high boiling point solvent is used as the precipitation solvent, and the solvent is heated and the cooling rate is slowed down at a high temperature, it is possible to obtain a large particle size. Substantially spherical fine powder can be obtained, and conversely, if it is quickly cooled at a low temperature and precipitated quickly,
Substantially spherical fine powder with a small particle size can be obtained. Further, by a method such as precipitation under pressure, a fine powder having an arbitrary degree of crystallinity and particle size distribution can be obtained. There are no particular limitations on the precipitation solvent used at this time, as long as it dissolves the lactam at room temperature or below its boiling point and does not dissolve the polyethylene terephthalate resin.

Next, the resin intermediate fine powder crystallized in this way is filtered, washed and dried, and then placed under a reduced pressure of, for example, 5 mlHg or less or in an inert gas atmosphere, at a temperature lower than the melting point of the resin fine powder. Solid state polymerization is also carried out at a temperature in the lower range of 5 to 100°C. The reaction time at this time is appropriately selected depending on the required physical properties of the powder seismic product.

This solid phase polymerization increases the degree of polymerization and crystallinity of the fine resin powder, and almost completely removes lactam from the powder.

The thus obtained polyethylene terephthalate-based fM fat fine powder has an intrinsic viscosity of less than 0.7 and a crystallinity of 60% or more. In the raw material polyethylene terephthalate resin used in the present invention, the solid phase polymerization reaction rate is relatively slow, and it is difficult to obtain a material with a substantial intrinsic viscosity of 0.7 or more. If one dares to obtain such a product, coloring problems and fusion phenomena occur, and the production cost increases.

Therefore, in the present invention, it is necessary that the intrinsic viscosity of the fine resin powder be less than 7.

Effects of the invention The polyethylene terephthalate resin fine powder of the present invention is
Since it is composed of particles with an average particle size of 20 μm or less and a smooth surface and substantially spherical shape, it can be expected to have excellent powder properties such as dispersibility, smoothness, smoothness, and texture, and is especially useful for cosmetics. When used for purposes, it has astringent properties, sebum absorption properties,
Water resistant, skin protection, adhesion to the skin, stretch, slip,
Improves gloss, pearl effect, light shielding effect, etc. In addition to cosmetics, the fine powder is useful for lubricants, lubricants, porous polymer materials, powder coatings, fillers, cell culture media, and the like.

Furthermore, the method for producing fine resin powder of the present invention has a high yield and relatively easy control of particle size, degree of crystallinity, intrinsic viscosity, etc., and has extremely high industrial value.

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

Note that the intrinsic viscosity, crystallinity, and particle size distribution were determined as follows.

(1) Intrinsic viscosity sample 11 was dissolved in 0CP (o-chlorophenol) solvent 100
The value of the reduced viscosity measured at a constant temperature of 35°C using an improved Ubbelohde capillary viscometer is converted to the intrinsic viscosity.
This value was measured using a sample that was re-bath melted at 0°C for 1 minute.

(2) Crystallinity Calculated using a pitanometer using the density method 9 using the following calculation formula.

mo゛ Vicnometer (g) m6 Vicnometer 10 samples (2) mt, Pycnometer 10 samples (li) msl Vicnometer 10 samples (li) Pz
Specific gravity of solvent (2/s) Ethanol was used as the density measurement solvent, and Pz =
A directivity of 0.7893 (?/cA) was used.

Crystallinity α is calculated using a known formula %formula%) Measurements were made using various mesh sieves.

Examples 1 to 13 100 Mfj (parts) of dimethyl terephthalic acid, 68 parts by weight of ethylene glycol, and 0.5 parts by weight of manganese acetate are heated to a temperature of 140 to 220°C under a nitrogen atmosphere, and the generated methanol is continuously discharged from the system. After performing a transesterification reaction for 2.5 hours while distilling off, 0.03 parts by weight of trimethyl phosphate and 0.5 parts by weight of titanium dioxide were added to the transesterification reaction.
1 part by weight and 0.05 part by weight of antimony trioxide were added.

Next, the temperature of this transesterified product was raised to 295°C, excess ethylene glycol was distilled off, and then the transesterification product was heated to 295°C.
The polycondensation reaction was carried out under a reduced pressure of 5 ml and 11 Hg for 0.15 hours with stirring.

The obtained polycondensate had a melt viscosity of 12 voids when melted at 275°C, and when it was taken out in a nitrogen atmosphere and slowly cooled, it became a relatively brittle solid. This thing has an intrinsic viscosity of U0.15, crystallinity of 15%, and density of 1.350? /c! Met.

The polyethylene terephthalate resin thus obtained was added to ε-caglolactam heated to 220° C. at the ratio shown in the attached table while stirring, and dissolved by heating for about 10 minutes. After dissolution, this bath liquid was added dropwise to the precipitation solvent shown in the table while stirring, and was cooled to room temperature to cause crystallization to obtain a fine powder dope. This dope was filtered, further washed with a precipitation solvent, and subjected to a drying process to obtain intermediate polyethylene terephthalate fine powder.

Next, the polyethylene terephthalate fine powder was transferred to a solid phase polymerization apparatus, and 501
After drying at 140°C for 2 hours under a reduced pressure of 1Hg,
The temperature was raised to 230° C., and a solid phase polymerization reaction was carried out under a reduced pressure of 1.0 IIIHg for the times shown in the table to obtain a final product fine powder. The measured values of this fine powder are shown in the table. The intrinsic viscosity of this fine powder is 0.51, and the crystallinity is 92.
%, the density is 1.456 f/cA.

For comparison, a fine powder was produced using the raw material polyethylene terephthalate resin of the example by a conventional pulverization method using a mill. The intrinsic viscosity of this fine powder is Q, 1
5. Crystallinity is 53mm, density is 1.347F, /c! Met.

Comparative Examples 1 to 3 An attempt was made to obtain intermediate polyethylene terephthalate resin fine powder in exactly the same manner as in Example 5, except for using the raw material polyethylene terephthalate resin having an intrinsic viscosity as shown in the attached table and the precipitation solvent. Almost no body was obtained, and a solid lump was obtained. Since this product has a relatively high intrinsic viscosity, the final product, L, and various physical properties were measured using this intermediate. The results are shown in the table.

Comparative Example 4 An attempt was made to obtain intermediate polyethylene terephthalate resin fine powder in exactly the same manner as in Example 2, except that the blending ratio of the raw material polyethylene terephthalate resin and ε-cabrolactam was changed as shown in the attached table. was not obtained at all, and a solid lump was obtained. This product was used as a final product, and its physical properties were measured. The results are shown on the cloth.

Procedural amendment October 14, 1985, Licensing Office Officer Black 1) Mr. Akihiro 1, Indication of the case 1985 Patent Application No. 240571 2, Name of the invention Resin fine powder book and its manufacturing method 3, Amendment Patent applicant 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture (OO3) Asahi Kasei Industries, Ltd. Representative Masaomi Seko 4, attorney 6, number of inventions increased by amendment 0 7, amendment Claims column 8 of the specification
, Contents of the amendment (1) The scope of the patent claims will be amended as shown in the attached sheet.

(2) On page 3, line 10 of the specification, "Polyethylene V-terephthanate resin" will be corrected to "Polyethylene Terephthane-7 resin."

(3) "Solid viscosity" in line 5 of page 7 will be corrected to "intrinsic viscosity."

(4) On page 8, lines 14-15, "polyethylene terephthal resin" has been corrected to "polyethylene terephthal resin."

(5) On page 14, lines 11-12, "Polynitride terephthalate resin" has been corrected to "Polynitride terephthalate resin."

Claim 1: A fine resin powder having an average particle size of 20 μm or less and made of a polyethylene tenfuta v-) resin having an intrinsic viscosity of less than 02 and a crystallinity of 60% or more.

2. The fine resin powder according to claim 1, which has an average particle size of 10 μm or less, a maximum particle size of 20 μm or less, has a dusty and smooth surface, and is substantially spherical.

3. A raw material polyethylene terephtha v-) type resin having an intrinsic viscosity of less than 0.3 is converted into a polyethylene terephthalate resin having a general formula (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
(n is an integer of 1 to 12) and crystallize the resulting intermediate resin powder. Resin fine powder with an average particle size of 20 μm or less, consisting of a polyethylene terephtha V-) resin with an intrinsic viscosity of less than 07 and a crystallinity of 60% or more, characterized by solid phase polymerization at a temperature in the lower range of ~100°C. 7 manufacturing methods.

4. The manufacturing method according to claim 3, wherein the raw material polyethylene terephthalate resin has an intrinsic viscosity of less than 0.25.

5. The particles of the ultrafine resin powder obtained by solid phase polymerization have an average particle size of 10 μm or less, a maximum particle size of 20 μm or less, and have a smooth surface and are substantially spherical. Or the manufacturing method described in item 4.

Claims (1)

[Scope of Claims] 1. Fine resin powder having an average particle size of 20 μm or less and made of a polyethylene terephthalate resin with an intrinsic viscosity of less than 0.7 and a crystallinity of 60%. 2. The fine resin powder according to claim 1, which has an average particle size of 10 μm or less, a maximum particle size of 20 μm or less, has a smooth surface, and is substantially spherical. 3 The raw material polyethylene terephthalate resin with an intrinsic viscosity of less than 0.3 is prepared using the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R in the formula is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
(n is an integer of 1 to 12) and crystallize the resulting intermediate resin fine powder under reduced pressure or an inert gas atmosphere. A method for producing fine resin powder with an average particle size of 20 μm or less, consisting of a polyethylene terephthalate resin with an intrinsic viscosity of less than 0.7 and a crystallinity of 60% or more, characterized by solid-phase polymerization at a temperature in the range of ~100° C. . 4. The manufacturing method according to claim 3, wherein the raw material polyethylene terephthalate resin has an intrinsic viscosity of less than 0.25. 5. Particles of ultrafine resin powder obtained by solid phase polymerization have an average particle size of 10 μm or less, a maximum particle size of 20 μm or less, have a smooth surface, and are substantially spherical, or The manufacturing method according to item 4.