JP2002265719A - Aqueous dispersion of 4-methyl-1-pentene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a mold release agent capable of forming a film, excellent in heat resistance, water resistance, chemicals resistance, mold release property, and cohesive property to various materials, and to prepare an aqueous dispersion of the mold release agent. SOLUTION: This aqueous dispersion is prepared by dispersing in water a 4-methyl-1-pentene polymer (A) or its modified material (B) as spherical particles with an average particle diameter of not greater than 100 μm which is measured by an electric resistance method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous dispersion comprising a release agent, and more particularly to an aqueous dispersion of a 4-methyl-1-pentene polymer or a modified product thereof.

[0002]

BACKGROUND OF THE INVENTION Conventionally, various polymers which can be dispersed in water have been known. Among aqueous dispersions of these polymers dispersed in water, fluid dispersions containing water in an amount of 30% by weight or more are known. An aqueous dispersion having a property (hereinafter, referred to as an aqueous dispersion in the present invention) is used for various purposes.

[0003] Specifically, an aqueous dispersion is applied to the surface of a substrate such as paper, fiber, plastic molded product, wood, metal, etc., and dried, and a resin film is formed on the surface to form a water-resistant material on the substrate. It is used for imparting chemical resistance and the like, and for forming a heat seal layer on the surface of a resin film or the like. Since such an aqueous dispersion uses water as a dispersion medium, there are problems when a solvent is used, such as danger to fire and toxicity to the human body, further deterioration in working environment, difficulty in handling, and the like. It can improve problems and is used in a wide range of fields.

[0004] Such an aqueous dispersion is used as a release agent (polymer).
In the case of an aqueous dispersion of, for example, in the production of electronic components, electrical components, and the like, used for releasing the electronic components from the mold for molding, release paper used in the production of synthetic leather It is used for coating a resin to release synthetic leather and release paper. In the manufacture of electronic parts and electric parts, there are many cases where various elements are encapsulated in a thermosetting resin mold such as epoxy resin to produce products (cast molding method). In order to easily remove the molded product from the mold, a mold release agent is applied to the surface of the mold. Examples of the release agent dispersible in water used in this case include waxes such as low molecular weight polypropylene, low molecular weight silicone resins, and the like, and aqueous dispersions of these release agents are used.

[0005] When synthetic leather is produced from a vinyl chloride resin, a urethane resin, or the like, a release paper for synthetic leather in which a resin (release agent) is coated on the surface of paper is used. Examples of the release agent dispersible in water used in this case include a silicone resin and an acrylic resin.
Aqueous dispersions of these release agents are used. But,
Although such a release agent can be used as an aqueous dispersion, heat resistance, release properties, and the like are insufficient. Therefore, development of a new release agent and an aqueous dispersion of the release agent has been desired. .

[0006]

The object of the present invention is to provide heat resistance, water resistance, chemical resistance,
It is an object of the present invention to provide a release agent capable of forming a film having excellent release properties and excellent adhesion to various materials, and an aqueous dispersion thereof.

[0007]

SUMMARY OF THE INVENTION The aqueous dispersion according to the present invention comprises a 4-methyl-1-pentene polymer (A) or a modified product thereof (B).
Are dispersed in water as spherical particles having an average particle diameter of 100 μm or less as measured by an electric resistance method.

4-methyl-1-pentene polymer (A)
Is a random copolymer of 4-methyl-1-pentene and an α-olefin, in which 4-methyl-1-pentene units are 80 to 99.9% by weight, and α-olefin units having 2 to 20 carbon atoms are Desirably, it comprises 0.1 to 20% by weight.

Further, the α-olefin is one or more α-olefins selected from 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Is desirable. Further, the modified product (B) of the 4-methyl-1-pentene polymer is a modified product obtained by grafting an unsaturated carboxylic acid and / or an acid anhydride thereof to the 4-methyl-1-pentene polymer. Is also desirable.

4-methyl-1-pentene polymer (A)
Alternatively, the modified product (B) is also preferably a low molecular weight substance having an intrinsic viscosity of 1.0 or less. Further, the low-molecular-weight product is a low-molecular-weight product obtained by adding an organic peroxide to the 4-methyl-1-pentene-based polymer (A) or its modified product (B) and melt-extruding the same. It is also desirable.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. The aqueous dispersion of the present invention is obtained by dispersing a 4-methyl-1-pentene polymer (A) or a modified product thereof (B), or a low-molecular-weight product thereof. 4-Methyl-1-pentene polymer (A) First, 4-methyl-1-pentene constituting the aqueous dispersion of the present invention.
The pentene polymer (A) will be described.

The 4-methyl-1-pentene polymer (A) used in the present invention has an intrinsic viscosity [η] (measured at 135 ° C. in decalin (decahydronaphthalene)) of preferably 0.1 to 0.1. 5 dl / g, more preferably 0.2 to 2
dl / g. When the intrinsic viscosity [η] is in the above range, it becomes easy to obtain the aqueous dispersion of the present invention.

The above 4-methyl-1-pentene polymer (A) can be produced by copolymerization according to a conventionally known method. Examples of such a 4-methyl-1-pentene polymer (A) include a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and an α-olefin (4-methyl-1-pentene). (Excluding pentene). When the copolymer is a polymerization reaction,
α-olefin is usually 1 to the total molar amount of the reactants.
The reaction is performed under the condition of 5 mol% or less, preferably 9 mol% or less.

When the 4-methyl-1-pentene polymer (A) used in the present invention is the above-mentioned copolymer, the present invention relates to a random copolymer of 4-methyl-1-pentene and an α-olefin. It is particularly preferred that they are united. The 4-methyl-1-pentene / α-olefin random copolymer has a 4-methyl-1-pentene unit of 80 to 9;
9.9% by weight, preferably 90 to 98% by weight, 0.1 to 20% by weight of α-olefin unit, preferably 2 to 10% by weight.
% By weight.

As the α-olefin for forming the 4-methyl-1-pentene / α-olefin random copolymer, those having 2 to 20 carbon atoms can be used.
For example, ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Octadecene and 1-eicosene are exemplified, and preferably 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene are exemplified. These α-olefins are used alone or in combination of two or more.

In the present invention, 4-methyl-1-
The pentene-based polymer (A) may contain various additives as needed, as long as the object of the present invention is not impaired. Examples of the additives include a silane coupling agent, a weather stabilizer, a heat stabilizer, a slip agent, a nucleating agent, a pigment, and a dye. Modified product of 4-methyl-1-pentene polymer (B) Intrinsic viscosity [η] (1) of modified product (B) used in the present invention
(Measured in decahydronaphthalene at 35 ° C.) is preferably 0.5 to 5 dl / g, more preferably 0.5 to 2 dl / g.
dl / g. When the intrinsic viscosity [η] is within this range, it is easy to obtain the aqueous dispersion of the present invention.

Here, 4-methyl-1 used in the present invention is used.
-The method for producing the modified pentene polymer (B) will be described. The modified product (B) can be produced by a known graft polymerization method such as a solution method and a melt kneading method. Specifically, it can be obtained by graft copolymerizing an unsaturated carboxylic acid and / or an acid anhydride thereof with a 4-methyl-1-pentene polymer before modification.

It is preferable for the purpose of the present invention that the modified product (B) has a linear structure and substantially no cross-linked structure, and this structural feature is characterized by being dissolved in an organic solvent such as p-xylene. However, it can be confirmed by the absence of a gel. The unsaturated carboxylic acid and / or anhydride thereof used as the graft monomer in the graft polymerization method preferably has 3 to 20 carbon atoms. Specifically, acrylic acid, unsaturated monocarboxylic acids such as methacrylic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, mesaconic acid, glutaconic acid, nadic ^TM, methylnadic acid, tetrahydrophthalic acid ,
Unsaturated dicarboxylic acids such as methyl hexane tetrahydrophthalic acid; maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, glutaconic acid, nadic acid ^TM, methylnadic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride And unsaturated dicarboxylic anhydrides such as phthalic acid. Of these, maleic acid, maleic anhydride, nadic acid ^TM and nadic acid ^TM are preferred. These can be used alone or in combination of two or more.

The graft ratio of the unsaturated carboxylic acid and / or the acid anhydride thereof is more than 0 and not more than 20% by weight, preferably 0.01 to 15% by weight, more preferably 0.1% by weight.
-10% by weight. Here, the graft ratio is defined as the weight ratio (%) of the structural units derived from the graft monomer in the modified poly-4-methyl-1-pentene resin.

When the graft ratio is in the above range,
Excellent adhesion to poly-4-methyl-1-pentene resin and other materials (eg, other resins, metals, paints, inks, etc.) is obtained. In the present invention, the modified product (B) of the 4-methyl-1-pentene polymer may contain various additives as needed, as long as the object of the present invention is not impaired. Examples of the additives include a silane coupling agent, a weather stabilizer, a heat stabilizer, a slip agent, a nucleating agent, a pigment, and a dye.

Low molecular weight substance The low molecular weight substance used in the present invention has an intrinsic viscosity of 1.0 or less, preferably 0.8 or less, more preferably 0.01 or less.
Refers to a low-molecular-weight 4-methyl-1-pentene polymer or a modified product thereof having a molecular weight of from 0.5 to 0.5, particularly preferably from 0.1 to 0.4. This low molecular weight compound is a compound of the above-mentioned 4-methyl-1-
It can be produced by adding an organic peroxide to the pentene polymer (A) or its modified product (B), and extruding it.

4-methyl-1-pentene polymer (A)
Alternatively, by modifying the modified product (B) into a low-molecular-weight product having an intrinsic viscosity within the above range, the dispersion particles can be miniaturized. Aqueous Dispersion of 4-Methyl-1-pentene Polymer The aqueous dispersion according to the present invention comprises the above-mentioned 4-methyl-1-pentene polymer (A), a modified product thereof (B), or a low-polymer thereof. The molecular weight has an average particle diameter of 100 μm or less, preferably 50 μm or less, more preferably 0.01 to 20 μm, particularly preferably 0.1 to
It is dispersed as 5 μm spherical particles.

The average particle size was measured using a Coulter counter (manufactured by Coulter Co., Ltd.) as an instrument, and using aperture tubes having aperture diameters of 15, 50, 100, 200 and 400 μm. In the underwater dispersion according to the present invention, the spherical particles composed of the 4-methyl-1-pentene polymer (A), the modified product thereof (B), or the low molecular weight thereof are added to the aqueous dispersion 100 g. It is desirable that it be present in an amount of 1 to 50 g, preferably 5 to 30 g, more preferably 10 to 20 g.

The aqueous dispersion according to the present invention can be obtained by known methods as exemplified below, but is not limited to the methods exemplified below. JP-A-61-123
664 according to the present invention by applying the method described in US Pat.
An aqueous dispersion of a methyl-1-pentene polymer can be produced. For example, the 4-methyl-1-pentene polymer (A) used in the present invention is melted, a basic substance and water are added to the melt-kneaded product, and the mixture is melt-kneaded.
The aqueous dispersion according to the present invention can be produced from the step of inverting the phase of the polymer (A) into an aqueous dispersion and the step of adding an additional amount of water to the aqueous dispersion.

Alternatively, water is added to the 4-methyl-1-pentene polymer (A) used in the present invention, and the mixture is melt-kneaded under pressure to invert the phase of the polymer (A) into an aqueous dispersion. The aqueous dispersion according to the present invention can also be produced from the step and the step of adding an additional amount of water to the aqueous dispersion.

The aqueous dispersion of the 4-methyl-1-pentene polymer according to the present invention can be produced by applying the method described in JP-B-58-42207.
For example, the 4-methyl-1-pentene polymer (A) used in the present invention is melted and kneaded, and an aqueous solution of a basic substance (heated to the melting point of the polymer (A) or more) is stirred while stirring. The melt-kneaded product is added. After the stirring is further continued, the aqueous dispersion according to the present invention can be produced by cooling to room temperature.

The aqueous dispersion according to the present invention contains
The methyl-1-pentene polymer (A), or its modified product (B), or one or more of these low-molecular-weight polymers may be dispersed.

[0028]

According to the present invention, there is provided a release agent capable of forming a film having excellent heat resistance, water resistance, chemical resistance, release properties and adhesion to various materials, and an aqueous dispersion thereof. can do.

[0029]

EXAMPLES Hereinafter, the aqueous dispersion containing the 4-methyl-1-pentene polymer of the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, peel strength, surface roughness, evaluation of coating adhesion, and evaluation of releasability were performed as follows. <Peel strength> The tensile peeling machine was used to measure the interlaminar peel strength of a strip test piece having a width of 15 mm. The measurement was performed at a test speed of 300 mm / min in a 180 ° peel test. <Surface roughness> According to JIS B0601, the surface roughness was measured using a surf test 401 (manufactured by Mitutoyo Corporation). <Evaluation of adhesion of film> A polymer film was formed on a mold, a cellophane tape was applied to the film, and it was observed whether or not the film peeled off when the cellophane tape was peeled off, and the adhesion of the film was evaluated. . <Evaluation of releasability> The rubber composition shown in the following Table 1 was poured into a mold on which a film was formed, and heated at a mold temperature of 160 ° C. for 15 minutes to perform vulcanization (curing). Remove the vulcanizate. After this operation was repeated 10 times, the adhesion of rubber to the mold was observed, and the releasability was evaluated.

The 4-methyl-1-pentene polymer used in the examples and its modified products were produced under the following conditions.

[0031]

[Production Example 1] 4-methyl -1-pentene polymer 4-methyl-1-pentene polymer [trade name: TPX
MX002 (manufactured by Mitsui Chemicals, Inc.)] [Intrinsic viscosity [η]
2.4, Comonomer composition: 93% by weight of 4-methyl-1-pentene unit, a mixture of olefins having 16,18 carbon atoms (trade name: DIALEN D-168) unit
7% by weight] and 100 parts by weight of 1,3-bis (tert-butyloxyisopropyl) benzene were mixed with 0.5 part by weight of a tumbler blender to uniformly adhere to the pellet surface.

Then, the pellets were extruded at 300 ° C. in a nitrogen atmosphere by an extruder to obtain a low molecular weight product of a 4-methyl-1-pentene polymer [intrinsic viscosity [η] 0.4, copolymer monomer composition 4-methyl-1-
Mixture of olefins with pentene unit 93% by weight and carbon number of 16,18 (trade name: DIALEN D-168)
7% by weight].

[0033]

[Production Example 2] Modification of 4-methyl-1-pentene polymer
Production of 4-methyl-1-pentene polymer [trade name: TPX
MX002 (manufactured by Mitsui Chemicals, Inc.)] [Intrinsic viscosity [η]
2.4, Comonomer composition: 93% by weight of 4-methyl-1-pentene unit, a mixture of olefins having 16,18 carbon atoms (trade name: DIALEN D-168) unit
7% by weight], 100 parts by weight, 0.5 part by weight of 1,3-bis (tert-butyloxyisopropyl) benzene, and 1 part by weight of maleic anhydride were mixed by a tumbler blender to uniformly adhere to the pellet surface. .

Next, the pellets were extruded at 300 ° C. under a nitrogen atmosphere by an extruder to obtain a low molecular weight modified product of a 4-methyl-1-pentene polymer [intrinsic viscosity [η] 0.4, Composition; 4-methyl-1
A mixture of olefins having 93% by weight of pentene units and 16,18 carbon atoms (trade name: DIALEN D-16)
8) Unit 7% by weight, graft ratio; maleic anhydride 1% by weight] was produced.

[0035]

[Production Example 3] the propylene polymer produced propylene polymer [trade name: F 327 (manufactured by Grand Helsingborg mer Ltd.)] (MFR 13, density 0.910)
0.5 parts by weight of l, 3-bis (tert-butyloxyisopropyl) benzene was mixed with 100 parts by weight using a tumbler blender, and was uniformly adhered to the pellet surface.

Next, the pellets were extruded at 300 ° C. in a nitrogen atmosphere with an extruder to produce a low molecular weight propylene polymer (intrinsic viscosity [η] 0.3).

[0037]

[Production Example 4] Production propylene polymer modified product of the propylene-based polymer [trade name: F 327 (manufactured by Grand Helsingborg mer Ltd.)] (MFR 13, density 0.910)
To 100 parts by weight, 0.5 part by weight of 1,3-bis (tert-butyloxyisopropyl) benzene and maleic anhydride 1
The parts by weight were mixed by a tumbler blender and uniformly attached to the pellet surface.

Next, the pellets were extruded at 300 ° C. under a nitrogen atmosphere by an extruder to thereby obtain a low-molecular-weight modified propylene polymer (intrinsic viscosity [η] of 0.5%) grafted with 1% by weight of maleic anhydride. , Density 0.9
10) was manufactured.

[0039]

Example 1 A pressure-resistant homomixer having a capacity of 4 liters
Add 1500 cc of water, 1.5 g of sodium hydroxide and 1.5 g of potassium oleate and heat to 250 ° C.
While stirring at 5000 rpm, 200 g of a low-molecular-weight 4-methyl-1-pentene polymer as a molten bear obtained in Production Example 1 was supplied by a gear pump over 1 hour.

After stirring for an additional 30 minutes, the particles in the aqueous dispersion obtained by cooling to room temperature had an average particle diameter of 5 μm as measured by a Coulter counter (aperture diameter: 15 μm).
The dispersion had the following spherical shape, and almost no phase separation was observed after the dispersion was allowed to stand for 7 days. Next, this aqueous dispersion onto a paper substrate (Hokuetsu Paper Co., Ltd., basis weight 125g / cm ²⁾ 10
It was coated at a thickness of 0 g / m ² and dried in an air oven at 100 ° C. for 60 minutes. Then 220
After heated with hot air of 60 ° C. for 60 seconds, the molten resin was fixed on the paper by pressing with a mirror roll of 250 ° C. to obtain a 4-methyl-1-pentene polymer-coated paper.

The peel strength between the 4-methyl-1-pentene polymer layer of the obtained 4-methyl-1-pentene polymer-coated paper and the paper was measured. Further, the 4-methyl-1-
Uncured vissol was brush-coated on the 4-methyl-1-pentene polymer surface of the pentene polymer-coated paper at a thickness of 1000 g / m ² . Then, it was left in an air oven at 200 ° C. for 3 minutes to cure the PVC sol.

The peel strength of the cured PVC layer was measured, and the surface roughness of the PVC sheet was measured. The results are shown in Table 2.

[0043]

Example 2 80% by weight of a low-molecular weight 4-methyl-1-pentene polymer obtained in Production Example 1 and 4% obtained in Production Example 2
-Methyl-1-pentene polymer low molecular weight modified product 2
0% by weight was melt mixed at 250 ° C. Next, 1500 cc of water and 1.5 g of sodium hydroxide were put into a pressure-resistant homomixer having a capacity of 4 liters, and heated to 250 ° C.
With stirring at 5000 rpm, 200 g of the above-mentioned polymer mixture in a molten state was supplied over 1 hour by a gear pump.

Further, the particles in the aqueous dispersion obtained by cooling to room temperature after stirring for 30 minutes are spherical with an average particle diameter of 5 μm or less, and the phase separation of this dispersion after standing for 7 days is almost zero. I couldn't see it. It was then coated to a thickness of 100 g / m ² of the aqueous dispersion on a clay coated paper. The coated paper was dried in an air oven at 100 ° C. for 60 minutes. Then, after heating with hot air at 220 ° C for 60 seconds, pressing with a mirror roll at 250 ° C,
The molten resin was fixed to paper to obtain 4-methyl-1-pentene polymer-coated paper.

The peel strength between the 4-methyl-1-pentene polymer layer of the obtained 4-methyl-1-pentene polymer coated paper and the paper was measured. Further, the 4-methyl-1-
Uncured PVC salt was brush-coated to a thickness of 1000 g / m ^{2 on} the 4-methyl-1-pentene polymer surface of the pentene polymer coated paper. Then, it was left in an air oven at 200 ° C. for 8 minutes to cure the PVC sol.

The peel strength of the cured PVC layer was measured, and the surface roughness of the PVC sheet was measured. The results are shown in Table 2.

[0047]

Example 3 The aqueous dispersion obtained in Example 2 (4-methyl-
Low molecular weight l-pentene polymer and 4-methyl-1
-Comprising a mixture of low molecular weight modifications of a penten polymer) on a clay-coated paper at a thickness of 1000 g / m < ² >. The coated paper was dried in an air oven at 100 ° C. for 60 minutes, and then dried at 220 ° C.
After heating with hot air for 60 seconds, the resin was fixed on a clay-coated paper by pressing with a mirror roll at 250 ° C. to obtain a 4-methyl-1-pentene polymer-coated paper.

The peel strength between the 4-methyl-1-pentene polymer layer of the obtained 4-methyl-1-pentene polymer-coated paper and the paper was measured. Further, the 4-methyl-1-
An uncured PVC salt was brush-coated to a thickness of 1000 g / m ^{2 on} the 4-methyl-1-pentene polymer surface of the penten polymer-coated paper. Then, it was left in an air oven at 200 ° C. for 8 minutes to cure the PVC sol.

The peel strength of the cured PVC layer was measured, and the surface roughness of the PVC sheet was measured. The results are shown in Table 2.

[0050]

Example 4 The aqueous dispersion obtained in Example 2 (4-methyl-
Low molecular weight l-pentene polymer and 4-methyl-1
-A mixture of a low molecular weight modified product of a pentene polymer) was applied to the inner surface of a commercially available casting mold (coating amount:
170 g / m ² , in terms of solid content).

Next, after drying at 80 ° C. for 10 hours, 250 ° C.
For 120 seconds to form a film having a thickness of 20 μm. The adhesion and releasability of this film were evaluated according to the above methods. The results are shown in Table 2.

[0052]

[Comparative Example 1] A pressure-resistant homomixer with a capacity of 4 liters
Add 1500 cc of water, 1.5 g of sodium hydroxide and 1.5 g of potassium oleate and heat to 250 ° C.
While stirring at 5000 rpm, 200 g of a low-molecular-weight propylene-based polymer in the molten state obtained in Production Example 3 was added thereto.
Was supplied over 1 hour by a gear pump.

After stirring for further 30 minutes, the particles in the aqueous dispersion obtained by cooling to room temperature were spherical with an average particle diameter of 5 μm or less, and the phase separation of this dispersion after standing for 7 days was hardly observed. I couldn't. Next, this aqueous dispersion was coated on a paper substrate (manufactured by Hokuetsu Paper Mill, basis weight 125 g / m ² ) at a thickness of 100 g / m ² , and dried in an air oven at 100 ° C. for 60 minutes. Then, with hot air at 220 ° C,
After heating for 0 second, pressure bonding was performed with a mirror roll at 250 ° C. to fix the molten resin to the paper, thereby obtaining a propylene-based polymer-coated paper.

The peel strength between the propylene polymer layer of the obtained propylene polymer coated paper and the paper was measured. Further, the uncured PVC salt was brush-coated at a thickness of 100 g / m ^{2 on} the propylene polymer coated surface of the propylene polymer coated paper. This was left in an air oven at 200 ° C. for 3 minutes to cure the PVC sol.

The peel strength of the cured PVC layer was measured, and the surface roughness of the PVC sheet was measured. The results are shown in Table 2.

[0056]

COMPARATIVE EXAMPLE 2 80% by weight of the low-molecular-weight propylene polymer obtained in Production Example 3 and 20% by weight of the modified propylene-based polymer obtained in Production Example 4 were melt-mixed at 250 ° C. Next, into a 4 liter pressure-resistant homomixer,
1500 cc of water and 1.5 g of sodium hydroxide were added, heated to 250 ° C., and 200 g of the above-mentioned polymer mixture in a molten state was supplied by a gear pump for 1 hour while stirring at 5000 rpm.

Further, after stirring for 30 minutes, the particles in the aqueous dispersion obtained by cooling to room temperature are spherical with an average particle diameter of 5 μm or less, and the phase separation of this dispersion after standing for 7 days is almost zero. I couldn't see it. Next, this aqueous dispersion was coated on clay-coated paper at a thickness of 100 g / m ² , and dried in an air oven at 100 ° C. for 60 minutes. Then, after heating with 220 ° C hot air for 60 seconds, 2
The melted resin was fixed to the paper by pressing with a mirror roll at 50 ° C. to obtain a propylene-based polymer-coated paper.

The peel strength between the propylene polymer layer of the obtained propylene polymer coated paper and the paper was measured. Further, an uncured PVC salt was brush-coated on the propylene polymer surface of the propylene polymer coated paper at a thickness of 1000 g / m ² . Then, it was left in an air oven at 200 ° C. for 3 minutes to cure the PVC sol.

The peel strength of the cured PVC layer was measured, and the surface roughness of the PVC sheet was measured. The results are shown in Table 2.

[0060]

Comparative Example 3 The aqueous dispersion (composed of a mixture of a low molecular weight propylene polymer and a low molecular weight modified propylene polymer) obtained in Comparative Example 2 was coated on a clay-coated paper at 1000 g / m ^2. Coated with thickness. The coated paper was dried in an air oven at 100 ° C. for 60 minutes. Then, it was heated with hot air at 220 ° C. for 60 seconds, and then pressed with a mirror-finished roll at 250 ° C. to fix the melted resin to the clay-coated paper to obtain a propylene-based polymer-coated paper.

The peel strength between the propylene polymer layer of the obtained propylene polymer coated paper and the paper was measured. next,
The propylene polymer coated paper propylene polymer body surface to the uncured salt Bizoru was brushing to a thickness of 1000 g / m ^2. Then, it was left in an air oven at 200 ° C. for 3 minutes to cure the PVC sol.

The peel strength of the cured PVC layer was measured, and the surface roughness of the PVC sheet was measured. The results are shown in Table 2.

[0063]

Comparative Example 4 The aqueous dispersion (composed of a mixture of a low molecular weight propylene polymer and a low molecular weight modified propylene polymer) obtained in Comparative Example 2 was applied to the inner surface of a commercially available casting mold. coated (coating amount: 170g / m ^2, in terms of solid content). Then, after drying at 80 ° C. for 10 hours, 250
The film was heated with hot air of 120 ° C. for 120 seconds to form a film having a thickness of 20 μm.

The adhesion and the releasability of this film were evaluated according to the above-mentioned methods. The results are shown in Table 2.

[0065]

[Table 1]

[0066]

[Table 2]

Continued on the front page (72) Inventor Hiromi Shigemoto 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture F-term (reference) 4J002 BB171 EK006 HA07 4J026 AA11 BA25 BA34 BA35 DB08 DB13 FA04 GA09 4J100 AA15Q AA17P AA21Q CA04 DA09 HA53 HC36

Claims (6)

[Claims] 1. A 4-methyl-1-pentene polymer (A)
Alternatively, an aqueous dispersion, wherein the modified product (B) is dispersed in water as spherical particles having an average particle diameter of 100 μm or less as measured by an electric resistance method. 2. A 4-methyl-1-pentene polymer (A)
Is a random copolymer of 4-methyl-1-pentene and an α-olefin, wherein 4-methyl-1-pentene units are 80 to 99.9% by weight, and α-olefin units having 2 to 20 carbon atoms are The aqueous dispersion according to claim 1, comprising 0.1 to 20% by weight. 3. The α-olefin is selected from the group consisting of 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.
3. The aqueous dispersion according to claim 2, wherein the aqueous dispersion is one or more α-olefins. 4. A modified product of the modified 4-methyl-1-pentene polymer (B), which is obtained by grafting an unsaturated carboxylic acid and / or an acid anhydride thereof to a 4-methyl-1-pentene polymer. The aqueous dispersion according to any one of claims 1 to 3, wherein 5. A 4-methyl-1-pentene polymer (A)
5. The aqueous dispersion according to claim 1, wherein the modified product (B) is a low molecular weight substance having an intrinsic viscosity of 1.0 or less. 6. The low molecular weight product is obtained by adding an organic peroxide to a 4-methyl-1-pentene polymer (A) or a modified product thereof (B) and melt-extruding the same. The aqueous dispersion according to claim 5, characterized in that: