JPWO2019239913A1 - Method for manufacturing biodegradable laminate - Google Patents

Abstract

In a method for producing a biodegradable laminate composed of a paper base material and a resin layer by crimping a resin material to a paper base material using a pressure-bonding surface and then peeling the resin material from the pressure-bonding surface. The resin material is the formula (A): [-CHR-CH2-CO-O-] (in the formula, R is an alkyl group represented by CnH2n + 1, and n is an integer of 1 or more and 15 or less). It is a resin material containing 100 parts by weight of polyhydroxyalkanoate containing the indicated repeating unit and 1 to 20 parts by weight of (B) glycerin ester compound.

Description

The present invention relates to a method for producing a biodegradable laminate composed of a paper base material and a resin layer, a method for improving the surface state of the resin layer, and a biodegradable laminate.

Poly (3-hydroxyalkanoate) -based resin [Poly (3-hydroxyalkanoate); hereinafter may be abbreviated as "P3HA") is a heat produced and accumulated as an energy storage substance in the cells of many microbial species. It is a plastic polyester. P3HA is completely biodegraded by microorganisms in the soil and water, and is also easily biodegraded in a natural environment such as the ocean and incorporated into the natural carbon cycle process. Therefore, it can be said that P3HA is an environmentally friendly plastic that has almost no adverse effect on the ecosystem.

Laminated paper produced by laminating such P3HA on a paper base material is extremely promising from the viewpoint of environmental protection because both paper and P3HA are environmentally degradable materials.

Generally, laminated paper is produced by laminating a paper base material and a resin material by extrusion laminating or thermal laminating. However, P3HA easily adheres to the cooling roll during the laminating process, and when it is peeled off from the roll, a large force is applied to form fine irregularities on the surface of the resin layer, causing cloudy unevenness and deteriorating the appearance of the resin layer. was there. Further, since the peelability from the roll is poor, there is a problem that continuous laminating process for a long time becomes difficult.

In order to solve such a problem, in order to avoid contact between P3HA and the cooling roll, P3HA and a polyolefin resin are coextruded onto a paper substrate to prepare a three-layer laminate, and then the laminate is formed. A method for producing a laminated paper composed of a paper base material and a P3HA layer by peeling a polyolefin resin layer from the laminate is known. However, this method has a problem in terms of waste treatment because the polyolefin resin film peeled off from the laminate is discarded.

In Patent Document 1, P3HA and a polycondensable polyester of dicarboxylic acid and glycol having good processability are coextruded onto a paper base material to produce a three-layer biodegradable laminate, which is cooled. It is described to prevent blocking to rolls. Further, Patent Document 2 describes that a mixture of P3HA and polycondensation polyester or polylactic acid is extruded onto a paper substrate to prevent blocking on a cooling roll.

However, since the polycondensable polyester and polylactic acid used in Patent Document 1 and Patent Document 2 are resins having low environmental degradability, they are not desirable components for providing laminated paper having environmental degradability. ..

Japanese Unexamined Patent Publication No. 10-6444 Japanese Unexamined Patent Publication No. 10-6445

In view of the above situation, the present invention provides a biodegradable laminate by laminating a paper base material and P3HA from a pressure-bonded surface such as a cooling roll without using a resin material having low environmental degradability. It is an object of the present invention to improve the peelability of the resin layer of the above, to produce a biodegradable laminate having a good surface condition and high environmental degradability.

As a result of intensive research to solve the above problems, the present inventors have mixed a predetermined amount of a glycerin ester compound with P3HA, and by forming a resin layer with this compound, from a pressure-bonded surface such as a cooling roll. We have found that a biodegradable laminate having a good surface condition can be produced by improving the peelability of the resin layer of the above, and have reached the present invention.

That is, in the present invention, a biodegradable laminate composed of the paper base material and the resin layer is formed by crimping the resin material to the paper base material using the crimping surface and then peeling the resin material from the crimping surface. A method for producing a body, wherein the resin material is an alkyl group represented by the _{formula (A): [-CHR-CH 2-} CO-O-] (in the formula, R is C _n H _{2n + 1, and n} Is a biodegradable resin material containing 100 parts by weight of a polyhydroxyalkanoate containing a repeating unit represented by 1 to 15 parts by weight and (B) 1 to 20 parts by weight of a glycerin ester compound. The present invention relates to a method for producing a laminate. Preferably, the resin composition further contains 0.1 to 5 parts by weight of the (C) aliphatic amide compound. Preferably, the polyhydroxyalkanoate is a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoate. Preferably, the step of crimping the resin material to the paper base material using the crimping surface is a step of extruding the molten resin material into a film by an extrusion laminating method and then cooling and crimping to the separately fed paper base material with a cooling roller. It is a process. Preferably, the pulling force when peeling the resin material from the pressure-bonded surface is 25 N or less.

Further, in the present invention, using a pressure-bonded surface, [-CHR-CH _2- CO-O-] (in the formula, R is _{an alkyl group represented by C n} H _{2n + 1} , and n is an integer of 1 or more and 15 or less. A resin material containing a polyhydroxyalkanoate containing a repeating unit represented by ()) is pressure-bonded to a paper substrate, and then the resin material is peeled off from the pressure-bonded surface to produce the paper substrate and a resin. A method for improving the surface condition of the resin layer in a biodegradable laminate composed of layers, wherein 1 to 20 parts by weight of glycerin ester per 100 parts by weight of the polyhydroxyalkanoate with respect to the resin material. It also relates to a method for improving the surface condition of the resin layer, which is characterized by blending a compound.

Further, the present invention is a biodegradable laminate in which a resin layer is laminated on one side or both sides of a paper base material, and the resin layer is a formula (A): [-CHR-CH _2- CO-O-] (. In the formula, R is _{an alkyl group represented by C n} H _{2n + 1} , and n is an integer of 1 or more and 15 or less.) 100 parts by weight of polyhydroxyalkanoate containing a repeating unit represented by), and (B) glycerin. It also relates to a biodegradable laminate containing 1 to 20 parts by weight of an ester compound. Preferably, the biodegradable laminate has a rolled form.

According to the present invention, when a paper base material and P3HA are laminated to produce a biodegradable laminate, the peelability of the resin layer from a pressure-bonded surface such as a cooling roll can be improved without using another resin material. It is possible to produce a biodegradable laminate that is improved, has a good surface condition, and is highly environmentally degradable. Further, according to the present invention, it is possible to stably carry out continuous laminating processing for a long period of time.

Embodiments of the present invention will be described in detail below.

(Polyhydroxy alkanoate (A))
In the biodegradable laminate composed of the paper base material and the resin layer according to the present invention, the main resin material constituting the resin layer is a poly (3-hydroxyalkanoate) resin, specifically, the formula. : [-CHR-CH _2- CO-O-] (in the formula, R is _{an alkyl group represented by C n} H _{2n + 1} , and n is an integer of 1 or more and 15 or less). It is a polyhydroxy alkanoate.

The repeating unit represented by the above formula contained in the P3HA may be only one type or two or more types. In the latter case, the type of copolymerization is not particularly limited and may be random copolymerization, alternate copolymerization, block copolymerization, graft copolymerization or the like, but random copolymerization is preferable because it is easily available.

The repeating unit constituting the P3HA may be only the repeating unit represented by the above formula, or may include other repeating units in addition to the repeating unit represented by the above formula. Examples of other repeating units include 4-hydroxyalkanoate units such as 4-hydroxybutyrate units.

Specific examples of P3HA include poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), and poly (3-hydroxybutyrate-co-3-hydroxyvariate). , Poly (3-hydroxybutyrate-co-4-hydroxybutyrate), Poly (3-hydroxybutyrate-co-3-hydroxyoctanoate), Poly (3-hydroxybutyrate-co-3-hydroxyoctanoate) Decanoate) and the like. Among them, poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), and poly (3-hydroxybutyrate-co-) are easy to produce industrially. 3-Hydroxyvariate) and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) are preferred.

Furthermore, by changing the composition ratio of the repeating unit, the melting point and crystallinity can be changed, and the physical properties such as Young's rate and heat resistance can be changed, and the physical properties between polypropylene and polyethylene can be imparted. Polyethylene, which is a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid, is possible, and as described above, it is industrially easy to produce and is a physically useful plastic. 3-Hydroxybutyrate-co-3-hydroxyhexanoate) is preferred. Among P3HA, the poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) has poor peelability from the pressure-bonded surface during the laminating process, and the surface condition of the resin layer of the obtained laminated paper deteriorates. The problem of ease was remarkable, but by applying the present invention, it is possible to improve the surface condition of laminated paper using poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) as a resin material. it can.

Specific methods for producing poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) are described, for example, in International Publication No. 2010/0134883. Examples of commercially available products of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) include Kaneka Corporation "Kaneka Biodegradable Polymer PHBH" (registered trademark).

In addition, the composition ratio of the repeating unit of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) is set to 3-hydroxybutyrate unit / 3-hydroxyhexanoate from the viewpoint of the balance between flexibility and strength. The composition ratio of the unit is preferably 80/20 to 99/1 (mol / mol), and more preferably 85/15 to 97/3 (mo1 / mo1). The reason is that 99/1 or less is preferable from the viewpoint of flexibility, and 80/20 or more is preferable from the viewpoint that the resin has an appropriate hardness.

The weight average molecular weight of P3HA used in the present invention (hereinafter, may be referred to as Mw) is not particularly limited, but is preferably 100,000 to 2.5 million, more preferably 150,000 to 2 million, and further 200,000 to 1,000,000. preferable. If the weight average molecular weight is less than 100,000, the mechanical properties and the like may be inferior, and if it exceeds 2.5 million, molding may become difficult. In the present application, the weight average molecular weight of P3HA is determined by gel permeation chromatography (GPC) (“Shodex GPC-101” manufactured by Showa Denko Co., Ltd.), and polystyrene gel (“Shodex K-804” manufactured by Showa Denko Co., Ltd.) is used for the column. It can be determined as the molecular weight when chloroform is used as the mobile phase and converted to polystyrene.

In the resin layer constituting the biodegradable laminate of the present invention, one type of P3HA may be used alone, or two or more types may be used in combination.

The resin layer contains an aliphatic polyester resin such as polybutylene succinate adipate, polybutylene succinate, and polylactic acid, and an aliphatic aromatic polyester such as polybutylene adipate terephthalate, as long as the effects of the present invention are not impaired. One or more biodegradable resins other than P3HA, such as resins, may be contained.

However, since biodegradable resins other than P3HA have low environmental degradability in normal environments such as soil and the ocean, their use may reduce the environmental degradability of the biodegradable laminate. Therefore, the content of the resin other than P3HA is preferably as small as possible so as not to impair the environmental degradability of P3HA. Specifically, the content of the resin other than P3HA is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 10 parts by weight or less, based on 100 parts by weight of P3HA. Further, the resin layer constituting the biodegradable laminate of the present invention may contain only P3HA as a resin component, that is, may not contain any resin other than P3HA.

(Glycerin ester compound (B))
In the present invention, by forming the resin layer constituting the biodegradable laminate with a resin composition in which P3HA is mixed with a glycerin ester compound, the peelability from the pressure-bonded surface such as a cooling roll in the laminating process is improved. The resin layer is less likely to adhere to the crimping surface, the resin layer can be smoothly peeled off from the crimping surface, and a biodegradable laminate having a good surface condition can be produced.

The glycerin ester compound is a compound in which the hydroxyl group of glycerin forms an ester bond with, for example, a compound having a carboxyl group. The ester compound may be either a monoester of glycerin, a diester of glycerin, or a triester of glycerin. From the viewpoint of improving the peelability from the pressure-bonded surface, a glycerin triester is preferable, and a glycerin diacet monoester is more preferable. Specific examples of the glycerin diacet monoester include glycerin diacet monolaurate, glycerin diacet monooleate, glycerin diacet monostearate, glycerin diacet monocaprelate, and glycerin diacet monodecanoate. Only one kind of glycerin ester compound may be used, or a plurality of glycerin ester compounds may be used in combination.

The blending amount of the glycerin ester compound in the resin composition is 1 to 20 parts by weight with respect to 100 parts by weight of P3HA. If the blending amount of the glycerin ester compound is less than 1 part by weight, it becomes difficult to obtain the effect of improving the peelability from the crimping surface, and if it is more than 20 parts by weight, the glycerin ester compound bleeds during crimping and the cooling roll. There is a problem that it adheres to the crimping surface such as, etc., and continuous processing for a long time becomes difficult. The blending amount of the glycerin ester compound is preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight.

(Aliphatic amide compound (C))
The resin composition constituting the biodegradable laminate of the present invention may contain an aliphatic amide compound in addition to P3HA and a glycerin ester compound. By blending the aliphatic amide compound, the peelability from the pressure-bonded surface can be further improved. However, the aliphatic amide compound is an arbitrary component, and the resin composition may not contain the aliphatic amide compound.

Aliphatic amide compounds are a type of additive conventionally known as a lubricant added to a resin. The aliphatic amide compound is not particularly limited, and examples thereof include saturated or unsaturated fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, bechenic acid amide, oleic acid amide, and erucic acid amide. , Methylenebisstearic acid amide, alkylene fatty acid amides such as methylenebisstearic acid amide and the like. Of these, fatty acid amides are preferable from the viewpoint of improving the peelability from the pressure-bonded surface. Only one kind of aliphatic amide compound may be used, or a plurality of kinds may be used in combination.

The blending amount of the aliphatic amide compound in the resin layer is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of P3HA. By setting the blending amount of the aliphatic amide compound to 0.1 parts by weight or more, the effect of improving the peelability by blending the aliphatic amide compound can be obtained. However, if the blending amount of the aliphatic amide compound exceeds 5 parts by weight, the aliphatic amide compound bleeds during crimping and adheres to the crimping surface of a cooling roll or the like, which makes continuous processing for a long time difficult. The blending amount of the aliphatic amide compound is more preferably 0.3 to 4 parts by weight, still more preferably 0.5 to 3 parts by weight.

(Pentaerythritol (D))
The resin layer constituting the biodegradable laminate of the present invention may contain pentaerythritol in addition to P3HA and a glycerin ester compound. By blending pentaerythritol, the peelability from the pressure-bonded surface can be further improved. However, pentaerythritol is an arbitrary component, and the resin layer may not contain pentaerythritol.

The blending amount of pentaerythritol in the resin layer is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of P3HA. By setting the blending amount of pentaerythritol to 0.1 parts by weight or more, the effect of improving the peelability by blending pentaerythritol can be obtained. However, if the blending amount of pentaerythritol exceeds 5 parts by weight, pentaerythritol bleeds during crimping and adheres to the crimping surface of a cooling roll or the like, which makes continuous processing for a long time difficult. The blending amount of pentaerythritol is more preferably 0.3 to 4 parts by weight, still more preferably 0.5 to 3 parts by weight.

In addition to the glycerin ester compound, the aliphatic amide compound of the optional component, and the pentaerythritol of the optional component, other additives usually added to the resin material are added to the resin layer as long as the effects of the present invention are not impaired. For example, inorganic fillers, pigments, colorants such as dyes, odor absorbers such as activated charcoal and zeolite, fragrances such as vanillin and dextrin, plasticizers, antioxidants, antioxidants, weather resistance improvers, and ultraviolet absorbers. , Crystal nucleating agent, lubricant, mold release agent, water repellent, antibacterial agent, slidability improving agent, and other secondary additives may be added in one or more. The content of these additives can be set as appropriate.

The thickness of the resin layer (each resin layer when the biodegradable laminate has two or more resin layers) in the biodegradable laminate of the present invention is not particularly limited, but prevents water absorption on the paper. However, from the viewpoint of ensuring sufficient flexibility, it is preferably 5 to 300 μm, more preferably 10 to 200 μm.

(Paper base material)
The paper base material constituting the biodegradable laminate of the present invention is not particularly limited as long as it can form a resin layer on one side or both sides thereof. Specific examples include kraft paper, woodfree paper, coated paper, thin leaf paper, glassine paper, paperboard, glassine paper, cellophane and the like. The type of paper substrate may be selected according to the use of the biodegradable laminate. Further, the surface of the paper base material may be subjected to surface treatment such as corona treatment, frame treatment, and anchor coating treatment.

(Laminating method)
In the present invention, a biodegradable laminate composed of a paper base material and resin layers formed on one or both sides thereof is produced by a laminating method. The laminating method is a biodegradable laminate in which a resin material is crimped to a paper base material using a crimping surface such as a cooling roll, and then a resin layer composed of the resin material is peeled off from the crimping surface. It is a method of manufacturing. The laminating method is not particularly limited as long as it is a method of crimping the resin material and the paper base material using the crimping surface, but specifically, the resin material melted from the T-die is extruded into a film and then fed separately. Examples thereof include an extrusion laminating method in which a cold roll is used to cool and crimp the paper base material, and a thermal laminating method in which a resin film prepared in advance is heated and crimped onto the paper base material. Here, the pressure-bonded surface may be any material that can pressure-bond the resin and the paper base material, and examples thereof include a plate-shaped surface and a roll surface.

The extrusion laminating method is continuously carried out, in which the molten resin material is cooled and pressure-bonded to a paper base material, and immediately after that, the resin layer is peeled off from the cooling roll. Therefore, in the conventional method, when P3HA is used as the resin material, it is difficult for the resin layer to be smoothly peeled off from the cooling roll, and a phenomenon that the resin layer temporarily adheres to the cooling roll is likely to occur. As a result, there has been a particularly remarkable problem that a force is applied when the adhered portion is peeled off from the roll, causing cloudy unevenness (fine unevenness) on the surface of the resin layer at the portion. However, by applying the present invention, it is possible to produce a biodegradable laminate having a good surface condition of the resin layer by improving the peelability from the cooling roll even in the extrusion lamination method. According to the present invention, the pulling force when peeling the resin material containing P3HA from the pressure-bonded surface of a cooling roll or the like can be reduced to preferably 25 N or less, more preferably 20 N or less.

Further, according to the present invention, in order to avoid contact between the P3HA layer and the pressure-bonded surface, other resins such as a polyolefin resin layer and a polycondensation polyester layer of dicarboxylic acid and glycol are placed on the P3HA layer as in the conventional method. There is no need to provide a separate layer. Therefore, it is possible to avoid the above-mentioned problem of waste treatment and the problem that the biodegradable laminate contains a resin material having low environmental degradability.

In the extrusion laminating method, the surface temperature of the cooling roll is not particularly limited as long as it can cool and crimp the resin layer, and can be appropriately determined, but may be in the range of, for example, 10 to 60 ° C.

(Biodegradable laminate)
The present invention is also a biodegradable laminate containing a paper substrate and resin layers formed on one or both sides thereof. The resin layer is a resin layer containing the above-mentioned P3HA and a glycerin ester compound as essential components. In the biodegradable laminate of the present invention, the resin layer is laminated so as to be in contact with the paper base material, and an adhesive layer or another resin layer is interposed between the resin layer and the paper base material. It is preferable that there is no such thing. Further, in the biodegradable laminate of the present invention, a resin layer other than the resin layer mainly composed of P3HA in the present invention (for example, a polyolefin resin layer or a layer composed of a polycondensed polyester of dicarboxylic acid and glycol) is formed. It is preferable that it is not contained.

The biodegradable laminate of the present invention is preferably a long biodegradable laminate continuously produced by the above-mentioned laminating method, and is wound on a take-up roll after crimping and peeling by the laminating method. It is preferable that it is a biodegradable laminate having a roll-like form that can be produced in the above.

The use of the biodegradable laminate of the present invention is not particularly limited, and examples thereof include paper cups, paper bags, cartons, trays, and wallpaper for interiors.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Manufacturing example 1>
KNK-631 strain (see International Publication No. 2009/145164) was used for culture production.

The composition of Tanehaha medium 1w / v% Meat-extract, 1w / v% Bacto-Tryptone, 0.2w / v% Yeast-extract, 0.9w / v% Na 2 HPO 4 · 12H 2 O, 0.15w / V% KH ₂ PO ₄ , (pH 6.8).

The composition of the preculture medium _{1.1w / v% Na 2 HPO 4} · 12H 2 O, 0.19w / v% KH 2 PO 4, 1.29w / v% (NH 4) 2 SO 4, 0.1w / _{v% MgSO 4 · 7H 2 O} , 0.5v / v% trace metal salt solution (1.6 w in 0.1N HCl _{/ v% FeCl 3 · 6H 2} O, 1w / v% CaCl 2 · 2H 2 O, 0 _{.02w / v% CoCl 2 · 6H} 2 O, 0.016w / v% CuSO 4 · 5H 2 O, 0.012w / v% NiCl 2 · 6H 2 O what dissolved), and the. As the carbon source, palm kernel oil was added all at once at a concentration of 10 g / L.

The composition of the P3HA production medium _{0.385w / v% Na 2 HPO 4} · 12H 2 O, 0.067w / v% KH 2 PO 4, 0.291w / v% (NH 4) 2 SO 4, 0.1w / _{v% MgSO 4 · 7H 2 O} , 0.5v / v% trace metal salt solution (1.6 w in 0.1N HCl _{/ v% FeCl 3 · 6H 2} O, 1w / v% CaCl 2 · 2H 2 O, 0 _{.02w / v% CoCl 2 · 6H} 2 O, 0.016w / v% CuSO 4 · 5H 2 O, 0.012w / v% NiCl 2 · 6H 2 O what dissolved), 0.05w / v% BIOSPUREX200K (Anti-foaming agent: manufactured by Cognis Japan Co., Ltd.).

First, a glycerol stock (50 μl) of the KNK-631 strain was inoculated into a seed medium (10 ml) and cultured for 24 hours to perform seed mother culture. Next, 1.0 v / v% of the seed mother culture solution was inoculated into a 3 L jar fermenter (MDL-300 type manufactured by Maruhishi Bioengineer) containing 1.8 L of preculture medium. The operating conditions were a culture temperature of 33 ° C., a stirring speed of 500 rpm, an aeration rate of 1.8 L / min, and the culture was carried out for 28 hours while controlling the pH between 6.7 and 6.8, and pre-culture was performed. A 14% aqueous solution of ammonium hydroxide was used for pH control.

Next, the preculture solution was inoculated at 1.0 v / v% into a 10 L jar fermenter (MDS-1000 type manufactured by Maruhishi Bioengineer) containing 6 L of P3HA production medium. The operating conditions were a culture temperature of 28 ° C., a stirring speed of 400 rpm, an aeration rate of 6.0 L / min, and a pH controlled between 6.7 and 6.8. A 14% aqueous solution of ammonium hydroxide was used for pH control. Palm kernel oil was used as the carbon source. The culture was carried out for 64 hours, and after the culture was completed, the cells were collected by centrifugation, washed with methanol, freeze-dried, and the weight of the obtained dried cells was measured.

100 ml of chloroform was added to 1 g of the obtained dried cells, and the mixture was stirred at room temperature for 24 hours to extract P3HA in the cells. The cell residue was filtered off, concentrated with an evaporator until the total volume reached 30 ml, 90 ml of hexane was gradually added, and the mixture was allowed to stand for 1 hour with slow stirring. The precipitated P3HA was filtered off and then vacuum dried at 50 ° C. for 3 hours to obtain P3HA A1.

The 3HH composition analysis of the obtained P3HA was measured by gas chromatography as follows. To 20 mg of dried P3HA, 2 ml of a sulfuric acid-methanol mixed solution (15:85) and 2 ml of chloroform were added and sealed, and the mixture was heated at 100 ° C. for 140 minutes to obtain a methyl ester of a P3HA decomposition product. After cooling, 1.5 g of sodium hydrogen carbonate was added little by little to neutralize the mixture, and the mixture was left to stand until the generation of carbon dioxide gas stopped. After adding 4 ml of diisopropyl ether and mixing well, the mixture was centrifuged, and the monomer unit composition of the polyester decomposition product in the supernatant was analyzed by capillary gas chromatography. The gas chromatograph used was Shimadzu GC-17A, and the capillary column used was NEUTRA BOND-1 manufactured by GL Science Co., Ltd. (column length 25 m, column inner diameter 0.25 mm, liquid film thickness 0.4 μm). He was used as the carrier gas, the column inlet pressure was 100 kPa, and 1 μl of the sample was injected. The temperature conditions were such that the initial temperature was raised from 100 to 200 ° C. at a rate of 8 ° C./min, and further raised from 200 to 290 ° C. at a rate of 30 ° C./min.

As a result of analysis under the above conditions, it was confirmed that the obtained P3HA A1 was poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (P (3HB-co-3HH)). The weight average molecular weight Mw measured by GPC was 740,000. The 3-hydroxyhexanoate (3HH) composition was 11.4 mol%.

<Manufacturing example 2>
The P3HA A1 obtained in Production Example 1 was treated with a high acceleration life test device (PC-422R5E manufactured by Hirayama Seisakusho) at 120 ° C. and 100% humidity for 2 hours to obtain P (3HB-co) as P3HA A2. -3HH) was obtained. The weight average molecular weight Mw of P3HA A2 was 540,000, and the composition of 3HH was 11.4 mol%.

<Manufacturing example 3>
P (3HB-co-3HH) was obtained as P3HA A3 in the same manner as in Production Example 1 except that the KNK-005 strain (see US Pat. No. 7,384,766) and palm oil was used as the carbon source. The weight average molecular weight Mw of P3HA A3 was 570,000, and the composition of 3HH was 5.6 mol%.

<Manufacturing example 4>
The P3HA A3 obtained in Production Example 3 was treated with a high acceleration life test device (PC-422R5E manufactured by Hirayama Seisakusho) at 120 ° C. and 100% humidity for 2 hours to obtain P (3HB-) as P3HA A4. co-3HH) was obtained. The weight average molecular weight Mw of P3HA A4 was 440,000, and the composition of 3HH was 5.6 mol%.

<Examples 1 to 11>
(Manufacturing of biodegradable laminate)
Each component is blended at the blending ratio shown in Table 1 (the blending ratio in the table is indicated by the weight part), and the set temperature is 100 to 100 using a same-direction meshing twin-screw extruder (manufactured by Japan Steel Works: TEX30). A biodegradable resin composition was obtained by melt-kneading at 140 ° C. (outlet resin temperature 160 ° C.) and a screw rotation speed of 100 rpm. The resin temperature was measured by directly measuring the molten resin coming out of the die with a K-type thermocouple. The biodegradable resin composition was taken from the die in the form of strands and cut into pellets.

Subsequently, after the pellets of the obtained biodegradable resin composition were sufficiently dried at 60 ° C., a single-screw extruder equipped with a T-shaped die having a width of 150 mm and a lip width of 0.25 mm (Toyo Seiki Seisakusho Co., Ltd.) Using a "20C200 type" lab plast mill) manufactured by Extruding under the conditions of molding temperature: 130 to 160 ° C. and screw rotation speed: 30 rpm, the cooling roll was temperature-controlled to 30 ° C. using a laminator (roll diameter 100 mm). A biodegradable laminate was obtained by laminating on one side of unbleached kraft paper having a basis weight of 150 g / m ^{2 with a thickness of 100 μm.}

As P3HA, A1 obtained in Production Example 1, A2 obtained in Production Example 2, A3 obtained in Production Example 3, or A4 obtained in Production Example 4 was used.

As the glycerin ester compound B1, glycerin diacet monolaurate (manufactured by Riken Vitamin Co., Ltd., “Rikemar PL012”) was used.

As the aliphatic amide compound C1, erucic acid amide (manufactured by Nippon Fine Chemical Co., Ltd., “Neutron-S”) was used.

As pentaerythritol D1, pentaerythritol (“Neurizer P” manufactured by Nippon Synthetic Chemistry Co., Ltd.) was used.

(Roll peelability)
The peelability from the cooling roll during the laminating process was evaluated by measuring the force (pulling force) of the laminated body from the cooling roll with a force gauge (Mechanical Force Gauge FB-100N manufactured by Imada Co., Ltd.). The smaller the pulling force, the better the peelability from the cooling roll. The results are shown in Table 1.

(Surface of laminated body)
The surface property of the biodegradable laminate after the laminating process was evaluated by visually observing the surface state of the laminated resin layer. When the surface of the resin layer has cloudy unevenness, it is judged to be defective, and when there is no such unevenness and the resin surface is smooth and transparent, it is judged to be good. The results are shown in Table 1.

<Comparative Examples 1 to 7>
A biodegradable laminate was obtained in the same manner as in Examples 1 to 11 except that the compounding ratios shown in Table 1 were followed, and the roll peelability and the surface property of the laminate during the laminating process were evaluated. Is shown in Table 1.

<Reference example 1>
A biodegradable laminate was obtained in the same manner as in Examples 1 to 11 except that the compounding ratios shown in Table 1 were followed, and the roll peelability and the surface property of the laminate during the laminating process were evaluated. Is shown in Table 1.

As shown in Table 1, in Examples 1 to 11 in which the glycerin ester compound was blended, the pulling force during the laminating process was small and the releasability from the cooling roll was good. Moreover, the surface properties of each of the obtained biodegradable laminates were good.
On the other hand, in Comparative Examples 1 to 7 in which the glycerin ester compound was not used, the pulling force during the laminating process was large and the peelability from the cooling roll was poor. Therefore, continuous processing for a long time was impossible. In addition, the surface properties of each of the obtained biodegradable laminates were poor and could not be used as a product.

As is clear from these results, by adding the glycerin ester compound to P3HA, the peelability from the cooling roll during the laminating process on paper is improved, and the surface property of the obtained biodegradable laminate is good. It becomes a thing. In particular, in Comparative Examples 1 and 3 to 7, although the amide compound and / or pentaerythritol was blended, the glycerin ester compound was not blended, so that the peelability from the cooling roll and the surface property of the biodegradable laminate were improved. There wasn't. From this, it can be seen that the effect of improving the peelability and the surface property is peculiar to the glycerin ester compound.

On the other hand, in Reference Example 1 in which 30 parts by weight of the glycerin ester compound was blended with respect to 100 parts by weight of P3HA, the pulling force during the laminating process was small and the surface property of the obtained biodegradable laminate was also good, but the laminating process was performed. Occasionally, the glycerin ester compound bleeds onto the cooling roll, making continuous processing for long periods of time impossible.

Claims (8)

A method for producing a biodegradable laminate composed of the paper base material and the resin layer by crimping the resin material to the paper base material using the crimping surface and then peeling the resin material from the crimping surface. There,
The resin material is
Formula (A): Represented by [-CHR-CH _2- CO-O-] (in the formula, R is _{an alkyl group represented by C n} H _{2n + 1} , and n is an integer of 1 or more and 15 or less). 100 parts by weight of polyhydroxyalkanoate containing repeating units, and
(B) A method for producing a biodegradable laminate, which is a resin material containing 1 to 20 parts by weight of a glycerin ester compound. The production method according to claim 1, wherein the resin composition further contains 0.1 to 5 parts by weight of the (C) aliphatic amide compound. The production method according to claim 1 or 2, wherein the polyhydroxy alkanoate is a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoate. The process of crimping the resin material to the paper base material using the crimping surface is the process of extruding the molten resin material into a film by the extrusion laminating method and then cooling and crimping it to the separately fed paper base material with a cooling roller. , The manufacturing method according to any one of claims 1 to 3. The manufacturing method according to any one of claims 1 to 4, wherein the pulling force when peeling the resin material from the pressure-bonded surface is 25 N or less. Using the pressure-bonded surface, it is indicated by [-CHR-CH _2- CO-O-] (in the formula, R is _{an alkyl group represented by C n} H _{2n + 1} , and n is an integer of 1 or more and 15 or less). A raw material composed of the paper base material and a resin layer, which is produced by crimping a resin material containing a polyhydroxyalkanoate containing a repeating unit to a paper base material and then peeling the resin material from the pressure-bonded surface. A method for improving the surface condition of the resin layer in a decomposable laminate.
A method for improving the surface condition of a resin layer, which comprises blending 1 to 20 parts by weight of a glycerin ester compound per 100 parts by weight of the polyhydroxyalkanoate with the resin material. A biodegradable laminate in which a resin layer is laminated on one side or both sides of a paper base material.
The resin layer is the formula (A): [-CHR-CH _2- CO-O-] (in the formula, R is _{an alkyl group represented by C n} H _{2n + 1} , and n is an integer of 1 or more and 15 or less. 100 parts by weight of polyhydroxyalkanoate containing the repeating unit indicated by), and
(B) A biodegradable laminate containing 1 to 20 parts by weight of a glycerin ester compound. The biodegradable laminate according to claim 7, which has a rolled form.