JP6377579B2 - Polyethylene terephthalate laminated paper - Google Patents

Description

  The present invention relates to a method for producing a laminated paper in which a resin composition containing polyethylene terephthalate as a main component is melt-extruded laminated on a paper substrate.

  Paper containers are widely used as direct food containers. On the inner surface of these paper containers, a laminate in which a polyolefin resin layer, particularly a polyethylene resin layer is provided, is often used so that water resistance can be imparted and heat-sealing can be performed.

  However, since polyolefin resin has the property of easily adsorbing and sorbing highly aromatic components and fat-soluble components contained in foods and losing a part of the taste and fragrance, it needs aroma retention. It could not be used for food containers. Further, the polyolefin resin has a temperature of around 160 ° C. even in the polypropylene resin having the highest melting point, and cannot be used in a high temperature range exceeding this (for example, oven heating at around 200 ° C.).

  Polyethylene terephthalate (hereinafter referred to as PET) resin is listed as one of inexpensive materials with excellent fragrance retention, heat resistance and oil resistance, and paper containers having PET resin laminated on the inner surface are also on the market. .

However, when a PET resin having a property that the viscosity is remarkably lowered when it is in a molten state is melt-laminated with a paper substrate, there are the following problems.
(1) The phenomenon that the product film width called neck-in or drawdown becomes narrower than the die exit width occurred, and the yield of collected products was reduced.
(2) When considering commercial production, it is necessary to increase the speed of the laminating process. However, since the above-mentioned neck-in and draw-down become more conspicuous, it is necessary to process at a low speed.

  As a means for solving this neck-in and drawdown, the present inventors have added chain extension of PET resin, glycidyl (meth) acrylate, styrene-methyl (meth) acrylate-glycidyl methacrylate, epoxidized soybean oil, etc. A method for producing a PET resin laminated paper by adding an agent and extruding it onto a paper layer was developed (Patent Document 1).

  Similarly to PET resin, polybutylene terephthalate (hereinafter referred to as PBT) resin, which has neck-in and draw-down problems, is also one molecule such as epoxidized soybean oil or ethylene- (meth) acrylate glycidyl copolymer. A method has also been developed in which an organic compound having two or more epoxy groups is blended therein and extruded onto a paper substrate to produce a PBT resin laminated paper (Patent Document 2).

Japanese Patent No. 5180272 JP2013-193210A

  In the method of Patent Document 1, the PET resin of the laminate has a crystallinity of less than 15% and can be heat-sealed between the PET resin layers. However, the chain extender is generally in the form of liquid or powder, and when a masterbatch is prepared using PET resin in order to increase its uniform dispersibility, the chain extender is very reactive with the PET resin. In the meantime, since the reaction proceeds, there is a problem that the amount used is increased, which is not preferable economically. In addition, when the laminates are stacked and left for a long time, there is a problem in that they are difficult to separate individually due to blocking even when they are in a raw fabric state or formed in a container.

  In the method of Patent Document 2, since the PBT resin originally has no heat sealability, the laminated paper cannot be used for applications requiring sealing.

  The object of the present invention is to solve the neck-in and drawdown when laminating the PET resin, heat seal between the resin layers, and to make a paper container excellent in aroma retaining property, heat resistance, oil resistance and free from blocking problems. Another object of the present invention is to provide a method capable of producing a PET resin laminated paper that can be produced at low cost.

  As a result of intensive studies to solve these problems, the present inventors have reacted when PBT is used as a resin for making a master batch of an organic compound having at least two epoxy groups in one molecule that functions as a chain extender. It was found that the amount of the organic compound consumed can be reduced by suppressing the consumption of the organic compound because the property is not as high as that of PET. And when PBT was used for resin for master batches, it discovered that the problem of blocking could also be eliminated. This is presumably because the crystallization temperature of the PBT resin is higher than that of the PET resin, and thus the crystallization of the PBT resin starts first in the cooling after the lamination.

  The present invention has been made on the basis of these findings. A master batch was prepared by melt-kneading an organic compound having at least two epoxy groups in one molecule in a polybutylene terephthalate resin. The present invention provides a method for producing a polyethylene terephthalate resin laminated paper, which is melt-kneaded in addition to a resin and extruded and laminated on a paper substrate.

  In the present invention, by using PBT as a resin for producing a masterbatch, the reaction of an organic compound having at least two epoxy groups in one molecule during the production of the masterbatch is suppressed, thereby reducing the amount used. Furthermore, the blocking problem of the PET resin layer laminated using this master batch could be solved.

It is a figure which shows an example of the paper container formed using the PET resin laminated paper of invention.

  The basic structure of the PET resin laminated paper produced by the present invention is such that a PET resin layer is melt laminated on a paper substrate.

The paper used for the substrate can be selected arbitrarily depending on the type of paper container, etc., but is typically kraft paper, bleached kraft paper, etc., with a basis weight of 20 to 400 g / m ² . Used.

  A resin composition layer mainly composed of polyethylene terephthalate (PET) resin is provided on at least one surface of the paper substrate. The polyethylene terephthalate resin is obtained by condensation reaction of terephthalic acid and ethylene glycol, but may be a copolymer containing a third component as long as the function of the present invention is not impaired. This third component includes dicarboxylic acids such as adipic acid and isophthalic acid, and diol compounds such as neopentyl glycol. A PET resin having an intrinsic viscosity of 0.55 to 0.90 dl / g, preferably 0.65 to 0.88 dl / g is used.

  This intrinsic viscosity is measured according to JIS K7367-5 using a mixed solvent of phenol: tetrachloroethane in a volume ratio of 1: 1. When the intrinsic viscosity of the PET resin is less than 0.55 dl / g, the film spreading called drawdown or neck-in becomes insufficient during melt lamination on the base material, while when the viscosity exceeds 0.90 dl / g. In addition, the viscosity of the PBT resin is remarkably increased and the laminated thickness becomes unnecessarily thick, and the flexibility and flexibility are poor.

The PET resin layer contains 0.1 to 1.0 part by weight, particularly 0.4 to 0.7 part by weight of an organic compound having two or more epoxy groups in one molecule with respect to 100 parts by weight of the PET resin. It is preferable. By blending this compound, the melt viscosity and melt tension of the PET resin are properly maintained, and there is an effect of suppressing drawdown and neck-in during lamination. If the amount is less than 0.1 parts by weight, this effect cannot be expected, which is not preferable. On the other hand, if it exceeds 1.0 part by weight, it can not be melt viscosity of P E T resin is thin excessively increased by laminating thickness, since the flexibility and bending property becomes poor undesirably.

  Examples of organic compounds having two or more epoxy groups (hereinafter referred to as epoxy group-containing organic compounds) include glycidyl (meth) acrylate, styrene-methyl (meth) acrylate-glycidyl methacrylate, and large epoxidation. Examples include bean oil, epoxidized linseed oil, ethylene- (meth) acrylate glycidyl copolymer, epoxidized polybutadiene, and the like, but are not particularly limited as long as they are organic compounds having a polyfunctional epoxy group.

  The resin composition forming the PET resin layer can contain a third component as long as the properties are not impaired. Examples include resin components such as polyethylene naphthalate (PEN) and polytrimethylene terephthalate (PTT), polyolefins, lubricants such as calcium stearate and oleic amide, and fillers such as calcium carbonate and talc. Can be mentioned.

  The thickness of the PET resin layer is preferably 5 μm or more and less than 40 μm, more preferably 12 to 20 μm. If the thickness is less than 5 μm, the film tends to be defective. On the other hand, if the thickness is 40 μm or more, the flexibility and the flexibility are deteriorated, the handling of the subsequent process is hindered, and a defective product is likely to be generated. This is not preferable because it causes a rise in

  In the present invention, when a PET resin layer is melt-laminated, a master batch of an epoxy group-containing organic compound is first prepared. In that case, PBT is used as a resin for the master batch.

  The masterbatch can be considered to knead an epoxy group-containing organic compound with the PET resin, which is the main component of the PET resin layer, but the compound is rich in reactivity with the PET resin and will be described later in the masterbatch production process by high-temperature melting. The amount of consumption other than the reaction expected in the laminating process is large, which is economically undesirable.

  On the other hand, the PBT resin has a lower melting point than PET and is slow in reactivity with the epoxy compound, so that an effective amount to be blended into the master batch is small and economically preferable.

P B T resin, and terephthalic acid, 4-but-butanediol is obtained by condensation reaction are the same as the PET resin functions to the extent that does not impair that may include a third component of the present invention . The intrinsic viscosity is 0.55 to 0.90 dl / g, preferably 0.65 to 0.88 dl / g. The concentration of the epoxy group-containing organic compound in the master batch is 2 to 35% by weight, preferably 10 to 30% by weight, more preferably 15 to 25% by weight, and the PBT resin concentration is 65 to 98% by weight, preferably 70 to 90% by weight. %, More preferably about 75 to 85% by weight.

  If the concentration of the epoxy group-containing organic compound is less than 2% by weight, the ratio of the master batch at the time of melt-extrusion is increased, and the cost for producing the master is excessively increased. On the other hand, if the concentration of the organic compound exceeds 35% by weight, the ratio of the master batch at the time of melt extrusion decreases, and the uniformity of the resin composition layer decreases, which is not preferable.

The master batch ratio is preferably determined in consideration of the ratio of the PET resin and the PBT resin in the formed PET resin layer. When the PET / PBT ratio is 90/10 or less by weight , the heat sealability is insufficient, which is not preferable. Since it will react excessively when it becomes 99.9 / 0.1 or more, it is not preferable. A preferred ratio is about 90/10 to 99.9 / 0.1, particularly about 95/5 to 95.5 / 4.5.

In producing the master batch, it is preferable to melt and knead the PBT resin and the epoxy group-containing organic compound uniformly at a temperature of less than 10 ° C. at a PBT melting point (around 228 ° C.) under a high shear rate of 10 to 100 sec- ¹ .

  If the kneading temperature at the time of masterbatch production exceeds 10 ° C from the melting point of the PBT resin, the reactivity between the two (PBT and organic compound) is significantly increased, and the thickening required during melt extrusion is deactivated, and the desired effect can be obtained. This is not preferable. On the other hand, melt kneading is not possible if the melting point is lower than the PBT melting point.

  Other conditions for producing the master batch may be in accordance with known methods.

  A laminate anchor agent is preferably applied in advance to the surface or printed surface of the paper substrate on which the resin composition is melt-laminated. The laminate anchor agent used is preferably a polyimine-based agent. Since the secondary amine present at the molecular chain end of the polyimine is covalently bonded to the hydroxyl group or carboxyl group present at the molecular chain end of the molten PET resin, the lamination adhesive strength with the paper substrate is enhanced. When an epoxy group-containing organic compound is blended in the resin composition and the epoxy group is left unreacted, the laminate adhesive strength is further strengthened by the covalent bond between the secondary amine and the epoxy group. . The most preferred polyimine is polyethyleneimine. Laminate anchor agents containing this as a main component are commercially available.

  The PET resin is pre-dried when the resin composition is melt-laminated, and then mixed with other components, and the dried PET resin and PBT master batch are mixed with a blender, and the resulting mixture is fed into an extruder for extrusion laminating. Add and melt extrude. The preliminary drying is preferably performed so that the water content is about 50 ppm or less. The melt extrusion temperature is a wide range, usually about 230 to 340 ° C, and preferably about 270 to 300 ° C. If it is less than 230 ° C., it becomes less than the melting point of the PET resin and cannot be melt-extruded. On the other hand, if it exceeds 340 ° C., it is not preferable because thermal degradation or significant decrease in melt viscosity occurs.

  The resin composition melt extruded from the T die of the extruder is laminated on the paper substrate. In this step, it is preferable that the air gap from the T die to the substrate surface is as short as possible, and the nip roll after lamination is a cooling roll. Since the crystallization speed of the PET resin is fast, it is preferable to cool it as quickly as possible. Thereby, the crystallinity degree of PET resin can be made small and a softness | flexibility and a flexibility can be kept favorable. The crystallinity of the PET layer can be less than 15%, preferably less than 10%, more preferably less than 8%. The minimum is not particularly limited, and may be 0%.

The crystallinity in this specification is a value obtained as χ _{C in the} equation (a) from the melting enthalpy ΔH _m and the crystallization enthalpy ΔH _CL detected in the differential scanning calorimeter (DSC) analysis.

χ _C = 100 × (ΔH _m −ΔH _CL ) /140.0 (a)
Although the use of the paper container using this PET resin laminated paper is not particularly limited, it can be preferably used as a food container. An example of a box-shaped container is shown in FIG. In the figure, the right side surface is glued to the flag portion.

  In that case, the surface having the resin composition layer containing PET as a main component is used as the inner surface, punched out into a blank of a desired paper container, and boxed with a dedicated boxing machine such as a carton or cup.

  If the paper container is an application that does not require heat resistance, the boxed paper container can be used as it is. Since the inner surface of the container is made of PET resin having excellent fragrance retention properties, a wide variety of foods can be accommodated.

In applications that require heat resistance, the degree of crystallization may be increased by heating in advance, or it may be utilized that crystallization is promoted by heat during cooking to increase heat resistance. For example, when a container containing food is heated at 130 to 200 ° C. for 30 minutes or longer during cooking in the oven, the crystallinity of the PET resin increases and heat resistance of 200 ° C. or higher is developed. The crystallinity (χ _C ) can be 15% or more. Although the upper limit is not particularly limited, it is practically up to about 70%.

  Sealing (heat-sealing) a paper container with an opening on the top surface is an aluminum foil laminate film or the like with a heat-sealable PET layer on the inner surface. Hold with a heat seal plate and heat seal at about 230-240 ° C. Materials that can be heat sealed with PET and can withstand oven heating include PET and PET copolymers.

In the laminating process by melt extrusion, the resin composition is allowed to flow from the T die in order to adjust the extruding conditions before the laminating, resulting in a lump process loss. In the present invention, the massive loss material is recovered and pulverized, and the organic compound having 20 to 35 % by weight of at least two epoxy groups in one molecule is contained with respect to 65 to 80% by weight of the resin composition. It can be reused as a master batch that is re-blended and uniformly melt-kneaded at a temperature below PET melting point (around 260 ° C.) + 10 ° C. under high shear.

  Similarly, a loss of the resin composition occurs when removing both ends by slitting in order to collect a regular product from the PET resin laminated paper. The organic compound having at least two epoxy groups in one molecule with respect to 100 parts by weight of the loss excluded from the end of the laminated paper and 100 parts by weight of the resin composition which is the lump loss collected and pulverized ~ 0.7 part by weight, and using a multilayer melt extruder, the recycled resin composition is laminated on the paper substrate lamination surface, and the resin composition comprising the virgin raw material described in the present invention is laminated on the other surface. May be.

  Although the resin composition of the present invention is excellent in neck-in inhibiting property in the melt extrusion process, the neck-in rate is not zero. In order to minimize the loss at both ends at the time of manufacture, a deck is provided inside the T die (inner deck), and the discharge corresponding to the neck-in width is limited, and the end loss of the molten resin component is minimized. It is also useful to do.

  In the laminate using the resin composition of the present invention, the neck-in at the time of melt extrusion is remarkably eliminated, so that the lamination process speed can be increased up to 200 m / min.

  The laminated paper obtained in the present invention is not heat-sealable and is blended with a PBT resin having a higher crystallization temperature than PET resin. Crystallization occurs, followed by crystallization of PET (main material) having a low crystallization temperature. For this reason, the heat sealability is maintained, but a laminated body that is difficult to block is obtained.

The present invention will be described more specifically with reference to examples.
<Preparation of specimen>

70% by weight of PBT resin “500FP” (manufactured by Polyplastics Co., Ltd., intrinsic viscosity = 0.875 dl / g) and 30% by weight of epoxidized soybean oil “O-130P” (manufactured by Asahi Denka Co., Ltd.) The obtained resin composition was melt-kneaded under the conditions of an extrusion temperature of 235 ° C. and a shear rate of 21 sec ⁻¹ using a co-rotating twin screw extruder equipped with a screw having a diameter = 40 mm and L / D = 32. A master batch V "was prepared by granulation.

PET resin "CR8816" (the China Resources Ltd., intrinsic viscosity = 0.810dl / g) 100 by weight parts as the "masterbatch V" 1.7 parts by weight of the resin composition was mixed with stirring, Hitachi Zosen Co., Ltd. A polyethyleneimine anchor coating agent (manufactured by Nippon Shokubai Co., Ltd.) was introduced into a twin screw extruder “HMT100” (L / D = 38, T die width = 1600 mm) rotated in the same direction and melt kneaded at an extrusion temperature = 280 ° C. Epomin ") was previously applied on a paper substrate at 0.1 g / m ² (in terms of solid content after drying). After melt lamination so that the thickness of the PET resin layer was 20 μm on 70 g / m ² bleached kraft paper, it was rapidly cooled while being sandwiched by a cooling roll adjusted to 25 ° C. to obtain a laminated paper. The crystallinity of the resin composition layer of this laminated paper was 10.8%.

Example 1 A resin composition obtained by stirring and mixing 70% by weight of a lump loss lump spilled to prepare conditions for preparing a specimen and 30% by weight of epoxidized soybean oil “O-130P” (Asahi Denka Co., Ltd.) "Masterbatch R" is granulated by melt-kneading under the conditions of extrusion temperature of 235 ° C and shear rate of 21 sec ^-1 using a co-rotating twin screw extruder equipped with a screw of = 40 mm and L / D = 32 Produced.

A resin composition obtained by stirring and mixing 100 parts by weight of PET resin “CR8816” (manufactured by Huajun, intrinsic viscosity = 0.810 dl / g) and 1.7 parts by weight of “Masterbatch R” was added to a polyethyleneimine anchor coating agent (Japan) A laminated paper was obtained through the same operation as in Example 1 except that “Epomin” (catalyst) was previously applied on a paper substrate at 0.1 g / m ² (in terms of solid content after drying). The crystallinity of the resin composition layer of this laminated paper was 9.3%.

Comparative Example 1

Resin composition obtained by stirring and mixing 100 parts by weight of PET resin “CR8816” (manufactured by Huajun, intrinsic viscosity = 0.810 dl / g) and 0.5 parts by weight of epoxidized soybean oil “O-130P” (manufactured by Asahi Denka Co., Ltd.) The product is put into a twin screw extruder “HMT100” (L / D = 38, T die width = 1600 mm) manufactured by Hitachi Zosen Co., Ltd. and melt-kneaded at an extrusion temperature of 280 ° C. After being melt-laminated so that the thickness of the resin composition layer becomes 20 μm on / m ² bleached kraft paper, it was rapidly cooled while being sandwiched by a cooling roll adjusted to 25 ° C. to obtain a laminated paper. The crystallinity of the resin composition layer of this laminated paper was 8.4%.

Comparative Example 2

PET resin “CR8816” (manufactured by Huajun, intrinsic viscosity = 0.810 dl / g), a twin-screw extruder “HMT100” (L / D = 38, T die width = 1600 mm) manufactured by Hitachi Zosen Corporation ), Melt-kneaded on a 70 g / m ² bleached kraft paper so that the thickness of the resin composition layer is 20 μm while melt-kneading at an extrusion temperature of 280 ° C., and then quickly adjusting to 20 ° C. Laminated paper was obtained by quenching while being sandwiched by a heated cooling roll. The crystallinity of the resin composition layer of this laminated paper was 8.2%.

Comparative Example 3

Resin composition obtained by stirring and mixing 100 parts by weight of PET resin “CR8816” (manufactured by Huajun, intrinsic viscosity = 0.810 dl / g) and 1.0 part by weight of epoxidized soybean oil “O-130P” (manufactured by Asahi Denka Co., Ltd.) The product is put into a twin screw extruder “HMT100” (L / D = 38, T die width = 1600 mm) manufactured by Hitachi Zosen Co., Ltd. and melt-kneaded at an extrusion temperature of 280 ° C. After being melt-laminated so that the thickness of the resin composition layer becomes 20 μm on / m ² bleached kraft paper, it was rapidly cooled while being sandwiched by a cooling roll adjusted to 20 ° C. to obtain a laminated paper. The crystallinity of the resin composition layer of this laminated paper was 8.4%.

Comparative Example 4

A laminated paper having a thickness of 20 μm is obtained through the same operation as in Example 1 except that low-density polyethylene (“NOVATEC LC604” manufactured by Nippon Polyethylene is set at an extrusion temperature = 330 ° C.) on a bleached kraft paper of 70 g / m ^2. It was.

<Evaluation of trimming loss as a neck-in index>
An inner deckle is used to limit the T dice discharge width to X ₀ (m) so that laminated paper having a laminated thickness of 20 ± 4 (μm) can be collected at a product width of 1000 mm. At this time, the discharge resin amount W ₀ (g) corresponding to 1 m melt-laminated on the paper base material is
Approximate to W ₀ = 20 × X ₀ × 1 × 1.4 (PET density).
The amount of laminated resin W ₁ (g) with a product width of 1 x 1 (m) is
W ₁ = 20 × 1 × 1 × 1.4 = 28.0 (g).
Therefore, the trimming loss amount is expressed by W ₀ −W ₁ (g / m ² ).
However, the above Comparative Example 4 is
Approximate with W ₀ = 20 × X ₀ × 1 × 0.92 (LDPE density)
The trimming loss amount was calculated as W ₁ = 20 × 1 × 1 × 0.92 = 18.4 (g).

<Adsorption resistance evaluation of aromatic components>
20 g of commercially available instant coffee is sprayed on the laminated surface of the test pieces obtained by cutting the specimens obtained in Examples and Comparative Examples to 100 × 100 mm, and left in an oven adjusted to 60 ° C. for 24 hours. This was taken out, the coffee powder was removed, and after cooling to room temperature, the odor remaining on the test piece was subjected to sensory evaluation.
The judgment criteria were the following three stages.
S ... No smell A ... Small smell B ... Smell very strong

<Evaluation of heat resistance>
Hot plate for home appliances in which the specimens obtained in Examples 1 and 2 and Comparative Examples 2 and 3 were cut to 100 × 100 mm and coated with flour dissolved in water in the form of paste with water and adjusted to 200 ° C. Heated for 5 minutes above. After heating, the presence or absence of burns on the flour paste was confirmed, the laminated resin of the test piece was peeled and washed, and the crystallinity was measured by DSC.
The result list is shown in Table 1.

<Blocking evaluation>
After stacking two laminates (cut to 10 x 10 cm) and placing a 10 x 10 cm x 1 kg load at 23 ° C x 50% RH x 24 hr, use the resistance to peel off the two piles as an index.
◯: Peels without resistance Δ: Slight resistance ×: Does not peel easily

実施例では予めＰＢＴマスターバッチを作製して、それを成膜原料として投入している。一方、比較例は全ての製膜原料を同時投入し且つ本発明に有効なＰＢＴ成分も入っていない。したがって、後者はエポキシの反応が過剰となり結晶化度が低下し、ブロッキングが生じやすくなっている。

In the embodiment, a PBT master batch is prepared in advance and is used as a film forming raw material. On the other hand, in the comparative example, all the film forming raw materials are simultaneously added, and no PBT component effective for the present invention is contained. Therefore, in the latter, the epoxy reaction becomes excessive, the crystallinity is lowered, and blocking is likely to occur.

  The present invention can efficiently laminate a resin composition containing polyethylene terephthalate as a main component on a paper substrate, and since this laminate is excellent in aroma retention, heat resistance, oil resistance, etc., various containers In particular, it can be widely used in food containers that can be cooked as they are.

Claims (9)

An organic compound having at least two epoxy groups in one molecule is melt-kneaded with polybutylene terephthalate resin to prepare a masterbatch, which is added to the polyethylene terephthalate resin and the ratio of polyethylene terephthalate resin / polybutylene terephthalate resin is weighted. A method for producing a polyethylene terephthalate resin laminated paper, characterized by melt kneading as a ratio of 90/10 to 99.9 / 0.1 and extrusion laminating on a paper substrate . Master batch is 65-80 wt% polybutylene terephthalate resin and 20-35 wt% organic compound having at least two epoxy groups in one molecule under high shear, melting point of polybutylene terephthalate (around 228 ° C.) + 10 ° C. The production method according to claim 1, wherein the mixture is uniformly melt-kneaded at a temperature below . The production method according to claim 1 or 2, wherein the intrinsic viscosity of the polyethylene terephthalate resin in a mixed solvent of phenol: tetrachloroethane = 1: 1 is 0.55 to 0.90 dl / g . The degree of crystallinity of the melt-laminated polyethylene terephthalate resin layer is obtained by the following formula (a) from the melting enthalpy ΔH _m and the crystallization enthalpy ΔH _CL detected in the differential scanning calorimeter (DSC) analysis. 4. The production method according to claim 1, wherein _C is less than 15% .
χ _C = 100 × (ΔH _m −ΔH _CL ) /140.0 (a)
Ii) Equilibrium heat of fusion of polyethylene terephthalate crystals (Δ _HM = 140.0 J / g) To produce a product layer sheet in any of the manufacturing method of claims 1 to 4, differential scanning calorimetry of a polyethylene terephthalate resin layer heated treating the laminated paper at 130 to 200 ° C. (DSC) analysis and Equation (a) A method for producing a laminated paper , wherein the crystallinity χ _C obtained in step 1 is 15% or more . A laminated paper is produced by the production method according to any one of claims 1 to 4, and the resin composition is an end loss that has been slit-excluded at that time , and a block loss that is discharged for condition determination during the melt lamination step. Collect and re-blend 0.1 to 0.7 parts by weight of the organic compound having at least two epoxy groups in one molecule with respect to 100 parts by weight of the resin composition, and melt in a multilayer manner Using an extruder, a masterbatch is prepared by melting and kneading the recycled resin composition on the paper base material lamination surface, polybutylene terephthalate resin on the other surface and an organic compound having at least two epoxy groups in one molecule. , in addition to a polyethylene terephthalate resin polyethylene terephthalate resin / polybutylene terephthalate ratio of the resin in a weight ratio of the resin composition was melt-kneaded as 90/10 to 99.9 / 0.1 to this, Method for producing a laminated sheet, wherein the product layer to Rukoto began to. In the manufacturing method in any one of Claims 1-4, with respect to 65 to 80 weight% of the resin composition which collect | recovered and grind | pulverized the block loss discharged for the conditions determination at the time of the process of extrusion laminating on a paper base material Uniform at a temperature below polyethylene terephthalate melting point (approx. 260 ° C.) + 10 ° C. under high shear by re-blending 20 to 35% by weight of the organic compound having at least two epoxy groups in one molecule. melt kneading, the manufacturing method of laminated paper, wherein the second to Rukoto used as a masterbatch to add this to the polyethylene terephthalate resin. 2. A polyimine-based laminate anchor agent is preliminarily applied to the surface of a paper base material in the step of melt-kneading the master batch with polyethylene terephthalate resin and extrusion laminating on the paper base material. The manufacturing method in any one of -4 . Add a masterbatch to polyethylene terephthalate resin, melt knead, and provide a deckle inside the die (inner deckle) in the process of extruding and laminating onto a paper substrate , limiting the discharge corresponding to the neck-in width, and the molten resin component The manufacturing method according to any one of claims 1 to 4, wherein the stacking is performed with a minimum end loss .

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