JP2721945B2 - laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive sheet, an adhesive sheet, a synthetic resin film, a paper or cloth release substrate used as a base material for release paper and adhesive tape used for casting film formation, or coffee soup / miso soup.・ Laminates such as base materials used for cups used for foods and drinks such as instant noodles, and base materials used for paper containers used as trays used for trays used for foods such as pizza, prepared foods and microwave oven foods. is there.

[0002]

2. Description of the Related Art Laminates obtained by laminating a synthetic resin of a base material such as paper or cloth are used for various purposes. For example, as a release base material, a low-density polyethylene having a long-chain branch or a low-density polyethylene and a high-density polyethylene which are usually obtained by a high-pressure method at 315 to 345 ° C. as a filler layer on one or both sides of conventional paper or cloth are blended. It is well known that a composition obtained by blending a medium-density polyethylene or a low-density polyethylene with polypropylene is used, and a release layer is provided on the filling layer.

In the current method for producing a release substrate, it is necessary to melt-coat the above-mentioned polyolefin used as a sealing layer at a high temperature of 315 ° C. or higher in order to strengthen the adhesion and adhesion to the substrate. For this reason, it is inevitable that a large amount of smoke is generated due to oxidative deterioration of the polyolefin itself, the working environment is deteriorated, and environmental pollution in the vicinity due to smoke emission outside the factory is also a major problem, and improvement is strongly demanded. I have. In addition, since the used release paper has a non-biodegradable polyolefin laminated on the substrate, it is not treated simply by burying it in the soil, and when the paper is to be recovered, the used release paper is used. Since the substrate is immersed in an aqueous alkali solution and the polyolefin is peeled off, it is a very laborious and labor-intensive process.Therefore, a release substrate that is biodegradable together with a biodegradable substrate such as paper or cloth Development is strongly required.

On the other hand, paper cups used for hot food and drink,
A paper container such as a paper tray is a low-density polyethylene having a long-chain branch usually obtained by a high-pressure method as a water-repellent layer on at least one side in contact with the contents such as liquid, or a blend of low-density polyethylene and high-density polyethylene A medium-density polyethylene or a laminate of a composition comprising low-density polyethylene and polypropylene has been used.

A method for producing a base material for a paper container such as a paper cup or a paper tray currently used for warm foods and drinks is to use the above-mentioned polyolefin composition used as a water-repellent layer in order to strengthen adhesion and adhesion to paper. It is necessary to laminate at a high temperature of ℃ or more. For this reason, the polyolefin itself is inevitably oxidatively degraded, and the odor of oxidatively degraded resin composition remains in the paper laminate, and a large amount of smoke is generated in the laminating process, which deteriorates the molding work environment. There are problems such as pollution of the surrounding area due to smoke emission, and measures to reduce these odors and smoke are strongly demanded.

Further, used paper cups, paper trays, etc.
Since the paper is laminated with a non-microbial degradable polyolefin composition, it does not decompose even when buried in the soil, and when trying to recover the paper, soak the used paper cup and paper tray in an aqueous alkaline solution. Since the separation of the polyolefin composition is very troublesome and requires labor and cost, a composition for a water-repellent layer that biodegrades together with paper is strongly demanded.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a sealing layer for a release substrate, which can be formed at a low temperature in order to reduce fumes during melt coating, and can be adhered to a substrate such as paper or cloth. The development of a release base material which is a polymer with good adhesiveness and is stopped by a polymer which can be easily decomposed by microorganisms in the soil which is very common in nature,
In addition, it solves the problem of the odor of polyolefin remaining on the product base due to high-temperature lamination and the generation of large amounts of smoke, and at the same time, imparts microbial degradability to paper containers, and the non-degradability associated with disposal of used containers The purpose is to develop a base material for paper containers that is advantageous for preserving the natural environment in which substances accumulate.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a method for measuring a temperature of 190.
An aliphatic polyester resin having a melt viscosity of 1.0 × 10 ^{3 to} 1.0 × 10 ⁵ poise at a shear rate of 100 (sec ⁻¹ ) and a melting point of 70 to 200 ° C. is melt-extruded onto a substrate. By developing a release substrate characterized by being coated, the melt viscosity at a temperature of 190 ° C. and a shear rate of 100 (sec ⁻¹ ) is further increased to 1.0 × 10 ^3.
~ 1.0 × 10 ⁵ poise, melting point 85-200 ° C.
Each of the above objects has been achieved by developing a paper container base material characterized by laminating the aliphatic polyester resin described above on base paper.

The aliphatic polyester referred to in the present invention is mainly composed of a polyester synthesized from a glycol and an aliphatic polybasic acid or an acid anhydride thereof. Is obtained by synthesizing a relatively high-molecular-weight polyester prepolymer having a hydroxyl group, and then coupling these prepolymers with a coupling agent.

Conventionally, a low molecular weight polyester prepolymer having a hydroxyl group at the terminal group and having a number average molecular weight of 2,000 to 2,500 is reacted with diisocyanate to form a polyurethane, rubber, foam, paint, adhesive It is widely used as an agent.

However, the polyester prepolymer used for these polyurethane foams, paints and adhesives is a low molecular weight prepolymer having a number average molecular weight of 2,000 to 2,500.
In order to obtain practical physical properties as a polyurethane with respect to 00 parts by weight, the amount of diisocyanate used should be 10 to
It must be 20 parts by weight. When such a large amount of diisocyanate is added to a low-molecular-weight polyester melted at 150 ° C. or higher, gelation occurs and a melt-moldable resin cannot be obtained.

Also, as in the case of polyurethane rubber,
A method of converting a hydroxyl group into an isocyanate group by adding a diisocyanate and further increasing the number average molecular weight with a glycol may be considered, but the amount of the diisocyanate used may be reduced as described above. 10 parts by weight or more is required per part by weight. At this time, if a heavy metal-based catalyst is used for the synthesis of the polyester, the reactivity of the isocyanate group is remarkably promoted, resulting in poor storage stability, crosslinking reaction, and branch formation, so that the polyester prepolymer is synthesized without a catalyst. As a result, the number average molecular weight is limited to about 2,500 at the highest.

The polyester prepolymer for obtaining the aliphatic polyester used in the present invention is a polyester prepolymer obtained by reacting a glycol with an aliphatic polybasic acid or an anhydride thereof, wherein the terminal group substantially has a hydroxyl group. A saturated aliphatic polyester having a relatively high molecular weight of 5,000 or more, preferably 10,000 or more, and a melting point of 60 ° C. or more.

When the number average molecular weight is less than 5,000,
Even with a small amount of the coupling agent of 0.1 to 5 parts by weight, a polyester having good physical properties cannot be obtained. Polyester prepolymers having a number average molecular weight of 5,000 or more have a hydroxyl value of 30 or less, and use of a small amount of a coupling agent does not cause gelation during the reaction even under severe conditions such as a molten state. Polyester can be synthesized.

The glycols used include, for example, ethylene glycol, 1,4-butanediol, 1,6
-Hexanediol, decamethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol and the like. Ethylene oxide can also be used. These glycols may be used in combination.

The aliphatic polybasic acids or derivatives thereof which form aliphatic polyesters by reacting with glycols include succinic acid, adipic acid, suberic acid, sebacic acid,
There are lower alcohol diesters such as dodecanoic acid, succinic anhydride, adipic anhydride and dimethyl ester thereof, and these are commercially available and can be used in the present invention. An aliphatic polybasic acid or a derivative thereof may be used in combination.

These glycols and polybasic acids are mainly composed of aliphatic compounds, but may be used in combination with small amounts of other components, for example, trifunctional or tetrafunctional polyhydric alcohols, oxycarboxylic acids or polycarboxylic acids. preferable.

The trifunctional polyhydric alcohol component is typically trimethylolpropane, glycerin or its anhydride, and the tetrafunctional polyhydric alcohol component is pentaerythritol.

As the trifunctional oxycarboxylic acid, malic acid is practically advantageous, and citric acid is practical because a commercially available tetrafunctional oxycarboxylic acid component can be easily obtained at low cost.

As the trifunctional polycarboxylic acid (or acid anhydride) component, for example, trimesic acid, propanetricarboxylic acid and the like can be used, but trimellitic anhydride is advantageous in practical use.

Examples of the tetrafunctional polycarboxylic acid (or an acid anhydride thereof) include pyromellitic anhydride, benzophenonetetracarboxylic anhydride, cyclopentanetetracarboxylic anhydride and the like.

The proportion of the polyfunctional component used is such that the number of moles of either the glycol component or the aliphatic (including cycloaliphatic) dicarboxylic acid (or acid anhydride) component is 100 mol% and the trifunctional component is used. In the case of a component, it is 5 mol% or less, preferably 0.5 mol% or more and 3 mol% or less, and in the case of a 4-functional component, it is 3 mol% or less, preferably 0.2 mol% or more and 2 mol% or less.

If the proportion of the trifunctional component is more than 5 mol%, or if the proportion of the tetrafunctional component is more than 3 mol%, the risk of gelling during the esterification reaction is significantly increased.

The polyester prepolymer for aliphatic polyester used in the present invention has a terminal group substantially having a hydroxyl group. For this purpose, glycols and polybasic acids (or acid anhydrides thereof) used in the synthesis reaction are used. The proportion used requires the use of some excess of glycols.

In order to synthesize a polyester prepolymer having a relatively high molecular weight, it is preferable to use a deglycol-reaction catalyst at the time of the deglycolization reaction following the esterification in order to ensure the high molecular weight.

Examples of the deglycol-reaction catalyst include titanium compounds such as acetoacetoyl-type titanium chelate compounds and organic alkoxytitanium compounds.
These titanium compounds can be used in combination. Examples of these include diacetacetoxyoxytitanium (“Nasem Titanium” manufactured by Nippon Chemical Industry Co., Ltd.), tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium and the like. The use ratio of the titanium compound is 0.001 to 100 parts by weight of the polyester prepolymer.
To 1 part by weight, preferably 0.01 to 0.1 part by weight. The titanium compound may be added from the beginning of the esterification, or may be added immediately before the deglycolization reaction.

As a result, the polyester prepolymer usually has a number average molecular weight of 5,000 or more, preferably 10,000.
A material having a melting point of 0 or more and a melting point of 60 ° C. or more can be easily obtained, and it is more preferable that the material has crystallinity.

In order to obtain the aliphatic polyester of the present invention, the number average molecular weight is more than 5,000, preferably 1
Coupling agents are used to increase the number average molecular weight of polyester prepolymers having at least 000 terminal hydroxyl groups.

Examples of the coupling agent include diisocyanate, oxazoline, diepoxy compound, acid anhydride and the like, and diisocyanate is particularly preferable.

In the case of an oxazoline or diepoxy compound, it is necessary to react a hydroxyl group with an acid anhydride or the like and convert the terminal to a carboxyl group before using a coupling agent.

The diisocyanate is not particularly limited,
For example, 2,4-tolylene diisocyanate, 2,4-
A mixture of tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, Isophorone diisocyanate is preferred, and hexamethylene diisocyanate is particularly preferred from the viewpoints of the hue of the formed resin, reactivity when adding polyester, and the like.

The addition amount of these coupling agents is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight based on 100 parts by weight of the polyester prepolymer.

If the amount is less than 0.1 part by weight, the coupling reaction is insufficient, and if it exceeds 5 parts by weight, gelation occurs.

The addition is desirably carried out under conditions in which the polyester prepolymer is in a homogeneous molten state and can be easily stirred. It can be added to a solid polyester prepolymer and melted and mixed through an extruder, but it is added to an aliphatic polyester production apparatus or to a molten polyester prepolymer (for example, in a kneader). It is practical.

The aliphatic polyester resin has a temperature of 190.
It is preferable that the melt viscosity at 100 ° C. and a shear rate of 100 (sec ⁻¹ ) is 1.0 × 10 ^{3 to} 1.0 × 10 ⁵ poise. If the melt shear viscosity is less than 1.0 × 10 ³ poise, the melt viscosity is too small, so that surging during extrusion molding and non-uniform resin temperature are apt to occur and lack in extrusion stability,
During lamination molding, there is a drawback that the neck-in of the molten film becomes large, so that lamination molding becomes difficult, and the thickness of the resulting laminated film becomes large. Further, if the melt shear viscosity exceeds 1.0 × 10 ⁵ poise, the melt viscosity is too high, so that the motor load during extrusion molding increases and productivity decreases, and it is difficult to reduce the thickness of the molten film during lamination molding. There are drawbacks. Preferably, the melt shear viscosity is 2.0 × 10 ^{3 to} 2.0 × 10 ⁴ poise. More preferably, the melt shear viscosity is 2.5 × 10 ^{3 to} 1.2 ×
It is in the range of 10 ⁴ poise.

In the present invention, the melting point of the aliphatic polyester used for the release substrate is preferably from 70 ° C. to 200 ° C. If the temperature is lower than 70 ° C., the heat resistance in the silicone coating or pressure-sensitive adhesive coating process becomes insufficient, and a low-temperature treatment is required. On the other hand, if the temperature exceeds 200 ° C., the heat resistance is sufficient, but the biodegradation rate is undesirably slow. Preferably from 60 ° C to 150 ° C, more preferably from 80 ° C to 1
30 ° C.

The melting point of the aliphatic polyester when used for paper containers is preferably from 85 to 200 ° C. When the melting point is less than 85 ° C., the heat resistance when putting hot food or drink into the formed paper cup and paper tray is insufficient, and the laminated aliphatic polyester composition may peel, melt or peel off at the joint. Is not preferred. Melting point 2
When the temperature exceeds 00 ° C., when the formed paper cups and paper trays are decomposed by microorganisms in soil, the biodegradation rate is undesirably slow. Preferably the melting point is 90-150 ° C
The melting point is more preferably 100 to 140 ° C.

In the present invention, the aliphatic polyester resin has a number average molecular weight of 10,000 or more and a urethane bond of 0.03 to 3.0% by weight. Only when the number average molecular weight is 10,000 or more, a substrate having a strong polyester layer can be obtained, and it can be used for various applications. If it is less than 10,000, the heat resistance is lowered and the strength becomes brittle, and it is not suitable as a substrate having practical strength.

In the present invention, a laminated product can be produced by laminating the aliphatic polyester resin produced by the above method on a substrate by the T-die method. The resin temperature to be extruded at this time is 150 ° C. to 290
° C. If the resin temperature is lower than 150 ° C., the melt viscosity is too high, so that the motor load at the time of extrusion molding is increased and the productivity is reduced, and it is difficult to reduce the thickness of the molten film at the time of lamination molding. On the other hand, when the resin temperature exceeds 290 ° C., the resin composition is deteriorated, surging or the like occurs, and extrusion stability is lacking, or neck-in of the molten film at the time of laminating is performed. Refers to the phenomenon that the width becomes narrower in the space before contacting the substrate, and is indicated by the difference between the width of the molten film at the exit of the T-die and the width of the laminated film laminated on the substrate. There are drawbacks in that it is difficult to mold, and furthermore, there is a large amount of smoke generated during molding, which worsens the working environment and worsens the odor of the formed paper laminate. Preferably, the resin temperature is 160 to 270 ° C, more preferably, the resin temperature is 170 to 250 ° C.

In the present invention, in particular, a polyhydric alcohol having three or more alcoholic hydroxyl groups (—OH) in one molecule,
Or three or more carboxyl groups (—COO
The aliphatic polyester produced by using a small amount (0.2 to 5.0 mol%) of the polybasic acid monomer having H) has a wide molecular weight distribution and long chain branching. In the case where lamination is performed using a T-die, neck-in is small, phenomena such as surging are reduced, and film formability is significantly improved.

In the present invention, when the aliphatic polyester produced by the above method is laminated by the T-die method, it may be molded using only a linear polyester containing no long-chain branches. The polyester having the shape of the chain and the polyester having a long-chain branch may be mixed with an arbitrary composition, or may be molded only with the polyester having a long-chain branch.

When it is desired to reduce neck-in, it is preferable to use a mixture of an aliphatic polyester having a long chain branch and a linear polymer.

In using the polyester resin of the present invention, it is needless to say that a lubricant, a wax, a coloring agent, a filler, and the like can be used in combination, if necessary. Particularly, in addition to the conventional lubricant, a lubricant such as VITON was very effective in improving the surface smoothness. Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.

[0044]

【Example】

(Example 1) After replacing a 700 L reactor with nitrogen,
183 kg of 1,4-butanediol, 224 k of succinic acid
g. The temperature was raised in a nitrogen stream, and 195
~ 210 ° C for 3.0 hours, further stop nitrogen and 15 ~
The esterification reaction by dehydration condensation was performed under a reduced pressure of 5 mmHg for 3.5 hours. The collected sample had an acid value of 6.3 mg / g, a number average molecular weight (Mn) of 5,200,
The weight average molecular weight (Mw) was 10,100.
Subsequently, 3.4 g of tetraisopropoxytitanium as a catalyst was added under a nitrogen stream at normal pressure. The temperature was raised, and a deglycol-reaction was performed at a temperature of 215 to 220 ° C. under a reduced pressure of 5 to 0.2 mmHg for 7.5 hours. The collected sample had a number average molecular weight (Mn) of 18,600 and a weight average molecular weight (Mw) of 50,300. The yield of this polyester (A1) was 339 kg excluding condensed water.

To a reactor containing 339 kg of polyester (A1), 4070 g of hexamethylene diisocyanate was added, and a coupling reaction was carried out at 180 to 200 ° C. for 1 hour. The viscosity increased rapidly but no gelling occurred. Next, 1700 g of Irganox 1010 (manufactured by Ciba Geigy) as an antioxidant and 1700 g of calcium stearate as a lubricant were added, and stirring was continued for another 30 minutes. This reaction product was extruded into water with an extruder and cut into a pellet by a cutter. The yield of the polyester (B1) after vacuum drying at 90 ° C. for 6 hours was 270 kg.

The obtained polyester (B1) is a slightly ivory white wax-like crystal having a melting point of 110.
° C, the number average molecular weight (Mn) is 29,500, the weight average molecular weight (Mw) is 127,000, the MFR (190 ° C) is 9.2 g / 10 min, the viscosity of a 10% solution of orthochlorophenol is 170 poise, Temperature 190 ° C, shear rate 10
The melt viscosity at ⁰ sec ^-1 was 8.0 × 10 ³ poise. The average molecular weight is measured by Shodex GPC
System-11 (gel chromatography manufactured by Showa Denko KK), solvent: CF ₃ COONa 5 mmol solution of hexafluoroisopropyl alcohol, concentration 0.1% by weight, calibration curve: PMMA standard sample manufactured by Showa Denko KK
Performed on a Shodex Standard M-75.
Next, this polyester resin (B1)
0mmφ, L / D = 28 extruder with 320mm width T-
Using a die, extrude at a die lip gap of 0.8 mm, an air gap of 120 mm, and a resin temperature of 220 ° C. at a speed of 15
It was laminated with a thickness of 20 μm on high quality paper (70 g / m ² ) supplied at 0 m / min to produce a release substrate.
At the time of lamination molding, the molten film was stable and excellent in film formation stability, and there was little smoke and the working environment was good. The obtained release substrate had sufficient adhesion between the paper and the polyester film, and when subjected to a release test, interfacial peeling did not occur, and cohesive failure of the paper was observed. The evaluation of the obtained base material is shown in Table 1.

The release base material was cut into a rectangle of 10 cm × 20 cm, and this release paper was attached to a square box made of stainless steel with a polyethylene net. This was buried in soil having a depth of 10 cm, and the biodegradability was evaluated.
The place is the garden of Showa Denko KK Kawasaki Resin Laboratory (Kawasaki-ku, Kawasaki City). When dug out three months later, it was found that the polyester thin film was more decomposed than the paper fiber and had become ragged.

Example 2 In the same manner as in Example 1, the aliphatic polyester resin (B1) was extrusion-laminated on a base paper fed at a speed of 100 m / min at a resin temperature of 190 ° C. and an average thickness of 30 μm. Obtained. The adhesion between the paper and the polyester layer was sufficient, and the paper was cohesively broken when a peel test was performed. A heat resistance test was performed on the obtained laminate in a circulating air oven at 100 ° C. As a result, the number of pinholes was 2, and the change in surface gloss was small and sufficient. When the biodegradability was evaluated in the same manner as in Example 1, three months later, the film was perforated and ragged. The evaluation of the substrate is shown in Table 1.

[0049]

[0050]

Example 3 A 700 L reactor was purged with nitrogen, and 183 kg of 1,4-butanediol and 224 kg of succinic acid were charged. The temperature was raised in a nitrogen stream, and the esterification reaction by dehydration condensation was performed at 192 to 220 ° C. for 3.5 hours, and further with the nitrogen stopped for 3.5 hours under a reduced pressure of 20 to 2 mmHg. The collected sample had an acid value of 9.2 mg / g, a number average molecular weight (Mn) of 5,160, and a weight average molecular weight (Mw) of 10,67.
It was 0. Subsequently, 34 g of tetraisopropoxytitanium as a catalyst was added under a nitrogen stream at normal pressure. Raise the temperature to 15-0.2 mmHg at a temperature of 215-220 ° C.
The deglycol-reaction was performed under reduced pressure for 5.5 hours. The collected sample had a number average molecular weight (Mn) of 16,800,
The weight average molecular weight (Mw) was 43,600.
The yield of this polyester (A2) is 33 when condensed water is removed.
9 kg.

5320 g of hexamethylene diisocyanate was added to a reactor containing 339 kg of polyester (A2), and a coupling reaction was carried out at 180 to 200 ° C. for 1 hour. The viscosity increased rapidly but no gelling occurred. Next, 1700 g of Irganox 1010 (manufactured by Ciba Geigy) as an antioxidant and 1700 g of calcium stearate as a lubricant were added, and stirring was further continued for 30 minutes. This reaction product was extruded into water with an extruder and cut into a pellet by a cutter. 90 ° C
The yield of polyester (B2) after vacuum drying for 6 hours was 300 kg.

The obtained polyester (B2) is a slightly ivory white wax-like crystal having a melting point of 110.
° C, the number average molecular weight (Mn) is 35,500, the weight average molecular weight (Mw) is 170,000, the MFR (190 ° C) is 1.0 g / 10 min, the viscosity of a 10% solution of orthochlorophenol is 230 poise, Temperature 190 ° C, shear rate 10
The melt viscosity at ⁰ sec ^-1 was 1.5 × 10 ⁴ poise. The average molecular weight is measured by Shodex GPC
System-11, solvent: CF ₃ COONa 5 mmol solution of hexafluoroisopropyl alcohol, concentration 0.1% by weight, calibration curve: Showa Denko KK PMMA standard sample Shodex Standard M-75
I went in.

Then, the polyester (B2) was extrusion-laminated on high-quality paper (70 g / m ² ) at 230 ° C. and a line speed of 100 m / min using the laminator used in Example 1, and a 30 μm paper release substrate was obtained. I got At the time of molding, there was no fuming, the thin film ears were stable, and a laminate having a uniform film width and thickness was obtained.

The heat resistance of the obtained paper release substrate was sufficient, and the paper adhesion was also strongly tested by a peel test. When the biodegradability was evaluated in the same manner as in Example 1, after three months, the polyester film had countless small holes, and the film partially disappeared, and the degradability was extremely advanced. Was confirmed.
The evaluation of the obtained base material is shown in Table 1.

Example 4 A 700 L reactor was purged with nitrogen and charged with 177 kg of 1,4-butanediol, 198 kg of succinic acid, and 25 kg of adipic acid. The temperature is increased under a nitrogen stream, and the temperature is increased to 190 to 210 ° C. for 3.5 hours.
2. Further stop nitrogen, and under a reduced pressure of 20 to 2 mmHg.
The esterification reaction by dehydration condensation was performed for 5 hours. The collected sample had an acid value of 9.6 mg / g, a number average molecular weight (Mn) of 6,100, and a weight average molecular weight (M
w) was 12,200. Subsequently, 20 g of tetraisopropoxy titanium as a catalyst was added under a nitrogen stream at normal pressure. Raise the temperature to 15 at a temperature of 210-220 ° C.
The deglycol-reaction was performed under a reduced pressure of 0.2 mmHg for 6.5 hours. The collected sample has a number average molecular weight (M
n) is 17,300 and the weight average molecular weight (Mw) is 4
6,400. The yield of this polyester (A3) was 337 kg excluding condensed water.

4.66 kg of hexamethylene diisocyanate was placed in a reactor containing 333 kg of polyester (A3).
Was added and a coupling reaction was performed at 180 to 200 ° C. for 1 hour. The viscosity increased rapidly but no gelling occurred. Next, Irganox 1010 was used as an antioxidant.
1700 g (manufactured by Ciba Geigy) and 1700 g of calcium stearate as a lubricant were added, and stirring was further continued for 30 minutes. This reaction product was extruded into water with an extruder and cut into a pellet by a cutter. 9
Polyester (B3) after vacuum drying at 0 ° C for 6 hours
Was 300 kg.

The obtained polyester (B3) is a slightly ivory white wax-like crystal having a melting point of 103.
° C, number average molecular weight (Mn) is 36,000, weight average molecular weight (Mw) is 200,900, MFR (190 ° C) is 0.52 g / 10 min, and 10% of orthochlorophenol.
The solution has a viscosity of 680 poise, a temperature of 190 ° C. and a shear rate of 1.
The melt viscosity at 00 sec ^-1 was 2.2 × 10 ⁴ poise. The average molecular weight is measured by Shodex GPC
System-11, solvent: CF ₃ COONa 5 mmol solution of hexafluoroisopropyl alcohol, concentration 0.1% by weight, calibration curve: Showa Denko KK PMMA standard sample Shodex Standard M-75
I went in.

The polyester (B3) was heated at 270 ° C., 1
20μ thickness at 50m / min on high quality paper (70g / m ² )
m was extruded. The film height was slightly raised during film formation, but the film width and thickness during film formation were stable, and stable molding was possible.

Some smoke was generated, but not so much as to cause a problem. When the obtained laminate was subjected to a heat resistance test at 100 ° C., the number of pinholes was small and the change in gloss was small. Adhesion with paper was sufficient, and the paper was cohesively broken.

When the biodegradability was tested in the same manner as in Example 1, after two months, the film had already opened countless holes and had been tattered. The evaluation of the obtained base material is shown in Table 1.

Example 5 After a 700 L reactor was purged with nitrogen, 200 kg of 1,4-butanediol, 250 kg of succinic acid and 2.84 k of trimethylolpropane were used.
g. The temperature was increased in a nitrogen stream, and 192
At 220 ° C. for 3.5 hours, further stopping nitrogen and
The esterification reaction by dehydration condensation was performed under a reduced pressure of 2 mmHg for 2.5 hours. The collected sample had an acid value of 2.5 mg / g, a number average molecular weight (Mn) of 8,660,
The weight average molecular weight (Mw) was 9,520. Subsequently, 37 g of tetraisopropoxytitanium as a catalyst was added under a nitrogen stream at normal pressure. Raise the temperature, temperature 2
7. Under a reduced pressure of 15 to 0.3 mmHg at 15 to 220 ° C.
The deglycol reaction was performed for 0 hours. The collected sample had a number average molecular weight (Mn) of 16,200 and a weight average molecular weight (Mw) of 67,900. The theoretical yield of this polyester (A4), excluding condensed water, was 367 kg.

330 g of hexamethylene diisocyanate was added to a reactor containing 367 kg of polyester (A4), and a coupling reaction was carried out at 170 to 185 ° C. for 1 hour. The viscosity increased rapidly but no gelling occurred. Next, 3 Irganox 1010 was added as an antioxidant.
70 g and calcium stearate 370 as a lubricant
g was added and stirring was continued for another 30 minutes. This reaction product was extruded into water with an extruder and cut into a pellet by a cutter. The yield of the polyester (B4) after vacuum drying at 90 ° C. for 6 hours was 360 kg.

The obtained polyester (B4) is a slightly ivory white wax-like crystal having a melting point of 110.
° C, the number average molecular weight (Mn) was 25,600, and the weight average molecular weight (Mw) was 122,000 (Mw / Mn = 4.
8), MFR (190 ° C.) 18 g / 10 min, temperature 19
The melt viscosity at 0 ° C. and a shear rate of 100 sec ⁻¹ is 4.
It was 0 × 10 ³ poise. The measurement of the average molecular weight is carried out by
Odex GPC System-11, solvent is CF ₃
COONa 2mmol hexafluoroisopropyl alcohol solution, concentration 0.1% by weight, calibration curve is Showa Denko KK PMMA standard sample Shodex Sta.
ndard M-75.

Next, this polyester resin (B4) was fed to an extruder having a screw diameter of 50 mmφ and L / D = 28 to a width of 32 mm.
Using a 0 mm T-die, die lip gap 0.8 m
m, air gap 120mm, resin temperature 220 ° C, extrusion at a speed of 150m / min, fine paper (70g
/ M ² ) with a thickness of 20 μm to produce a release substrate. At the time of molding, the ears of the thin film were stable, almost no smoke was found, and stable molding was possible.

The adhesiveness between the paper of the obtained release substrate and the polyester film was sufficient. When a peel test was conducted, no interfacial peeling occurred, and cohesive failure of the paper was observed. The evaluation of the obtained base material is shown in Table 1.

The release substrate was cut into a rectangle of 10 cm × 20 cm, and this release paper was attached to a square box made of stainless steel with a polyethylene net. This was buried in soil having a depth of 10 cm, and the biodegradability was evaluated.
The place is the garden of Showa Denko KK Kawasaki Resin Laboratory (Kawasaki-ku, Kawasaki City). When dug out three months later, it was found that the polyester thin film was more decomposed than the paper fiber and had become ragged.

(Example 6) The aliphatic polyester resin (B4) obtained in Example 5 and the aliphatic polyester resin (B1) obtained in Example 1 were mixed at a ratio of 3: 7 and pelletized. Using the same laminator as in Example 1, molding was performed under the same conditions as in Example 1 except that the molding temperature was 190 ° C. and the line speed was 150 m / min. During molding, stable molding could be performed without fuming. The average thickness of the polyester layer of the obtained release substrate was 25 μm.

The adhesion between the paper and the polyester layer was sufficient, and the paper was subjected to a peeling test. A heat resistance test was performed on the obtained laminate in a circulating air oven at 100 ° C. As a result, the number of pinholes was 2, and the change in surface gloss was small and sufficient. When the biodegradability was evaluated in the same manner as in Example 1, three months later, the film was perforated and ragged. The evaluation of the substrate is shown in Table 1.

Example 7 The aliphatic polyester resin (B1) produced in Example 1 was screwed to a diameter of 50 mm.
A 320 mm wide straight manifold T-die was used in an extruder with φ, L / D = 28, and a die lip gap of 0.
Base paper (280 g) extruded at 8 mm, air gap 120 mm, resin temperature 220 ° C., and subjected to corona discharge treatment (processing amount 30 w min / m ² ) supplied at a speed of 150 m / min.
/ M ² ) with a thickness of 20 μm to produce a paper container base material. At the time of lamination molding, the molten film was stable and excellent in film formation stability, and there was little smoke and the working environment was good. The evaluation of the obtained base material is shown in Table 2.

The paper container base material was cut into a rectangle of 10 cm × 20 cm, and was attached to a square box made of stainless steel with a polyethylene net sandwiching the release paper.
This was buried in soil having a depth of 10 cm, and the biodegradability was evaluated. The place is the garden of Showa Denko KK Kawasaki Resin Laboratory (Kawasaki-ku, Kawasaki City). When dug out three months later, it was found that the polyester thin film was more decomposed than the paper fiber and had become ragged.

Example 8 In the same manner as in Example 7, an aliphatic polyester resin (B1) was extrusion-laminated at a resin temperature of 190 ° C. and a thickness of 20 μm on base paper supplied at a speed of 100 m / min. I got At the time of lamination molding, the molten film was stable, the film formation stability was excellent, there was little smoke, and the working environment was good. The evaluation of the obtained base material is shown in Table 2.

[0073]

[0074]

(Example 9) The aliphatic polyester (B2) produced in Example 3 in the same manner as in Example 7 was coated on a base paper fed at a speed of 100 m / min.
-Extruded at a thickness of 30 µm to obtain a paper container base material. During lamination molding, the film formation stability was good, there was little smoke, and the working environment was good. The evaluation of the obtained base material is shown in Table 2.

Example 10 An aliphatic polyester resin (B3) was extruded onto a base paper fed at a speed of 100 m / min at a resin temperature of 270 ° C. and a thickness of 20 μm. Wood was obtained. At the time of lamination molding, the neck-in was slightly large, but the judgment was ○, and the film formation stability was good. In addition, there was some smoke emission and the judgment was △, but the working environment was at a level where there was no concern about deterioration. The evaluation of the obtained base material is shown in Table 2.

(Example 11) The aliphatic polyester resin (B4) produced in Example 5 was screwed with a screw diameter of 50 m.
Using a 320 mm wide straight manifold T-die in an extruder with mφ and L / D = 28, die lip gap 0.8 mm, air gap 120 mm, resin temperature 220
Base paper (28) extruded at a temperature of 150 ° C. and subjected to a corona discharge treatment (processing amount 30 w min / m ² ) supplied at a speed of 150 m / min.
0 g / m ² ) to give a thickness of 20 μm to produce a paper container base material. At the time of lamination molding, the molten film was stable and excellent in film formation stability, and there was little smoke and the working environment was good. The evaluation of the obtained base material is shown in Table 2.

The paper container base material was cut into a rectangle of 10 cm × 20 cm, and was attached to a square box made of stainless steel with a polyethylene net sandwiching the release paper.
This was buried in soil having a depth of 10 cm, and the biodegradability was evaluated. The place is the garden of Showa Denko KK Kawasaki Resin Laboratory (Kawasaki-ku, Kawasaki City). When dug out three months later, it was found that the polyester thin film was more decomposed than the paper fiber and had become ragged.

Example 12 In the same manner as in Example 7, an aliphatic polyester resin (B4) was extrusion-laminated on a base paper fed at a speed of 100 m / min at a resin temperature of 190 ° C. and a thickness of 30 μm. Wood was obtained. At the time of lamination molding, the molten film was stable, the film formation stability was excellent, there was little smoke, and the working environment was good. The evaluation of the obtained base material is shown in Table 2.

(Example 13) The aliphatic polyester resin (B1) obtained in Example 1 and the aliphatic polyester resin (B4) obtained in Example 5 were pelletized with an extruder having a diameter of 50 mm to obtain a 1: 1 mixture. A mixed polyester resin was obtained. This aliphatic polyester resin composition was extruded on a base paper supplied at 180 m / min at a resin temperature of 210 ° C. and a thickness of 20 μm,
In the same manner as in Example 7, a paper container base material was obtained. The neck-in during lamination was small, and the film formation stability was extremely good. There was little smoke and the working environment was good.

The laminated molded laminate was evaluated for biodegradability in the same manner as in Example 7. The place is the garden of Showa Denko Kawasaki Resin Research Institute. When dug out three months later, it was found that the polyester film had been decomposed more than the paper fibers, and had been ragged.

<< Experimental Results >> The measuring methods in Examples 1 to 6 are as follows. (1) Film-forming stability: The neck-in stability of the molten film and the uneven thickness stability of the laminate film were evaluated. ：: The neck-in of the molten film during lamination molding was 80 mm
In the following, there is almost no variation, and the thickness deviation of the laminated film is within 10% except for the ears. Δ: Intermediate between ○ and ×. ×: The neck-in of the molten film during lamination molding was 80 mm.
When the variation is 10 mm or more on one ear and the thickness deviation of the laminated film exceeds 10% excluding the ear part.

(2) Smoke emission: The smoke emission state of the molten film during lamination molding was observed and evaluated. It is preferable that there is an evaluation of Δ or more. ：: Very little smoke is generated during lamination molding, and the driving side can be clearly seen from the operation side around the T-die. Δ: Smoke was slightly generated during lamination molding, and it was anxious to see the drive side from the operation side around the T-die, but the working environment was not deteriorated. ×: A large amount of smoke was generated during lamination molding, the driving side was not clearly seen from the operation side around the T-die, and the working environment was poor.

(3) Heat resistance: Judgment was made based on the change in gloss and the number of pinholes after being left in a circulating oven at 100 ° C. or 110 ° C. for 2 minutes. ：: Gloss change 5% or less △: 〃 5 to 10% ×: 〃 10% or more

(4) Pinholes: A colored alcohol is applied to the surface with a brush, and the number of pinholes per 0.1 m ² is counted.

(5) Adhesion: The paper laminate was torn by hand and the laminate film was peeled off from the paper, and the state was observed. ：: A state in which the tearing of the laminate film is small in tearing, and the peeling is accompanied by cohesive failure of the paper and the peeling of the laminate film alone does not occur. Δ: Many tears of the laminate film occurred in tearing, and peeling caused partial peeling of the laminate film at the interface.
The peel resistance is strong. X: A state in which the laminate film is stretched without being cut by tearing, and interfacial peeling of the laminated film occurs without strong resistance by peeling.

(6) Biodegradability: A 10 cm × 20 cm paper laminate is sandwiched between stainless steel molds provided with a polyethylene net at the window, and buried in a 10 cm deep soil.
After months, it was dug and its biodegradability was evaluated. It is preferable that the evaluation is ○. ：: When the aliphatic polyester composition of the paper laminate is more decomposed than paper, and the surface of the composition is perforated with perforations. ×: when the decomposition of paper has progressed from the aliphatic polyester composition of the paper laminate and the aliphatic polyester is still firm.

[0088]

[Table 1]

The measurement methods in Examples 7 to 13 were the same as those described above except that the following methods were used for odor and heat resistance.

(7) Odor: The air odor of the odor bag was organoleptically evaluated. The odor bag was prepared by cutting the paper laminate into 20 cm × 20 cm, filling the inside with fresh air, and heat-sealing the resin surface on the inner surface. The evaluation of the air odor was made by comparative sensory evaluation based on the air odor of a paper laminate made of low-density polyethylene used for existing paper cups. The sensory evaluation was based on a paneler who was able to distinguish five standard odors. ：: When the air odor of the paper laminate of the present invention is equal to or lower than the reference air odor. ×: When the air odor of the paper laminate of the present invention is stronger than the reference air odor.

(8) Heat resistance: A paper cup for a vending machine was manufactured from the resulting base material, and boiling hot water was poured into the paper cup to evaluate oozing of hot water and peeling of a joint. ：: No oozing of hot water and no peeling of joints. ×: Exudation of hot water or peeling of the joint was observed.

[0092]

[Table 2]

[0093]

The present invention has a temperature of 190 ° C. and a shear rate of 100.
The melt viscosity at sec ^-1 is 1.0 × 10 ^{3 to} 1.0 ×
By using an aliphatic polyester resin having 10 ⁵ poises as a sealing layer of an adhesive sheet, an adhesive tape or the like, a release substrate having high adhesion to the substrate even when laminated at a low temperature could be obtained.

In particular, since the temperature of the melt coating is low, there is no, if any, smoke which has been a problem in the past, and there is no problem due to the working environment and smoke discharge outside the factory. .

Further, this resin can be laminated at a relatively low temperature while producing a base material for paper containers, even though it is a base material used for hot beverages and the like, and thermal decomposition of the resin is minimized. Paper containers made from paper laminates (base materials) have the advantage of eliminating the odor of oxidative degradation of the resin, and laminating at low temperatures can prevent a large amount of smoke, greatly improve the work environment, It is advantageous for preserving the natural environment around the factory.

Since the aliphatic polyester resin to be laminated is biodegradable and has a small calorific value of combustion as compared with the conventionally used polyolefin resin, it must be incinerated when disposing of used containers. Is also a very advantageous paper container base material to be buried in the soil.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location // C09J 7/02 C09J 7/02 (72) Inventor Koji Furuichi Chidoricho, Kawasaki-ku, Kawasaki-shi, Kawasaki-ku, Kanagawa Prefecture 3-2 Showa Denko KK Kawasaki Resin Laboratory (72) Inventor Eiichiro Takiyama 4-12-4 Nishi-Kamakura, Kamakura-shi, Kanagawa (56) References JP-A-4-325245 (JP, A) 109830 (JP, U)

Claims (2)

(57) [Claims] 1. A temperature of 190 ° C. and a shear rate of 100 (sec.)
^-1 ) has a melt viscosity of 1.0 × 10 ^{3 to} 1.0 × 10
A release substrate, characterized in that an aliphatic polyester resin having a melting point of 70 to 200 ° C. having a melting point of ⁵ poise is melt-extruded and coated on the substrate. 2. A temperature of 190 ° C. and a shear rate of 100 (sec.)
^-1 ) has a melt viscosity of 1.0 × 10 ^{3 to} 1.0 × 10
^{1. A} base material for a paper container, wherein an aliphatic polyester resin having a melting point of 85 to 200 [deg.] C., which is ⁵ poise, is laminated on a base paper.