JP4440144B2 - Biodegradable resin composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a biodegradable resin composition that has excellent antistatic properties and antifogging properties while maintaining molecular weight, and particularly to a polylactic acid resin composition that is a plant-derived renewable resource. It is.

  Plastics such as polypropylene, polyethylene, and polyvinyl chloride, which are made from petroleum and other fossil resources, are transformed into food packaging films, electrical appliances, industrial materials, etc., and are indispensable for our lives. . However, it is well known that such plastics remain semipermanent in nature after they are unnecessary because they are not biodegradable, which has a major impact on the ecosystem and leads to environmental destruction in various ways. It is a fact.

  Under these circumstances, biodegradable resins are attracting attention. Among them, plants that are not biodegradable and are trying to convert from plastics derived from fossil resources are used as raw materials. That is, it is a plant-derived biodegradable resin. Of particular interest in recent years is the polylactic acid-based resin whose production volume is dramatically increasing. The factors that have attracted the attention of polylactic acid-based resins are various factors that use fossil resources as raw materials in the context of a material recycling system that conserves limited fossil resources and thoroughly recycles them. While plastics are greatly out of the circulation system, it is possible to construct a material circulation system that recycles sugar obtained from plants such as corn or potato or polylactic acid synthesized from lactic acid obtained by fermenting them. It is because it is expected as a thing.

  The raw material of polylactic acid resin is synthesized from sugars obtained from cereals such as corn or potato, which are renewable resources, or lactic acid obtained by fermenting them. After being easily hydrolyzed and decomposed by microorganisms, it finally becomes water and carbon dioxide.

  It is also known that resin molded bodies such as films and sheets made of biodegradable resins such as polylactic acid-based resins exhibit the same performance as conventional plastics. Among these, polylactic acid-based resins have very high transparency, and can be used for packaging applications that place importance on transparency.

  However, biodegradable resins that have a number of advantages and can be used in molded articles such as films and sheets are very easy to be charged because they have resin-specific electrical insulation properties as well as general resins. There are many problems due to electrification such as ink repellency during printing, scattering when packing the contents, or dust adhering to the product and deteriorating its appearance.

In addition, food packaging films are required to show the appearance of packaged foods, but they come from the low hydrophilicity inherent in plastics, such as the film surface becoming clouded by water droplets caused by water vapor generated from foods. There is also a problem.

In such applications, the surface of a molded article such as a film or sheet is usually used by printing with a printing ink, and printing on the film surface includes screen printing, flexographic printing, offset printing and gravure printing. The method is used. Printing inks are broadly classified into organic solvent and water. However, printing with water-based ink is gradually performed because of the danger of explosion due to the flammability of organic solvent, environmental damage due to leakage of outside air, and the effects of toxicity on the human body. It is being broken. However, because of the low surface energy peculiar to plastics, printing ink does not adhere to the surface as it is, so the surface energy is increased by applying corona discharge treatment, ozone treatment, plasma treatment, etc. In terms of ink transferability and adhesiveness, it is still not sufficient.

  As a means for solving charging, Patent Document 1 discloses that an antistatic property is imparted by applying an aqueous coating liquid containing a surfactant to at least one surface of an aliphatic polyester film. Alternatively, Patent Document 2 shows that antistatic properties can be imparted by applying a specific anionic surfactant or a specific nonionic surfactant-containing liquid to a polylactic acid biaxially stretched film.

  However, in general, the coating method increases the number of coating steps after resin molding, resulting in an increase in cost, and there are problems such as slipperiness, poor transparency, or lack of sustainability of the antistatic performance specific to the coating method.

  As a means for solving such a problem, there is a kneading method in which a surfactant is previously added to a resin. In the kneading method, after the molding, the surfactant oozes out from the inside of the molded body (bleed out), and the surface of the surfactant layer is formed so that performances such as antistatic properties and antifogging properties are exhibited. Furthermore, even if the surface-active agent is wiped off, the effect is recovered by the bleed-out of the surface active agent inside the resin, and it has a certain degree of sustainability. In this way, the kneading method expresses performance by bleeding out the surfactant from the resin, but the degree of this bleed out depends on the crystallinity of the resin such as crystallinity and crystal orientation, and the resin. It is said that it largely depends on the compatibility with the surfactant. In particular, the crystallinity of the resin and the compatibility of the surfactant have a great influence on the appearance of the resin.

  Patent Document 3 discloses that a polylactic acid resin contains a polyhydric alcohol and a fatty acid ester thereof to provide an antistatic film and sheet. Patent Document 4 discloses that polylactic acid contains a nonionic surfactant made of glycerin fatty acid ester to impart antistatic properties. Patent Document 5 discloses that a caprolactone-based resin that is a biodegradable resin is provided with an antistatic property by including a nonionic surfactant containing a glycerin fatty acid ester. Further, Patent Document 6 contains an anionic surfactant alkyl sulfonate, a polyhydric alcohol, and a fatty acid alkylolamide compound, thereby suppressing deterioration of transparency due to the alkyl sulfonate and exhibiting antistatic properties. . However, these technologies do not necessarily have practical antistatic properties, and surfactants that are inadequate in compatibility with the resin have a significant effect on the appearance of the resin. With polylactic acid, there is a significant hindrance to transparency.

While antistatic properties and antifogging properties are required for plastic products, it is necessary that the surfactant to be added itself can withstand a high kneading temperature of 180 to 250 ° C. Nonionic surfactants have heat resistance, but as described above, antistatic properties do not reach satisfactory performance. In addition, although an anionic activator exhibits a certain level of antistatic properties, its compatibility with the resin is poor and the appearance is impaired. On the other hand, cationic surfactants such as quaternary ammonium salts, which are generally antistatic, as specified in the Examples of Patent Document 1, have very low heat resistance and are particularly biodegradable. For the resin, the biodegradable resin is easily hydrolyzed by amines or acids generated by the decomposition of the quaternary ammonium salt due to the thermal history during the resin processing, causing a decrease in the molecular weight. It greatly affects various physical properties such as strength. Patent Document 7 discloses a quaternary ammonium salt having a SO ₃ ^— group in a counter ion. However, when they are blended in a biodegradable resin, the molecular weight retention of the biodegradable resin is not sufficient. When processed into a molded body, there may be a problem that the strength is inferior. Further, it cannot be said that the antistatic property, antifogging property, and transparency are sufficiently satisfactory.

Furthermore, as a method for improving the printability of water-based ink in a polyolefin film, Patent Document 8 discloses a method using an amide-based antistatic agent. However, the above-described antistatic property and antifogging property are used in biodegradable resins. Is not satisfactory enough.

  Therefore, the antistatic property, antifogging property, maintenance of molecular weight, printability, and the transparency required when the biodegradable resin is polylactic acid are required from these conventional techniques. However, it cannot be said that satisfactory performance has been obtained for all of the above, and further improvement has been demanded. Furthermore, it can be said that a molded body such as a film or sheet obtained by processing a resin is preferable if the surface has slipperiness in the production process, but appropriate slipperiness has also been found in this respect. Absent.

JP-A-10-86307 (page 1-14) Japanese Patent Laid-Open No. 14-12687 (page 1-6) Japanese Patent Laid-Open No. 9-221587 (page 1-9) JP 10-36650 A (page 1-14) Japanese Patent Laid-Open No. 14-60603 (page 1-5) Japanese Patent Laid-Open No. 15-261757 (page 1-6) JP-A-9-278936 (page 1-14) JP-A-7-164608 (page 1-6)

  The object of the present invention is to such an extent that the strength of the molded body can be satisfied practically without impairing the appearance of the resin because it has sufficient heat resistance even in the kneading method including the heating step under such circumstances. Another object of the present invention is to provide a biodegradable resin composition capable of exhibiting excellent antistatic properties, antifogging properties, printability and surface lubricity while maintaining the molecular weight.

[Ｒ_１は、炭素数が１〜３０の直鎖もしくは分岐鎖のアルキル基、アルケニル基、ヒドロキシアルキル基、アルキルアリール基、又はアリールアルキル基を示す。Ｒ_２、Ｒ_３はそれぞれ独立して水素、又は炭素数が２〜３０のアシル基を示す。ｍとｎはｍ＋ｎ＝０〜１００となる０以上の整数を示す。Ｘは、

を示す。Ｙ、Ｚはそれぞれ独立して１種又は２種以上の
−Ｒ_４Ｏ−
（Ｒ_４は炭素数２〜４のアルキレン基を示す。）である。ＹとＺは互いに同一でも異なっていても良い。]
また、本発明の好ましい態様に、該ホウ酸エステル系界面活性剤が、多価アルコール類を高級脂肪酸でエステル化した化合物とホウ酸との反応物、又はその反応物の塩、更に本発明の別の好ましい態様に、該ホウ酸エステル系界面活性剤が、多価アルコール類とホウ酸でエステル化をした化合物と高級脂肪酸との反応物、又はその反応物の塩である前記生分解性樹脂組成物がある。本発明の生分解性樹脂組成物は特に帯電防止性、防曇性、印刷適性及び滑性に優れ、又ポリ乳酸系樹脂においても好ましい効果を発揮する。更に本発明は上記樹脂組成物からなるフィルム、シート等の樹脂成形体でもある。 As a result of intensive studies to solve the above problems, the present inventors have completed the invention of a biodegradable resin composition having excellent antistatic properties and the like. That is, the present invention is a borate ester system having 90 to 10% by weight of a nitrogen-containing surfactant (A) represented by the following general formula (1) and one or more hydrophobic groups having 1 to 30 carbon atoms. The present invention relates to a biodegradable resin composition containing 0.05 to 5.0% by weight of a surfactant composition comprising 10 to 90% by weight of surfactant (B).

[R ₁ represents a linear or branched alkyl group, alkenyl group, hydroxyalkyl group, alkylaryl group, or arylalkyl group having 1 to 30 carbon atoms. R ₂ and R ₃ each independently represent hydrogen or an acyl group having 2 to 30 carbon atoms. m and n represent an integer of 0 or more that satisfies m + n = 0-100. X is

Indicates. Y and Z are each independently one or more
-R ₄ O-
(R ₄ represents an alkylene group having 2 to ₄ carbon atoms). Y and Z may be the same or different. ]
Further, in a preferred embodiment of the present invention, the boric acid ester-based surfactant is a reaction product of a compound obtained by esterifying a polyhydric alcohol with a higher fatty acid and boric acid, or a salt of the reaction product. In another preferred embodiment, the biodegradable resin, wherein the borate ester surfactant is a reaction product of a compound esterified with a polyhydric alcohol and boric acid and a higher fatty acid, or a salt of the reaction product. There is a composition. The biodegradable resin composition of the present invention is particularly excellent in antistatic properties, antifogging properties, printability and lubricity, and also exhibits favorable effects in polylactic acid resins. Furthermore, this invention is also resin molded objects, such as a film and a sheet which consist of the said resin composition.

The biodegradable resin containing the surfactant composition of the present invention is such that even if a kneading method including a heating step is adopted, the strength of the molded body can be satisfied practically without impairing the appearance of the resin. While maintaining the molecular weight, excellent antistatic properties, antifogging properties, printability and surface lubricity can be exhibited. In addition, since the molecular weight retention rate is dramatically improved as compared with biodegradable resins containing known surfactants, films, sheets, injection molded articles, filaments, nonwoven fabrics, bottles, yarns, and the like made of the same The strength of the molded article is sufficiently satisfactory, and can be suitably used as a wide range of materials such as (food) packaging materials, agriculture, civil engineering / architecture, marine products, compost materials and the like.
The reason why the surfactant composition according to the present invention has good heat resistance is not clear, but it is considered that the nitrogen-containing surfactant is coordinated to the borate ester surfactant in the system. There seems to be a relationship.

The present invention will be described in detail below.
In the present invention, the surfactant composition contained in the biodegradable resin composition needs to combine a nitrogen-containing surfactant (A) and a borate ester surfactant (B).

である。
Ｙは、１種又は２種以上の−Ｒ_４Ｏ−を示す。Ｒ_４は炭素数２〜４のエチレン、プロピレン、ブチレン等のアルキレン基であるが、好ましくはエチレン、プロピレンが良い。−Ｒ_４Ｏ−が２種以上の場合、それらはブロック付加又はランダム付加でも特に限定されない。Ｚは前記Ｙと互いに同一でも異なっていても良い。或いは、Ｙ又はＺは存在しなくても良い。 In the general formula (1), R ₁ has 1 to 30 carbon atoms, and preferably has an antistatic property in the range of 8 to 22 carbon atoms. There will be no deterioration of working environment due to smoke. Further, R ₁ may be a linear or branched alkyl group, alkenyl group, hydroxyalkyl group, alkylaryl group, or arylalkyl group. Specific examples include capryl group, 2-ethylhexyl group, lauryl group, myristyl group, palmityl group, stearyl group, isostearyl group, oleyl group, linoleyl group, and behenyl group. is not.
R ₂ and R ₃ are each independently hydrogen or an acyl group having 2 to 30 carbon atoms, preferably at least one of R ₂ and R ₃ is hydrogen and the other is a range having 8 to 22 carbon atoms. If it is, favorable antistatic property will be acquired, and the working environment by the smoke of a nitrogen-containing compound will not be caused in the resin processing process.
m and n represent an integer of 0 or more such that m + n = 0 to 100, preferably 1 to 50, more preferably 1 to 10, and most preferably 1 to 5.
X is

It is.
Y represents one or more of —R ₄ O—. R ₄ is an alkylene group having 2 to ₄ carbon atoms such as ethylene, propylene and butylene, preferably ethylene and propylene. -R 4 If _O- is two or more, they are not particularly limited in block addition or random addition. Z may be the same as or different from Y. Alternatively, Y or Z may not be present.

含窒素界面活性剤（Ａ−２）

含窒素界面活性剤（Ａ−３）

含窒素界面活性剤（Ａ−４）

含窒素界面活性剤（Ａ−５）

含窒素界面活性剤（Ａ−６）

含窒素界面活性剤（Ａ−７）

含窒素界面活性剤（Ａ−８）

が挙げられるがこれに限定されるものではなく、これらを単独で用いても、２種以上を併用しても良い。 As a specific example of the nitrogen-containing surfactant of the present invention, a nitrogen-containing surfactant (A-1)

Nitrogen-containing surfactant (A-2)

Nitrogen-containing surfactant (A-3)

Nitrogen-containing surfactant (A-4)

Nitrogen-containing surfactant (A-5)

Nitrogen-containing surfactant (A-6)

Nitrogen-containing surfactant (A-7)

Nitrogen-containing surfactant (A-8)

However, the present invention is not limited to this, and these may be used alone or in combination of two or more.

The nitrogen-containing surfactant according to the present invention can be obtained by a known method, but the production method is not particularly limited.

The borate ester surfactant according to the present invention has one or more hydrophobic groups having 1 to 30 carbon atoms. The borate ester surfactant can be obtained by reacting a compound obtained by esterifying a polyhydric alcohol with a higher fatty acid and boric acid, and a compound obtained by esterifying a polyhydric alcohol with boric acid. It can also be obtained by reacting with a higher fatty acid.

The borate ester-based surfactant according to the present invention can be synthesized from polyhydric alcohols, higher fatty acids, and boric acid, and is obtained as a mixture of a plurality of compounds such as monomers, multimers, and reaction byproducts. Therefore, even if the same raw material is used, the structure of the final compound differs strictly depending on the synthesis procedure.

The polyhydric alcohols according to the present invention include glycerin, diglycerin, triglycerin, polyglycerin, arabitol, sorbitol, pentaerythritol, polypentaerythritol, glucose, lactose, monosaccharide, sucrose and / or ethylene oxide thereof, Examples include alkylene oxide adducts such as propylene oxide, ethylene glycol, propylene glycol, butylene glycol and the like, but are not particularly limited.

The higher fatty acid according to the present invention has 1 to 30 carbon atoms, may be a saturated fatty acid or an unsaturated fatty acid, and may have a linear or branched chain. Specifically, caprylic acid, 2-ethylhexanoic acid, capric acid, nonanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, docosanoic acid, behenic acid, etc. However, it is not limited to these. If the number of carbon atoms is 8 to 24, good antistatic properties can be obtained, and the working environment is not deteriorated due to the generation of surfactant in the resin processing step, which is preferable.

The boric acid ester-based surfactant according to the present invention includes a reaction product of a higher fatty acid ester of a polyhydric alcohol and boric acid and a salt of a reaction product of a boric acid ester of a polyhydric alcohol and a higher fatty acid. . Specific examples include alkali metal salts such as sodium salts, potassium salts and magnesium salts of the reactants, alkaline earth metal salts, and organic amine salts such as ammonia, diethanolamine and triethanolamine, preferably sodium. Salt and potassium salt are good.

A borate ester surfactant obtained by reacting a compound obtained by esterifying the polyhydric alcohol according to the present invention with a higher fatty acid and boric acid can be obtained by a known method.

The esterification reaction of the polyhydric alcohol and the higher fatty acid can be carried out by a known method, and the reaction molar ratio is not particularly limited, but preferably the higher fatty acid is 1.0 to 2.0 with respect to 1 mol of the polyhydric alcohol. The mole is good. Depending on the reaction molar ratio of the polyhydric alcohol and the higher fatty acid, a monoester, a diester, or an ester of a triester or higher can be obtained. Higher monoester purity by molecular distillation is desirable, but the degree of esterification is not particularly limited, and these may be mixed. On the other hand, the reaction of boric acid with a compound obtained by esterifying a polyhydric alcohol with a higher fatty acid can also be carried out by a known method, and the reaction molar ratio is not particularly limited, but preferably the polyhydric alcohol is made of a higher fatty acid. The amount of boric acid is 0.1 to 5.0 moles, more preferably 0.5 to 2.0 moles per mole of the esterified compound.

As the boric acid ester surfactant obtained by the above method, specifically, a reaction product of glycerin monolaurate and boric acid, a reaction product of glycerin monostearate and boric acid, or a reaction product of glycerin monooleate and boric acid. Reaction product, reaction product of glycerin dilaurate and boric acid, reaction product of glycerin distearate and boric acid, reaction product of diglycerin monolaurate and boric acid, reaction product of diglycerin monostearate and boric acid , A reaction product of diglycerin monooleate and boric acid, a reaction product of diglycerin dilaurate and boric acid, a reaction product of diglycerin distearate and boric acid, a reaction product of diglycerin trilaurate and boric acid, Reaction product of polyglycerol monolaurate and boric acid, reaction product of polyglycerol dilaurate and boric acid, polyoxyethylene Reaction product of glyceryl monolaurate and boric acid, reaction product of polyoxypropylene glycerol monolaurate and boric acid, reaction product of sorbitol monolaurate and boric acid, reaction of sorbitol monostearate and boric acid , Reaction product of sorbitol monooleate and boric acid, reaction product of polyoxyethylene sorbitol monolaurate and boric acid, reaction product of polyoxyethylene sorbitol monostearate and boric acid, pentaerythritol monolaurate and boric acid Reaction product of acid, reaction product of pentaerythritol monostearate and boric acid, reaction product of pentaerythritol dilaurate and boric acid, reaction product of sucrose monolaurate and boric acid, sucrose monostearate and boric acid Reaction with acid, reaction with sucrose monooleate and boric acid, poly Reaction product of tylene glycol monolaurate and boric acid, reaction product of polypropylene glycol monolaurate and boric acid, sodium salt of reaction product of glycerol monolaurate and boric acid, reaction of glycerol monooleate and boric acid Sodium salt of reaction product, potassium salt of reaction product of glycerol distearate and boric acid, sodium salt of reaction product of diglycerol monolaurate and boric acid, calcium of reaction product of polyglycerol monostearate and boric acid Salt, sodium salt of a reaction product of sorbitol monolaurate and boric acid, calcium salt of a reaction product of pentaerythritol monostearate and boric acid, and the like, but are not limited to these, May be used alone or in combination of two or more.

A borate ester surfactant obtained by reacting a compound obtained by esterifying the polyhydric alcohol according to the present invention with boric acid and a higher fatty acid can be obtained by a known method.

The esterification reaction between the polyhydric alcohol and boric acid can be carried out by a known method, and the reaction molar ratio is not particularly limited, but preferably higher fatty acid is 0.5-2. 0 mole is good. On the other hand, the reaction of higher fatty acids with a compound obtained by esterifying polyhydric alcohols with boric acid can also be carried out by a known method, and the reaction molar ratio is not particularly limited, but preferably polyhydric alcohols are reacted with boric acid. The higher fatty acid acid is preferably 1.0 to 2.0 moles per mole of the esterified compound.

Specific examples of borate ester surfactants obtained by the above method include glycerol borate-laurate, glycerol borate-palmitate, glycerol borate-stearate, glycerol borate-oleate based on glycerol, diglycerol, and polyglycerol, respectively. Glycerol borate-isostearate, glycerol borate-hydroxystearate, polyoxyethylene glycerol borate-laurate added with alkylene oxide, polyoxyethylene glycerol borate-palmitate, polyoxyethylene glycerol borate-stearate, polyoxyethylene glycerol borate -Oleate, polyoxyethylene glycerol borate-isostearate, polyoxy Examples include, but are not limited to, ruxylene borate-stearate, diglycerol borate-laurate, sodium salt of glycerol borate-laurate, potassium salt of diglycerol borate-stearate, calcium salt of polyoxyethylene glycerol borate-isostearate, etc. However, these may be used alone or in combination of two or more.

In the present invention, the surfactant composition must be composed of 90 to 10% by weight of the nitrogen-containing surfactant (A) and 10 to 90% by weight of the borate ester surfactant (B), More preferably, it is composed of (A) 90 to 50% by weight and (B) 10 to 50% by weight. If the nitrogen-containing surfactant (A) exceeds 90% by weight, the anti-static and anti-fogging effects are good, but the lubricity of the biodegradable resin surface becomes poor. On the other hand, when the nitrogen-containing surfactant (A) is less than 10% by weight, sufficient antistatic and antifogging effects cannot be obtained.

The content of the surfactant composition of the present invention relative to the biodegradable resin is 0.05% to 5.0% by weight, preferably 0.1% to 2.0% by weight, and more preferably. Is 0.5 wt% to 1.0 wt%. The antistatic property and antifogging property are improved in proportion to the content of the surfactant composition of the present invention. However, even if it exceeds 5.0% by weight, the antistatic property and antifogging property are not greatly improved. The excessive addition may affect the cost and mechanical properties of the biodegradable resin.

A biodegradable resin composition containing 0.05 to 5.0% by weight of the surfactant composition of the present invention can exhibit excellent antistatic properties and lubricity. Specifically, according to the present invention, a biodegradable resin composition having a dynamic friction coefficient of 0.4 or less and a surface specific resistance value LOG of 13.0 [Ω] or less can be obtained.

The surfactant composition of the present invention is desirably dried in advance in order to prevent hydrolysis of the biodegradable resin due to moisture. The water content in the surfactant of the present invention is preferably 1.0% by weight or less.

The surfactant composition of the present invention can be used alone for a biodegradable resin, but as long as it does not impair the purpose of the present invention, known anionic surfactants other than the present invention, cationic surfactant Agents, nonionic surfactants and amphoteric surfactants may be used alone or in combination of two or more.

The surfactant composition of the present invention can also be used in a method of coating on the surface of a plastic product in order to impart the antistatic property and antifogging property intended by the present invention. In use, the surfactant of the present invention is diluted by about 50 to 100 times with a solvent such as ethanol or isopropyl alcohol, and a known utility method such as a method of applying with a sprayer or a bar coater is mentioned. There are no particular restrictions.

Hereinafter, the biodegradable resin according to the present invention will be described.
The biodegradable resin used in the present invention is, for example, at least one or two selected from hydroxycarboxylic acids, aliphatic polyhydric alcohols, aromatic polyhydric alcohols, aliphatic polycarboxylic acids, and aromatic polycarboxylic acids. These are aliphatic polyesters and aromatic polyesters composed of the above, and are biodegradable thermoplastic resins.
It can also take the form of a homopolymer or copolymer (random, block, comb, etc.).
For example, polylactic acid resin, polyethylene succinate resin, polyethylene succinate adipate resin, polybutylene succinate resin, polybutylene succinate adipate resin, polybutylene succinate carbonate resin, polyethylene carbonate resin described later, Examples thereof include polyethylene terephthalate adipate resin, polybutylene succinate terephthalate resin, polybutylene adipate terephthalate resin, polycaprolactone resin, and polyglycolic acid resin.
In particular, polylactic acid-based resins, which will be described later, and also polylactic acid, polycaprolactone, polybutylene succinate, polybutylene succinate adipate, polybutylene terephthalate adipate, and polyethylene terephthalate adipate are already commercially available and inexpensive and easily available. .
The monomer units constituting these may be chemically modified or may be a copolymer of different monomers. Also, one or more of hydroxycarboxylic acids such as glycolic acid and 3-hydroxybutyric acid, polyvalent carboxylic acids such as succinic acid and adipic acid, polysaccharides such as cellulose acetate and ethylcellulose, and polyhydric alcohols such as ethylene glycol and diethylene glycol The copolymer of 2 or more types and the mixture of the monomer which comprises the said resin may be sufficient. Furthermore, for example, starch-based resins, chitosan-based resins, polyvinyl alcohol-based resins, and petroleum-based resins may be blended as long as the object of the present invention is not impaired.

  The molecular weight of the biodegradable resin used in the present invention is preferably a weight average molecular weight (Mw) of 6 to 1,000,000, more preferably 80 to 500,000, and most preferably 100,000 to 300,000. In general, when the weight average molecular weight (Mw) is less than 60,000, the mechanical properties of the molded product obtained by molding the resin composition is insufficient, or conversely when the molecular weight exceeds 1 million, The melt viscosity at the time of molding may become extremely high, making it difficult to handle or making it uneconomical in production.

Similarly, the molecular weight distribution (Mw / Mn) is not particularly limited as long as it can be substantially molded and exhibits substantially sufficient mechanical properties. -6 is more preferable, and 2-5 is most preferable.

In the present invention, the polylactic acid-based resin means a polymer composition containing as a main component a polymer containing 50% by weight or more, preferably 75% by weight or more of lactic acid units. For example, L-lactic acid, D-lactic acid, DL-lactic acid or a mixture thereof or lactide which is a cyclic dimer of lactic acid can be used. The polyethylene succinate-based resin means a polymer composition mainly composed of a polymer containing 50% by weight or more, preferably 75% by weight or more of ethylene succinate units. The same applies to the other biodegradable resins.

[Composition ratio of lactic acid units in polylactic acid resin]
As a structure of the lactic acid unit in the polylactic acid-based resin, there are L-lactic acid, D-lactic acid, and a mixture thereof, which can be appropriately selected depending on the application. When polylactic acid is used as the polylactic acid-based resin, it is preferable that D-lactic acid: L-lactic acid = 1: 99 to 30:70 when L-lactic acid is the main component. It is also possible to blend two or more types of polylactic acid having different constituent ratios of D-lactic acid and L-lactic acid. On the contrary, when D-lactic acid is the main component, L-lactic acid: D-lactic acid = 1: 99 to 30:70 is preferable, and two or more kinds of poly-polyethylenes having different constituent ratios of D-lactic acid and L-lactic acid are used. It is also possible to blend lactic acid.

As long as the object of the present invention is not impaired, the other component is an aliphatic hydroxycarboxylic acid having 2 to 10 carbon atoms other than lactic acid, an aliphatic dicarboxylic acid, an aliphatic diol or the like, or an aromatic such as terephthalic acid. It may contain a compound. Homopolymers, copolymers and mixtures thereof based on these may also be included. Moreover, you may mix other resin in the range which does not impair the physical property of this invention remarkably.

A known method is used as a method for producing the biodegradable resin used in the present invention.
For example, in the case of the polylactic acid resin preferably used in the present invention, a known method such as a method of directly dehydrating condensation polymerization of lactic acid or a method of ring-opening polymerization of lactide which is a cyclic dimer of lactic acid is used. It is not limited to this. As a method for producing the polylactic acid-based resin, a publicly known method can be used. For example,
(1) A method of direct dehydration polycondensation using lactic acid or a mixture of lactic acid and aliphatic hydroxycarboxylic acid as a raw material (for example, a production method shown in US Pat. No. 5,310,865)
(2) A ring-opening polymerization method in which a cyclic dimer (lactide) of lactic acid is melt-polymerized (for example, a production method disclosed in US Pat. No. 2,758,987)
(3) A ring-opening polymerization method in which a cyclic dimer of lactic acid and an aliphatic hydroxycarboxylic acid, such as lactide or glycolide, and ε-caprolactone is melt-polymerized in the presence of a catalyst (for example, US Pat. No. 4,057,537) Disclosed manufacturing method)
(4) A method of directly dehydrating polycondensation of a mixture of lactic acid, an aliphatic dihydric alcohol and an aliphatic dibasic acid (for example, a production method disclosed in US Pat. No. 5,428,126)
(5) A method of condensing a polymer of polylactic acid, an aliphatic dihydric alcohol and an aliphatic dibasic acid in the presence of an organic solvent (for example, a production method disclosed in European Patent Publication 0712880 A2)
(6) In producing a polyester polymer by carrying out a dehydration polycondensation reaction in the presence of a catalyst with lactic acid, there can be mentioned a method of solid-phase polymerization in at least a part of the process, etc. Is not particularly limited. Alternatively, a small amount of trimethylolpropane, aliphatic polyhydric alcohol such as glycerin, aliphatic polybasic acid such as butanetetracarboxylic acid, polyhydric alcohol such as polysaccharides may be co-polymerized. Further, the molecular weight may be increased by using a binder (polymer chain extender) such as a diisocyanate compound.

The biodegradable resin of the present invention includes plasticizers, compatibilizers, antioxidants, lubricants, colorants, ultraviolet absorbers, light stabilizers, pigments, inorganic fillers and the like as long as the object of the present invention is not impaired. Various additives, modifiers, and fillers can be added as additional components.

To the biodegradable resin of the present invention, a resin other than the biodegradable resin exemplified above within a range not impairing the object of the present invention, for example, a resin made from a fossil resource such as polypropylene, polyethylene or polyvinyl chloride is added. Can be mixed as a component.

When the biodegradable resin is heat-processed, it is preferably dried to suppress hydrolysis due to moisture.

As a method for adding the surfactant of the present invention, a known method can be used. Usually, after a surfactant is mixed with a biodegradable resin in powder form or pellet form with a ribbon blender or the like, the composition is extruded and pelletized with a single screw extruder or a twin screw extruder and used for molding.
For example, (1) a method of supplying the pellets obtained by the above method to a molding machine, and (2) melt kneading while simultaneously feeding a surfactant when the biodegradable resin pellets are melt kneaded by a twin screw extruder. (3) Once a biodegradable resin composition (masterbatch) containing a high concentration of surfactant is produced, the biodegradable resin composition is used as a master batch for modification. The master batch is diluted with biodegradable resin pellets and supplied to a molding machine.

  When adopting the masterbatch method of (3) above, the dilution ratio of the masterbatch for modification varies depending on the concentration of the surfactant in the masterbatch, but is usually 2 to 50 times, preferably 3 to 40 times, More preferably, it is 5-30 times, More preferably, it is 7-30 times. In this range, the surfactant is uniformly dispersed and can be preferably used.

When producing a high-concentration masterbatch, it is preferable to use a compatibilizer that improves the compatibility between the biodegradable resin and the surfactant. When melt-kneading the biodegradable resin and the antistatic agent, In addition, when a compatibilizer is added, it becomes possible to melt and knead to a high concentration, and the storage stability of the obtained pellets is improved.

Examples of the compatibilizer used in the present invention include glycerin fatty acid ester, diglycerin fatty acid ester, polyglycerin fatty acid ester, sorbitol fatty acid ester, sorbitan fatty acid ester, pentaerythritol fatty acid ester, trimethylolpropane fatty acid ester, and sucrose fatty acid. Esters, ester type compounds such as citric acid fatty acid ester, ether type compounds such as polyalkylene glycol polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyethylene polyoxypropylene glycol ether, polyalkylene glycol fatty acid ester, polyoxy Alkylene glycerin fatty acid ester, polyoxyalkylene diglycerin fatty acid ester, polyoxyalkylene polyglyceride Phosphoric fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene pentaerythritol fatty acid esters, polyoxyalkylene trimethylolpropane fatty acid esters, polyoxyalkylene sucrose fatty acid esters, and ether / ether type compounds, Examples include a reaction product of the ester or ether type compound and an inorganic acid such as phosphoric acid.

The addition amount of the compatibilizer is preferably 10 to 300 parts by weight, more preferably 20 to 200 parts by weight, and still more preferably 50 parts by weight with respect to 100 parts by weight of the surfactant. 200 parts by weight, most preferably 75 to 150 parts by weight is preferred.

As a biodegradable resin composition (masterbatch) containing such a surfactant and optionally a compatibilizer in a high concentration, 1 to 100 surfactants are used per 100 parts by weight of the biodegradable resin. A biodegradable resin composition comprising 2 parts by weight, preferably 2 to 50 parts by weight, more preferably 5 to 30 parts by weight of a surfactant is preferred. A known kneading technique can be applied to a known kneading of the master batch and the biodegradable resin.

[Molded body and its manufacturing method]
The biodegradable resin composition according to the present invention is a suitable material that can be applied to publicly known molding methods, and the obtained molded body is not particularly limited, and examples thereof include films, sheets, monofilaments, fibers, and nonwoven fabrics. Thermoformed bodies such as multifilaments, injection-molded bodies, blow-molded bodies, laminates, foams, and vacuum-formed bodies are exemplified.
In addition, the biodegradable resin composition according to the present invention has good moldability when stretch-oriented and crystallized, and the effects of the present invention are remarkably exhibited. A film / sheet obtained by stretching, a tape yarn, a stretch blow molded article, Suitable for production of (mono, multi) filaments.

As a molding method of a molded product obtained from the biodegradable resin composition according to the present invention, an injection molding method, a blow molding method (injection stretch blow, extrusion stretch blow, direct blow), balloon method, inflation molding, co-extrusion method , Calendering method, hot pressing method, solvent casting method, (extension) extrusion molding, extrusion lamination method with paper and aluminum, profile extrusion molding, thermoforming such as vacuum (pressure air) molding, melt spinning (monofilament, multifilament, span Bond method, melt blown method, defibrating yarn method, etc.), foam molding method, compression molding method, etc., and any method can be applied.
In particular, in the case of a molding method capable of taking a step of orientation orientation crystallization such as extrusion molding, melt spinning, etc., it is possible to improve the practical strength and appearance such as strength, heat resistance, impact resistance and transparency of the obtained molded body. It can be used more preferably.
The molded product obtained from the biodegradable resin composition according to the present invention includes, for example, a molded product obtained by a publicly known / official molding method, and there is no limitation on the shape, size, thickness, design and the like.

[Specific examples of applications]
A biodegradable resin composition according to the present invention obtained from the above molding method, such as a bottle, a film or a sheet, a hollow tube, a laminate, a vacuum (pressure air) molded container, a (mono, multi) filament, a nonwoven fabric, a foam, etc. The molded body is, for example, a shopping bag, a paper bag, a shrink film, a garbage bag, a compost bag, a lunch box, a container for sugar beet, a food / confectionery packaging film, a food wrap film, a cosmetic / cosmetic wrap film, a diaper, Sanitary napkins, pharmaceutical wrap films, pharmaceutical wrap films, surgical adhesive wrap films for stiff shoulders and sprains, agricultural and horticultural films, agricultural chemical wrap films, greenhouse films, fertilizer bags, Packaging band, film for packaging magnetic tape cassette products such as video and audio, film for flexible disk packaging Film, plate-making film, adhesive tape, tape, yarn, seedling pot, waterproof sheet, sandbag bag, architectural film, weed prevention sheet, vegetation net, etc., various packaging films for food, electronic, medical, pharmaceutical, cosmetics, etc. It can be suitably used as a wide range of materials, such as those used in the electric / automobile manufacturing industry, agriculture / civil engineering / fishery fields.

[Example of printing method]
As one embodiment of the present invention, there is one in which at least one surface of a film is printed with printing ink. For printing on the film surface, commonly used methods such as screen printing, flexographic printing, offset printing and gravure printing can be used.

Examples of the solvent of the organic solvent ink that can be used in the present invention include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, ketone solvents such as methyl ethyl ketone, and the like. . On the other hand, water-based inks use water as a solvent, and may use alcohols, preferably lower alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, etc., without any particular limitation. Also, common inorganic and organic pigments can be used as colorants for both inks, such as soluble and insoluble organic pigments such as azo, phthalocyanine, and naphthol, titanium oxide, calcium carbonate, petals, and carbon. Inorganic pigments such as black are exemplified. The resin binder may be any styrene-acrylic acid-based, styrene-maleic acid-based acrylic resin, polyurethane resin, rosin-modified resin, or the like that can be produced with a stable ink, and is used alone or in combination. be able to. In addition, waxes, antifoaming agents, dispersing agents and the like may be used as additives. In order to adjust the viscosity of the ink at the time of printing, the above solvent may be used for the organic solvent-based ink, and a diluent in which water and alcohol are used in combination for the water-based ink.

  When printing on the film of the present invention with a known printing machine using the above organic solvent-based ink or water-based ink, the film surface is subjected to a known method such as corona discharge treatment, ozone treatment, plasma treatment, etc. prior to printing. If surface activation treatment is performed, the ink familiarity and adhesiveness can be improved. Therefore, it is desirable to perform surface activation treatment by some method.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to an Example. The following comparative compounds (1) and (2) were compared with the examples.

<Comparative Compound (1): Nonionic Surfactant>
Glycerol monostearate (Anstex MG-100 manufactured by Toho Chemical Industry Co., Ltd.)
<Comparative Compound (2): Anionic Surfactant>
Sodium myristyl sulfonate (Anstex HT-100 manufactured by Toho Chemical Industry Co., Ltd.)

<Synthesis of nitrogen-containing surfactant (A-1)>
A glass autoclave is charged with 1 mol of laurylamine, N ₂ substitution is performed, and 2.0 mol of ethylene oxide is added at 155 ° C. over 2 hours to synthesize the nitrogen-containing surfactant (A-1) of the present invention described above. did.

<Synthesis of nitrogen-containing surfactant (A-2)>
A glass autoclave was charged with 1 mol of diethanolamine, N ₂ substitution was performed, and 1.0 mol of stearic acid was reacted at 155 ° C. for 2 hours to synthesize the nitrogen-containing surfactant (A-2) of the present invention described above. .

<Synthesis of nitrogen-containing surfactant (A-3)>
A glass autoclave was charged with 1 mol of laurylamine, N ₂ substitution was performed, 2.0 mol of ethylene oxide was added at 155 ° C. over 2 hours, and then 1.0 mol of lauric acid was added to 1.0 mol of the obtained compound. Eight moles were charged, the temperature was raised to 160 ° C. while introducing N ₂ gas, and esterification was performed for 4 hours to synthesize the nitrogen-containing surfactant (A-3) of the present invention described above.

<Synthesis of borate ester surfactant (B-1)>
A glass autoclave was charged with 1.0 mol of glycerin and 1.0 mol of lauric acid, heated to 220-250 ° C. in the presence of 0.3% by weight of potassium hydroxide while introducing N ₂ gas, and esterified for 5 hours. Glycerol monolaurate (including diester or higher ester as a by-product. The same applies to the same below) was synthesized. Subsequently, 1.0 mol of boric acid is charged per 1.0 mol of the synthesized glycerin monolaurate, gradually heated and dehydrated to 130 to 135 ° C, and then gradually heated to 230 ° C to obtain the desired glycerin monolaurate. A reaction product (B-1) of laurate and boric acid was synthesized.

<Synthesis of borate ester surfactant (B-2)>
A glass autoclave was charged with 1.0 mol of glycerin and 1.0 mol of boric acid, heated to 220-250 ° C. while introducing N ₂ gas, and esterified for 5 hours to synthesize glycerol borate. Subsequently, 1.0 mol of oleic acid was charged with respect to 1.0 mol of glyceryl borate synthesized, and the temperature was raised to 220 to 250 ° C. in the presence of 0.3% by weight of potassium hydroxide while introducing N ₂ gas. Esterification was carried out for 5 hours to synthesize the desired glyceryl borate oleate (including diester or higher ester as a by-product. The same applies in the following cases) (B-2).

<Surfactant composition of the present invention>
Nitrogen-containing surfactants (A-1) to (A-3) of the present invention and borate ester surfactants (B-1) and (B-2) are shown in Table 1 in the blending ratio (% by weight). And used for the test described later as surfactant compositions (1) to (6).

As the biodegradable resin, polylactic acid [LACEA H-400 (trade name: sold by Mitsui Chemicals, Inc.)] 100 parts by weight of the surfactant composition (1) to (6) of the present invention described above, a comparative compound (1) and (2) were blended in the blending amounts shown in Table 2, and a 200 μm sheet was formed at a melting temperature of 210-230 ° C. with a T-die extruder equipped with a dehumidifying dryer. Next, this sheet was heated in an oven set at a temperature of 70 to 75 ° C. for 1 minute, then stretched 3.0 times in length and 3.0 times in width, further heated to 150 ° C. and heated at 150 ° C. for 1 minute. The film was fixed to obtain a film having a thickness of 20 μm. This stretched film was allowed to stand for 14 days under a constant temperature and humidity condition of a temperature of 23 ° C. and a relative humidity of 50%, and then the molecular weight retention, transparency, antistatic property, antifogging property, printability, and lubricity were evaluated. The evaluation results are shown in Table 2.

<Evaluation method>
The performance evaluation of the film-forming film was specifically carried out by the following method.

(1) Molecular weight retention rate Tosoh Corporation chromatographic column TSKgel SUPER HZM-M (× 2) was mounted on Shimadzu Corporation chromatography SCL-10Avp, and the eluent chloroform, flow rate 0.6 ml / min. The measurement was carried out under the conditions of a column temperature of 40 ° C., a sample concentration of 0.05 wt%, a sample injection amount of 50 μl, and a detector RI, and the weight average molecular weight of the formed film was calculated in terms of polystyrene. The weight average molecular weights of the standard polystyrene used are 1090000, 706000, 355000, 190000, 96400, 37900, 19600, 10200, 5570, 2630, 870, 500.

  The molecular weight retention rate (%) was calculated by [(weight average molecular weight of film with surfactant added) / (weight average molecular weight of film with no surfactant added)] × 100. The target molecular weight retention is 80% or more.

(2) The HAZE value of the film-forming film was measured with a transparent HAZE measuring device (HAZEMETER TC-HIIIDPK manufactured by Tokyo Denshoku Co., Ltd.), and evaluated by the difference ΔHAZE from the film with no surfactant added. The smaller ΔHAZE is, the closer the transparency is to a film with no surfactant added. The target for ΔHAZE is 10 or less.

(3) Antistatic property According to JIS-K-6911, the surface specific resistance value of the film-forming film was measured using a super insulation meter P-616 manufactured by Kawaguchi Electric Co., Ltd. The smaller the value, the better the antistatic property. The target of Log (surface resistivity Ω / □) is 13 or less.

(4) Anti-fogging property (evaluation of drip resistance)
The anti-fogging property of the film-forming film in low and high temperature environments was evaluated.
Low-temperature antifogging property: 5 ° C. water was put into a beaker and then covered with a biodegradable resin film. The wet state of the film after 6 hours at an external temperature of 5 ° C. was evaluated.
High temperature antifogging property: 90 ° C. water was put into a beaker and then covered with a biodegradable resin film. The wet state of the film after 30 minutes at an external temperature of 25 ° C. was evaluated.
The antifogging property was evaluated according to the following criteria.
◎: Wet evenly on the entire surface and transparent ○: More than half is transparent △: More than half is opaque ×: Completely opaque

(5) Printability evaluation (ink transferability)
Using a gravure printing machine on the corona discharge treated surface of the film-forming film, an organic solvent-based ink and a water-based ink were printed to evaluate the ink transferability with the film surface.
In the transferability evaluation, the printed surface was observed with an optical microscope, and the transfer amount of repelling ink was evaluated according to the following criteria.
◎: No repelling is observed, and the amount of ink transferred is large. ○: Almost no repelling is observed, and the amount of transferred ink is somewhat large. △: Some repelling is observed, and the amount of ink transferred is normal. , Ink transfer amount is also low XX: Toyo Ink Manufacture's “LP Super” is an organic solvent-based ink that has very high repellency and low ink transfer amount. Diluted to ˜30% by weight was used.
As the water-based ink, “Aqua Ecole” manufactured by Toyo Ink Mfg. Co., Ltd. was used to dilute it to a solid concentration of 20 to 30% by weight and an alcohol concentration of 30% or less using a dedicated diluent solvent.

(6) The lubricity of the film-forming film was evaluated based on the dynamic friction coefficient using tribogear TYPE HEIDON-14DR (manufactured by HEIDON) based on JIS K7125-ISO8295. The target is a coefficient of dynamic friction of 0.4 or less.

Further, various molding methods and molded articles obtained from various biodegradable resin compositions according to the present invention were also evaluated as Examples 9 and 10 below using the surfactant composition (1) of the present invention. The evaluation methods for molecular weight retention, transparency, antistatic properties (surface resistivity), antifogging properties, and lubricity are the same as described above.

Example 9-1 (T-die extrusion molding)
Polylactic acid [LACEA H-400 (trade name: sold by Mitsui Chemicals, Inc.)] 10 kg as biodegradable resin, surfactant composition (1) and polyglycerol monostearate as compatibilizer in polylactic acid H-400 After blending 0.5 kg of pellets obtained by melting and kneading 10 wt% of the blended product (mixing ratio: 25 wt% / 75 wt%) with a T-die extruder equipped with a dehumidifying dryer, the melting temperature is 210-230 ° C. Was formed into a sheet. The thickness of this sheet was 200 μm, the molecular weight retention rate was 87.2%, and the surface resistivity was 11.8. Next, this sheet was heated in an oven set at a temperature of 70 to 75 ° C. for 1 minute, then stretched 3.0 times in length and 3.0 times in width, further heated to 150 ° C. and heated at 150 ° C. for 1 minute. Fixed. The obtained film had a thickness of 20 μm and a surface resistivity of 11.6. As a result of evaluating the antifogging property of this stretched film, both the low temperature antifogging property and the high temperature antifogging property were uniformly wetted on the entire surface and were transparent. Furthermore, as a result of evaluating the printability of the stretched film, no repellency was observed and the amount of ink transferred was large.

Example 9-2 (T-die extrusion molding)
Example 9 except that polybutylene terephthalate adipate [Ecoflex (trade name: manufactured by BASF Corp.)] and pellets obtained by melting and kneading 10% by weight of the surfactant composition (1) in Ecoflex were used as the biodegradable resin. -1 was performed. The thickness of the obtained Ecoflex sheet was 200 μm, the molecular weight retention was 86.4%, and the surface resistivity was 11.8. Next, the sheet was heated in an oven set at a temperature of 60 to 70 ° C. for 1 minute, then stretched to 3.0 times in length and 3.0 times in width, further heated to 110 ° C. and heated at 110 ° C. for 1 minute. Fixed. The obtained film had a thickness of 20 μm and a surface resistivity of 11.5. As a result of evaluating the antifogging property of this stretched film, both the low temperature antifogging property and the high temperature antifogging property were uniformly wetted on the entire surface and were transparent. Furthermore, as a result of evaluating the printability of the stretched film, no repellency was observed and the amount of ink transferred was large.

Example 9-3 (T-die extrusion molding)
Other than using polybutylene succinate [Bionore # 1010 (trade name: manufactured by Showa Kogyo Co., Ltd.)] as a biodegradable resin, pellets obtained by melting and kneading 10% by weight of the surfactant composition (1) in Bionore This was carried out according to Example 9-1. The thickness of the resulting Bionore sheet was 200 μm, the molecular weight retention was 88.9%, and the surface specific resistance value was 12.1. Next, the sheet was heated in an oven set at a temperature of 60 to 70 ° C. for 1 minute, then stretched to 3.0 times in length and 3.0 times in width, further heated to 110 ° C. and heated at 110 ° C. for 1 minute. Fixed. The obtained film had a thickness of 20 μm and a surface resistivity of 11.7. As a result of evaluating the antifogging property of this stretched film, both the low temperature antifogging property and the high temperature antifogging property were uniformly wetted on the entire surface and were transparent. Furthermore, as a result of evaluating the printability of the stretched film, no repellency was observed and the amount of ink transferred was large.

Example 9-4 (T-die extrusion molding)
Other than using polybutylene succinate [GS Pla (trade name: manufactured by Mitsubishi Chemical Corporation)] as a biodegradable resin, pellets obtained by melt-kneading 10% by weight of the surfactant composition (1) with GS Pla, It carried out according to Example 9-1. The thickness of the obtained GS Pla sheet was 200 μm, the molecular weight retention was 90.4%, and the surface resistivity was 11.7. Next, this sheet is heated in an oven set at a temperature of 60 to 65 ° C. for 1 minute, and then stretched 3.0 times in length and 3.0 times in width, and further heated to 110 ° C. and heated at 110 ° C. for 1 minute. Fixed. The obtained film had a thickness of 20 μm and a surface resistivity of 11.5. As a result of evaluating the antifogging property of this stretched film, both the low temperature antifogging property and the high temperature antifogging property were uniformly wetted on the entire surface and were transparent. Furthermore, as a result of evaluating the printability of the stretched film, no repellency was observed and the amount of ink transferred was large.

Example 10-1 (inflation molding)
As a biodegradable resin, polylactic acid [LACEA H-100 (trade name: sold by Mitsui Chemicals)] 5.0 kg, polybutylene succinate adipate [Bionore # 3001 (trade name: Showa Polymer Co., Ltd.)] 4.0 kg of polylactic acid H-100 was melt kneaded with a surfactant composition (1) and a blend of glycerin monostearate as a compatibilizer (blending ratio: 25 wt% / 75 wt%). After dry blending 1.0 kg of pellets, a cylinder temperature of 150 to 180 ° C., a die temperature of 165 to 175 ° C., and a blow-up ratio of 2.3 are set using a φ30 mm inflation molding machine equipped with a dehumidifying dryer, and a width of 225 mm. A tube having a thickness of 30 μm was formed. The obtained film had a molecular weight retention of 91.1% and a surface resistivity of 11.6. As a result of evaluating the antifogging property of this stretched film, both the low temperature antifogging property and the high temperature antifogging property were uniformly wetted on the entire surface and were transparent. Furthermore, as a result of evaluating the printability of the stretched film, no repellency was observed and the amount of ink transferred was large.

Example 10-2 (inflation molding)
As a biodegradable resin, polylactic acid [LACEA H-280 (trade name: sold by Mitsui Chemicals)] 5.0 kg, polybutylene terephthalate adipate [Ecoflex (trade name: manufactured by BASF Corporation)] 4.0 kg, H The same procedure as in Example 10-1 was performed except that 1.0 kg of pellets obtained by melt-kneading 15% by weight of the surfactant composition (1) with -280 was dry blended. The obtained film had a molecular weight retention of 89.7% and a surface resistivity of 11.6. As a result of evaluating the antifogging property of this stretched film, both the low temperature antifogging property and the high temperature antifogging property were uniformly wetted on the entire surface and were transparent. Furthermore, as a result of evaluating the printability of the stretched film, no repellency was observed and the amount of ink transferred was large.

Example 10-3 (inflation molding)
As a biodegradable resin, polylactic acid [LACEA H-280 (trade name: sold by Mitsui Chemicals)] 5.0 kg, polybutylene succinate adipate [GS plastic (trade name: manufactured by Mitsubishi Chemical Corporation)] 4. The same procedure as in Example 10-1 was performed except that 1.0 kg of pellets obtained by melt-kneading 15 wt% of the surfactant composition (1) in 0 kg, H-280 were dry blended. The obtained film had a molecular weight retention of 88.5% and a surface resistivity of 12.1. As a result of evaluating the antifogging property of this stretched film, both the low temperature antifogging property and the high temperature antifogging property were uniformly wetted on the entire surface and were transparent. Furthermore, as a result of evaluating the printability of the stretched film, no repellency was observed and the amount of ink transferred was large.

As shown in the results of Examples 1 to 10 above, the biodegradable resin containing the surfactant composition of the present invention maintains the molecular weight and has excellent antistatic and anti-static properties without impairing the appearance of the resin. It can exhibit haze, printability and surface lubricity. Films, sheets, injection molded articles, filaments, non-woven fabrics, bottles, yarns and other molded articles made of the same are used for (food) packaging materials, agriculture, electrical machinery / automobile manufacturing, civil engineering / architecture, and marine products. It can be suitably used as a wide range of materials such as materials and compost materials.

Claims (10)

90 to 10% by weight of a nitrogen-containing surfactant (A) represented by the following general formula (1) and a borate ester surfactant (B) having 1 or 2 or more hydrophobic groups having 1 to 30 carbon atoms ) A biodegradable resin composition containing 0.05 to 5.0% by weight of a surfactant composition comprising 10 to 90% by weight.

[R ₁ represents a linear or branched alkyl group, alkenyl group, hydroxyalkyl group, alkylaryl group, or arylalkyl group having 1 to 30 carbon atoms. R ₂ and R ₃ each independently represent hydrogen or an acyl group having 2 to 30 carbon atoms. m and n represent an integer of 0 or more that satisfies m + n = 0-100. X is

Indicates. Y and Z are each independently one or more
-R ₄ O-
(R ₄ represents an alkylene group having 2 to ₄ carbon atoms). Y and Z may be the same or different. ] The biodegradable resin composition according to claim 1, wherein the boric acid ester surfactant is a reaction product of a compound obtained by esterifying a polyhydric alcohol with a higher fatty acid and boric acid, or a salt of the reaction product. . 2. The biodegradable resin composition according to claim 1, wherein the borate ester surfactant is a reaction product of a compound obtained by esterifying a polyhydric alcohol with boric acid and a higher fatty acid, or a salt of the reaction product. . Excellent antistatic properties (surface resistivity is less than 1.0E + 13 [Ω / □]), antifogging properties, transparency, printability, and lubricity (dynamic friction coefficient is less than 0.4) while maintaining molecular weight The biodegradable resin composition according to any one of claims 1 to 3, comprising: The resin composition according to any one of claims 1 to 4, wherein the biodegradable resin is a polylactic acid resin. The resin molding which consists of a resin composition of any one of Claims 1-5. The film which consists of a resin composition of any one of Claims 1-5. The sheet | seat which consists of a resin composition of any one of Claims 1-5. 90 to 10% by weight of a nitrogen-containing surfactant (A) represented by the general formula (1) and a borate ester surfactant (B) having one or more hydrophobic groups having 1 to 30 carbon atoms ) Antistatic agent for biodegradable resin obtained by mixing 10 to 90% by weight. Use of the antistatic agent according to claim 9 for a biodegradable resin.