WO2018235716A1 - Release agent for polycarbonate resin - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition having excellent peelability and a polycarbonate resin release agent for a molded article of the resin composition. The present invention relates to a polycarbonate resin release agent characterized in that it contains a pentaerythritol tetra fatty acid ester which is composed of pentaerythritol and a fatty acid having a number of carbon atoms ranging from at 22 and containing a metal element Ca in an amount greater than or equal to 16 mg / kg.

Description

Release agent for polycarbonate resin

The present invention relates to a mold release agent for polycarbonate resin, a polycarbonate resin composition containing the mold release agent, and a molded article of the resin composition.

Conventionally, polycarbonate resins have excellent physical properties, transparency and heat resistance, and are widely used in electric and electronic parts, optical disc substrates, automobile parts and the like.

In addition, although the polycarbonate resin composition is used after being formed into a required shape by an injection molding method or the like, the shape of the molded product is complicated, and the molded product is often large. In some cases, it is difficult to mold, and further, there is a problem that deformation at the time of demolding, reduction in dimensional accuracy of the molded product due to internal strain, strength reduction, appearance defect and the like occur.

As a method for solving these problems, methods of blending fatty acid esters are widely known, and pentaerythritol fatty acid esters, glycerin fatty acid esters and the like are widely used. Patent documents 1 to 12 are disclosed as prior art in which fatty acid esters such as pentaerythritol fatty acid ester are used as a mold release agent, and although certain effects can be obtained, they are not sufficiently satisfactory from the viewpoint of mold releasability. The

Unexamined-Japanese-Patent No. 6-107920 JP 2001-192543 A Unexamined-Japanese-Patent No. 2001-342337 JP 2003-327818 A Unexamined-Japanese-Patent No. 2004-027105 Japanese Patent Application Laid-Open No. 2004-083850 JP 2004-137423 A JP 2004-137472 A JP 2005-042003 JP 2012-251013 JP, 2014-084428, A JP, 2014-189535, A

An object of the present invention is to provide a polycarbonate resin composition excellent in releasability and a release agent for polycarbonate resin used for a molded article of the resin composition.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest research in order to solve the said subject, this inventor discovered that the said subject was solved by adjusting the amount of metallic element Ca contained in pentaerythritol tetra fatty-acid ester. The present inventors have further studied based on these findings to complete the present invention. That is, the present invention consists of the following.
[1] Releasing for polycarbonate resin, characterized in that it contains pentaerythritol tetra fatty acid ester composed of pentaerythritol and fatty acid having 8 to 22 carbon atoms, and the content of metallic element Ca is 16 mg / kg or more. Agent.
[2] A polycarbonate resin composition comprising the polycarbonate resin and the release agent for a polycarbonate resin according to the above [1], and a molded article of the resin composition.
[3] The polycarbonate resin composition according to the above [2] and the resin composition, wherein the proportion of the releasing agent for polycarbonate resin is 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the polycarbonate resin Molded articles.
[4] The mold release agent for polycarbonate resin described in the above [1] is added to a polycarbonate resin (or resin composition) to improve or improve the releasability of the polycarbonate resin (or resin composition or a molded article thereof) how to.

The mold release agent for a polycarbonate resin of the present invention exhibits the effect of improving the releasability of a molded article of the resin composition and not losing the physical properties by being blended with the polycarbonate resin composition.

[Release agent for polycarbonate resin]
The mold release agent for polycarbonate resin of the present invention (hereinafter also referred to as "the mold release agent of the present invention") contains pentaerythritol tetrafatty acid ester composed of pentaerythritol and a fatty acid having 8 to 22 carbon atoms. .

A commercial item can be used as pentaerythritol which comprises the mold release agent of this invention, For example, pentarit, pentarit-TS (brand name; Hiroei Chemical Industries Co., Ltd. make), pentaerythritol (brand name; Mitsubishi Gas Chemical Company, Ltd.) And the like. Commercially available pentaerythritol may contain a condensate such as dipentaerythritol or tripentaerythritol as an impurity, but such pentaerythritol can also be used in the present invention.

The fatty acid constituting the release agent of the present invention is a fatty acid having 8 to 22 carbon atoms. The fatty acid may be either a saturated fatty acid or an unsaturated fatty acid. For example, caprylic acid, berargonic acid, capric acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearin Acid, nonadecyl acid, arachidic acid, henicosic acid, behenic acid, eicosapentaenoic acid, lignoceric acid, cerotic acid, montanic acid, elaidic acid, erucic acid, oleic acid, linoleic acid, linoleic acid, ricinoleic acid, hydroxystearic acid, isostearin An acid etc. are mentioned and a behenic acid, a stearic acid, a palmitic acid, myristic acid are preferable when the melting point of pentaerythritol tetra-fatty acid ester is considered. These may be used alone or in combination of two or more.

There are no particular restrictions on the raw materials from which the above fatty acids are derived, and there are no particular limitations, for example, vegetable fats and oils such as rapeseed oil, sunflower oil, corn oil, soybean oil, rice oil, safflower oil, cottonseed oil, coconut oil, palm oil and linseed oil, and beef tallow, Animal fats and oils such as pork fat and fish oil are mentioned.

The releasing agent of the present invention is a reaction product (esterification product) obtained by a reaction such as an esterification reaction of pentaerythritol with a fatty acid, or a transesterification reaction of pentaerythritol with a lower alcohol ester of a fatty acid. In the present invention, the reaction product obtained by any reaction may be used, but in consideration of productivity, it is preferable to adopt an esterification reaction.
The reactant is a mixture of unreacted fatty acid and pentaerythritol, pentaerythritol monofatty acid ester, pentaerythritol difatty acid ester, pentaerythritol trifatty acid ester, pentaerythritol tetrafatty acid ester and the like. The mold release agent of the present invention is pentaerythritol tetrafatty acid ester, but may be a mixture containing such pentaerythritol tetrafatty acid ester. When the release agent of the present invention is the mixture, the content of pentaerythritol tetrafatty acid ester is preferably 75% or more, more preferably 85% or more, and still more preferably 95% or more. .

The pentaerythritol tetra fatty acid ester content in the mixture containing pentaerythritol tetra fatty acid ester can be calculated, for example, by a binomial distribution function using the following arguments.
[argument]
Number of successes: 4
Number of trials: 4 (= pentaerythritol valence)
Success rate: Esterification rate (%)
The esterification rate (%) can be determined by the following equation.
Esterification ratio (%) = (saponification value-acid value) / (saponification value + hydroxyl value-oxidation value) x 100 "

The content of the metal element Ca contained in the releasing agent of the present invention (for example, pentaerythritol tetrafatty acid ester or a mixture containing pentaerythritol tetrafatty acid ester) is preferably 16 mg / kg or more (for example, 18 mg / kg or more). Is 20 mg / kg or more. It is preferable in order to exhibit the effect of this invention as it is said content.
The upper limit of the content of the metallic element Ca is not particularly limited, but when the content of the metallic element Ca is large, the physical properties of the polycarbonate resin composition containing the releasing agent and the molded article of the resin composition are lowered. Therefore, the content of the metal element Ca is preferably 100 mg / kg or less, more preferably 80 mg / kg or less (eg, 60 mg / kg or less), still more preferably 50 mg / kg or less, 45 mg / Kg or less (40 mg / kg or less, 35 mg / kg or less, 30 mg / kg or less, etc.).

There is no particular limitation on the method of setting the content of metallic element Ca to 16 mg / kg or more, and any known method can be adopted. For example, raw materials containing metallic element Ca (for raw materials such as pentaerythritol and fatty acid, Either the method of producing a reactant using metal element Ca by the production method etc., the method of using a catalyst containing metallic element Ca when producing a reactant, or the method of producing a reactant The method of adding the calcium salt etc. which contain metallic element Ca at a process, the method which combined the said method, etc. are mentioned.

Examples of the catalyst containing the metallic element Ca and the calcium salt containing the metallic element Ca include, for example, inorganic calcium salts such as calcium hydroxide, calcium oxide, calcium carbonate and calcium phosphate, calcium octanoate, calcium decanoate, calcium laurate, myristic acid Examples thereof include calcium salts of long chain fatty acids such as calcium palmitate, calcium stearate, calcium behenate, calcium oleate and calcium montanate. These may be used alone or in combination of two or more.

The content of the metal element (hereinafter also referred to as "other metal element") other than the metal element Ca contained in the release agent of the present invention is not particularly limited, but preferably 20 mg / kg or less, more preferably 10 mg / kg. It is at most kg, even more preferably at most 5 mg / kg. When the content of the other metal element is in the above range, the heat resistance, colorability and physical properties of the polycarbonate resin composition containing the releasing agent and the molded article of the resin composition are improved, which is preferable. In addition, as said other metal element, Na, Sn, Zn etc. are mentioned, for example. The content of these other metal elements is preferably such that each of the other metal elements is in the above range.

There is no particular limitation on the method of reducing other metal elements to 20 mg / kg or less, and known methods can be adopted. For example, the reaction product is selected from raw materials containing or not containing other metal elements. Method of preparation, method of not using a catalyst containing other metal elements when preparing a reactant, method of removing other metal elements in any step of preparing a reactant, combining the above methods with other methods And the like, and the like.

As the method for producing the release agent of the present invention, known methods are adopted as described above. For example, as the production method by esterification reaction, the following method can be exemplified.
For example, as a method of producing using a catalyst containing metallic element Ca, the following method may be mentioned.
In a normal reaction vessel equipped with a stirrer, a jacket for heating, a nitrogen introducing pipe, a moisture measuring pipe, an air-cooling pipe, etc., pentaerythritol and fatty acid are charged, a catalyst containing metallic element Ca is added, and mixed by stirring. Under an atmosphere, dipentaerythritol tetra fatty acid ester containing metallic element Ca is obtained by heating at a predetermined temperature using a temperature controller while removing water generated by the esterification reaction out of the system.
Here, the feed molar ratio of the fatty acid is preferably 3.5 to 4.5 moles, more preferably 3.8 to 4.0 moles with respect to 1.0 mole of pentaerythritol. The amount of the catalyst containing the metallic element Ca is preferably 0.0016 to 0.010% by mass as a Ca element in the catalyst containing the metallic element Ca based on the total amount of pentaerythritol and fatty acid used. Preferably, it is 0.0020 to 0.0070% by mass. The reaction temperature is usually in the range of about 190 to 250 ° C., preferably in the range of about 210 to 240 ° C. The reaction pressure conditions may be under reduced pressure or normal pressure. The end point of the reaction is usually determined by measuring the acid value of the reaction mixture and about 3.0 or less.

For example, as a method of producing using a calcium salt containing metallic element Ca, the following method may be mentioned.
In a normal reaction vessel equipped with a stirrer, a jacket for heating, a nitrogen introducing pipe, a water measuring pipe, an air cooling pipe, etc., pentaerythritol and fatty acid are charged, and a catalyst containing no metallic element Ca is added or not, Stir and mix, heat at a predetermined temperature using a temperature controller while removing water generated by the esterification reaction out of the system under a nitrogen gas atmosphere, and then, if necessary, neutralize, treat with an adsorbent, and filter As a result, the esterification reaction product (esterification product) is obtained. Thereafter, a calcium salt of long-chain fatty acid is added in the range of 80 to 160 ° C. of the obtained reaction product to obtain pentaerythritol tetra fatty acid ester containing metallic element Ca.
Here, conditions such as the feed molar ratio of fatty acid, reaction temperature, reaction pressure conditions, end point of reaction and the like can be exemplified the same conditions as described in the method of producing using a catalyst containing metallic element Ca.

In each of the above methods, the amount of the catalyst containing no metallic element Ca is 0.01 to 1% by mass, preferably 0.05 to 0.2%, based on the total amount of pentaerythritol and fatty acid used. %.
The catalyst containing no metallic element Ca is not particularly limited, but tin catalysts such as tin (II) oxide, tin (II) octylate, dibutyltin dilaurate (IV), dibutylthitin oxide (IV), titanium Metal-based catalysts such as titanium catalysts such as tetraisopropoxide and titanium tetra-n-butoxide can be mentioned. One or more of these may be used in combination.

The reactant (esterification product) obtained by the esterification reaction is optionally subjected to excess fatty acid in the esterification product, unreacted pentaerythritol, or the ester reaction by a method such as molecular distillation or chromatography. It is also possible to remove the water etc. generated in
As the molecular distillation method, for example, a falling film type molecular distillation machine or a centrifugal molecular distillation machine may be used. Specifically, first, usually, a temperature of about 100 to 200 ° C. and a vacuum condition of about 20 to 10 Pa The low-boiling compounds such as water are removed under the following conditions, and then the unreacted fatty acid etc. is removed as a fraction under high vacuum conditions, usually about 200 ° C. to 300 ° C. and high vacuum conditions of about 10 Pa to 0.1 Pa. Product can be obtained.

When it is desired to reduce the content of the other metal element of the reactant obtained by the esterification reaction, a treatment for removing the other metal element can be performed. Specifically, there is a treatment method in which other metal elements are removed by adsorbent treatment, neutralization treatment, and the like. As a specific example of the adsorbent treatment, an adsorbent containing aluminum silicate, magnesium silicate, magnesium oxide, aluminum hydroxide and the like is added in any of the production steps, optionally mixed by heating, and then the adsorbent is filtered. The removal method etc. are mentioned.

Here, the addition amount of the adsorbent is not particularly limited, but, for example, 0.1 to 5 parts by mass with respect to 100 parts by mass of the substance containing another metal element, and the adsorption treatment in the case of heating and mixing if desired The temperature may be, for example, 70 to 100 ° C., and the treatment time of the adsorption treatment may be, for example, 0.5 to 3.0 hours. As a specific example of the said adsorption agent, Kyo Ward 200, Kyo Ward 700 (a brand name; Kyowa Chemical Industry Co., Ltd. make), etc. are mentioned.

The acid value of the release agent of the present invention is not particularly limited, but is preferably 3.0 mg KOH / g or less, more preferably 1.5 mg KOH / g or less from the viewpoint of physical properties and heat resistance.
The hydroxyl value of the releasing agent of the present invention is not particularly limited, but is preferably 0.1 to 30 mg KOH / g, more preferably 0.5 to 20 mg KOH / g, and more preferably 1 to 10 mg KOH / g from the viewpoint of physical properties and heat resistance. g is even more preferred.

[Polycarbonate Resin Composition and Molded Article of the Resin Composition]
The polycarbonate resin used in the polycarbonate resin composition of the present invention may be obtained by the phosgene method in which dihydric phenol and phosgene are reacted, or the transesterification method in which dihydric phenol and carbonate ester such as carbonate precursor are reacted. It is union. Specifically, reaction of dihydric phenol and phosgene, transesterification of dihydric phenol and diphenyl carbonate, and the like can be mentioned.

As the above dihydric phenol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, Bis (4-hydroxyphenyl) alkanes such as 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane; bis (4-hydroxyphenyl) cycloalkanes, bis (4) -Hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone Etc. These dihydric phenols may be homopolymers of one type or copolymers of two or more types.

Examples of the carbonate precursor include carbonyl halides, haloformates, and carbonates, and specific examples include phosgene, dihaloformates of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate.

The polycarbonate resin used in the present invention may have a branched structure, and as a branching agent for introducing the branched structure, for example, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′ , Α ''-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 1- [α-methyl-α- (4'-hydroxyphenyl) ethyl] -4- [α ', α' And -bis (4 ′ ′-hydroxyphenyl) ethyl] benzene, phloroglucin, trimellitic acid, and isatin bis (o-cresol).

The viscosity average molecular weight of the polycarbonate resin used in the present invention is usually 10,000 to 100,000, preferably 10,000 to 40,000, from the viewpoint of the physical properties of the resin composition.

The addition amount of the release agent of the present invention used in the polycarbonate resin composition of the present invention is 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate resin from the viewpoint of releasability, moldability, physical properties, etc. -3.0 parts by mass is preferable, and 0.2-2.0 parts by mass is more preferable.

In the polycarbonate resin composition of the present invention, other additives that are generally used in polycarbonate resin compositions can be blended, as long as the effects of the present invention are not impaired. As other additives, for example, release agents other than the release agent of the present invention, weathering agents, UV absorbers, fluidity improvers, antistatic agents, inorganic fillers, flame retardants, flame retardant aids, coloring Agents, antibacterial agents, compatibilizers and the like.

Other resins or elastomers may be added to the polycarbonate resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of other resins include polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate and polybutylene terephthalate. Etc., acrylonitrile / styrene-acrylonitrile resin, styrene resin such as acrylonitrile / butadiene / styrene copolymer, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin And polymethacrylate resin, silicone resin, phenol resin, epoxy resin and the like. Examples of the elastomer include acrylic elastomers, olefin elastomers, polyester elastomers, polyamide elastomers, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, methyl methacrylate / styrene / butadiene rubber, methyl methacrylate / acrylonitrile / Styrene rubber etc. are mentioned.

As a molding method of the polycarbonate resin composition of the present invention, a polycarbonate resin, the mold release agent of the present invention, and optionally, other additives, other resins, elastomers, etc. are blended, and premixed with a ribbon blender, drum tumbler, etc. Then, they are pelletized by kneading with a single-screw or multi-screw extruder, Henschel mixer, Banbury mixer, etc., then injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum A method of forming a molded article by a molding method, a foam molding method or the like can be mentioned. The heating temperature at the time of kneading and molding is preferably 240 to 300.degree.

The molded article of the polycarbonate resin composition of the present invention thus obtained can be used as an optical material such as an optical disc substrate, a copier, a facsimile, a television, a radio, a tape recorder, a video deck, a personal computer, a printer, a telephone, an information terminal , OA equipment such as refrigerators and microwaves, home appliances, electric and electronic equipment parts, etc.

The invention will now be described by way of example, which is merely illustrative of the invention and is not limiting.

<Preparation of mold release agent for polycarbonate resin>
[Preparation of pentaerythritol tetra fatty acid ester 1]
In a four-necked flask equipped with a temperature controller, a nitrogen inlet tube, a stirrer and a cooling tube, 184.0 g of pentaerythritol (trade name: Pentalite TS; manufactured by Hiroei Kagaku Co., Ltd.), stearic acid 300 (trade name: Shin Nippon Rika Co., Ltd.) 1060.8 g and palmtic acid 98 (trade name; manufactured by Natural Oleo) were added thereto, and 0.088 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst. These are reacted at normal pressure until the acid value becomes 3.0 or less while distilling off the reaction water at 235 ° C. under a nitrogen stream, and then cooled to 80 ° C. to obtain 1400 g of pentaerythritol tetra fatty acid ester 1 I got Pentaerythritol tetrafatty acid ester 1 corresponds to an example of the present invention.
The contents of the metal elements Ca, Na and Sn of the pentaerythritol tetra-fatty acid ester obtained by the above method are summarized in Table 1. The acid value (mg KOH / g), hydroxyl value (mg KOH / g), saponification value (mg KOH / g), esterification ratio (%) and tetraester content (%) are also shown in Table 1. Further, the above-mentioned items of pentaerythritol tetra fatty acid esters 2 to 7 described later are also shown in Table 1.
The contents of the metallic elements Ca, Na and Sn were measured by acid decomposition-inductively coupled plasma emission spectrometry (ICP-AES method) using an ICP emission analyzer (ICPE-9800 manufactured by Shimadzu Corporation). It is a thing. In addition, metal elements other than the above, such as Zn can be measured in the same manner.
Furthermore, the acid value and the hydroxyl value are [2.3.1-2013 acid value] and [2.3.6.2-1996] of "Standard oil and fat analysis test method (I)" (The Japan Oil Chemistry Association edition). It was measured in accordance with the hydroxyl value].
In addition, the saponification value is measured in accordance with [3.3.2-1996 Saponification value] of "Standard Oil and Fat Analysis Test Method (I)" (The Japan Oil Chemistry Society ed.), And the esterification ratio is And tetra-ester content rate is computed by said Formula and method.

[Preparation of pentaerythritol tetra fatty acid ester 2]
In the preparation of pentaerythritol tetra-fatty acid ester 1, 187.8 g of pentaerythritol (trade name: Pentalite TS; manufactured by Hiroe Kagaku Co., Ltd.) and 187.8 g, stearic acid 300 (trade name; manufactured by Shin Nippon Rika Co., Ltd.) 1060.8 g In the same manner as in Example 9 except that .9 g and 355.2 g of palmitic acid 98 (trade name; manufactured by Natural Oleo) were changed to 847.3 g, 1400 g of pentaerythritol tetrafatty acid ester 2 was obtained. Pentaerythritol tetra fatty acid ester 2 corresponds to an example of the present invention.

[Method of producing pentaerythritol tetra fatty acid ester 3]
In the preparation of pentaerythritol tetra-fatty acid ester 2, 1400 g of pentaerythritol tetra-fatty acid ester 3 was obtained in the same manner except that 0.088 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 0.060 g. . Pentaerythritol tetra fatty acid ester 3 corresponds to an example of the present invention.

[Method of producing pentaerythritol tetra fatty acid ester 4]
In a four-necked flask equipped with a temperature controller, a nitrogen inlet tube, a stirrer and a cooling tube, 188.8 g of pentaerythritol (trade name: Pentalite TS; manufactured by Koei Chemical Co., Ltd.), and stearic acid 300 (trade name: Shin Nippon Rika Co., Ltd.) 1059.2 g and Myristic acid 98 (trade name; manufactured by Natural Oleo) were added, and 0.088 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst. These are reacted at normal pressure until the acid value becomes 3.0 or less while distilling off reaction water at 235 ° C. in a nitrogen stream, and then cooled to 80 ° C. to obtain 1400 g of pentaerythritol tetra fatty acid ester 4 I got Pentaerythritol tetra fatty acid ester 4 corresponds to an example of the present invention.

[Method of producing pentaerythritol tetra fatty acid ester 5]
In a four-necked flask equipped with a temperature controller, a nitrogen inlet tube, a stirrer and a cooling tube, 172.8 g of pentaerythritol (trade name: Pentalite TS; manufactured by Koei Chemical Co., Ltd.), and stearic acid 300 (trade name: Shin Nippon Rika Co., Ltd.) 1120 g and benjonic acid (trade name: Behenic acid-85; manufactured by Godrej) were added, and 0.088 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst. These are reacted at normal pressure until the acid value becomes 3.0 or less while distilling off reaction water at 235 ° C. in a nitrogen stream, and then cooled to 80 ° C. to obtain 1400 g of pentaerythritol tetra fatty acid ester 5 I got Pentaerythritol tetra fatty acid ester 5 corresponds to an example of the present invention.

[Preparation of pentaerythritol tetra fatty acid ester 6]
In a four-necked flask equipped with a temperature controller, a nitrogen inlet tube, a stirrer and a cooling tube, 184.0 g of pentaerythritol (trade name: Pentalite TS; manufactured by Hiroei Kagaku Co., Ltd.), stearic acid 300 (trade name: Shin Nippon Rika Co., Ltd.) 1060.8 g and palmitic acid 98 (trade name; manufactured by Natural Oleo) were added, and 0.8 g of tin oxide (trade name: manufactured by Wako Pure Chemical Industries, Ltd.) was added as a catalyst. These were reacted at normal pressure until the acid value became 1.0 or less while distilling off the reaction water at 235 ° C. in a nitrogen stream, and then cooled to 130 ° C. As neutralization treatment, 1.376 g of 85% phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed for 30 minutes, followed by cooling to 90 ° C. Furthermore, Kyo Ward 200 (trade name: manufactured by Kyowa Chemical Industry Co., Ltd., aluminum hydroxide adsorbent) and Kyo Ward 700 (trade name; manufactured by Kyowa Chemical Industries, aluminum silicate adsorbent) as treatments for removing metal elements After adding 3.2 g of each and stirring and mixing for 30 minutes, 1400 g of pentaerythritol tetra fatty acid ester 6 was obtained by removing the said adsorption agent by filtration. Pentaerythritol tetra fatty acid ester 6 corresponds to a comparative example of the releasing agent of the present invention.

[Preparation of pentaerythritol tetra fatty acid ester 7]
In the preparation of pentaerythritol tetra-fatty acid ester 2, 187.8 g of pentaerythritol (trade name: Pentalite TS; manufactured by Hiroei Kagaku Co., Ltd.) is added to 188.8 g of pentaerythritol (trade name: Pentalit; manufactured by Hiroei Kagaku Co.) Trade name: manufactured by Shin Nippon Rika Co., Ltd.) at 564.9 g at 1056.0 g, and palmitic acid 98 (trade name; manufactured by Natural Oleo) at 845.2 g at 355.2 g, and no catalyst was used. The same procedure was repeated to obtain 1400 g of pentaerythritol tetra fatty acid ester 7. Pentaerythritol tetra fatty acid ester 7 corresponds to a comparative example of the releasing agent of the present invention.

<Production of Polycarbonate Resin Composition and Molded Article of the Resin Composition>
(1) Raw material polycarbonate resin (trade name: Panlite L-1225Y; manufactured by Teijin Chemicals Ltd.)
Pentaerythritol tetra-fatty acid ester 1 to 7 (obtained by the above method)

(2) Blending of Polycarbonate Resin Composition Table 2 shows the blending composition of the polycarbonate resin composition produced using the above-mentioned raw materials and the molded product of the resin composition. The polycarbonate resin compositions 1 to 5 are examples, the polycarbonate resin compositions 6 and 7 are comparative examples, and the polycarbonate resin composition 8 is a reference example.

<Method of Producing Polycarbonate Resin Composition>
Twenty times the amount of the raw materials listed in Table 2 are extruded by melt-kneading using a twin-screw extruder (type: TP20-T; manufactured by Thermo Plastics Co., Ltd.) equipped with a strand die at a molding temperature of 280 ° C. The product was cut into pellets and dried in a thermostat (model: GPHH-201; manufactured by ESPEC Corporation) at 120 ° C. for 5 hours to obtain polycarbonate resin compositions 1 to 8 in pellet form.

<Preparation of Molded Article of Polycarbonate Resin Composition and Its Evaluation>
(1) Releasability evaluation Mold and injection molding machine equipped with a mold release force evaluation device (manufactured by FUTABA CORPORATION) with about 60 g of any one of polycarbonate resin compositions 1 to 8 (model: IS 55 EPN; manufactured by Toshiba Machine Co., Ltd.) Using the following mold processing conditions to produce molded articles of the cup-shaped polycarbonate resin compositions 1 to 8 respectively, and measuring the force (mold release force) required when the molded article is removed from the mold with a projecting pin did. The measurement was performed 10 times and it was made the average value. As the mold release force, the smaller the value, the better the mold release property. The average value obtained was symbolized by the following evaluation criteria. The results are shown in Table 3.
(Molding condition of injection molding machine)
Molding temperature: NH / H1 / H2 / H3 = 300 ° C./300° C./280° C./260° C.
Injection pressure: 89MPa
Holding pressure: 30MPa
Back pressure: 2 MPa
Screw rotation speed: 100 rpm
Mold temperature: 80 ° C
Cooling time: 30 seconds (evaluation criteria)
○: The release force is less than 30 kg.
Δ: 30 kg or more and less than 50 kg of mold release force.
X: The mold release force is 50 kg or more.

(2) Evaluation of physical properties (tensile strength) About 50 g of any of polycarbonate resin compositions 1 to 8 was tested using an injection molding machine (model: IS 55EPN; manufactured by Toshiba Machine Co., Ltd.) under the following molding conditions Piece-shaped molded articles (dumbbell-shaped test pieces) were respectively produced, and physical properties of molded articles of polycarbonate resin compositions 1 to 8: a tensile test (JIS K-7161) was performed. The measurement was carried out five times, and the maximum point stress at the time of tensile test was taken as an average value as an index of physical properties. The maximum point stress indicates that the higher the value, the higher the strength of the molded article. The average value obtained was symbolized by the following evaluation criteria. The results are shown in Table 3.
(Molding condition of injection molding machine)
Molding temperature: NH / H1 / H2 / H3 = 300 ° C./300° C./280° C./260° C.
Injection pressure: 89MPa
Holding pressure: 30MPa
Back pressure: 2 MPa
Screw rotation speed: 100 rpm
Mold temperature: 80 ° C
Cooling time: 30 seconds (evaluation criteria)
:: The decrease in tensile maximum point stress is less than 3.0 MPa as compared with the case where no release agent is added.
Δ: The decrease in maximum tensile stress is 3.0 or more and less than 5.0 MPa as compared with the case where no release agent is added.
X: The reduction of the tensile maximum point stress is 5.0 MPa or more as compared with the case where no release agent is added.

　結果より、本発明の離型剤（ペンタエリスリトールテトラ脂肪酸エステル１～５）を用いたポリカーボネート樹脂組成物１～５の成形品は、離型性を向上することができた。また、物性（引っ張り強さ）を維持することもできた。
　一方、離型剤としてペンタエリスリトールテトラ脂肪酸エステル６を用いたポリカーボネート樹脂組成物６の成形品は、物性（引っ張り強さ）を維持しているが、離型性を向上することはできなかった。また、離型剤としてペンタエリスリトールテトラ脂肪酸エステル７を用いたポリカーボネート樹脂組成物７の成形品は、離型性を向上することはできず、更に物性（引っ張り強さ）を維持できなかった。

From the results, molded articles of polycarbonate resin compositions 1 to 5 using the mold release agent (pentaerythritol tetra fatty acid ester 1 to 5) of the present invention were able to improve the mold releasability. In addition, physical properties (tensile strength) could be maintained.
On the other hand, although the molded article of the polycarbonate resin composition 6 using pentaerythritol tetra fatty acid ester 6 as a mold release agent maintains physical properties (tensile strength), it was not possible to improve the mold release property. Moreover, the molded article of polycarbonate resin composition 7 using pentaerythritol tetra-fatty acid ester 7 as a mold release agent can not improve the releasability and can not maintain physical properties (tensile strength).

According to the present invention, a mold release agent for polycarbonate resin and the like can be provided.

Claims (2)

A mold release agent for a polycarbonate resin, comprising pentaerythritol tetrafatty acid ester composed of pentaerythritol and a fatty acid having 8 to 22 carbon atoms, and having a content of metal element Ca of 16 mg / kg or more. A polycarbonate resin composition comprising the polycarbonate resin and the mold release agent for polycarbonate resin according to claim 1 and a molded article of the resin composition.