JPH07252352A - Branched polylactone and branched polylactone composition - Google Patents

Abstract

PURPOSE:To obtain a polylactone and a polylactone composition each of which has high melt tension and improved moldability. CONSTITUTION:This polylactone is the one obtained by effecting the ring opening polymerization of a lactone by using an at least trifunctional initiator, having a molecular weight of 10000 or above and showing a load of 0.15g or above when the resin flowing out of the 1mmphi orifice of a capillary type rheometer at 120 deg.C is taken up at a draw-down ratio of 50. The composition in the title is the one containing at least 1wt.%, based on the total resin, of this branched polylactone. The composition is molded into a molding.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention contains a polylactone composition having improved moldability, more specifically, by containing a branched polylactone, for example, thermoforming such as blow molding or vacuum molding, and other resins. The present invention relates to a polylactone composition exhibiting excellent moldability during melt kneading.

[0002]

2. Description of the Related Art In general, polylactones represented by polycaprolactone are not limited to raw materials such as urethane resins, but also polycarbonate resins, polyterephthalate resins,
In order to improve the fluidity and the appearance of ABS resin and the like, they have been melt-kneaded or polylactone alone has been used for various molded articles and molding materials. Further, recently, the biodegradability of polylactone has come to the fore, and it has come to be used alone or in a mixture with other thermoplastic resins for a wide range of applications such as bottles, films and fibers.

[0003]

However, polylactone represented by polycaprolactone has a low melt tension as compared with other thermoplastic resins having a high molding temperature, and it is difficult to melt-knead with such a resin. When the blended product is blow-molded or vacuum-molded, there is a problem that excessive drawdown is likely to occur, uneven thickness is generated in the molded product, and air bubbles are easily mixed in the molded product. Further, even in the case of molding polylactone alone, in the case of conventional linear polylactone, since the melt tension is low, there are various restrictions such as severe restrictions on molding conditions and poor production efficiency. It was very limited.

For practical use, it was indispensable to raise the melt tension significantly. In order to increase the melt tension of polylactone, it is considered desirable to apply a general method that is also applied to thermoplastic polyesters and polycarbonates, for example, a method using a high degree of polymerization polymer or a method using a branched polymer. To be

However, in order to obtain a linear high-polymerization degree polylactone, it is necessary to set the molar amount of the monofunctional or bifunctional initiator to the lactone monomer to an extremely small amount and a precise molar ratio. It is necessary to make the amount of water contained in the monomer extremely small.

In fact, there is no report that the melt tension of the polylactone is increased by spending such an effort, for example, Japanese Patent Publication Nos. 40-23917 and 40-26.
557, JP-B-40-14739 and JP-A-56-4.
Although 9728 and the like describe highly polymerized polylactone, there is no description about melt tension.

Regarding the possibility of using the other branched polymer, for example, Japanese Patent Publication No. 34-529.
3, Japanese Patent Publication 41-19559 and Japanese Patent Publication 47-137
There is a description of a branched polylactone polymerized by using a trifunctional or higher functional initiator such as glycerin or pentaerythritol such as 83, but this polylactone is an oligomer having a molecular weight of 10,000 or less and is very meltable. The tension was not satisfactory.

[0008]

Therefore, the inventors of the present invention have diligently studied to solve the above-mentioned problems, and as a result, 3
Using a functional or more initiator, and by using a branched polylactone polymerized until reaching a sufficiently high degree of polymerization, alone or if necessary, by linear kneading with a linear polylactone and / or other thermoplastic resin by melt-kneading, The melt tension at the time of high temperature molding is high, and therefore, for example, in thermoforming such as blow molding and vacuum forming, a molded product having a small drawdown and no uneven thickness or bubbles can be easily obtained with good workability.

That is, the present invention "is obtained by ring-opening polymerization of a lactone monomer from a trifunctional or higher-functional polyfunctional initiator, has a molecular weight of 10,000 or more, and has a diameter of 1 mm at 120 ° C using a capillary rheometer. When the resin flowing out from the orifice of No. 2 is dropped and the ratio is 50, the load is 0.
The present invention provides a "branched polylactone having a weight of 15 g or more", a "polylactone composition", and a "molded product".

It is essential that the branched polylactone of the present invention has a molecular weight of 10,000 or more, preferably 50,000 or more, and more preferably 70,000.
It is about 0 to 200,000. If the molecular weight is less than 10,000, the melt tension is low and drawdown is likely to occur. On the contrary, it is difficult to produce a polymer having a molecular weight of more than 200,000. The molecular weight is measured using gel permeation chromatography.

The branched polylactone of the present invention has a molecular weight of 10,
And a resin rheometer having a diameter of 1 mm at a temperature of 120 ° C. and having a ratio of 50 and a load of 0.
It is essential that the amount is 15 g or more.

The lactone monomers that can be used in the present invention include δ-valerolactone, ε-caprolactone, 7-hydroxyheptanoic acid lactone, 8-hydroxyoctanoic acid lactone, 12-hydroxydodecanoic acid lactone and 13-hydroxytridecanoic acid. Lactone, 14
-Hydroxytetradecanoic acid lactone, 15-hydroxypentadecanoic acid lactone and their alkyl and alkoxy derivatives. Furthermore, 3-ethyl-2-keto 1,4-dioxane, 1,4-dioxane-
Dioxane such as 2-one is also applied.

These lactone monomers may be used alone or in combination with 2.
It can also be used as a mixture of two or more species. Of these lactone monomers, ε-caprolactone, methylated caprolactone, δ-valerolactone, which have the greatest practical value, and 3
-Ethyl-2-keto-1,4-dioxane and the like are preferably used.

The polyfunctional initiator for producing the branched polylactone of the present invention is a compound or polymer containing three or more active hydrogens such as hydroxyl group, amino group, carboxyl group and thiol group in the molecule. Glycerin,
Radicals in the molecule such as trimethylolpropane, trimethylolethane, pentaerythritol, pyrogallol, oxyhydroquinone, aminopropanediol, erythrose, malic acid, tartaric acid, pentaerythritol-tetramercaptoacetate, 2-ethylhydroxy (meth) acrylate. Oligomers of compounds having both a polymerizable double bond and a hydroxyl group, copolymers with other radically polymerizable monomers and graft modified products on various polymers, ethylene oxide, graft modified products on various polymers of propylene oxide, Examples thereof include sugar, starch, cellulose, and polybutadiene having a hydroxyl group.

The method for producing a branched polylactone by ring-opening polymerization of a lactone monomer using a polyfunctional initiator is not particularly limited, but a polyfunctional initiator and, if necessary, a bifunctional initiator such as ethylene glycol can be used. Generally in the presence of 80 to 230 ° C, preferably 100 to 200 ° C
It is desirable to add 0.1 to 1000 ppm, preferably 1 to 200 ppm of the metal catalyst at the temperature of 1, and ring-opening polymerize the lactone monomer. When the reaction temperature is lower than 80 ° C., the reaction rate is slow, and when it is higher than 230 ° C., coloring due to the oxidation reaction or decomposition reaction of the resulting polymer is unfavorable.

The molecular weight is adjusted by adjusting the charged molar ratio of the lactone monomer and the polyfunctional initiator. The amount of water present in the lactone monomer is 0.1% or less, preferably 0.01%, more preferably 0.005.
It is desirable to add a polyfunctional initiator after adjusting the amount to 1% or less.

As the metal catalyst, in addition to a tin catalyst and a titanium-based catalyst, a compound such as aluminum, aene, molybdenum, zirconium, an alkali metal, an alkaline earth metal, or a lanthanoid is used. In particular, a monobutyltin compound,
Stannous chloride, tetrabutyl titanate and the like are preferable from the viewpoint of easy handling and polymerizability.

When the amount of the catalyst is less than 0.1 ppm, the reaction rate is slow, and when it exceeds 1000 ppm, the hue and thermal stability of the polylactone produced are unfavorable.

Further, in the method for producing a branched lactone,
Any polymerization method such as bulk polymerization, solution polymerization and suspension polymerization can be used without problems.

As the organic solvent which can be used for solution polymerization,
Aromatic hydrocarbons such as toluene and xylene are preferable because they are inert to the reaction and have a relatively high boiling point.

The solvent is preferably substantially anhydrous.

The type of the production apparatus for the branched polylactone is not particularly limited. For example, batch type, semi-continuous and continuous ordinary stirring type reactors, kneader type reactors, screw extruder type reactors, sulzer mixer type reactors and the like can be used without problems. Further, the pressure and gas atmosphere in the reaction system are not particularly limited, and the reaction can be arbitrarily performed under the conditions of an atmosphere such as an inert gas such as 0.01 Torr to 10 atm nitrogen and air. The branched polylactone in the present invention is mixed with the linear polylactone and / or other thermoplastic resin in an arbitrary ratio of 1% or more by an arbitrary method. When the proportion of the branched polylactone in the total resin is 1% by weight or less, there is almost no effect of improving the moldability, which is not preferable. Usually, in order to improve moldability, the proportion of branched polylactone in the total polylactone is 10% by weight or more, and the proportion of branched polylactone in the total polylactone is 3% when mixed with other thermoplastic resin.
It is preferably 0% by weight or more and the proportion of the branched polylactone in the whole resin is 1% by weight or more, more preferably 30% by weight, 50% by weight or 2% by weight or more.
As the mixing method, for example, first, a branched polylactone is produced and then melt-kneaded with another resin, a polyfunctional initiator in the present invention and, if necessary, a bifunctional initiator such as ethylene glycol is added as a lactone monomer or Generally, a method of mixing with a metal catalyst and directly melt-kneading with another thermoplastic resin, and a method of copolymerizing with another monomer capable of forming a condensation-type polymer.

The polylactone composition of the present invention contains a branched polylactone as an essential component, and optionally a linear polylactone by ring-opening polymerization of a lactone monomer from a monofunctional initiator such as butanol and a bifunctional initiator such as ethylene glycol. Obtained.

Any other thermoplastic resin can be used. For example, thermoplastic polyester resin, polycarbonate resin, polystyrene resin, polyacrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, etc. are compatible with polylactone. Other preferred examples include polyamide resins, polyolefin resins such as polyethylene and polypropylene, polyphenylene oxide resins, polyether resins, and various copolymer resins.

The thermoplastic polyester resin is a glycol component having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butanediol,
Examples of glycols such as neopentyl glycol and hexanediol and dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, maleic acid, succinic acid,
Polyester having a skeleton combined with a dicarboxylic acid such as adipic acid and, if necessary, other components such as lactoneoxycarboxylic acid, alcohol, trifunctional or higher polyhydric alcohol, carboxylic acid, trifunctional or higher polycarboxylic acid Is a polyester having a skeleton.

The polycarbonate resin is a polycarbonate produced by reacting a dihydric phenol such as bis A with phosgene (phosgene method) or by reacting a dihydric phenol with a carbonic acid ester (transesterification method).

The polystyrene resin is a polymer polymerized from styrene monomer and monomers such as acrylonitrile, butadiene, (meth) acrylic acid ester, and specifically, polystyrene resin, HIPS resin,
Examples include AS resin, ABS resin, MMA-styrene copolymer and the like. For the polylactone composition of the present invention, thermosetting resins such as epoxy resin, urethane resin and melanin resin, naturally occurring biodegradable polymers such as starch and cellulose, modified products thereof, and glass fiber , Talc, mica, silica, titanium oxide, aluminum oxide, inorganic fillers such as metal powder, and further optionally one or more additives such as heat stabilizers, lubricants, flame retardants, pigments, plasticizers and the like. it can.

Particularly, 30 to 99.8% by weight of silica (silicon oxide), aluminum oxide or the like is added to 70 to 99.8% by weight of the branched polylactone or polylactone composition in the present invention.
The addition of 0.2% by weight improves the heat resistance of the surface of the molded product, so that it is preferably used depending on the application.

The present invention is described in detail below with reference to examples, but the present invention is not limited to the examples.
In addition, "%" described in Examples and Comparative Examples means "% by weight" unless otherwise specified.

[Example 1 / Production of branched polylactone] ε-caprolactone (water content 0.003%) 13 was placed in a polymerization tank.
00 kg, trimethylolpropane 1.5 as an initiator
3 kg and 0.1 kg of monobutyltin tris (2-ethylhexanate) as a metal catalyst were charged, and the mixture was heated at 180 ° C. for 5 hours while introducing nitrogen gas. The obtained branched polylactone (hereinafter referred to as branched PCL) is U
After pelleting with WC, it was dried at 40 ° C. for 10 hours.

Standard polystyrene-equivalent number average molecular weight in gel permeation chromatography of this branched PCL, molecular weight distribution value = weight average molecular weight / number average molecular weight, and melt viscosity measured using a capillary rheometer (temperature 120 ° C., orifice Length 20 mm, orifice diameter 1 mm Melt tension (temperature 120 ° C, orifice diameter 1 m
m and withdrawal ratio 50) are also shown in Table 1.

[Comparative Example 1] For comparison, using the same apparatus as in Example 1, ethylene glycol 0, 7 k was used as an initiator.
Polymerization was carried out under exactly the same charge and conditions as in Example 1 except that g was used, and then the obtained linear polylactone (hereinafter referred to as linear PCL) was cut and dried.

Gel permeation chromatography and a capillary rheometer were measured in the same manner as in Example 1, and the results are also shown in Table 1. (Hereinafter blank) Table 1 Branch PCL, linear physical properties of the PCL] gel permeation chroma capillary rheometer preparative chromatography number average molecular weight molecular weight distribution melt viscosity melt tension (poise) (g) Example 1 123,000 1.72 2.38 × 10 ⁵ 0.28 branched PCL Comparative Example 1 123,000 1.69 1.04 × 10 ⁵ 0.14 chain PCL Although branched PCL and linear PCL have almost the same molecular weight, branched PCL is entangled between molecules, It is clear that the melt tension is significantly improved.

[Examples 2 to 5, Comparative Example 2] Blow moldability (drawdown, breakage during blowing, of a polylactone composition obtained by mixing branched PCL and linear PCL with different composition ratios,
The rate of variation in wall thickness of the molded product and the appearance (surface irregularities such as rough skin) were evaluated, and the results are shown in Table 2.

Drawdown: the time until the length of the parison extruded from the blow molding machine reaches 120 mm,
The value of the ratio to the time required to reach 600 mm was evaluated as the drawdown index. If there is no drawdown,
The drawdown index is 5 and is 1 for the resin that is instantly drawn down.

Variation in wall thickness: A molded product is cut, the thickness of the upper part, the center part and the lower part of the cylinder is measured with a micrometer, and the variation in thickness is expressed as the average% of the difference between the maximum value and the minimum value with respect to the average wall thickness. Indicated.

Molding machine: Blow molding machine made by Placo S-45ND Die (die diameter 50 mm, die interval 3 mm) Molding temperature 180 ° C. Mold temperature 40 ° C., suction pressure 5 kg / c
m2 molded product: average thickness 2.5mm, internal capacity 500c
c Cylindrical hollow container [Examples 6 to 11, Comparative Examples 3 to 8] The formability of an inflation film using a polylactone composition containing branched PCL and linear PCL was evaluated, and the results are shown in Table 3. .

Method: The amount of winding per minute and the appearance (rate of variation in film thickness in the circumferential direction) with an inflation device were measured.

Sample: A, branched PCL B, straight-chain PCLC, polybutylene terephthalate resin (Duranex 700F) manufactured by Polyplastics Co., Ltd. Molding machine: Inflator manufactured by Placo, Die diameter 400 mm, slit 0 0.7 mm, spiral mold upward molding temperature 250 ° C., film thickness 50 μm [Examples 12-18, Comparative Examples 9-17] Branched PCL and other thermoplastic resins are melt-kneaded using an extruder and the take-off property of the strand ( (Breaking, blocking, surging)
Was evaluated. For comparison, a linear PCL was used instead of the branched PCL, and the same evaluation was performed. The results are shown in Table 4.

Sample: A, branched PCL B, linear PCL C, polycarbonate resin (Upilon S-3000) D manufactured by Mitsubishi Gas Chemical Co., Inc., aliphatic polyester resin (Biopol) E manufactured by ICI Japan Co., Ltd., Talc Extruder; Labo Plastomill Extruder 2D20 manufactured by Toyo Seiki
-C Die hole number 3 Hole diameter 4 mm Extrusion temperature 250 ° C, Discharge rate 2 kg / hr Table 2 [Results of blow moldability of each composition] Example Comparative example 2 3 4 5 2 Formability branched PCL (%) 100 80 50 20 Linear PCL (%) 20 50 80 100 Blow moldability Drawdown index 3.82 2.98 2.31 2.25 2.25 Broken at blow No No No No Yes Variation in wall thickness (%) 5 10 15 22 26 Appearance Excellent Good Table 3 [Results of blown film moldability of each composition] Example 6 7 8 9 10 11 Conditions / Evaluation Resin composition A (%) 100 50 10 10 10 10 B (%) 50 90 90 C (%) 90 90 Winding speed (m / min) 14 14 14 14 7 7 Winding amount 1946 1943 1945 2495 974 1248 (g) Variation in film thickness (%) ± 0.5 ± 1.0 ± 2.5 ± 3.0 ± 1 ± 1.2 Comparative example 3 4 5 6 7 8 conditions and evaluation resin A (%) B (%) 100 10 100 10 100 10 C (%) 90 90 winding speed (m / min) 14 14 7 7 3 take-up amount 1682 0 965 1217 405 524 (g ) Film thickness variation (%) ± 7.8 break ± 4.4 ± 6.4 ± 3.2 [extrusion of the results of each composition] ± 4.8 wrinkles Yes Wrinkles Yes Table 4 implementation Example 12 13 14 15 16 16 17 18 Resin composition A (%) 100 50 10 80 10 80 50 B (%) 50 90 C (%) 90 D (%) 20 50 E (%) 20 Collection speed (m / min) ) 2 2 2 2 2 2 2 existence Mu nothingness NO NO NO NO No ratio of existence Mu nothingness NO NO NO NO No surging break blocking compare example 9 10 11 12 13 14 15 16 17 resin composition a (%) B ( %) 100 100 80 80 10 10 80 80 50 C (%) 90 90 D (%) 20 20 50 E (%) 20 20 Collection speed (m / min) 2 1 2 1 2 1 2 2 1 1 Breaking / blocking the presence or absence of the presence or absence breaking * breaking No breaking * breaking * breaking the surging of - Yes - Yes - Yes - Yes - in the observation record of the presence or absence of break-blocking, and * Showing a part blocking ".
(Below margin)

[Procedure amendment]

[Submission date] April 8, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title: Branched polylactone and branched polylactone composition

[Claims]

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention contains a polylactone composition having improved moldability, more specifically, by containing a branched polylactone, for example, thermoforming such as blow molding or vacuum molding, and other resins. The present invention relates to a polylactone composition exhibiting excellent moldability during melt kneading.

[0002]

2. Description of the Related Art In general, polylactones represented by polycaprolactone are not limited to raw materials such as urethane resins, but also polycarbonate resins, polyterephthalate resins,
In order to improve the fluidity and the appearance of ABS resin and the like, they have been melt-kneaded or polylactone alone has been used for various molded articles and molding materials. Further, recently, the biodegradability of polylactone has come to the fore, and it has come to be used alone or in a mixture with other thermoplastic resins for a wide range of applications such as bottles, films and fibers.

[0003]

However, polylactone represented by polycaprolactone has a low melt tension as compared with other thermoplastic resins having a high molding temperature, and it is difficult to melt-knead with such a resin. When the blended product is blow-molded or vacuum-molded, there is a problem that excessive drawdown is likely to occur, uneven thickness is generated in the molded product, and air bubbles are easily mixed in the molded product. Further, even in the case of molding polylactone alone, in the case of conventional linear polylactone, since the melt tension is low, there are various restrictions such as severe restrictions on molding conditions and poor production efficiency. It was very limited.

For practical use, it was indispensable to raise the melt tension significantly. In order to increase the melt tension of the polylactone, as a general method that is also applied in the thermoplastic polyester or polycarbonate, is possible to apply the method using a poly M a to have a method and branch using, for example, highly polymerized polymer desirably To be

However, in order to obtain a linear high-polymerization degree polylactone, it is necessary to set the molar amount of the monofunctional or bifunctional initiator to the lactone monomer to an extremely small amount and a precise molar ratio. It is necessary to make the amount of water contained in the monomer extremely small.

In fact, there is no report that the melt tension of the polylactone is increased by spending such an effort, for example, Japanese Patent Publication Nos. 40-23917 and 40-26.
557, JP-B-40-14739 and JP-A-56-4.
Although 9728 and the like describe highly polymerized polylactone, there is no description about melt tension.

Regarding the possibility of using the other branched polymer, for example, Japanese Patent Publication No. 34-529.
3, Japanese Patent Publication 41-19559 and Japanese Patent Publication 47-137
There is a description of a branched polylactone polymerized by using a trifunctional or higher functional initiator such as glycerin or pentaerythritol such as 83, but this polylactone is an oligomer having a molecular weight of 10,000 or less and is very meltable. The tension was not satisfactory.

[0008]

Therefore, the inventors of the present invention have diligently studied to solve the above-mentioned problems, and as a result, 3
Using a functional or more initiator, and by using a branched polylactone polymerized until reaching a sufficiently high degree of polymerization, alone or if necessary, by linear kneading with a linear polylactone and / or other thermoplastic resin by melt-kneading, The melt tension at the time of high temperature molding is high, and therefore, for example, in thermoforming such as blow molding and vacuum forming, a molded product having a small drawdown and no uneven thickness or bubbles can be easily obtained with good workability.

That is, the present invention "is obtained by ring-opening polymerization of a lactone monomer from a trifunctional or higher-functional polyfunctional initiator, has a molecular weight of 10,000 or more, and has a diameter of 1 mm at 120 ° C using a capillary rheometer. When the resin flowing out from the orifice of No. 2 is dropped and the ratio is 50, the load is 0.
The present invention provides a "branched polylactone having a weight of 15 g or more", a "polylactone composition", and a "molded product".

It is essential that the branched polylactone of the present invention has a molecular weight of 10,000 or more, preferably 50,000 or more, and more preferably 70,000.
It is about 0 to 200,000. If the molecular weight is less than 10,000, the melt tension is low and drawdown is likely to occur. Conversely, what molecular weight exceeds 200,000 0 are difficult to manufacture. The molecular weight is measured using gel permeation chromatography.

The branched polylactone of the present invention has a molecular weight of 10,
And a resin rheometer having a diameter of 1 mm at a temperature of 120 ° C. and having a ratio of 50 and a load of 0.
It is essential that the amount is 15 g or more.

The lactone monomers that can be used in the present invention include δ-valerolactone, ε-caprolactone, 7-hydroxyheptanoic acid lactone, 8-hydroxyoctanoic acid lactone, 12-hydroxydodecanoic acid lactone and 13-hydroxytridecanoic acid. Lactone, 14
-Hydroxytetradecanoic acid lactone, 15-hydroxypentadecanoic acid lactone and their alkyl and alkoxy derivatives. Furthermore, 3-ethyl-2-keto 1,4-dioxane, 1,4-dioxane-
Dioxane such as 2-one is also applied.

These lactone monomers may be used alone or in combination with 2.
It can also be used as a mixture of two or more species. Of these lactone monomers, ε-caprolactone, methylated caprolactone, δ-valerolactone, which have the greatest practical value, and 3
-Ethyl-2-keto-1,4-dioxane and the like are preferably used.

The polyfunctional initiator for producing the branched polylactone of the present invention is a compound or polymer containing three or more active hydrogens such as hydroxyl group, amino group, carboxyl group and thiol group in the molecule. Glycerin,
Radicals in the molecule such as trimethylolpropane, trimethylolethane, pentaerythritol, pyrogallol, oxyhydroquinone, aminopropanediol, erythrose, malic acid, tartaric acid, pentaerythritol-tetramercaptoacetate, 2-ethylhydroxy (meth) acrylate. Oligomers of compounds having both a polymerizable double bond and a hydroxyl group, copolymers with other radically polymerizable monomers and graft modified products on various polymers, ethylene oxide, graft modified products on various polymers of propylene oxide, Examples thereof include sugar, starch, cellulose, and polybutadiene having a hydroxyl group.

The method for producing a branched polylactone by ring-opening polymerization of a lactone monomer using a polyfunctional initiator is not particularly limited, but a polyfunctional initiator and, if necessary, a bifunctional initiator such as ethylene glycol can be used. Generally in the presence of 80 to 230 ° C, preferably 100 to 200 ° C
It is desirable to add 0.1 to 1000 ppm, preferably 1 to 200 ppm of the metal catalyst at the temperature of 1, and ring-opening polymerize the lactone monomer. When the reaction temperature is lower than 80 ° C., the reaction rate is slow, and when it is higher than 230 ° C., coloring due to the oxidation reaction or decomposition reaction of the resulting polymer is unfavorable.

The molecular weight is adjusted by adjusting the charged molar ratio of the lactone monomer and the polyfunctional initiator. The amount of water present in the lactone monomer is 0.1% or less, preferably 0.01%, more preferably 0.005.
It is desirable to add a polyfunctional initiator after adjusting the amount to 1% or less.

As the metal catalyst, in addition to a tin catalyst and a titanium-based catalyst, a compound such as aluminum, aene, molybdenum, zirconium, an alkali metal, an alkaline earth metal, or a lanthanoid is used. In particular, a monobutyltin compound,
Stannous chloride, tetrabutyl titanate and the like are preferable from the viewpoint of easy handling and polymerizability.

When the amount of the catalyst is less than 0.1 ppm, the reaction rate is slow, and when it exceeds 1000 ppm, the hue and thermal stability of the polylactone produced are unfavorable.

Further, in the method for producing a branched lactone,
Any polymerization method such as bulk polymerization, solution polymerization and suspension polymerization can be used without problems.

As the organic solvent which can be used for solution polymerization,
Aromatic hydrocarbons such as toluene and xylene are preferable because they are inert to the reaction and have a relatively high boiling point.

The solvent is preferably substantially anhydrous.

The type of the production apparatus for the branched polylactone is not particularly limited. For example, batch type, semi-continuous and continuous ordinary stirring type reactors, kneader type reactors, screw extruder type reactors, sulzer mixer type reactors and the like can be used without problems. Further, the pressure and gas atmosphere in the reaction system are not particularly limited, and the reaction can be arbitrarily performed under the conditions of an atmosphere such as an inert gas such as 0.01 Torr to 10 atm nitrogen and air. In any proportion of 1 wt or more branch polylactone such as linear polylactone and / or other thermoplastic resin in the present invention can be mixed using any method. When the proportion of the branched polylactone in the total resin is 1% by weight or less, there is almost no effect of improving the moldability, which is not preferable. Usually, in order to improve the moldability, the proportion of branched polylactone in the total polylactone is 10% by weight or more, and when mixed with other thermoplastic resin, the proportion of the branched polylactone in the total polylactone is 30% by weight or more. Further, the proportion of the branched polylactone in the whole resin is preferably 1% by weight or more, more preferably 30% by weight, 50% by weight or 2% by weight or more. As a mixing method, for example, a method of producing a first branched polylactone, and melt-kneading this with another resin,
A method in which a polyfunctional initiator in the present invention and, if necessary, a bifunctional initiator such as ethylene glycol are mixed with a lactone monomer or a metal catalyst, and directly melt-kneaded with another thermoplastic resin, and other condensation polymer-forming ability. The method of copolymerizing with a certain monomer is common.

Claims 2 and 3 of the present invention
The polylactone composition described in the item 1 contains a branched polylactone as an essential component, and optionally a linear polylactone and / or other polylactone.
Of thermoplastic resin and / or inorganic filler
It can be obtained with. The linear polylactone is obtained by ring-opening polymerization of a lactone monomer from a monofunctional initiator such as butanol and a bifunctional initiator such as ethylene glycol.

Any other thermoplastic resin can be used. For example, thermoplastic polyester resin, polycarbonate resin, polystyrene resin, polyacrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, etc. are compatible with polylactone. Other preferred examples include polyamide resins, polyolefin resins such as polyethylene and polypropylene, polyphenylene oxide resins, polyether resins, and various copolymer resins.

The thermoplastic polyester resin is a glycol component having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butanediol,
Examples of glycols such as neopentyl glycol and hexanediol and dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, maleic acid, succinic acid,
Polyester having a skeleton combined with a dicarboxylic acid such as adipic acid and, if necessary, other components such as lactoneoxycarboxylic acid, alcohol, trifunctional or higher polyhydric alcohol, carboxylic acid, trifunctional or higher polycarboxylic acid Is a polyester having a skeleton.

The polycarbonate resin is a polycarbonate produced by reacting a dihydric phenol such as bis A with phosgene (phosgene method) or by reacting a dihydric phenol with a carbonic acid ester (transesterification method).

The polystyrene resin is a polymer polymerized from styrene monomer and monomers such as acrylonitrile, butadiene, (meth) acrylic acid ester, and specifically, polystyrene resin, HIPS resin,
Examples include AS resin, ABS resin, MMA-styrene copolymer and the like. For the polylactone composition of the present invention, thermosetting resins such as epoxy resin, urethane resin and melanin resin, naturally occurring biodegradable polymers such as starch and cellulose, modified products thereof, and glass fiber , Talc, mica, silica, titanium oxide, aluminum oxide, inorganic fillers such as metal powder, and further optionally one or more additives such as heat stabilizers, lubricants, flame retardants, pigments, plasticizers and the like. it can.

Particularly, 30 to 99.8% by weight of silica (silicon oxide), aluminum oxide or the like is added to 70 to 99.8% by weight of the branched polylactone or polylactone composition in the present invention.
The addition of 0.2% by weight improves the heat resistance of the surface of the molded product, so that it is preferably used depending on the application.

The present invention is described in detail below with reference to examples, but the present invention is not limited to the examples.
In addition, "%" described in Examples and Comparative Examples means "% by weight" unless otherwise specified.

[Example 1 / Production of branched polylactone] ε-caprolactone (water content 0.003%) 13 was placed in a polymerization tank.
00 kg, trimethylolpropane 1.5 as an initiator
3 kg and 0.1 kg of monobutyltin tris (2-ethylhexanate) as a metal catalyst were charged, and the mixture was heated at 180 ° C. for 5 hours while introducing nitrogen gas. The obtained branched polylactone (hereinafter referred to as branched PCL) is U
After pelleting with WC, it was dried at 40 ° C. for 10 hours.

Standard polystyrene-equivalent number average molecular weight in gel permeation chromatography of this branched PCL, molecular weight distribution value = weight average molecular weight / number average molecular weight, and melt viscosity measured using a capillary rheometer (temperature 120 ° C., orifice Length 20 mm, orifice diameter 1 mm Melt tension (temperature 120 ° C, orifice diameter 1 m
m and withdrawal ratio 50) are also shown in Table 1.

[Comparative Example 1] For comparison, using the same apparatus as in Example 1, ethylene glycol 0, 7 k was used as an initiator.
Polymerization was carried out under exactly the same charge and conditions as in Example 1 except that g was used, and then the obtained linear polylactone (hereinafter referred to as linear PCL) was cut and dried.

Gel permeation chromatography and a capillary rheometer were measured in the same manner as in Example 1, and the results are also shown in Table 1. (Hereinafter blank) Table 1 Branch PCL, linear physical properties of the PCL] gel permeation chroma capillary rheometer preparative chromatography number average molecular weight molecular weight distribution melt viscosity melt tension (poise) (g) Example 1 123,000 1.72 2.38 × 10 ⁵ 0.28 branched PCL Comparative Example 1 123,000 1.69 1.04 × 10 ⁵ 0.14 chain PCL Although branched PCL and linear PCL have almost the same molecular weight, branched PCL is entangled between molecules, It is clear that the melt tension is significantly improved.

[Examples 2 to 5, Comparative Example 2] Blow moldability (drawdown, breakage during blowing, of a polylactone composition obtained by mixing branched PCL and linear PCL with different composition ratios,
The rate of variation in wall thickness of the molded product and the appearance (surface irregularities such as rough skin) were evaluated, and the results are shown in Table 2.

Drawdown: the time until the length of the parison extruded from the blow molding machine reaches 120 mm,
The value of the ratio to the time required to reach 600 mm was evaluated as the drawdown index. If there is no drawdown,
The drawdown index is 5 and is 1 for the resin that is instantly drawn down.

Variation in wall thickness: A molded product is cut, the thickness of the upper part, the center part and the lower part of the cylinder is measured with a micrometer, and the variation in thickness is expressed as the average% of the difference between the maximum value and the minimum value with respect to the average wall thickness. Indicated.

Molding machine: Blow molding machine made by Placo S-45ND Die (die diameter 50 mm, die interval 3 mm) Molding temperature 180 ° C. Mold temperature 40 ° C., suction pressure 5 kg / c
m2 molded product: average thickness 2.5mm, internal capacity 500c
c Cylindrical hollow container [Examples 6 to 11, Comparative Examples 3 to 8] The formability of an inflation film using a polylactone composition containing branched PCL and linear PCL was evaluated, and the results are shown in Table 3. .

Method: The amount of winding per minute and the appearance (rate of variation in film thickness in the circumferential direction) with an inflation device were measured.

Sample: A, branched PCL B, straight-chain PCLC, polybutylene terephthalate resin (Duranex 700F) manufactured by Polyplastics Co., Ltd. Molding machine: Inflator manufactured by Placo, Die diameter 400 mm, slit 0 0.7 mm, spiral mold upward molding temperature 250 ° C., film thickness 50 μm [Examples 12-18, Comparative Examples 9-17] Branched PCL and other thermoplastic resins are melt-kneaded using an extruder and the take-off property of the strand ( (Breaking, blocking, surging)
Was evaluated. For comparison, a linear PCL was used instead of the branched PCL, and the same evaluation was performed. The results are shown in Table 4.

Sample: A, branched PCL B, linear PCL C, polycarbonate resin (Upilon S-3000) D manufactured by Mitsubishi Gas Chemical Co., Inc., aliphatic polyester resin (Biopol) E manufactured by ICI Japan Co., Ltd., Talc Extruder; Labo Plastomill Extruder 2D20 manufactured by Toyo Seiki
-C Die hole number 3 Hole diameter 4 mm Extrusion temperature 250 ° C, Discharge rate 2 kg / hr Table 2 [Results of blow moldability of each composition] Example Comparative example 2 3 4 5 2 Formability branched PCL (%) 100 80 50 20 Linear PCL (%) 20 50 80 100 Blow moldability Drawdown index 3.82 2.98 2.31 2.25 2.25 Broken at blow No No No No Yes Variation in wall thickness (%) 5 10 15 22 26 Appearance Excellent Good Table 3 [Results of blown film moldability of each composition] Example 6 7 8 9 10 11 Conditions / Evaluation Resin composition A (%) 100 50 10 10 10 10 B (%) 50 90 90 C (%) 90 90 Winding speed (m / min) 14 14 14 14 7 7 Winding amount 1946 1943 1945 2495 974 1248 (g) Variation in film thickness (%) ± 0.5 ± 1.0 ± 2.5 ± 3.0 ± 1 ± 1.2 Comparative example 3 4 5 6 7 8 conditions and evaluation resin A (%) B (%) 100 10 100 10 100 10 C (%) 90 90 winding speed (m / min) 14 14 7 7 3 take-up amount 1682 0 965 1217 405 524 (g ) Film thickness variation (%) ± 7.8 break ± 4.4 ± 6.4 ± 3.2 [extrusion of the results of each composition] ± 4.8 wrinkles Yes Wrinkles Yes Table 4 implementation Example 12 13 14 15 16 16 17 18 Resin composition A (%) 100 50 10 80 10 80 50 B (%) 50 90 C (%) 90 D (%) 20 50 E (%) 20 Collection speed (m / min) ) 2 2 2 2 2 2 2 existence Mu nothingness NO NO NO NO No ratio of existence Mu nothingness NO NO NO NO No surging break blocking compare example 9 10 11 12 13 14 15 16 17 resin composition a (%) B ( %) 100 100 80 80 10 10 80 80 50 C (%) 90 90 D (%) 20 20 50 E (%) 20 20 Collection speed (m / min) 2 1 2 1 2 1 2 1 1 1 Breaking / blocking the presence or absence of the presence or absence breaking * breaking No breaking * breaking * breaking the surging of - Yes - Yes - Yes - Yes - in the observation record of the presence or absence of break-blocking, and * Showing a part blocking ".
(Below margin)

Claims (4)

[Claims] 1. A compound obtained by ring-opening polymerization of a lactone monomer from a trifunctional or higher-functional polyfunctional initiator, having a molecular weight of 10,000 or more, and using a capillary rheometer to obtain 120.
A branched polylactone having a load of 0.15 g or more when the resin flowing out from an orifice having a diameter of 1 mm at 0 ° C. is drawn down at a ratio of 50. 2. Obtained by ring-opening polymerization of a lactone monomer from a trifunctional or higher-functional polyfunctional initiator, having a molecular weight of 10,000 or more, and using a capillary rheometer.
A polylactone composition containing 1% by weight or more of a branched polylactone having a load of 0.15 g or more when the resin flown out from an orifice having a diameter of 1 mm at a temperature of 0. . 3. The branched polylactone 30 according to claim 2.
A polylactone composition comprising 100% by weight of a linear polylactone and / or 70 to 0% by weight of another thermoplastic resin and 30 to 0% by weight of an inorganic filler. 4. A molded product obtained by molding the polylactone composition according to claim 1.