JP2015227400A - Powder production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition in powder form which functions as a fluidity control material.SOLUTION: A powder production method uses a crusher which is provided with a charge inlet for a resin composition solid material (C) and carrier medium supply port and includes a crushing part (a) which converts the charged resin composition solid material (C) to a powder, a flow part (b) which is connected directly to the upper part of the crushing part and causes the powder obtained in the crushing part (a) to flow by using a carrier medium, and a discharge port (c) for powder of gran sizes equal to or smaller than a target value and a carrier medium arranged in the upper part of the flow part and controls the internal temperature of the crushing part (a) and the supply amount of the carrier medium.

Description

  The present invention comprises an autocatalytic resin (component A) containing a water-soluble monomer as a main component and a degradation regulator (component B), and the component A and / or component B incorporating the component B are exchange agents. It relates to the manufacturing method of the powder of the water-decomposable resin composition solid substance (C) containing the resin component which A component exchange-reacted as.

In recent years, for the purpose of protecting the global environment, resins that are easily decomposed in a natural environment have attracted attention and have been studied all over the world. Biodegradable polymers represented by aliphatic polyesters such as polylactic acid, polyglycolic acid, poly (3-hydroxybutyrate), and polycaprolactone are known as resins that are easily decomposed in a natural environment.
In particular, polylactic acid is a polymer material that is highly biosafe and environmentally friendly because it uses lactic acid obtained from plant-derived raw materials or derivatives thereof as raw materials. Therefore, the use as a general-purpose polymer is examined, and the use as a film, a fiber, an injection molded product, etc. is examined.

  However, polylactic acid has a problem that it has a relatively low degradation rate in the natural environment because it has a high crystallinity and a glass transition point among bioplastics and has a low degradability by water and enzymes. A low decomposition rate is suitable for applications that require a long life, but depending on the application, it is necessary to decompose quickly. For example, oil and gas drilling applications.

Oil and gas wells are drilled to recover hydrocarbons, including oil and gas, from the ground. At that time, drilling with mud water in the shaft and drilling with a drill, and then adding crushing fluid (fracturing fluid) into the formation and causing cracks to expand production (fracturing) ) Is performed.
Originally, it is desirable for the formation around the well to have high liquid permeability from the viewpoint of promoting the inflow of oil into the well through the formation, but in excavation work and fracturing, from the viewpoint of work efficiency. There are cases in which fluid permeation into the formation is temporarily suppressed. This is necessary, for example, to prevent escape through working well walls such as muddy water.

  The suppression of liquid permeability is mainly achieved and suppressed by a sealing material (agent) such as gravel, calcium carbonate or other inorganic particles or guar gum or other gel-like organic substance mixed in working water or the like. Recovery is achieved by dissolving the inorganic filler with acid or the like or using a gel-like organic decomposing agent. These materials are generally collectively referred to as fluidity control materials. On the other hand, in recent years, several proposals have been made to use aliphatic polyesters such as polyglycolic acid and polylactic acid as fluidity control materials (and / or gel decomposing agents) taking advantage of their natural degradability. (See Patent Documents 1-3).

However, these aliphatic polyesters can be hydrolyzed relatively quickly in water at 80 ° C. or higher, but in the case of high molecular weight polymers, sufficient degradability cannot be obtained at 40 to 80 ° C. Was an issue.
In particular, when polylactic acid that can be used for general purposes is applied to this application, the difficulty of decomposition at 40 to 80 ° C. was a major obstacle. In the case where the polyglycolic acid resin in the oligomer region having a molecular weight of 200 to 4000 (Patent Document 1) or 200 to 600 (Patent Document 2) has a satisfactory hydrolysis rate even in a low temperature region of 40 to 80 ° C. However, when such a resin is used as a fluidity control material, the property can be maintained only for a short period of time, so that the effect is limited, and there is a problem that it is difficult to use from the viewpoint of storage.

  Polylactic acid and polyglycolic acid, which are such biodegradable aliphatic polyesters, are used in the form of powders, powder dispersions or solutions in the above applications. Various methods for producing biodegradable aliphatic polyesters have been proposed, and it is generally known to cut and grind molten solids. Patent Document 4 discloses a method in which polylactic acid resin pellets and the like are cooled to an extremely low temperature of −50 to −180 ° C. and pulverized. If such a technique is used, it is possible to produce powder, but since a large amount of liquid nitrogen for cooling is used, complicated equipment is required, and productivity is greatly deteriorated. .

On the other hand, Patent Document 5 discloses a method in which a biodegradable aliphatic polyester is dissolved in an organic solvent and then dropped into water or the like, which is a poor solvent, and precipitated into fine particles. Since multi-step processes such as dissolution, precipitation, and drying are required, not only productivity is poor, but not only a large amount of waste solvent containing impurities is generated, but also the solvent remains in the product, There is also a risk of adversely affecting quality.
As described above, the production of biodegradable aliphatic polyester powder is a very difficult technique, and it is difficult to obtain industrially easily and inexpensively. There is a need for a method of manufacturing.

US Pat. No. 4,715,967 US Pat. No. 4,986,353 International Publication No. 2012/050187 Pamphlet JP 2001-288273 A JP 2000-7789 A

  The object of the present invention is to solve the above-mentioned conventional problems, to effectively function as a fluidity control material, and to produce a polylactic acid resin solid powder having sufficient degradability even at a low temperature of 40 to 80 ° C. It is to provide a method.

The present inventors have intensively studied a method for producing a powder of a resin composition solid material that functions effectively as a fluidity control material and has sufficient readily decomposability even at a low temperature of 40 to 80 ° C.
As a result, a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer and a decomposition accelerator (B component) functioning as an exchange agent for the A component are blended to maintain the high molecular weight while the B component is maintained. When the pulverization conditions are set to a specific range for a resin composition containing a resin component in which the A component is exchange-reacted with the A component and / or B component incorporated with As a result of finding out the efficient production of the powder and further intensive studies, the present invention has been achieved.

That is, the object of the present invention is to
1. A component and / or B composed of a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer and a degradation regulator (B component) that functions as an exchange agent for the A component. A resin composition containing a resin component in which components A are exchange-reacted with each other as an exchange agent, wherein the weight after 120 hours is 95% or less and the weight after 240 hours is 75% or less in water at 60 ° C. Resin composition solids (C)
A pulverizing section (I) comprising a resin composition solid (C) charging port and a transport medium supply port, and converting the charged resin composition solid (C) into powder.
A fluidized part (b) in which the powder obtained in the powder part (a) directly connected to the upper part of the grinding part is fluidized by a carrier medium;
At the upper part of the fluidized section, the discharge port (c) for the powder and the conveying medium below the target particle size,
Using a crusher having
The resin composition solid (C) is pulverized while controlling the temperature in the pulverization part (b) within the range of −20 ° C. to Tg−5 ° C. of the resin composition solid (C) by supplying a carrier medium. The amount of transport medium supplied to the crushing part (b) exceeds the flow rate at which the powder starts flowing in the crushing part (b) and exceeds the target particle size in the crushing part (b). The returned powder having a particle size equal to or smaller than the target particle size is achieved by a powder manufacturing method in which the flow rate is discharged from the discharge port (C) together with the carrier medium.
The above also includes the following.
2. 2. The method for producing a powder according to 1 above, wherein the carrier medium is a gas.

It can also be achieved by the following method.
3. A component and / or B composed of a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer and a degradation regulator (B component) that functions as an exchange agent for the A component. A resin composition containing a resin component in which components A are exchange-reacted with each other as an exchange agent, wherein the weight after 120 hours is 95% or less and the weight after 240 hours is 75% or less in water at 60 ° C. Resin composition solids (C)
A resin composition solid (C) charging port and a conveyance medium supply port are provided, and the obtained resin composition solid (C) is pulverized while the obtained powder is fluidized by the conveyance medium. Fluid department (d),
At the bottom of the pulverization fluid section, the discharge port (c) for the powder and the conveying medium below the target particle size,
Using a crusher having
By controlling the temperature in the pulverization fluidized section (d) within the range of −20 ° C. to Tg−5 ° C. of the resin composition solid (C) by supplying the carrier medium, the resin composition solid (C) A method for producing a powder, which is charged into the pulverization fluid section (d) and the supply amount of the conveyance medium is a flow rate at which the powder starts flowing in the pulverization fluid part (d).

Also included are:
4). 4. The method for producing a powder according to 3 above, comprising a step of separating the powder discharged from the pulverization fluidizing section (d) and the transport medium, and a step of drying the separated powder.
5. 5. The method for producing a powder according to 3 or 4 above, wherein the carrier medium is a liquid.
6). 6. The method for producing a powder according to any one of 1 to 5 above, wherein the component A is polylactic acid or polyglycolic acid.
7). 7. The method for producing a powder according to any one of 1 to 6 above, wherein the component B is an amine compound and / or an organic acid metal salt.
8). The method for producing a powder according to any one of 1 to 7 above, wherein the content of the B component is 0.01 to 30 parts by weight with respect to 100 parts by weight of the total of the A component and the B component.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the powder which functions effectively as a fluidity control material, and has sufficient easily decomposability even at a low temperature of 40 to 80 ° C. can be provided. Since the powder uses a resin having an autocatalytic action mainly composed of a water-soluble monomer, the powder is efficiently dissolved after decomposition in low-temperature water and does not require post-treatment using an acid or the like. Moreover, the decomposition accelerator (B component) which functions as an exchange agent of A component is mix | blended, and the resin component which A component exchange-reacted by using A component and / or B component which incorporated B component as an exchange agent is contained. Thus, easy degradability in low-temperature water can be imparted, and solubility in water can also be improved. The decomposition timing can be controlled by the amount of component B added.
Therefore, the powder obtained by the production method of the present invention exhibits a desired performance in the oil field excavation technique and can be suitably used.

The schematic diagram which showed the whole structure of the grinding | pulverization apparatus in case the conveyance medium which concerns on this invention is gas. The schematic diagram which showed the whole structure of the grinding | pulverization apparatus in case the conveyance medium which concerns on this invention is a liquid.

Hereinafter, the present invention will be described in detail.
<Resin having autocatalytic action mainly composed of water-soluble monomer (component A)>
In the present invention, the resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer is a resin in which a monomer produced by decomposition exhibits water solubility, and an acidic group produced by the decomposition has an autocatalytic action. It is. One resin may be sufficient and a mixture of two or more may be sufficient.
Here, water solubility means that the solubility in water at 25 ° C. is 0.1 g / L or more. The solubility of the water-soluble monomer in water is preferably 1 g / L or more, more preferably 3 g / L or more, from the viewpoint that the resin composition to be used does not remain in water after decomposition. More preferably, it is the above.

Further, the water-soluble monomer as the main component is preferably 90 mol% or more of the constituent components. If it is less than 90%, the water-insoluble monomer remains in the water, and the performance as a fluidity controlling material may deteriorate. From such a viewpoint, the water-soluble monomer as the main component is more preferably 95 to 100 mol%, and still more preferably 98 to 100 mol% of the constituent components.
Examples of the component A include at least one selected from the group consisting of polyester, polyamide, polyamideimide, polyimide, polyurethane, and polyesteramide. Preferably polyester is illustrated.

Examples of the polyester include a polymer or copolymer obtained by polycondensation of one or more selected from dicarboxylic acid or an ester-forming derivative thereof and diol or an ester-forming derivative thereof, hydroxycarboxylic acid or an ester-forming derivative thereof, or a lactone. Is exemplified. Preferred examples include polyesters made of hydroxycarboxylic acid or ester-forming derivatives thereof. More preferably, an aliphatic polyester composed of hydroxycarboxylic acid or an ester-forming derivative thereof is exemplified.
Such a thermoplastic polyester may contain a cross-linked structure treated with a radical generation source such as an energy active ray or an oxidizing agent for moldability and the like.

  Dicarboxylic acid or ester-forming derivatives include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4, Aromatic dicarboxylic acids such as 4′-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid and 5-sodium sulfoisophthalic acid can be mentioned. Moreover, aliphatic dicarboxylic acids, such as oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, and dimer acid, are mentioned. Moreover, alicyclic dicarboxylic acids, such as 1, 3- cyclohexane dicarboxylic acid and 1, 4- cyclohexane dicarboxylic acid, are mentioned. Moreover, these ester-forming derivatives are mentioned.

  Examples of the diol or ester-forming derivative thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5 -Pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol and the like.

  Further, long chain glycols having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly 1,3-propylene glycol, poly 1,2-propylene glycol, polytetramethylene glycol and the like can be mentioned. In addition, aromatic dioxy compounds, that is, 4,4'-dihydroxybiphenyl, hydroquinone, tert-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and the like can be mentioned. Moreover, these ester-forming derivatives are mentioned.

  Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropioic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and these Examples thereof include ester-forming derivatives. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

  Examples of the aliphatic polyester include a polymer mainly composed of an aliphatic hydroxycarboxylic acid, a polymer obtained by polycondensation of an aliphatic polyvalent carboxylic acid or an ester-forming derivative thereof and an aliphatic polyhydric alcohol as main components, and those polymers. Copolymers are exemplified.

  Examples of the polymer having an aliphatic hydroxycarboxylic acid as a main constituent component include polycondensates such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, and hydroxycaproic acid, and copolymers. Among these, polyglycolic acid, polylactic acid, poly-3-hydroxycarboxylic butyric acid, poly-4-polyhydroxybutyric acid, poly-3-hydroxyhexanoic acid or polycaprolactone, and copolymers thereof can be mentioned. Particularly, poly L-lactic acid, poly D-lactic acid, stereocomplex polylactic acid, and racemic polylactic acid can be mentioned.

  Moreover, the polymer which has aliphatic polyhydric carboxylic acid and aliphatic polyhydric alcohol as the main structural components is mentioned. As polyvalent carboxylic acids, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, dimer acid and other aliphatic dicarboxylic acids, 1,3-cyclohexanedicarboxylic acid, 1, Examples include alicyclic dicarboxylic acid units such as 4-cyclohexanedicarboxylic acid and ester derivatives thereof. Further, as the diol component, an aliphatic glycol having 2 to 20 carbon atoms, that is, ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6 -Hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol and the like. Further, long chain glycols having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly 1,3-propylene glycol, poly 1,2-propylene glycol, and polytetramethylene glycol can be mentioned. Specific examples include polyethylene adipate, polyethylene succinate, polybutylene adipate or polybutylene succinate, and copolymers thereof.

Polyester can be produced by a known method (for example, a saturated polyester resin handbook (written by Kazuo Yuki, published by Nikkan Kogyo Shimbun, published December 22, 1989)).
Furthermore, examples of the polyester include an unsaturated polyester resin obtained by copolymerizing an unsaturated polyvalent carboxylic acid or an ester-forming derivative thereof in addition to the polyester, and a polyester elastomer containing a low melting point polymer segment.

  Examples of the unsaturated polycarboxylic acid include maleic anhydride, tetrahydromaleic anhydride, fumaric acid, endomethylenetetrahydromaleic anhydride and the like. In order to control the curing characteristics, various monomers are added to the unsaturated polyester, and it is cured and molded by a curing treatment with an active energy beam such as thermal curing, radical curing, light, or electron beam.

  Further, in the present invention, the polyester may be a polyester elastomer obtained by copolymerizing a soft component. The polyester elastomer is a block copolymer composed of a high melting point polyester segment and a low melting point polymer segment having a molecular weight of 400 to 6,000 as described in known literatures such as JP-A-11-92636. When the polymer is formed only from the high melting point polyester segment, the melting point is 150 ° C. or more, which can be suitably used.

  In the present invention, the polyester is preferably a polyester comprising a hydroxycarboxylic acid or an ester-forming derivative thereof. Further, an aliphatic polyester composed of hydroxycarboxylic acid or an ester-forming derivative thereof is more preferable. Furthermore, the aliphatic polyester is particularly preferably at least one selected from the group consisting of poly L-lactic acid, poly D-lactic acid, racemic polylactic acid, and polyglycolic acid.

Furthermore, two or more of these aliphatic polyesters can be used in combination from the viewpoint of controlling the degradability in low-temperature water. In that case, it is preferable that polylactic acid is a main component, and two combinations of polylactic acid and polyglycolic acid are preferable.
The polylactic acid as the main component is preferably 50% or more of the weight of the component A, more preferably 70% or more, and further preferably 80% or more, from the viewpoint of ease of control of degradability. .

  Here, polylactic acid consists of lactic acid units whose main chain is represented by the following formula (1). The lactic acid monomer is preferably in a proportion of 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 98 to 100 mol% of the monomer constituting polylactic acid.

  The lactic acid unit represented by the formula (1) includes an L-lactic acid unit and a D-lactic acid unit, which are optical isomers. The main chain of the polylactic acid is preferably mainly an L-lactic acid unit, a D-lactic acid unit or a combination thereof. From the viewpoint of degradability at low temperatures, it is particularly preferable that the main chain of polylactic acid is mainly a combination of L-lactic acid units and D-lactic acid units. In that case, it is preferable that the other lactic acid unit is 1-20 mol% with respect to the main lactic acid unit. If it is less than 1 mol%, the decomposability in low-temperature water may be low. On the other hand, when the content is more than 20 mol%, the glass transition temperature is lowered, and the resin composition is melted or softened in low-temperature water, so that the effect as a fluidity controlling material may not be exhibited. From such a viewpoint, it is more preferable that the other lactic acid unit is 3 to 15 mol%, and further preferably 5 to 15 mol% with respect to the main lactic acid unit.

  When two or more of these aliphatic polyesters are used in combination as component A, the combination is preferably two of polylactic acid and polyglycolic acid. Polyglycolic acid is generally more degradable in water at a lower temperature than polylactic acid. However, due to its easy decomposability, when used alone, it may not be possible to maintain long-term properties as a fluidity control material. It may also be a problem from the viewpoint of storage. Therefore, it is preferable to combine polylactic acid and polyglycolic acid. When polylactic acid and polyglycolic acid are applied to the present invention as component A, the degradability at a lower temperature can be further accelerated than polylactic acid alone. The amount of polyglycolic acid is preferably less than 50%, more preferably less than 30%, and even more preferably less than 20%, based on the total weight of polylactic acid and polyglycolic acid, from the viewpoint of easy decomposability and storage properties.

When polylactic acid or a combination of polylactic acid and polyglycolic acid is used, the proportion of other units constituting the main chain is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, still more preferably 0 to 2 It is in the range of mol%.
Examples of other units constituting the main chain include units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. Or aromatic polyhydric alcohol etc., such as what added ethylene oxide to bisphenol, etc. are mentioned. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

The weight average molecular weight of the polylactic acid used is preferably in the range of 30,000 to 500,000, more preferably 50,000 to 350,000, and still more preferably 10 to 250,000 in order to achieve both the mechanical properties and moldability of the molded product. is there. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.
The main chain of polylactic acid may be stereocomplex polylactic acid including a stereocomplex phase formed by poly L-lactic acid units and poly D-lactic acid units.

  Polylactic acid can be produced by a conventionally known method. For example, it can be produced by ring-opening polymerization of L-lactide or D-lactide or a mixture thereof in the presence of a metal-containing catalyst. The low molecular weight polylactic acid containing a metal-containing catalyst is optionally crystallized or without crystallization, under reduced pressure or from normal pressure to increased pressure, in the presence or absence of an inert gas stream. It can also be produced by solid phase polymerization. Furthermore, it can be produced by a direct polymerization method in which lactic acid is subjected to dehydration condensation in the presence or absence of an organic solvent.

  The polymerization reaction can be carried out in a conventionally known reaction vessel. For example, in a ring-opening polymerization or direct polymerization method, a vertical reactor or a horizontal reactor equipped with a stirring blade for high viscosity, such as a helical ribbon blade, is used alone, or Can be used in parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.

  Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid, such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, ethylene glycol, trimethylolpropane, pentaerythritol, etc. Can be suitably used. It can be said that the polylactic acid prepolymer used in the solid-phase polymerization method is preferably crystallized in advance from the viewpoint of preventing resin pellet fusion. The prepolymer is in a solid state in a fixed vertical or horizontal reaction vessel, or in a reaction vessel (such as a rotary kiln) in which the vessel itself rotates, such as a tumbler or kiln, in the temperature range from the glass transition temperature of the prepolymer to less than the melting point. Polymerized.

  Metal-containing catalysts include alkali metals, alkaline earth metals, rare earths, transition metals, fatty acid salts such as aluminum, germanium, tin, antimony, titanium, carbonates, sulfates, phosphates, oxides, hydroxides , Halides, alcoholates and the like. Among them, fatty acid salts, carbonates, sulfates, phosphates, oxides, hydroxides containing at least one metal selected from tin, aluminum, zinc, calcium, titanium, germanium, manganese, magnesium and rare earth elements Products, halides, and alcoholates are preferred.

  Tin compounds due to low catalytic activity and side reactions, specifically stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate Tin-containing compounds such as tin stearate and tetraphenyltin are exemplified as preferred catalysts. Among these, tin (II) compounds, specifically, diethoxytin, dinonyloxytin, tin (II) myristate, tin (II) octylate, tin (II) stearate, tin (II) chloride and the like are suitable. Illustrated.

The amount of the catalyst used is 0.42 × 10 ^{−4 to} 100 × 10 ⁻⁴ (mole) per 1 kg of lactide, and 1.68 × 10 ^{−4 in} consideration of reactivity, color tone and stability of the resulting polylactides. To 42.1 × 10 ⁻⁴ (mol), particularly preferably 2.53 × 10 ^{−4 to} 16.8 × 10 ⁻⁴ (mol).
The metal-containing catalyst used for the polymerization of polylactic acid is preferably deactivated with a conventionally known deactivator prior to using polylactic acid. Examples of such a deactivator include an organic ligand having a group of chelate ligands having an imino group and capable of coordinating with a polymerized metal catalyst.

  Also, dihydridooxoline (I) acid, dihydridotetraoxodiphosphorus (II, II) acid, hydridotrioxoline (III) acid, dihydridopentaoxodiphosphoric acid (III), hydridopentaoxodi (II, IV) Acid, dodecaoxohexaphosphoric acid (III), hydridooctaoxotriphosphoric acid (III, IV, IV) acid, octaoxotriphosphoric acid (IV, III, IV) acid, hydridohexaoxodiphosphoric acid (III, V) acid, hexaoxodiacid Examples thereof include low oxidation number phosphoric acids having an acid number of 5 or less, such as phosphorus (IV) acid, decaoxotetraphosphoric (IV) acid, hendecaoxotetraphosphoric (IV) acid, and eneoxooxophosphorus (V, IV, IV) acid.

Further, orthophosphoric acid represented by the formula xH ₂ O · yP ₂ O ₅ and x / y = 3 may be mentioned. Moreover, polyphosphoric acid which is 2> x / y> 1, and is called diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid or the like based on the degree of condensation, and a mixture thereof can be mentioned. Moreover, the metaphosphoric acid represented by x / y = 1, especially trimetaphosphoric acid and tetrametaphosphoric acid are mentioned. Further, ultraphosphoric acid represented by 1> x / y> 0 and having a network structure in which a part of the phosphorus pentoxide structure is partially removed (these may be collectively referred to as a metaphosphoric acid compound) may be mentioned. . Moreover, the acid salt of these acids is mentioned. Moreover, the monovalent | monohydric and polyhydric alcohol of these acids, the partial ester of polyalkylene glycol, and complete ester are mentioned. Examples thereof include phosphono-substituted lower aliphatic carboxylic acid derivatives of these acids.

In view of the catalyst deactivation ability, orthophosphoric acid represented by the formula xH ₂ O · yP ₂ O ₅ and x / y = 3 is preferred. Moreover, 2> x / y> 1, and polyphosphoric acid referred to as diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid and the like, and a mixture thereof are preferable from the degree of condensation. Further, metaphosphoric acid represented by x / y = 1, particularly trimetaphosphoric acid and tetrametaphosphoric acid are preferable. Ultraphosphoric acid represented by 1> x / y> 0 and having a network structure in which a part of the phosphorus pentoxide structure is left (these may be collectively referred to as a metaphosphoric acid compound) is preferable. Moreover, the acidic salt of these acids is preferable. Further, monovalent or polyhydric alcohols of these acids or partial esters of polyalkylene glycols are preferred.

  The metaphosphoric acid compound used in the present invention is a cyclic metaphosphoric acid in which about 3 to 200 phosphoric acid units are condensed, an ultra-region metaphosphoric acid having a three-dimensional network structure, or an alkali metal salt or an alkaline earth metal salt thereof. Onium salts). Among them, cyclic sodium metaphosphate, ultra-region sodium metaphosphate, phosphono-substituted lower aliphatic carboxylic acid derivative dihexylphosphonoethyl acetate (hereinafter sometimes abbreviated as DHPA) and the like are preferably used.

The polylactic acid preferably has a lactide content of 5,000 ppm or less. The lactide contained in the polylactic acid deteriorates the resin and deteriorates the color tone at the time of melt processing, and in some cases, it may be disabled as a product.
Polylactic acid immediately after the melt ring-opening polymerization usually contains 1 to 5% by weight of lactide, but at any stage from the end of polylactic acid polymerization to the formation of polylactic acid, a conventionally known lactide weight loss method is used. That is, lactide can be reduced to a suitable range by carrying out vacuum devolatilization in a single-screw or multi-screw extruder, or high vacuum treatment in a polymerization apparatus alone or in combination.

  The smaller the lactide content, the better the melt stability and heat-and-moisture resistance of the resin, but there is also the advantage of lowering the resin melt viscosity, making it reasonable and economical to meet the desired purpose. is there. That is, it is reasonable to set it to 1,000 ppm or less, at which practical melt stability is achieved. More preferably, a range of 700 ppm or less, more preferably 500 ppm or less, particularly preferably 100 ppm or less is selected. By having a lactide content in such a range, the polylactic acid component improves the stability of the resin during the melt molding of the molded product of the present invention, and the advantage that the molded product can be efficiently manufactured and the heat-and-moisture stability of the molded product. , Low gas can be improved.

  The stereocomplex polylactic acid is prepared by bringing poly L-lactic acid and poly D-lactic acid into contact in a weight ratio of 10/90 to 90/10, preferably by melt contact, and more preferably melt kneading. Can be obtained. The contact temperature is preferably in the range of 220 to 290 ° C, more preferably 220 to 280 ° C, and even more preferably 225 to 275 ° C, from the viewpoint of improving the stability of polylactic acid when melted and the stereocomplex crystallinity.

  The method of melt kneading is not particularly limited, but a conventionally known batch type or continuous type melt mixing apparatus is preferably used. For example, a melt-stirred tank, a single-screw or twin-screw extruder, a kneader, a non-shaft vertical stirring tank, “Vibolac (registered trademark)” manufactured by Sumitomo Heavy Industries, Ltd., N-SCR, manufactured by Mitsubishi Heavy Industries, Ltd. ( Glasses blades, lattice blades or Kenix type stirrers made by Hitachi, Ltd., or Sulzer type SMLX type static mixer equipped pipe type polymerization equipment can be used. A non-axial vertical stirring tank, an N-SCR, a twin-screw extruder, or the like that is a polymerization apparatus is preferably used.

Moreover, what can be purchased for polylactic acid can be used. For example, polylactic acid “Ingeo ^™ ” manufactured by Nature Works LCC, polylactic acid “REVODE (registered trademark)” manufactured by Zhejiang Kaisei Biological Materials, and the like can be mentioned. The balance of the easily degradable and ^nature, Ingeo TM 4060D can be suitably used.
The weight average molecular weight of the polyglycolic acid used is preferably in the range of 10,000 to 500,000, more preferably 30,000 to 350,000, and still more preferably 5 to 250,000 in order to achieve both the mechanical properties and moldability of the molded product. It is. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

Polyglycolic acid can be produced by a conventionally known method. For example, it can be produced by ring-opening polymerization of glycolide in the presence of a metal-containing catalyst. Further, it can be produced by a direct polymerization method in which glycolic acid is subjected to dehydration condensation in the presence or absence of an organic solvent.
Moreover, the polyglycolic acid can use what can be purchased. Examples include polyglycolic acid “Kuredux (registered trademark)” manufactured by Kureha Co., Ltd., polyglycolic acid manufactured by Sigma-Aldrich, and the like.

<Decomposition accelerator (B component) that functions as an A component exchange agent>
In the present invention, the decomposition accelerator (B component) that functions as an A component exchange agent acts on the main chain or terminal of the A component and is incorporated into the A component to promote hydrolysis, and / or the A component. It is an agent that indirectly promotes hydrolysis by causing an exchange reaction between them. That is, it is an agent that has the effect of improving the affinity of the A component with water and / or introducing a skeleton that is more easily hydrolyzed than the main component into a part of the A component to serve as a starting point for the decomposition.

  In addition, an agent that promotes hydrolysis of the component A as a base catalyst due to its presence is also included, but a weakly basic agent is preferably used so as to have an auxiliary effect. When the basicity of the B component is strong, the storage property of the resin composition may be deteriorated, or the decomposition at a low temperature may be accelerated and may not function for a long time as a fluidity controlling material. Therefore, when a basic compound is used for the B component, the pKa of the conjugate acid of the B component is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less.

As an agent that acts on the main chain or terminal of the A component and is incorporated into the A component to improve the affinity of the A component with water and promote hydrolysis, a nucleophilic reaction is performed on the main chain or terminal of the A component. And an agent that seals the end. The bond that improves the affinity of the A component with water may be contained in the B component, or may be a bond that is generated during the reaction.
Examples of the hydrophilic bond include an amide bond, an ether bond, and an ester bond. The same applies to the bonds introduced by end capping. Furthermore, in the case of terminal sealing, the hydrophilic group contained in the sealing agent can also contribute to improving the affinity of the A component with water. Preferred hydrophilic groups include hydroxyl group, amino group, thiol group, amide group, carboxyl group and the like.

  Specific examples of the agent that undergoes a nucleophilic reaction include amine compounds, amide compounds, alcohol compounds, and alkoxide compounds. In the resin composition of the present invention, the storability of the resin composition is relatively good, and is an amine compound from the viewpoint that it is efficiently incorporated into the A component during reaction with the A component and exhibits an effect on easy decomposability. Can be suitably used.

  As the amine compound, generally known compounds can be used, and monoamine compounds, polyamine compounds higher than diamine, and combinations thereof can be used. Specific examples of the monoamine compound include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, t-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n- Heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, N-methylethylamine, N-methyl-n-propylamine, N-methyl-isopropylamine, N-methyl-n-butylamine, N-methyl-isobutylamine, N-methyl-t-butylamine, N-methyl-n-pentylua N-methyl-n-hexylamine, N-methylcyclohexylamine, N-methyl-n-heptylamine, N-methyl-n-octylamine, N-methyl-2-ethylhexylamine, N-methyl-n- Nonylamine, N-methyl-n-decylamine, N-methyl-n-undecylamine, N-methyl-n-dodecylamine, N-methyl-n-tridecylamine, N-methyl-n-tetradecylamine, N -Methyl-n-pentadecylamine, N-methyl-n-hexadecylamine, monoethanolamine, triethanolamine, pyrrolidine, piperidine, hexamethyleneimine, piperazine, N-methylpiperazine, N-ethylpiperazine, homopiperazine, Aniline, o-fluoroaniline, m-fluoroaniline, p-fluoro Aniline, o- anisidine, m- anisidine, p- anisidine, o- toluidine, m- toluidine, p- toluidine, 2-naphthylamine, 2-aminobiphenyl, 4-aminobiphenyl, and the like. Specific examples of polyamine-based compounds higher than diamine include m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 9,10-anthracenediamine, 2,7-diaminofluorene, 4,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether 3-sulfonic acid-4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3, 4'-diaminodiphenylsulfide, 4,4'-di Minodiphenyl sulfide, 4-aminobenzoic acid 4-aminophenyl ester, 9,9-bis (4-aminophenyl) fluorene, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′ , 3,3′-tetramethyl-4,4′-diaminobiphenyl, 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl)- 4,4′-diaminobiphenyl, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) bi Enyl, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis (3-amino-4) -Hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3 -Amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, 9,9- Bis (3-amino-4-hydroxyphenyl) fluorene, 2,2′-bis [N- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2′-bis [N— (4-aminobenzoyl) -3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2′-bis [N- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] propane, 2,2′- Bis [N- (4-aminobenzoyl) -3-amino-4-hydroxyphenyl] propane, bis [N- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] sulfone, bis [N- (4-amino) Benzoyl) -3-amino-4-hydroxyphenyl] sulfone, 9,9-bis [N- (3-aminobenzoyl) -3-amino -4-hydroxyphenyl] fluorene, 9,9-bis [N- (4-aminobenzoyl) -3-amino-4-hydroxyphenyl] fluorene, N, N'-bis (3-aminobenzoyl) -2,5- Diamino-1,4-dihydroxybenzene, N, N′-bis (4-aminobenzoyl) -2,5-diamino-1,4-dihydroxybenzene, N, N′-bis (3-aminobenzoyl) -4, 4′-diamino-3,3-dihydroxybiphenyl, N, N′-bis (4-aminobenzoyl) -4,4′-diamino-3,3-dihydroxybiphenyl, N, N′-bis (3-aminobenzoyl) ) -3,3'-diamino-4,4-dihydroxybiphenyl, N, N'-bis (4-aminobenzoyl) -3,3'-diamino-4,4-dihydroxybiphenyl 2- (4-aminophenyl) -5-aminobenzoxazole, 2- (3-aminophenyl) -5-aminobenzoxazole, 2- (4-aminophenyl) -6-aminobenzoxazole, 2- ( 3-aminophenyl) -6-aminobenzoxazole, 1,4-bis (5-amino-2-benzoxazolyl) benzene, 1,4-bis (6-amino-2-benzoxazolyl) benzene, 1,3-bis (5-amino-2-benzoxazolyl) benzene, 1,3-bis (6-amino-2-benzoxazolyl) benzene, 2,6-bis (4-aminophenyl) benzo Bisoxazole, 2,6-bis (3-aminophenyl) benzobisoxazole, 2,2′-bis [(3-aminophenyl) -5-benzoxazolyl] hexa Fluoropropane, 2,2′-bis [(4-aminophenyl) -5-benzoxazolyl] hexafluoropropane, bis [(3-aminophenyl) -5-benzoxazolyl], bis [(4- Aminophenyl) -5-benzoxazolyl], bis [(3-aminophenyl) -6-benzoxazolyl], bis [(4-aminophenyl) -6-benzoxazolyl], 1,3, 5-triaminobenzene, tris (3-aminophenyl) methane, tris (4-aminophenyl) methane, tris (3-aminophenyl) amine, tris (4-aminophenyl) amine, tris (3-aminophenyl) benzene , Tris (4-aminophenyl) benzene, 1,3,5-tris (3-aminophenoxy) benzene, 1,3,5-tris (4-aminophenyl) Noxy) benzene, 1,3,5-tris (4-aminophenoxy) triazine, melamine, 2,4,6-triaminopyrimidine, 1,2,4,5-tetraaminobenzene, 3,3 ', 4 4'-tetraaminobiphenyl, 3,3 ', 4,4'-tetraaminodiphenyl sulfone, 3,3', 4,4'-tetraaminodiphenyl sulfide, 2,3,6,7-tetraaminonaphthalene, 1 , 2,5,6-tetraaminonaphthalene, ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tetramethylhexanediamine, 1,12- (4 , 9-Dioxa) dodecanediamine, 1,8- (3,6-dioxa) Kutandiamine, cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), isophoronediamine, etc .; polyoxyethyleneamine, polyoxypropyleneamine known as Jeffamine (trade name, manufactured by Huntsman Corporation), and copolymerized compounds thereof Can be mentioned. Furthermore, a polyvalent amine represented by the following formula (2) can also be suitably used.

The above formula (2) corresponds to, for example, an intermediate of the compound described in International Publication WO2010 / 072111 pamphlet, and may be produced with reference to the description in the pamphlet. For example, o-nitrophenol and penta Nitro compound obtained by removing N, N-dimethylformamide after charging erythrityl tetrabromide, potassium carbonate and N, N-dimethylformamide in a nitrogen atmosphere and reacting them with hydrogen in the presence of a palladium carbon catalyst. It can be obtained by reduction.
As an agent that indirectly promotes hydrolysis by introducing a skeleton that is more easily hydrolyzed than the main component into a part of the A component by causing an exchange reaction between the A components, a transesterification catalyst, An agent having two or more groups that undergo a nucleophilic reaction at the main chain or terminal of the component A can be mentioned.

As the transesterification catalyst, generally known catalysts can be used. Examples thereof include metals, metal salts, sulfur acids, and nitrogen-containing basic compounds.
Examples of metals include manganese, magnesium, titanium, zinc, iron, aluminum, cerium, calcium, barium, cobalt, lithium, sodium, potassium, cesium, lead, strontium, tin, antimony, germanium, yttrium, lanthanum, indium, Zirconium etc. are mentioned.

Examples of the metal salt include salts composed of the above metals and organic acids such as carboxylic acid, sulfur acid, carbonic acid, and phenol, nitric acid, phosphoric acid, boric acid, and phosphoric acid ester. Examples of the metal salt include halides of the above metals (halogenated metal salts), hydroxides of the above metals (metal hydroxides), and the like.
Examples of sulfur acids include sulfuric acid, sulfonic acid compounds, sulfinic acid compounds, and sulfenic acid compounds.
Examples of the nitrogen-containing basic compound include quaternary amine salts, tertiary amines, secondary amines, primary amines, pyridines, imidazoles, ammonia and the like.

  In the present invention, a phosphoric acid ester metal salt can be suitably used because of appropriate exchange activity and stability of the resin after addition. As phosphate ester metal salts, trade names of “ADEKA STAB (registered trademark)” NA-11, “ADEKA STAB (registered trademark)” NA-71, aluminum bis (2,2′-methylene bis-4, manufactured by ADEKA Corporation) 6-di-t-butylphenyl phosphate) and the like.

Examples of the agent having two or more groups that undergo nucleophilic reaction at the main chain or terminal of the component A include amine compounds, amide compounds, alcohol compounds, alkoxide compounds, and the like, as with the nucleophilic reaction agent described above. It is done. In the resin composition of the present invention, the storability of the resin composition is relatively good, and is an amine compound from the viewpoint that it is efficiently incorporated into the A component during reaction with the A component and exhibits an effect on easy decomposability. Can be suitably used.
Examples of the amine compound include those similar to the above-described polyamine-based compounds having a diamine or higher.

  In the present invention, the decomposition accelerator (B component) that functions as an A component exchange agent acts on the main chain or terminal of the A component and is incorporated into the A component to promote hydrolysis, and / or the A component. Although it is an agent that indirectly promotes hydrolysis by causing an exchange reaction between them, an amine compound can be suitably used as an agent that effectively functions in both. In particular, when a polyamine compound such as a diamine or higher is used, a hydrophilic bond is formed by incorporation into the A component by nucleophilic reaction to the A component, and two or more amines act on different A components. Thus, since an exchange reaction between the components A is caused, easy decomposability in low-temperature hot water is effectively expressed. In addition to amine compounds, agents that act on the A component by the same mechanism can be suitably used as the B component.

<Resin composition>
In water at 60 ° C., the resin composition of the present invention has a weight after 120 hours of 95% or less and a weight after 240 hours of 75% or less.
The weight means the total weight of the solid that does not dissolve in water and remains as a solid.
Here, the weight of the resin composition is, for example, a value given by the following evaluation.

200 mg of the resin composition and 10 ml of distilled water are charged into a vial and treated with a constant temperature and humidity machine for a predetermined time. Then, it takes out and cools to 25 degreeC, it filters using a filter paper (JISP3801: 1995, 5 types A specification), The resin composition which remains on a filter paper is 60 degreeC and the vacuum of 133.3 Pa or less for 3 hours. After drying, the weight is measured, and the weight is determined from the following formula (i).
Weight (%) = [weight of resin composition after treatment / weight of initial resin composition] × 100 (i)
In this evaluation, as the size of the resin composition, for example, if it is in the form of pellets, a cube having a side of 1 mm to 5 mm or a rectangular parallelepiped can be usually used.
In addition to this, the weight of the resin composition may be given by an equivalent evaluation.

In the present invention, from the viewpoint of being suitably used as a fluidity control material for excavation or the like, it is important to control easy decomposability in low-temperature water at 40 to 80 ° C. That is, a resin composition that decomposes rapidly after holding the weight of the resin composition for a certain amount of time in this temperature range is preferable.
Here, the certain amount of time varies depending on the application, but is preferably 10 minutes or longer, more preferably 30 minutes or longer, and even more preferably 1 hour or longer from the viewpoint of achieving desired performance.

  Maintaining the weight of the resin composition varies depending on the application, but is preferably 50% or more, more preferably 70% or more, and still more preferably 90% or more from the viewpoint of exhibiting desired performance. Those that do not readily retain weight by being dissolved in low-temperature hot water may not be able to exhibit desired performance when used as a fluidity control material.

If the resin composition of this invention is less than 40 degreeC, the composition of this invention may decompose | disassemble slowly and may not have easy decomposability | degradability. Moreover, decomposition | disassembly is quick at temperature higher than 80 degreeC, and a desired performance may not be exhibited as a fluidity control material.
It is preferable that the resin composition of the present invention rapidly decomposes in low-temperature water, and the weight after 120 hours is 95% or less and the weight after 240 hours is 75% or less in 60 ° C. water.

The resin composition of the present invention contains a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer and a decomposition accelerator (B component) that functions as an A component exchange agent, and maintains a high molecular weight. However, since the A component in which the B component is incorporated and / or the B component is used as an exchange agent and the resin component is exchanged between the A components, the hydrolysis rate increases exponentially in low-temperature water. Therefore, when the decomposition proceeds and the weight reduction starts, the subsequent reduction is characterized. When used as a fluidity control material, a material that functions as a sealing material to suppress liquid permeability and then disappears quickly to restore liquid permeability is preferable. Features of the resin composition of the present invention Is important. Therefore, the resin composition preferably has a weight after 120 hours of 95% or less in water at 60 ° C., more preferably 90% or less, and still more preferably 85% or less, from the viewpoint of the performance of the fluidity control material. % Or less is particularly preferable. Similarly, the weight of the resin composition after 240 hours in water at 60 ° C. is preferably 75% or less, more preferably 70% or less, more preferably 65% or less, from the viewpoint of the performance of the fluidity control material, 60% or less is particularly preferable.
Further, from the viewpoint of exhibiting the performance of water treatment and fluidity control materials after use, the less water-insoluble content is better, and the weight after 1000 hours in water at 60 ° C. is preferably 40% or less, 35% The following is more preferable, and 30% or less is more preferable.

  The heat deformation temperature of the resin composition of the present invention is preferably 40 ° C to 300 ° C. Here, the heat distortion temperature refers to the melting point or softening point of the resin composition. Since the use of the resin composition is intended for 40 to 80 ° C. water, the resin composition can be used in a wider temperature range as the thermal deformation temperature of the resin composition is higher than 40 ° C. On the other hand, when the temperature is 300 ° C. or lower, molding of the resin composition of the present invention is relatively easy. Therefore, the heat distortion temperature of the resin composition is more preferably 60 ° C to 300 ° C, and further preferably 80 ° C to 280 ° C.

  In the resin composition of the present invention, the addition amount of the B component is 0.1 to 30 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. If the amount is less than 0.1 part by weight, sufficient readily decomposability may not be exhibited in low-temperature water at 40 to 80 ° C. On the other hand, when the amount is more than 30 parts by weight, the B component may bleed out from the resin composition, the moldability or storage property may be deteriorated due to a decrease in molecular weight, and the substrate characteristics may be modified. From this viewpoint, the addition amount of the B component is preferably 0.25 to 20 parts by weight, more preferably 0.35 to 15 parts by weight, with respect to 100 parts by weight of the total of the A component and the B component, 10 parts by weight is more preferable.

  In addition, polylactic acid can be suitably used as the component A of the resin composition of the present invention, but when the main chain of polylactic acid is a combination of L-lactic acid units and D-lactic acid units, the main lactic acid units. On the other hand, the other lactic acid unit is preferably 1 to 20 mol%. Furthermore, adjusting the amount of addition of the B component depending on the difference in the number of moles is important for achieving the desired easy decomposability in low-temperature water as a fluidity control material. That is, since polylactic acid has different decomposability depending on the amount of the other lactic acid unit relative to the main lactic acid unit, it is important to blend B component suitable for it. From the viewpoint of easy decomposability in low-temperature water when the other lactic acid unit is 1 to 5 mol% with respect to the main lactic acid unit, the B component is 100 parts by weight of the total of the A component and the B component. 5-30 weight part is preferable and 10-20 weight part is more preferable. In addition, when the other lactic acid unit is 5 to 15 mol% with respect to the main lactic acid unit, from the viewpoint of easy decomposability in low-temperature water, the total amount of A component and B component is 100 parts by weight. The component is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight. Furthermore, when the other lactic acid unit is 15 to 20 mol% with respect to the main lactic acid unit, from the viewpoint of easy decomposability in low-temperature water, the total amount of A component and B component is 100 parts by weight. The component is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight.

When two components of polylactic acid and polyglycolic acid are used as the A component of the resin composition, the B component functions effectively. Depending on the B component, an exchange reaction proceeds between polylactic acid and polyglycolic acid in addition to polylactic acid or between polyglycolic acids, and a polyglycolic acid skeleton is introduced into the main chain or terminal of polylactic acid. Arise. This can be expected to promote decomposition in low-temperature water.
Relationship decomposition rate _{V 2} at 60 ° C. 95% RH degradation rate _{V 1} and the resin composition in 60 ° C. 95% RH of the component A preferably satisfies the following formula (iii).
0.3 · V ₁ ≦ V ₂ ≦ 3.0 · V ₁ (iii)

The resin composition of the present invention is characterized by easy decomposability in low-temperature water. However, if the resin composition is not stable during storage or transportation, it may cause a problem in actual use. Therefore, it is preferable that the decomposition of the resin composition is suppressed to some extent. Also, resin compositions with good water affinity may lose weight in low-temperature water even when decomposition is slow, but if the decomposition is too slow, it may precipitate due to the action of other components in the water, It may become an obstacle when collecting water. Therefore, degradation rate V ₂ of the resin composition, be met is preferably close to the degradation rate V ₁ of the resin (A component) having an autocatalytic mainly composed of water-soluble monomer, the following formula (iv) More preferred.
0.5 · V ₁ ≦ V ₂ ≦ 2.0 · V ₁ (iv)

Here, the decomposition rate V ₂ at 60 ° C. and 95% RH is determined from the time t when the weight average molecular weight of the resin composition is treated at 60 ° C. and 95% RH at a start of the weight average molecular weight M to reach 0.5 · M. It is a value obtained by the following formula (v).
V ₂ = (0.5 · M) / t (v)
The decomposition rate V1 at 60 ° C. and 95% RH starts from the point where the component A has the same weight average molecular weight M as the resin composition, and is treated at 60 ° C. and 95% RH so that the weight average molecular weight becomes 0.5 · M. Is a value obtained by the following formula (vi) from the following time T.
V ₁ = (0.5 · M) / T (vi)

<Resin composition solid (C)>
The resin composition of the present invention is produced by melt-kneading a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer and a decomposition accelerator (B component) functioning as an A component exchange agent. Can do.

  When polylactic acid and polyglycolic acid are employed as the resin having a self-catalytic action mainly composed of a water-soluble monomer (A component), a decomposition accelerator that simultaneously functions as two component A exchange agents ( The resin composition of the present invention can be produced by mixing with component B). In addition, the resin composition of the present invention is mixed with one of the A component of polylactic acid and polyglycolic acid and a decomposition accelerator (B component) that functions as an exchange agent for the A component, and then the other A component is mixed. It can also be produced by mixing.

  When polylactic acid is used as the resin having a self-catalytic action mainly composed of a water-soluble monomer (component A), the poly L- of the resin having a self-catalytic action mainly composed of a water-soluble monomer (component A) Lactic acid, poly-D-lactic acid, and a decomposition accelerator (component B) that functions as an A component exchange agent are mixed to form a stereocomplex polylactic acid, and the resin composition of the present invention can be produced. The resin composition of the present invention is a mixture of poly L-lactic acid and poly D-lactic acid to form a stereocomplex polylactic acid, and then a decomposition accelerator (B component) that functions as an A component exchange agent. Can also be manufactured.

  There is no particular limitation on the method of adding and mixing the decomposition accelerator (B component) that functions as an A component exchange agent with the autocatalytic resin (component A) mainly composed of a water-soluble monomer. By adding as a master batch of a resin (component A) having an autocatalytic action mainly composed of a solution, a melt, or a water-soluble monomer to be applied, or a decomposition accelerator (component B) functioning as an A component exchanger ) Is dissolved, dispersed or melted into contact with a solid resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer, and a decomposition accelerator (B component) that functions as an A component exchange agent. Or the like can be taken.

  When adding a solution, a melt or a masterbatch of a resin (component A) having autocatalytic activity mainly composed of a water-soluble monomer to be applied, a method of adding using a conventionally known kneading apparatus Can be taken. In kneading, a kneading method in a solution state or a kneading method in a molten state is preferable from the viewpoint of uniform kneading properties. The kneading apparatus is not particularly limited, and examples thereof include conventionally known vertical reaction vessels, mixing tanks, kneading tanks or uniaxial or multiaxial horizontal kneading apparatuses such as uniaxial or multiaxial ruders and kneaders. The mixing time is not particularly specified, and depends on the mixing apparatus and the mixing temperature, but is selected from 0.1 minutes to 2 hours, preferably 0.2 minutes to 60 minutes, more preferably 0.2 minutes to 30 minutes. .

As the solvent, a solvent which is inactive with respect to a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer and a decomposition accelerator (B component) functioning as an A component exchange agent is used. it can. In particular, a solvent that has affinity for both and at least partially dissolves both is preferable.
As the solvent, for example, hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, halogen solvents, amide solvents and the like can be used.
Examples of the hydrocarbon solvent include hexane, cyclohexane, benzene, toluene, xylene, heptane, decane and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, and isophorone.

Examples of ester solvents include ethyl acetate, methyl acetate, ethyl succinate, methyl carbonate, ethyl benzoate, and diethylene glycol diacetate. Examples of the ether solvent include diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, triethylene glycol diethyl ether, diphenyl ether and the like. Examples of the halogen solvent include dichloromethane, chloroform, tetrachloromethane, dichloroethane, 1,1 ′, 2,2′-tetrachloroethane, chlorobenzene, dichlorobenzene and the like. Examples of the amide solvent include formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like. These solvents may be used alone or as a mixed solvent as desired.
In the present invention, the solvent is applied in the range of 1 to 1,000 parts by weight per 100 parts by weight of the resin composition. If the amount is less than 1 part by weight, there is no significance in applying the solvent. The upper limit of the amount of solvent used is not particularly limited, but is about 1,000 parts by weight from the viewpoints of operability and reaction efficiency.

  A solid that is a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer is brought into contact with a liquid in which a decomposition accelerator (B component) that functions as an A component exchange agent is dissolved, dispersed, or melted. When taking the method of infiltrating the decomposition accelerator (B component) that functions as a component exchange agent, the decomposition accelerator (B component) dissolved in the solvent as described above has a solid water-soluble The main component is a solid water-soluble monomer in the emulsion solution of a decomposition accelerator (B component) that functions as a replacement agent for the A component or a method of contacting a resin (A component) that has an autocatalytic action mainly comprising a reactive monomer Or a method of contacting a resin (component A) having an autocatalytic action. As a method of contact, a method of immersing a resin (A component) having a water-soluble monomer as a main component and having an autocatalytic action, or a method of applying a resin having a self-catalytic action (a component A) having a water-soluble monomer as a main component. The method of performing, the method of spraying, etc. can be taken suitably.

Nucleophilic reaction and exchange reaction of a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer by a decomposition accelerator (B component) that functions as an A component exchange agent is performed at room temperature (25 ° C.) to 300 Although it is possible at a temperature of about 0 ° C., the range of 50 to 280 ° C. is preferable from the viewpoint of reaction efficiency, and the range of 100 to 280 ° C. is more preferable. Resin that has autocatalytic action mainly composed of a water-soluble monomer (component A) is likely to react at a melting temperature, but volatilization of a decomposition accelerator (component B) that functions as a replacement for component A In order to suppress excessive decomposition of the component A, the reaction is preferably performed at a temperature lower than 300 ° C. Also, it is effective to apply a solvent in order to lower the melting temperature of the resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer and increase the stirring efficiency. At temperatures lower than 25 ° C., the desired reaction may not occur sufficiently.
In the present invention, two or more kinds of decomposition accelerators (component B) that function as an A component exchange agent may be used in combination. For example, a resin (A Separate components may be used for the B component mainly acting on the terminal of the component) and the B component mainly acting on the backbone of the main chain.

The resin composition of the present invention can be used by adding all known additives and fillers as long as the effects of the invention are not lost. For example, a stabilizer, a crystallization accelerator, a filler, a mold release agent, an antistatic agent, a plasticizer, an impact resistance improver and the like can be mentioned.
For the additive, from the viewpoint of not losing the effect of the invention, a component that deactivates the decomposition accelerator (B component) that functions as an A component exchange agent or a component that suppresses the effect is used. Preferably it is not.
From the viewpoint of controlling the decomposability and storability of the resin composition, a component that functions as a terminal blocking agent may be used. Although generally well-known things can be used as terminal blocker, For example, a carbodiimide compound, an epoxy compound, an oxazoline compound etc. are mentioned.
The resin composition solid according to the present invention can be prepared by using various pellets, if necessary, and using the produced pellets as a starting material by a melt extruder.

<Powder production method>
The first method in the present invention comprises a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer and a decomposition regulator (B component) that functions as an A component exchange agent. A resin composition containing a resin component in which the A component exchange-reacts with the A component and / or the B component incorporated as an exchange agent, and the weight after 120 hours in water at 60 ° C. is 95% or less and Resin composition solid (C) whose weight after 240 hours is 75% or less,
A pulverizing section (I) comprising a resin composition solid (C) charging port and a transport medium supply port, and converting the charged resin composition solid (C) into powder.
A fluidized part (b) in which the powder obtained in the powder part (a) directly connected to the upper part of the grinding part is fluidized by a carrier medium;
At the upper part of the fluidized section, the discharge port (c) for the powder and the conveying medium below the target particle size,
Using a crusher having
The resin composition solid (C) is pulverized while controlling the temperature in the pulverization part (b) within the range of −20 ° C. to Tg−5 ° C. of the resin composition solid (C) by supplying a carrier medium. The amount of transport medium supplied to the crushing part (b) exceeds the flow rate at which the powder starts flowing in the crushing part (b) and exceeds the target particle size in the crushing part (b). The returned powder having a particle size equal to or smaller than the target particle size is set to a flow rate discharged from the discharge port (c) together with the transport medium.

A well-known grinder provided with said (i)-(iii) can be used for a grinder. A pulverizer having a pulverization method that mechanically applies high shear and high impact to pulverize (impact pulverization) or shears the material with a blade is preferable. For example, a pulverizer, a turbo mill, a blade mill, a pin mill, a cutter mill and the like are preferably used. Although it is not pulverized by a roll mill, it is known that pulverization efficiency can be improved by pretreatment, so that it can be used in combination.
If the pulverization temperature is lower than the glass transition point (Tg) of the solid resin composition, the pulverization can be pulverized. This temperature is important because not only cannot be formed, but welding and solidification may occur in the apparatus. On the other hand, when the temperature is lower than −20 ° C., the solid resin composition is condensed, and when the temperature rises in the apparatus, it causes sticking and fusion.

In the production method of the present invention, a conveyance medium is used for controlling the pulverization temperature. By controlling the temperature of the carrier medium to −20 ° C. to (Tg-5) ° C., the powder can be pulverized while being cooled by the fluidized part (b). Further, the flow rate of the conveying medium needs to be equal to or higher than the flow rate at which the powder in the pulverizing section (a) starts to flow.
If the flow rate is less than or equal to the flow rate at which flow starts, the resin composition stays in the pulverizing section (a) and cannot be cooled, causing a problem of solidification in the apparatus.

  Further, if the flow rate of the conveying medium is equal to or greater than the target particle size in the fluidizing section (b), the flow rate is returned to the pulverizing section (b), and the flow rate below the target particle size is conveyed to the discharge port (c) as the target powder. It must be a flow rate. If the flow rate is less than the target particle size, it is preferable not only because the powder stays in the apparatus and the product cannot be taken out, but also there is a possibility of solidification in the apparatus due to pulverization heat generation. Absent. In addition, using a classifier in the upper part of the fluidized part (b), the one below the target particle size is selected, discharged to the outside, the remaining pulverized product is returned to the pulverized part (ii), and re-ground. It doesn't matter. The carrier medium is preferably a gas, and particularly preferably an inert gas such as air or nitrogen.

As a second method in the present invention,
A component and / or B composed of a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer and a degradation regulator (B component) that functions as an exchange agent for the A component. A resin composition containing a resin component in which components A are exchange-reacted with each other as an exchange agent, wherein the weight after 120 hours is 95% or less and the weight after 240 hours is 75% or less in water at 60 ° C. Resin composition solids (C)
A resin composition solid (C) charging port and a conveyance medium supply port are provided, and the obtained resin composition solid (C) is pulverized while the obtained powder is fluidized by the conveyance medium. Fluid department (d),
At the bottom of the pulverization fluid section, the discharge port (c) for the powder and the conveying medium below the target particle size,
Using a crusher having
By controlling the temperature in the pulverization fluidized section (d) within the range of −20 ° C. to Tg−5 ° C. of the resin composition solid (C) by supplying the carrier medium, the resin composition solid (C) The pulverized fluid part (d) is charged and the transport medium supply amount is set to a flow rate at which the powder starts flowing in the pulverized fluid part (d).
A well-known grinder provided with said (iii) and (d) can be used for a grinder. A pulverizer having a pulverization method that mechanically applies high shear and high impact to pulverize (impact pulverization) or shears the material with a blade is preferable. For example, a turbo mill with a screen, a blade mill, a pin mill, a cutter mill or the like is preferably used.

The carrier medium is preferably liquid, and is not particularly limited as long as it is a solvent that does not dissolve the resin composition solid (C), and water, lower alcohol, liquid nitrogen, or the like can be used. In particular, water is preferable because it has a large latent heat and can suppress heat generation in the pulverizer. A mixed solvent of a lower alcohol and water may be used. Liquid nitrogen is inferior to water in terms of cost and safety.
From the viewpoint of handling, it is preferable to have a step of separating the powder discharged from the pulverization fluidizing section (d) and the transport medium and a step of drying the separated powder.

  The shape of the powder is preferably relatively close to a sphere or close to a cube. A whisker-like shape (a shape stretched in the vicinity of the molten state from the rubber state) is observed in part, but may exist within a range that does not impair the flow characteristics. The whisker-like powder is preferably 50% or less, more preferably 20% or less of the total number of powders in the microscopic observation. When the whisker-shaped powder is 50% or more, the powder tends to agglomerate, and the fluidity is deteriorated. Moreover, since the dispersibility to a solvent falls, it cannot apply | coat uniformly and is unpreferable.

  Also, from the viewpoint of ease of handling, the obtained powder has an angle of repose (the angle between the slope of the mountain and the horizontal plane when the mountain shape remains stable when the powder is stacked in a mountain shape). It is preferable that the angle is 55 degrees or less. More preferably, the angle of repose is 45 degrees or less. By using such an angle of repose, it can be used without impairing fluidity. In order to reduce the angle of repose, for example, a method of reducing the content ratio of the whisker-like powder or increasing the particle size within an allowable range can be exemplified.

<Stabilizer>
The resin composition of the present invention can contain a stabilizer. As a stabilizer, what is used for the stabilizer of a normal thermoplastic resin can be used. For example, an antioxidant, a light stabilizer, etc. can be mentioned. By blending these agents, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.
Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphite compounds, thioether compounds, and the like.

  Examples of hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 ′). -Tert-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -Propionate], 2,2'-methylene-bis (4-methyl-tert-butylphenol), triethylene glycol-bis 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro ( 5,5) Undecane and the like can be mentioned.

  As a hindered amine compound, N, N′-bis-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis [3- (3′-Methyl-5′-tert-butyl-4′-hydroxyphenyl) propionyl] diamine, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyl ] Hydrazine, N-salicyloyl-N'-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N'-bis [2- {3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like. Preferably, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl) -4-hydroxyphenyl) propionate] methane and the like.

  As the phosphite compound, those in which at least one P—O bond is bonded to an aromatic group are preferable. Specifically, tris (2,6-di-tert-butylphenyl) phosphite, tetrakis ( 2,6-di-tert-butylphenyl) 4,4′-biphenylene phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, tris (mixed mono and di-no Ruphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4′-isopropylidenebis (phenyl-dialkylphosphite), 2,4,8,10-tetra-tert-butyl-6- [3- (3 -Methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine “Sumilyzer (registered trademark) GP” and the like.

  Specific examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like.

Specific examples of the light stabilizer include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, and the like.
Examples of the benzophenone compounds include benzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′. -Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy -2'-carbo Shi benzophenone, 2-hydroxy-4- (2-hydroxy-3-methyl - acryloxy-isopropoxyphenyl) benzophenone.

  Examples of the benzotriazole compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (Α, α-Dimethylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α Dimethylbenzyl) phenyl] -2H- benzotriazole, 2- (4'-octoxy-2'-hydroxyphenyl) benzotriazole.

Examples of the aromatic benzoate compounds include alkylphenyl salicylates such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate.
Examples of oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, and 2-ethoxy-3′-. Examples include dodecyl oxalic acid bisanilide.
Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3′-diphenyl acrylate and 2-ethylhexyl-cyano-3,3′-diphenyl acrylate.

  Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2, 6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarba Yloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) adipate, Bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, 1,2-bis (2,2,6,6-tetramethyl-4-piperidylo Cis) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) -Tolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl -4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- “2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid And 1,2,2, , 6-Pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol And the like.

In this invention, a stabilizer component may be used by 1 type and may be used in combination of 2 or more type. In addition, a hindered phenol compound and / or a benzotriazole compound is preferable as the stabilizer component.
The content of the stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight per 100 parts by weight of the resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer. is there.

<Crystallization accelerator>
The resin composition of the present invention can contain an organic or inorganic crystallization accelerator. By containing the crystallization accelerator, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
That is, by applying the crystallization accelerator, moldability and crystallinity are improved, and a molded product that is sufficiently crystallized even in normal injection molding and excellent in heat resistance and moist heat resistance can be obtained. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.
As the crystallization accelerator used in the present invention, those generally used as crystallization nucleating agents for crystalline resins can be used, and both inorganic crystallization nucleating agents and organic crystallization nucleating agents are used. be able to.

  As inorganic crystallization nucleating agents, talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride , Montmorillonite, neodymium oxide, aluminum oxide, phenylphosphonate metal salt and the like. These inorganic crystallization nucleating agents are treated with various dispersing aids in order to enhance the dispersibility in the composition and the effect thereof, and are in a highly dispersed state with a primary particle size of about 0.01 to 0.5 μm. Are preferred.

  Organic crystallization nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate , Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicy Organic carboxylic acid metal salts such as zinc acid, aluminum dibenzoate, β-naphthoic acid sodium, β-naphthoic acid potassium, sodium cyclohexanecarboxylic acid and the like, and organic sulfonic acid metal salts such as sodium p-toluenesulfonate and sodium sulfoisophthalate. Can be mentioned.

  Also, organic carboxylic acid amides such as stearic acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (tert-butylamide), low density polyethylene, high density polyethylene, polyiso Propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, branched polylactic acid, sodium salt of ethylene-acrylic acid copolymer, sodium of styrene-maleic anhydride copolymer Examples thereof include salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.

Among these, at least one selected from talc and organic carboxylic acid metal salts is preferably used. Only one type of crystallization accelerator may be used in the present invention, or two or more types may be used in combination.
The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts per 100 parts by weight of the resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer. Parts by weight.

<Filler>
The resin composition of the present invention can contain an organic or inorganic filler. By containing the filler component, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
Organic fillers such as rice husks, wood chips, okara, waste paper ground materials, clothing ground materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, coconut fibers Plant fibers such as pulp or cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, angora, cashmere and camel, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers , Paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like. From the viewpoint of moldability, powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable.

These organic fillers may be those directly collected from natural products, but may also be those obtained by recycling waste materials such as waste paper, waste wood and old clothes.
The wood is preferably a softwood material such as pine, cedar, oak or fir, or a hardwood material such as beech, shii or eucalyptus.
Paper powder is an adhesive from the viewpoint of moldability, especially emulsion adhesives such as vinyl acetate resin emulsions and acrylic resin emulsions that are usually used when processing paper, polyvinyl alcohol adhesives, polyamide adhesives Those containing hot melt adhesives such as are preferably exemplified.

In the present invention, the blending amount of the organic filler is not particularly limited, but from the viewpoint of moldability and heat resistance, per 100 parts by weight of resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer. The amount is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, still more preferably 10 to 150 parts by weight, and particularly preferably 15 to 100 parts by weight.
If the blending amount of the organic filler is less than 1 part by weight, the effect of improving the moldability of the composition is small, and if it exceeds 300 parts by weight, uniform dispersion of the filler becomes difficult, or other than moldability and heat resistance In addition, the strength and appearance of the material may decrease, which is not preferable.

The composition of the present invention preferably contains an inorganic filler. By combining the inorganic filler, a composition having excellent mechanical properties, heat resistance, and moldability can be obtained. As the inorganic filler used in the present invention, a fibrous, plate-like, or powder-like material used for reinforcing ordinary thermoplastic resins can be used.
Specifically, for example, carbon nanotube, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, imogolite, sepiolite, Asbestos, slag fiber, zonolite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, and other fibrous inorganic fillers, layered silicate, and organic onium ions Layered silicate, glass flake, non-swelling mica, graphite, metal foil, ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, powdered silicic acid, feldspar powder, potassium titanate, shirasuba Plates and particles of inorganic fillers such as carbon nanoparticles such as carbon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite and white clay fullerene Agents.

Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halosite, kanemite, and kenyanite, Li-type fluorine teniolite, Na And swellable mica such as Li-type fluorine teniolite, Li-type tetrasilicon fluorine mica and Na-type tetrasilicon fluorine mica. These may be natural or synthetic. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Li type fluorine teniolite and Na type tetrasilicon fluorine mica are preferable.
Among these inorganic fillers, fibrous or plate-like inorganic fillers are preferable, and glass fiber, wollastonite, aluminum borate whisker, potassium titanate whisker, mica, and kaolin, a cation-exchanged layered silicate. Is preferred. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.

Such a filler may be coated or converged with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. May be.
The blending amount of the inorganic filler is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight per 100 parts by weight of the resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer. Parts, more preferably 1-50 parts by weight, particularly preferably 1-30 parts by weight, most preferably 1-20 parts by weight.

<Release agent>
The resin composition of the present invention can contain a release agent. As the mold release agent used in the present invention, those used for ordinary thermoplastic resins can be used.
Specific examples of release agents include fatty acids, fatty acid metal salts, oxy fatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partial saponified esters, fatty acid lower alcohol esters, fatty acid polyvalents. Examples include alcohol esters, fatty acid polyglycol esters, and modified silicones. By blending these, a polylactic acid molded product excellent in mechanical properties, moldability, and heat resistance can be obtained.

Fatty acids having 6 to 40 carbon atoms are preferred. Specifically, oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montan Examples thereof include acids and mixtures thereof. The fatty acid metal salt is preferably an alkali metal salt or alkaline earth metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples include calcium stearate, sodium montanate, calcium montanate, and the like.
Examples of the oxy fatty acid include 1,2-oxystearic acid. Paraffin having 18 or more carbon atoms is preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like.

As the low molecular weight polyolefin, for example, those having a molecular weight of 5,000 or less are preferable, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Fatty acid amides having 6 or more carbon atoms are preferred, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.
The alkylene bis fatty acid amide is preferably one having 6 or more carbon atoms, and specifically includes methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide and the like. As the aliphatic ketone, those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones.

Examples of the fatty acid partial saponified ester include a montanic acid partial saponified ester. Examples of the fatty acid lower alcohol ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidonic acid ester, montanic acid ester, isostearic acid ester and the like.
Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol distearate, pentaerythrul Examples include tall monostearate, pentaerythritol adipate stearate, sorbitan monobehenate and the like. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters and polypropylene glycol fatty acid esters.

Examples of the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.
Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferred. Of these, montanic acid ester, montanic acid partial saponified ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferred, and particularly, montanic acid partial saponified ester and ethylene bisstearic acid amide are preferred. preferable.
A mold release agent may be used by 1 type and may be used in combination of 2 or more type. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts per 100 parts by weight of the resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer. Parts by weight.

<Antistatic agent>
The resin composition of the present invention can contain an antistatic agent. Examples of the antistatic agent include quaternary ammonium salt compounds such as (β-lauramidopropionyl) trimethylammonium sulfate and sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds.
In the present invention, the antistatic agent may be used alone or in combination of two or more. The content of the antistatic agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer. Parts by weight.

<Plasticizer>
The resin composition of the present invention can contain a plasticizer. As the plasticizer, generally known plasticizers can be used. Examples include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

As a polyester plasticizer, acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, Examples thereof include polyesters composed of diol components such as 1,4-butanediol, 1,6-hexanediol and diethylene glycol, and polyesters composed of hydroxycarboxylic acid such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol.
Examples of the glycerol plasticizer include glycerol monostearate, glycerol distearate, glycerol monoacetomonolaurate, glycerol monoacetomonostearate, glycerol diacetomonooleate, and glycerol monoacetomonomontanate.

Polyvalent carboxylic acid plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellitic acid tributyl, trimellitic acid trioctyl, Trimellitic acid esters such as trihexyl meritate, isodecyl adipate, adipic acid esters such as adipate-n-decyl-n-octyl, citrate esters such as tributyl acetylcitrate, and bis (2-ethylhexyl) azelate Examples include sebacic acid esters such as azelaic acid ester, dibutyl sebacate, and bis (2-ethylhexyl) sebacate.
Examples of the phosphate ester plasticizer include tributyl phosphate, tris phosphate (2-ethylhexyl), trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylhexyl phosphate, and the like.

Polyalkylene glycol plasticizers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide-propylene oxide) block and / or random copolymers, ethylene oxide addition polymers of bisphenols, tetrahydrofuran addition polymers of bisphenols, etc. And end-capping compounds such as a terminal epoxy-modified compound, a terminal ester-modified compound, and a terminal ether-modified compound.
Examples of the epoxy plasticizer include an epoxy triglyceride composed of alkyl epoxy stearate and soybean oil, and an epoxy resin using bisphenol A and epichlorohydrin as raw materials.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol-bis (2-ethylbutyrate), and fatty acids such as stearamide. Fatty acid esters such as amides and butyl oleate, oxy acid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritols, fatty acid esters of pentaerythritols, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins Etc.

As the plasticizer, polyester plasticizers, polyalkylene plasticizers, glycerin plasticizers, pentaerythritols, and pentaerythritol fatty acid esters can be preferably used. It is also possible to use two or more kinds in combination.
The content of the plasticizer is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight per 100 parts by weight of the resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer. More preferably, it is 0.1 to 10 parts by weight. In the present invention, each of the crystallization nucleating agent and the plasticizer may be used alone, or more preferably used in combination.

<Impact resistance improver>
The resin composition of the present invention can contain an impact resistance improver. The impact resistance improver is one that can be used to improve the impact resistance of a thermoplastic resin, and is not particularly limited. For example, at least one selected from the following impact resistance improvers can be used.
Specific examples of impact modifiers include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and their Alkali metal salts (so-called ionomers), ethylene-glycidyl (meth) acrylate copolymers, ethylene-acrylate copolymers (for example, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers), modified ethylene -Propylene copolymer, diene rubber (eg polybutadiene, polyisoprene, polychloroprene), diene and vinyl copolymer (eg styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer) Coalescence, styrene Soprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene graft copolymerized with styrene, butadiene-acrylonitrile copolymer), polyisobutylene, isobutylene and butadiene Or a copolymer with isoprene, natural rubber, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber and the like can be mentioned.

In addition, those having various cross-linking degrees, various micro structures such as those having a cis structure, a trans structure, etc., a core layer and one or more shell layers covering the core layer, and adjacent layers are composed of heterogeneous polymers. A so-called core-shell type multi-layered polymer can also be used.
Furthermore, the various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers, block copolymers and the like, and can be used as the impact resistance improver of the present invention.
The content of the impact modifier is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer. More preferably, it is 10 to 20 parts by weight.

<Others>
The resin composition of the present invention may contain a thermosetting resin such as a phenol resin, a melamine resin, a thermosetting polyester resin, a silicone resin, or an epoxy resin within a range not departing from the spirit of the present invention.
In addition, the resin composition of the present invention may contain a flame retardant such as bromine, phosphorus, silicone, antimony compound and the like within a range not departing from the spirit of the present invention.
Also, colorants containing organic and inorganic dyes and pigments, such as oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as bitumen, zinc chromate, etc. Sulfates such as chromate and barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine, phosphates such as manganese violet, carbon such as carbon black, metal colorants such as bronze powder and aluminum powder, etc. It may be included.
Also, nitroso type such as naphthol green B, nitro type such as naphthol yellow S, azo type such as naphthol red and chromophthal yellow, phthalocyanine type such as phthalocyanine blue and fast sky blue, and condensed polycyclic coloring such as indanthrone blue An additive such as a slidability improver such as a graphite or fluorine resin may be added.
These additives can be used alone or in combination of two or more.

  Hereinafter, the present invention will be described more specifically by way of examples. Each physical property was measured by the following methods.

(1) Weight average molecular weight (Mw):
The weight average molecular weight of the polymer was measured by gel permeation chromatography (GPC) and converted to standard polystyrene.
For GPC measurement, 10 μl of a sample of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) at a temperature of 40 ° C. and a flow rate of 1.0 ml / min was used with the following detector and column. Injected and measured.
Detector: Differential refractometer (manufactured by Shimadzu Corporation) RID-6A.
Column: Toso-Co., Ltd. TSKgelG3000HXL, TSKgelG4000HXL, TSKgelG5000HXL and TSKguardcolumnHXL-L connected in series, or Toso- Co., Ltd. TSKgelG2000HXL, TSKgelG3000HXL, TSKumHXL

(2) Carboxyl group concentration:
The carboxyl group concentration of the polymer was determined by dissolving the sample in purified o-cresol, dissolving in a nitrogen stream, and bromocresol blue as an indicator, and titrating with 0.05 N potassium hydroxide in ethanol.

(3) Identification of amine compounds by NMR:
The synthesized amine compound was confirmed by ¹ H-NMR. For NMR, JNR-EX270 manufactured by JEOL Ltd. was used. Deuterated chloroform was used as the solvent.

(4) Degradation evaluation in low temperature water:
200 mg of the resin composition and 10 ml of distilled water are charged into a vial, and treated with a thermo-hygrostat (LH21-11M, manufactured by Nagano Science Co., Ltd.) at 60 ° C. for 120 hours or 240 hours. Then, it takes out and cools to 25 degreeC, it filters using a filter paper (JISP3801: 1995, 5 types A specification), The resin composition which remains on a filter paper is 60 degreeC and the vacuum of 133.3 Pa or less for 3 hours. After drying, the weight was measured, and the weight was determined from the following formula (i).
Weight (%) = [weight of resin composition after treatment / weight of initial resin composition] × 100 (i)
In this evaluation, a pellet-shaped resin composition having sides of 1 to 1.5 mm was used.

(5) Particle size distribution measurement:
Using a low-tap type sieve shaker, 100 g of powder was passed, the weight under each sieve was measured, and the average particle size was determined when the cumulative weight fraction was 50%.

(6) Melting point, glass transition point:
The melting point of 5 mg of the sample was determined using a differential scanning calorimeter (DSC). The glass transition point was determined by quenching with liquid nitrogen and reheating.

(7) Grinding ability:
After the pulverization, the pulverizer was opened and visually observed for fusion and adhesion, and the pulverization ability was confirmed.
◎: The crushing operation can be performed without any problem, and when the crusher is opened, there is no fusion-bonded material. ○: The crushing operation is possible, but when the crusher is opened, some fusion-bonded material is generated. State x: Slight pulverization is possible, but a large number of pulverizers are generated around the pulverizer when the pulverizer is stopped and the pulverizer is released due to the occurrence of the fusion-bonded matter.

(8) Presence or absence of whiskers:
For the presence or absence of whiskers, 100 powders were randomly extracted in a specific area by microscopic observation, whiskers and spherical powders (cubic powders) were confirmed, and the number was counted.
A: Whisker-like powder is 20% or less of the total powder O: Whisker-like powder is 50% or less of the total powder X: The whisker-like powder is 50% or more of the total powder

Hereinafter, the compounds used in this example will be described.
<Resin having autocatalytic action mainly composed of water-soluble monomer (component A)>
The following polylactic acid and polyglycolic acid were used as a resin (component A) having an autocatalytic action mainly composed of a water-soluble monomer.
A1: Polylactic acid “Ingeo ^™ 4060D” manufactured by Nature Works (Mw is 200,000, carboxyl group concentration is 18.1 equivalent / ton)
A2: Polyglycolic acid (manufactured by Sigma-Aldrich, intrinsic viscosity is 1.4 to 1.8 dL / g (catalog value), melting point is 220 to 230 ° C. (catalog value))
A3: Polylactic acid “REVODE190” manufactured by Zhejiang Kaisei Biologicals (Mw is 180,000, carboxyl group concentration is 8 equivalents / ton)

<Decomposition accelerator (B component) that functions as an A component exchange agent>
The following additives were synthesized and used as a decomposition accelerator (B component) that functions as an A component exchange agent.

<Synthesis Example> Amine compound: B1

o- nitrophenol (0.11 mol) and pentaerythrityl tetra bromide (0.025 mol), potassium carbonate (0.33mol), N, N- dimethylformamide 200ml in reactor installed with a stirrer and a heating device _{N 2} After charging in an atmosphere and reacting at 130 ° C. for 12 hours, N, N-dimethylformamide was removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane and separated three times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and dichloromethane was removed under reduced pressure to obtain a nitro compound.
Next, nitro compound (0.1 mol), 5% palladium carbon (Pd / C) (1.25 g), and 500 ml of N, N-dimethylformamide were charged into a reactor equipped with a stirrer, and hydrogen substitution was performed 5 times. The reaction is carried out in a state where hydrogen is constantly supplied at 25 ° C., and the reaction is terminated when there is no decrease in hydrogen. Pd / C is recovered by filtration, and the filtrate is put into 3 L of water to precipitate a solid. By collecting and drying this solid, an amine compound (B1) represented by the above formula (2) was obtained. The structure of B1 was confirmed by NMR.
B2: 2,2′-ethylenedianiline (Tokyo Chemical Industry Co., Ltd.)
B3: 1,8-diaminooctane (manufactured by Tokyo Chemical Industry Co., Ltd.)
B4: “ADK STAB (registered trademark)” NA-11 (manufactured by ADEKA Corporation)

[Example 1]
A1 and B1 in a weight ratio shown in Table 1 were melt-kneaded at 200 degrees using a twin-screw extruder manufactured by Kobe Steel, then extruded into water and cut to form a 3 mm square cylindrical shape. Pellets were made. The obtained pellet was crystallized and dried at 100 ° C. to obtain a solid resin composition. This resin composition solid was pulverized by a pulverization type cutter mill in which the material was sheared with a blade having the structure shown in FIG. The carrier medium used air and the temperature was 20 ° C. The flow rate of the conveying medium was adjusted so that the fluidity in the pulverizer was confirmed and the powder having the target particle size was discharged from the discharge port. The pulverizer internal temperature at the time of pulverization was 40 ° C., and no fusing or adhering matter was observed inside the pulverizer, and continuous operation for 5 hours or more was possible. Moreover, the angle of repose of the obtained powder was 55 degrees or less.

[Examples 2 to 7]
In Examples 2 to 7, powders were obtained in the same manner as in Example 1 under the conditions shown in Table 1. All the powders had an angle of repose of 55 degrees or less.

[Example 8]
A1 and B1 in a weight ratio shown in Table 1 were melt-kneaded at 200 degrees using a twin-screw extruder manufactured by Kobe Steel, then extruded into water and cut to form a 3 mm square cylindrical shape. Pellets were made. The obtained pellet was crystallized and dried at 100 ° C. to obtain a solid resin composition. This resin composition solid was pulverized by a pin mill having the structure shown in FIG. The carrier medium used water and the temperature was 15 ° C. The flow rate of the conveying medium was adjusted so that the fluidity in the pulverizer was confirmed and the powder having the target particle size was discharged from the discharge port. The pulverizer internal temperature at the time of pulverization was 35 ° C., and no fusing or adhering matter was observed inside the pulverizer, and continuous operation for 5 hours or more was possible. The obtained solid was filtered and dried at 100 ° C. to obtain a powder. The angle of repose of the obtained powder was 55 degrees or less.

[Example 9]
The same procedure as in Example 8 was performed, except that the carrier medium was changed to water / ethylene glycol (90/10) and the carrier medium temperature was changed to −5 ° C. The results are shown in Table 1. The angle of repose of the obtained powder was 55 degrees or less.

[Comparative Example 1]
When pulverization was performed with a turbo mill (with screen mesh) in which the pulverizer does not have a fluidized portion, the internal temperature of the pulverizer immediately increased to 70 ° C. or higher. Inside the pulverizer, the resin composition solids were fused and fixed, and the pulverizer immediately stopped, so that powder could not be obtained efficiently.

[Comparative Example 2]
Grinding was carried out according to Example 8 except that the component B and no carrier medium were used. Instantly, the pulverizer internal temperature rose and was above 70 ° C. Since the resin composition solids were fused and fixed inside the pulverizer and the pulverizer immediately stopped, the powder could not be obtained efficiently.

[Comparative Example 3]
This was carried out in accordance with Example 8, except that the carrier medium of Example 8 was liquid nitrogen and the carrier medium temperature was -140 ° C. Although pulverization is possible, since it is necessary to use a large amount of liquid nitrogen, production cost is very high, and stable industrial production is not possible.

  The resin composition of the present invention exhibits desired performance as an oil field excavation technique, particularly as a fluidity control material, and can be suitably used as a powder for this application.

DESCRIPTION OF SYMBOLS 1 Resin composition solid substance inlet 2 Carrying medium inlet 3 Grinding part 4 Flowing part 5 Bag filter 6 Carrying medium flow control port 7 Powder discharge port 8 Blower
9 Crushing and fluidizing section 10 Filtration section 11 Transport medium outlet 12 Dryer

Claims (8)

A component and / or B composed of a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer and a degradation regulator (B component) that functions as an exchange agent for the A component. A resin composition containing a resin component in which components A are exchange-reacted with each other as an exchange agent, wherein the weight after 120 hours is 95% or less and the weight after 240 hours is 75% or less in water at 60 ° C. Resin composition solids (C)
A pulverizing section (I) comprising a resin composition solid (C) charging port and a transport medium supply port, and converting the charged resin composition solid (C) into powder.
A fluidized part (b) in which the powder obtained in the powder part (a) directly connected to the upper part of the grinding part is fluidized by a carrier medium;
At the upper part of the fluidized section, the discharge port (c) for the powder and the conveying medium below the target particle size,
Using a crusher having
The resin composition solid (C) is pulverized while controlling the temperature in the pulverization part (b) within the range of −20 ° C. to Tg−5 ° C. of the resin composition solid (C) by supplying a carrier medium. The amount of transport medium supplied to the crushing part (b) exceeds the flow rate at which the powder starts flowing in the crushing part (b) and exceeds the target particle size in the crushing part (b). A method for producing a powder, wherein the returned powder having a particle size equal to or smaller than the target particle size is set to a flow rate discharged from the discharge port (c) together with the carrier medium.   The method for producing a powder according to claim 1, wherein the carrier medium is a gas. A component and / or B composed of a resin (A component) having an autocatalytic action mainly composed of a water-soluble monomer and a degradation regulator (B component) that functions as an exchange agent for the A component. A resin composition containing a resin component in which components A are exchange-reacted with each other as an exchange agent, wherein the weight after 120 hours is 95% or less and the weight after 240 hours is 75% or less in water at 60 ° C. Resin composition solids (C)
A resin composition solid (C) charging port and a conveyance medium supply port are provided, and the obtained resin composition solid (C) is pulverized while the obtained powder is fluidized by the conveyance medium. Fluid department (d),
At the bottom of the pulverization fluid section, the discharge port (c) for the powder and the conveying medium below the target particle size,
Using a crusher having
By controlling the temperature in the pulverization fluidized section (d) within the range of −20 ° C. to Tg−5 ° C. of the resin composition solid (C) by supplying the carrier medium, the resin composition solid (C) A method for producing a powder, which is charged into the pulverization fluid section (d) and the supply amount of the conveyance medium is a flow rate at which the powder starts flowing in the pulverization fluid part (d).   The method for producing a powder according to claim 3, further comprising a step of separating the powder discharged from the pulverization fluidizing section (d) and the transport medium and a step of drying the separated powder.   The method for producing a powder according to claim 3 or 4, wherein the carrier medium is a liquid.   The method for producing a powder according to any one of claims 1 to 5, wherein the component A is polylactic acid or polyglycolic acid.   The method for producing a powder according to any one of claims 1 to 6, wherein the component B is an amine compound and / or an organic acid metal salt.   The method for producing a powder according to any one of claims 1 to 7, wherein the content of the B component is 0.01 to 30 parts by weight with respect to a total of 100 parts by weight of the A and B components.

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