CN115667327A

CN115667327A - Recycled styrene monomer, styrene resin, styrene- (meth) acrylic copolymer, polymer alloy, composition, sheet, film, laminate, molded body, and method for producing polymer

Info

Publication number: CN115667327A
Application number: CN202180036675.XA
Authority: CN
Inventors: 藤平卫; 大原伸一; 大门晃; 小代康敬
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2020-05-25
Filing date: 2021-05-20
Publication date: 2023-01-31
Also published as: WO2021241377A1; JPWO2021241377A1

Abstract

The invention provides a regenerated styrene monomer which is a regenerated product of waste polystyrene products and reduces energy consumption in production, a styrene resin, a styrene- (methyl) acrylic acid copolymer, a polymer alloy, a composition, a sheet, a film material, a laminated body and a molded body which use the regenerated styrene monomer, and a method for producing a polymer using the regenerated styrene monomer. The above object is achieved by a regenerated styrene monomer containing styrene and a method for producing a polymer comprising polymerizing a raw material of a polymer containing the regenerated styrene monomer, the regenerated styrene monomer being a product obtained by thermal decomposition treatment of a waste polystyrene product.

Description

Recycled styrene monomer, styrene resin, styrene- (meth) acrylic copolymer, polymer alloy, composition, sheet, film, laminate, molded body, and method for producing polymer

Technical Field

The present invention relates to a method for producing a recycled styrene monomer, a styrene resin, a styrene- (meth) acrylic copolymer, a polymer alloy, a composition, a sheet, a film, a laminate, a molded article, and a polymer.

Background

Synthetic resins, so-called plastics, are used anywhere in the world. As a representative example of the plastics, polystyrene containing styrene as a constituent component of the polymer is cited. Polystyrene is used in many fields such as trays for food packaging, housings of electric appliances and information devices, heat insulating materials, and cushioning materials.

Styrene is typically manufactured from petroleum. An example of a method for obtaining styrene from petroleum is shown below. First, petroleum is distilled and refined to obtain naphtha/gasoline fraction, kerosene, light oil, and residual oil. Next, the naphtha is decomposed and refined to obtain ethylene, propylene, B-B fraction, decomposed oil, and offgas/decomposed heavy oil. Further, aromatic compounds such as benzene, toluene, xylene and the like are extracted from naphtha. Then, ethylbenzene is synthesized by alkylation of benzene with ethylene. Further, styrene is synthesized by dehydrogenation of ethylbenzene (see, for example, patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. H03-109335

Disclosure of Invention

Problems to be solved by the invention

However, as described above, the process for producing styrene from petroleum spans a plurality of stages, requires a large amount of energy, and CO ₂ The discharge amount is also large.

In recent years, there has been a strong demand for reduction in environmental load, and reduction in energy consumption or CO during production, not styrene produced from petroleum, but ₂ Styrene having a discharged amount and a process for producing a polymer using the same.

The present invention aims to provide a recycled styrene monomer which is a recycled product of a waste polystyrene product and reduces energy consumption in production, a styrene resin, a styrene- (meth) acrylic copolymer, a polymer alloy, a composition, a sheet, a film, a laminate, a molded body and a method for producing a polymer using the recycled styrene monomer.

An object of the present invention is to provide a method for producing a polymer, which can produce a recycled polystyrene having improved strength and hue as compared with a polystyrene produced by material recycling, and which uses a recycled styrene monomer.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by chemical regeneration in which styrene is regenerated by thermally decomposing waste polystyrene products, and have completed the present invention.

That is, the present invention includes the following aspects.

[A1] A regenerated styrene monomer, characterized in that it is a product obtained by thermal decomposition treatment of a waste polystyrene product, and contains styrene.

[A2] The regenerated styrene monomer according to [ A1], which contains at least 1 selected from the group consisting of inorganic substances, aromatic compounds, cyclohexadiene-based compounds and cyclohexene-based compounds.

[A3] A styrene resin which is a polymer formed from a polymer raw material containing the regenerated styrene monomer described in [ A1] or [ A2 ].

[A4] The styrene-based resin according to [ A3], which is obtained by graft-polymerizing a rubber-like polymer in a continuous phase comprising a homopolymer of styrene containing the styrene contained in the regenerated styrene monomer and dispersing the particles.

[A5] A styrene-based resin according to [ A3] or [ A4], wherein the raw material of the above polymer contains a multi-branched macromonomer.

[A6] A polymer alloy characterized by comprising a styrenic resin according to any of [ A3] to [ A5] and a polymer other than the styrenic resin.

[A7] A composition comprising a styrenic resin as defined in any one of [ A3] to [ A5 ].

[A8] The composition according to [ A7], which is a coating agent.

[A9] The composition according to [ A7], which is an ink.

[A10] The composition according to [ A7], which is an adhesive.

[A11] A sheet comprising at least 1 selected from the polymer alloy recited in [ A6] and the composition recited in [ A7 ].

[A12] A film material, characterized by using at least 1 selected from the polymer alloy according to [ A6] and the composition according to [ A7 ].

[A13] A laminate characterized by having at least 1 selected from the sheet described in [ A11] and the film described in [ A12 ].

[A14] A molded article obtained by molding at least 1 selected from the group consisting of the sheet described in [ A11], the film described in [ A12] and the laminate described in [ A13 ].

[A15] The molded article according to [ A14], which is a food packaging container.

[B1] A regenerated styrene monomer, characterized in that it is a product obtained by thermal decomposition treatment of a waste polystyrene product, and contains styrene.

[B2] The regenerated styrene monomer according to [1], which contains at least 1 selected from the group consisting of inorganic substances, aromatic compounds, cyclohexadiene-based compounds and cyclohexene-based compounds.

[B3] A styrene- (meth) acrylic copolymer which is a copolymer formed from a raw material containing a polymer of the regenerated styrene monomer described in any one of [ B1] to [ B2] and a (meth) acrylic monomer.

[B4] A polymer alloy characterized by containing the styrene- (meth) acrylic acid-based copolymer according to [ B3] and a polymer other than the styrene- (meth) acrylic acid-based copolymer.

[B5] A composition comprising the styrene- (meth) acrylic copolymer according to [ B3 ].

[B6] The composition according to [ B5], which is a coating agent.

[B7] The composition according to [ B5], which is an ink.

[B8] The composition according to [ B5], which is an adhesive.

[B9] A sheet comprising at least 1 selected from the group consisting of the polymer alloy according to [ B4] and the composition according to [ B5 ].

[B10] A film material, characterized by using at least 1 selected from the group consisting of the polymer alloy according to [ B4] and the composition according to [ B5 ].

[B11] A laminate comprising at least 1 selected from the group consisting of the sheet described in [ B9] and the film described in [ B10 ].

[B12] A molded article characterized by being obtained by molding at least 1 selected from the group consisting of the sheet described in [ B9], the film described in [ B10] and the laminate described in [ B11 ].

[B13] The molded article according to [ B12], which is a food packaging container.

[C1] A method for producing a polymer, characterized by comprising polymerizing a raw material of a polymer containing a regenerated styrene monomer which is a product obtained by a thermal decomposition treatment of a waste polystyrene product and contains styrene.

[C2] The method for producing a polymer according to [ C1], wherein the polymerization comprises continuously reacting a mixture of raw materials containing the polymer in 2 or more reaction tanks.

Effects of the invention

According to the present invention, there can be provided a recycled styrene monomer which is a recycled product of a waste polystyrene product and which is reduced in energy consumption in production, a styrene resin, a styrene- (meth) acrylic copolymer, a polymer alloy, a composition, a sheet, a film, a laminate, a molded body, and a method for producing a polymer using the recycled styrene monomer, using the recycled styrene monomer.

Drawings

FIG. 1 is a schematic view showing one embodiment of a process for producing a regenerated styrene monomer.

FIG. 2 is a schematic view showing one embodiment of a method for producing a polymer using a continuous bulk polymerization line.

Detailed Description

(method for producing Polymer)

The method for producing the polymer of the present invention is not particularly limited as long as it is a method of polymerizing a raw material of the polymer containing a regenerated styrene monomer and, if necessary, other monomers.

The other monomer is not particularly limited, and examples thereof include a multi-branched macromonomer, (meth) acrylic monomer, and styrene-based monomer other than styrene. Details of these monomers will be described later.

< regenerated styrene monomer >

The regenerated styrene monomer of the present invention is a product obtained by thermal decomposition treatment of waste polystyrene products, and contains styrene.

Production of styrene by thermal decomposition treatment of waste polystyrene productsIn the case of olefins, energy consumption and CO can be expected more than in the case of styrene production from petroleum ₂ The reduction of the discharge amount is also preferable from the viewpoint of Life Cycle Assessment (LCA).

The regenerated styrene monomer is excellent in quality, but contains a small amount of impurities within a range that does not have any adverse effect on practical use.

As impurities, aromatic compounds such as toluene, benzene, cumene, dimer, trimer, ethylbenzene, α -methylstyrene, n-propylbenzene, phenylacetylene, and the like may be contained in a small amount in the regenerated styrene monomer without being completely removed.

As the impurities, inorganic substances such as silicon, copper, iron, titanium, and carbon may be contained.

In addition, as impurities, a small amount of cyclohexadiene compounds such as 1, 3-cyclohexadiene, 2-ethyl-1, 3-cyclohexadiene, 2-vinyl-1, 3-cyclohexadiene, 2-methyl-1, 3-cyclohexadiene, 1, 4-cyclohexadiene, 2-ethyl-1, 4-cyclohexadiene, 2-vinyl-1, 4-cyclohexadiene, and 2-methyl-1, 4-cyclohexadiene, and cyclohexene compounds such as cyclohexene and cyclohexenehexane may be contained.

The content of the impurities in the regenerated styrene monomer is usually not more than 10 mass%, may be not more than 5 mass%, may be not more than 3 mass%, and may be not more than 1 mass%, and the lower limit is not particularly limited, and is usually more than 0 mass%. These upper and lower limits may be arbitrarily combined. The content of impurities in the regenerated styrene monomer is usually more than 0 mass% and 10 mass% or less, may be more than 0 mass% and 5 mass% or less, may be more than 0 mass% and 3 mass% or less, and may be more than 0 mass% and 1 mass% or less.

The content of the inorganic component in the regenerated styrene monomer is usually not more than 0.1 mass%, may be not more than 0.01 mass%, and may be not more than 0.001 mass%, and the lower limit is not particularly limited, and is usually more than 0 mass%. These upper and lower limits may be arbitrarily combined. The content of the inorganic substance in the regenerated styrene monomer is usually more than 0 mass% and 0.1 mass% or less, may be more than 0 mass% and 0.01 mass% or less, may be more than 0 mass% and 0.001 mass% or less, and may be more than 0 mass% and 1 mass% or less.

The regenerated styrene monomer contains styrene as a constituent component in addition to the above impurities. The purity of styrene in the regenerated styrene monomer differs depending on the purification method of the regenerated styrene monomer.

The regenerated styrene monomer is obtained by thermal decomposition treatment of waste polystyrene products. An example of a method for obtaining a regenerated styrene monomer by thermal decomposition of waste polystyrene products will be described below.

The waste polystyrene product is a waste polystyrene product such as an unnecessary polystyrene product or a used polystyrene product. In the polystyrene product, the proportion of styrene as a constituent of the polymer is not particularly limited.

The waste polystyrene products subjected to the thermal decomposition treatment can be subjected to the thermal decomposition treatment in their entirety without being particularly screened.

For example, although the polystyrene product may have a colored product in addition to a non-colored product, only the non-colored polystyrene product can be used without any limitation in recycling the material. Colored polystyrene articles (e.g., black polystyrene articles) can only be recycled into articles for specific uses such as hangers. In the recycling of materials, there are a distinction between non-colored polystyrene products and colored polystyrene products in the recycling of products, and only non-colored polystyrene products other than colored polystyrene products are subjected to material recycling by the remelting method.

In one embodiment of the thermal decomposition treatment of the waste polystyrene product, the colored polystyrene product (for example, black polystyrene product) and the non-colored polystyrene product are not distinguished, but the regenerated styrene monomer and even the non-colored regenerated polystyrene product in which it is used can be produced from the waste polystyrene product including the colored polystyrene product (for example, black polystyrene product) and the non-colored polystyrene product.

Here, the colored (colored) polystyrene product refers to a polystyrene product to which a coloring agent such as a pigment is added to color a non-colored polystyrene product.

Before subjecting the waste polystyrene products to the thermal decomposition treatment, a step of pulverizing the waste polystyrene products to obtain pulverized waste polystyrene may be further provided as necessary.

That is, the waste polystyrene product may be pulverized to obtain a pulverized product of the waste polystyrene product, and the pulverized product may be subjected to thermal decomposition treatment. In the present specification, the thermal decomposition treatment of the pulverized product is also included in the "thermal decomposition treatment of the waste polystyrene product".

A condensable oil (hereinafter, sometimes referred to as "monomer oil component") containing styrene is obtained from a thermal decomposition product produced by thermally decomposing a waste polystyrene product, and the condensable oil is purified to obtain a regenerated styrene monomer containing styrene.

One embodiment of this method can be divided into the following steps.

A step of thermally decomposing waste polystyrene products using a thermal decomposition apparatus (hereinafter, may be referred to as "thermal decomposition treatment step")

A step of supplying steam generated by thermal decomposition to a condenser, and removing a gas flame component from a thermal decomposition product obtained by mixing a styrene-containing oil component and a gas flame (gas flare) component (hereinafter, may be referred to as "oil component obtaining step")

A step of distilling a styrene-containing oil component using a distillation column for purifying a regenerated styrene monomer (hereinafter, may be referred to as "distillation purification step")

Hereinafter, the details will be further described with reference to fig. 1.

< thermal decomposition treatment Process >)

In the thermal decomposition treatment step, the waste polystyrene product is thermally decomposed using a thermal decomposition apparatus.

As shown in fig. 1, when the waste polystyrene product 1 is thermally decomposed by the thermal decomposition device a, steam (decomposition gas) 10 is generated. The thermal decomposition product obtained in the form of steam comprises a monomer oil component 14 and a gas flame component 15.

Here, the gas flame component refers to a gas component and a coke component.

The type of the thermal decomposition device is not particularly limited as long as the thermal decomposition product containing the monomer oil component 14 and the gas flame component 15 can be obtained from polystyrene as described above, and for example, a thermal decomposition device using microwaves is preferable.

The term "microwave" means an electromagnetic wave having a wavelength of 1m to 1 mm or an electromagnetic wave having a frequency of 300MHz (0.3 GHz) to 300 GHz.

Preferably, the microwaves suitable for use in this embodiment are electromagnetic waves having a frequency of about 915MHz to about 2450 MHz.

Examples of the microwave source include a magnetron.

The waste polystyrene product subjected to the thermal decomposition treatment is preferably subjected to the addition of a catalyst for initiating the microwave thermal decomposition of the waste polystyrene product.

Such a catalyst is not particularly limited as long as it absorbs microwaves and transfers heat to the waste polystyrene products to contribute to the thermal decomposition reaction of the waste polystyrene products, and may be appropriately selected according to the purpose, and for example, a catalyst containing a compound having a high dielectric loss at the frequency of microwaves is preferable.

Alternatively, the catalyst may be a catalyst composed of carbonaceous residue from a previously performed thermal decomposition reaction, ceramic beads containing a microwave absorbing additive, particles containing a microwave absorbing additive, or a combination thereof. In this case, examples of the microwave absorbing additive include silicon carbide and boron nitride.

Alternatively, the catalyst may be a catalyst composed of a carbon compound containing about 80 to about 90 mass% of carbon, and examples thereof include graphite.

In the raw material to be subjected to the thermal decomposition treatment after combining the catalyst and the waste polystyrene product, the content of the catalyst is preferably 0.5 to 50% by mass, more preferably 0.5 to 5% by mass, and still more preferably 0.5 to 2.5% by mass.

The waste polystyrene products are heated in the thermal decomposition device by absorbing the microwaves and the catalyst in the inner wall of the thermal decomposition device using the microwaves and the catalyst for a time sufficient for the heat to be generated, thereby decomposing the polystyrene.

The temperature of the thermal decomposition treatment of the waste polystyrene is preferably about 300 to about 650 c, more preferably about 300 to about 450 c.

If the waste polystyrene product is thermally decomposed using the thermal decomposition device a, the above-mentioned steam (mixture of the monomer oil component and the gas flame component) 10 is generated. The slurry component 11 remains in the apparatus. The steam 10 is separated by condensation using a condenser c, thereby being separated into a monomer oil component 14 and a gas flame component 15.

When the waste polystyrene product is thermally decomposed using the thermal decomposition device a, thermal decomposition treatment using the thermal decomposition device a may be performed a plurality of times. The steam 10 may be obtained by setting a plurality of thermal decomposition treatment processes.

The thermal decomposition treatment is preferably performed without adding oxygen.

Here, "no oxygen is added" means that no molecular oxygen (O) is added ₂ ) And (4) qi.

In the thermal decomposition reaction of the present invention, it is preferable that molecular oxygen (O) is not added ₂ ) The thermal decomposition treatment is started when the oxygen content in the thermal decomposition apparatus is a residual amount suitable for thermal decomposition.

Here, the desired content of oxygen remaining in the thermal decomposition device is preferably about 10 vol% or less, and more preferably about 5 vol% or less.

The thermal decomposition device may be provided with an anaerobic means for purifying the thermal decomposition device.

Examples of the anaerobic means include the above-mentioned inert gas and fluid.

As the fluid, water may be used.

Examples of the inert gas include argon, nitrogen, and steam.

Further, as the anaerobic means, a vacuum source such as a vacuum pump or a venturi tube may be mentioned.

As the anaerobic means, the above-mentioned inert gas, fluid, vacuum source or a combination thereof may be used.

In the present invention, the steam generated by the evaporation of the initial water present in the product can purify the atmosphere in the thermal decomposition device to achieve anaerobic thermal decomposition.

Therefore, in the present invention, the thermal decomposition treatment is preferably performed under steam purging.

Alternatively, a predetermined amount of water may be added to the waste polystyrene products in order to reliably perform appropriate purification of the air by evaporation of water.

Molecular oxygen (O) ₂ ) Although the gas is not added to the thermal decomposition apparatus, the waste may contain a large amount of oxygen. In the present invention, if the moisture is evaporated and the temperature is raised before the thermal decomposition reaction is started, the air existing in the thermal decomposition device is discharged by the steam generated in the thermal decomposition device, and therefore the thermal decomposition reaction can be caused not in the air but in the steam atmosphere. The air is expelled and the thermal decomposition device is sealed when the air reaches a suitable temperature and internal pressure. In the present invention, the thermal decomposition may be carried out not by a thermal decomposition which is carried out in a nitrogen or argon atmosphere and does not contain oxygen at all, which is generally carried out as an anaerobic means, but by a steam thermal decomposition which does not introduce additional oxygen.

By performing thermal decomposition using microwaves, it is possible to uniformly heat polystyrene from the inside in the thermal decomposition device more efficiently than in a thermal decomposition furnace using a general external heater, to increase the thermal decomposition rate, and to improve the purity of styrene monomer in the monomer oil component.

< separation Process >)

The slurry component 11 produced in the thermal decomposition treatment step is preferably subjected to a separation step.

The separation step is a step of removing the solid matter 13 from the slurry component 11 by using the separator b for the slurry component 11 generated by the thermal decomposition.

That is, it is preferable that the slurry component 11 generated by thermal decomposition is subjected to a thermal decomposition treatment again by the thermal decomposition device a by removing solid matter from the slurry component 11 by the separation device b and removing solid matter from the clarified slurry 12 from which the solid matter has been removed.

For example, as shown in fig. 1, when polystyrene is thermally decomposed using a thermal decomposition device a, a slurry component 11 generated in the device is treated using a separation device b. The clarified slurry 12 and solid matter (coke/inorganic matter) 13 are separated by the separator b, and the clarified slurry 12 is fed again to the thermal separator a.

Here, the coke is a carbonaceous by-product generated by thermal decomposition.

The impurities contained in the waste polystyrene products, which are not required to be regenerated, can be removed by the separation device b. Examples of the inclusions include pigments used for coloring polystyrene products used in waste polystyrene products, molding components used for producing products, and the like.

By adding a separation step, a regenerated styrene monomer of good quality can be efficiently produced. Further, in the thermal decomposition device, accumulation of the solid matter 13 can be suppressed, the number of times of washing in the thermal decomposition furnace can be reduced, and the monomer oil can be continuously produced.

< oil component obtaining step >

In the oil component obtaining step, steam generated by thermal decomposition is supplied to a condenser, and the gas flame component is removed from a thermal decomposition product in which the oil component containing styrene and the gas flame component are mixed, thereby obtaining the oil component containing styrene.

For example, thermal decomposition products generated by thermal decomposition treatment of waste polystyrene products are condensed and separated by utilizing the difference in boiling point, and separated into the monomer oil component 14 and the gas flame component 15. Then, the monomer oil component 14 is supplied to a distillation purification step. As shown in fig. 1, steam 10 generated by the thermal decomposition process is supplied to the condenser c.

The condenser c includes a cooling pipe through which cooling water flows, and cools the steam (decomposition gas) discharged from the thermal decomposition device a to condense and separate the high boiling point component. In the condenser c, the monomer oil component 14 as the separated high boiling point component is supplied to the first distillation column d, and the gas flame component 15 as the uncondensed low boiling point component is discharged to the outside of the container of the condenser.

< distillation purification Process >)

In the distillation purification step, the oil component containing styrene is distilled using a distillation column for purifying the regenerated styrene monomer.

For example, the monomer oil component 14 is distilled and purified using a distillation column, and thereby separated into styrene and other components. As shown in fig. 1,2 distillation columns were used. In the first distillation column d, a benzene/toluene/ethylbenzene component 16 is mainly separated from the monomer oil 14, and the remaining component is supplied to the second distillation column e. Subsequently, in the second distillation column e, the dimer component/other (α -methylstyrene, etc.) component 17 is separated to obtain a regenerated styrene monomer 2.

Here, the dimer component may contain oligomers such as trimers in addition to dimers.

The regenerated styrene monomer thus obtained is a styrene monomer of good quality. Therefore, the regenerated polystyrene produced using the regenerated styrene monomer obtained in the present invention is a good regenerated polystyrene exhibiting the same strength and color as those of polystyrene derived from naphtha.

The production process of the regenerated styrene monomer for producing the regenerated styrene monomer through the thermal decomposition treatment process, the oil component obtaining process and the distillation purification process is CO ₂ The method of (4) is a production method in which the amount of discharge is suppressed.

Therefore, such a manufacturing process is considered to be a manufacturing method with a high Life Cycle Assessment (LCA) evaluation.

< polymerization method >

Polymerization reaction various general polymerization methods of styrenic monomers can be applied. The polymerization method is not particularly limited, and the reaction is preferably carried out by a solution polymerization method or a bulk polymerization method. In particular, in order to increase the weight molecular weight of the obtained resin, it is preferable to use the bulk polymerization method, and in this case, it is also possible to carry out the polymerization without adding an organic solvent, but when a small amount of an organic solvent is used in combination, the viscosity of the reaction product is lowered, and the control of the polymer molecular weight is easy, so that it is preferable.

As the organic solvent which can be used in the case of carrying out the polymerization by the solution polymerization or bulk polymerization method, it is preferable that the chain transfer constant is 0.1X 10 ^-5 ～1×10 ^-4 More preferably 0.2X 10, is used ^-5 ～0.8×10 ^-5 The organic solvent of (1). Examples thereof are preferably toluene, ethylbenzene, xylene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, anisole, cyanobenzene, dimethylformamide, N-dimethylacetamide, methyl ethyl ketone, and the like. The amount of the polymer is preferably 2 to 50 parts by mass, and more preferably 3 to 20 parts by mass, based on 100 parts by mass of the raw material of the polymer. When polymerization is carried out using an organic solvent, the formation of insoluble components in the organic solvent is also easily suppressed.

In particular, when the amount of the multi-branched macromonomer added is increased, the organic solvent is required to be used from the viewpoint of suppressing gelation. This makes it possible to increase the amount of the multi-branched macromonomer added.

In the method for producing a polymer, a radical polymerization initiator is substantially used. As such an initiator, a substance having a temperature of 65 to 165 ℃ with a half-life of 10 hours is preferable, and a substance having a temperature of 70 to 160 ℃ with a half-life of 10 hours is more preferable.

Examples of the radical polymerization initiator include peroxides such as 1, 1-bis (t-butylperoxy) cyclohexane, 2-bis (t-butylperoxy) butane and 2, 2-bis (4, 4-dibutylperoxycyclohexyl) propane, hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide and di-t-hexyl peroxide, diacyl peroxides such as benzoyl peroxide and dicumyl peroxide, peroxybenzoate, di-t-butyl peroxyisophthalate, peroxyesters such as t-butyl peroxyisopropylmonocarbonate, N ' -azobisisobutyronitrile, N ' -azobis (cyclohexane-1-carbonitrile), N ' -azobis (2-methylbutyronitrile), N ' -azobis (2, 4-dimethylvaleronitrile), and N, N ' -azobis [2- (hydroxymethyl) propionitrile ].

The amount of these additives is preferably 50ppm to 1000ppm, more preferably 100 to 500ppm, because when less than 50ppm is added to the raw material of the polymer, the productivity of the polymer decreases, and when more than 1000ppm, it is difficult to control the molecular weight.

Further, a chain transfer agent may be added so that the molecular weight of the resulting polymer is not excessively large. As the chain transfer agent, a monofunctional chain transfer agent having 1 chain transfer group may be used, and a polyfunctional chain transfer agent having a plurality of chain transfer agents may also be used. Examples of the monofunctional chain transfer agent include alkyl mercaptans and thioglycolates.

Examples of the polyfunctional chain transfer agent include those obtained by esterifying a hydroxyl group of a polyhydric alcohol such as ethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol or sorbitol with thioglycolic acid or 3-mercaptopropionic acid.

In the method for producing a polymer, for example, a mixture of raw materials containing a polymer is continuously reacted in 2 or more reaction tanks.

More specifically, in the method for producing a polymer, for example, a raw material of the polymer, an organic solvent, and an organic peroxide are uniformly mixed and continuously supplied to a reaction tank as a mixture. At this time, at least 2 or more reaction vessels are used, and the reaction vessels are connected so that the reaction rate of the monomer in the first reaction vessel becomes higher as the reaction vessel proceeds to the second and subsequent reaction vessels. In order to continuously react the monomers using each tank, the reaction can be carried out as follows: when the reaction has proceeded to some extent, the monomer is added, or a part of the reaction mixture in the previous reaction tank is allowed to flow in to advance the reaction. In this case, if the inflow amount and the outflow amount are relatively small, the reaction proceeds continuously, and if the number of reaction vessels is large, the inflow amount and the outflow amount can be increased. Of course, a semi-batch continuous production method may be employed, in which polymerization is carried out in the previous reaction tank and, when the target reaction rate is substantially reached, a reaction is carried out by adding an equivalent amount, for example, about half of the amount of the reaction tank, to the next reaction tank.

The number of reaction vessels in the method for producing a polymer is preferably 3 to 5 in terms of a general reaction vessel or cylindrical reactor, and is preferably 3 to 7 in the case of a circulation system.

In each reaction tank, the polymerization temperature of the reaction solution needs to be substantially uniformly stirred and mixed in the range of 100 to 170 ℃, and if the polymerization temperature is lower than 100 ℃, the polymerization time becomes long, the productivity is lowered, the economy is poor, and if it is higher than 170 ℃, dimers and trimers may be formed, and the physical properties of the obtained polymer may be lowered. The reaction temperature in each tank is preferably substantially constant, but it is preferable to set the temperature higher than that in the previous reaction tank because it is necessary to further progress the polymerization in the latter reaction tank.

The average residence time in each reaction vessel is preferably in the range of 1 to 7 hours. By setting the amount to this range, polymerization control can be stably performed, and a polymer with high quality can be produced. If the residence time is shorter than 1 hour, the amount of the radical polymerization initiator used may be increased, and the control of the polymerization reaction may be difficult. Preferably for 2 hours or more. If it exceeds 7 hours, the productivity is lowered, so that it is more preferably 6 hours or less. The reaction time in each tank may be substantially constant, but it is preferable to set the reaction time to be longer than that in the previous reaction tank because it is necessary to further advance the polymerization in the latter reaction tank.

In each reaction tank, heat is generated by the polymerization reaction and stirring, and therefore the polymerization temperature is controlled by heat removal and, in some cases, heating. Examples of the temperature control include jacket, heat transfer and heat removal or heating by circulation of a heat medium, and cooling and heating supply of the monomer.

In the final reaction tank, it is extremely important that the polymer content in the reaction mixture is substantially constant in the range of 40 to 100 mass%, and the polymer content is preferably in the range of 60 to 90 mass%, more preferably 65 to 85 mass%, in terms of stable production.

The method for producing the polymer is not particularly limited, and polymerization can be carried out in any of (1) a multistage complete mixing tank (STR), (2) a plurality of plug flow type reactors (PTR, tower polymerizers), and (3) STR + PTR.

Further, the method for producing a polymer by continuous bulk polymerization is not particularly limited, and is preferably a method in which in a continuous bulk polymerization line of a tubular reactor (tubular reactor having a static mixing member), which is a reaction tank in which one or more stirring type reactors (reaction tanks) and a plurality of mixing members having no movable parts fixed therein are combined, the uniformity of the molecular weight of the polymer can be maintained by continuously performing bulk polymerization while performing static mixing by the tubular reactor.

Examples of the plurality of mixing members fixed inside the tubular reactor include members for mixing the polymerization liquid by changing the flow direction and the division of the flow of the polymerization liquid flowing into the pipe and repeating the flow of the polymerization liquid, and examples of such tubular reactors include SMX type and SMR type Sulzer type tubular mixers, kenics type static mixers, and dongli type tubular mixers, and particularly preferred are SMX type and SMR type Sulzer type tubular mixers.

When a polymer is produced using such a continuous bulk polymerization line, the reflux ratio (R = F1/F2) is preferably in the range of 3 to 15, where F1 (liters/hour) is the flow rate of the mixed solution that does not flow out to the non-circulating polymerization line (II) composed of one or more stirring reactors but flows back in the circulating polymerization line (I) composed of a tubular reactor, and F2 is the flow rate of the mixed solution that flows out from the circulating polymerization line (I) to the non-circulating polymerization line (II).

Next, a method for producing a polymer using the continuous bulk polymerization line will be described with reference to the process diagram of fig. 2.

The raw materials of the polymer and the like are first fed to a stirring type reactor 102 by a plunger pump 101, and after initial polymerization is carried out under stirring, fed to a cyclic polymerization line (I) having

tubular reactors

104, 105 and 106 equipped with static mixing members and a gear pump 107 by a gear pump 103.

With respect to the initial polymerization in the stirred reactor 102, the total polymerization conversion rate to all monomers is carried out to 10 to 40% by mass, preferably 14 to 30% by mass at the outlet of the stirred reactor 102. The agitation type reactor 102 includes, for example, an agitation type tank reactor, an agitation type column reactor, and the like, and the agitation blades include, for example, anchor type, turbine type, screw type, double screw type, logbore type, and the like.

Subsequently, the polymerization liquid is circulated and polymerized in the circulating polymerization line I, and a part of the polymerization liquid is sent to the following non-circulating polymerization line II. Here, regarding the reflux ratio R, which is the ratio of the flow rate of the polymerization liquid circulating in the circulating polymerization line I to the flow rate of the polymerization liquid flowing out to the non-circulating polymerization line II, when the flow rate of the mixed solution that does not flow out to the non-circulating polymerization line II but flows back in the circulating polymerization line I is F1 (liter/hour) and the flow rate of the mixed solution flowing out from the circulating polymerization line I to the non-circulating polymerization line II is F2 (liter/hour), R = F1/F2 is preferably in the range of usually 3 to 15.

The polymerization in the circulating polymerization line I is carried out so that the total polymerization conversion of all the monomers at the outlet of the circulating polymerization line I is usually 30 to 70% by mass, preferably 35 to 65% by mass. As the polymerization temperature, 120 to 140 ℃ is suitable.

On the other hand, the

tubular reactors

108, 109, and 110 and the gear pump 111 form a non-circulating polymerization line II, and a part of the polymerization liquid in the circulating polymerization line I flows into the polymerization line II, and polymerization is performed in the polymerization line II to a desired degree of polymerization. The polymerization temperature in the non-circulating polymerization line II is usually 130 to 160 ℃ polymerization temperature, and polymerization is continued until the polymerization conversion rate reaches 60 to 90 mass%.

Then, the mixed solution is sent to a preheater and a subsequent devolatilization tank by means of a gear pump 111, and after unreacted monomers and a solvent are removed under reduced pressure, the mixed solution is pelletized to obtain a target polymer.

(styrene resin)

The styrene-based resins are 1 type of the polymer obtained by the method for producing a polymer of the present invention.

The styrenic resin can be obtained by polymerizing a raw material of a polymer containing a regenerated styrene monomer. In other words, a styrenic resin is a polymer formed from a raw material of a polymer containing the regenerated styrene monomer of the present invention.

Examples of the styrene resin include the following resins.

(1) Homopolymers of styrene

(2) Resin obtained by graft-polymerizing a rubber-like polymer in a continuous phase comprising a homopolymer of styrene and dispersing the polymer particles

(3) Resin obtained by graft-polymerizing a rubber-like polymer in a continuous phase comprising a copolymer of styrene and a multi-branched macromonomer to disperse the particles

(4) Copolymers of styrene and highly branched macromonomers

The copolymer can be obtained by polymerizing a raw material of a polymer containing a regenerated styrene monomer and a multi-branched macromonomer.

The above (2) and (3) may be referred to as "impact-resistant styrene resins".

In the present specification, a styrene-based resin means a polymer in which 98% by mass or more of the constituent components of the polymer is styrene. When the styrene-based resin contains a rubbery polymer, the rubbery polymer is not contained in the constituent components of the polymer.

The styrene constituting the styrene-based resin may contain styrene other than styrene contained in the regenerated styrene monomer. The ratio [ a/(a + B) ] of the styrene (a) and the other styrene (B) contained in the regenerated styrene monomer in the styrene-based resin is not particularly limited, but is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 100% by mass.

< impact-resistant styrene-based resin >)

Examples of the rubbery polymer contained in the impact-resistant styrene-based resin include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, and the like. Particularly preferably, polybutadiene or a styrene-butadiene copolymer is contained.

The flowability of the impact-resistant styrene-based resin is preferably in the range of 1 to 10g/10 min from the viewpoint of molding stability (thickness stability, molding processability).

The content of the rubbery polymer contained in the impact-resistant styrene-based resin is preferably 1.5 to 15.0% by mass from the viewpoint of achieving both impact strength and processing characteristics during stretch molding. As the impact-resistant styrene-based resin having such characteristics, a commercially available product can be used as it is, or a resin having a high content of a rubber component may be used after mixing a usual polystyrene to adjust the content and fluidity of the rubber component to appropriate ranges.

The impact-resistant styrene-based resin can be produced, for example, by a method for producing a rubber-modified styrene-based resin composition described in jp 2007-269848 a (specifically, for example, the production method described in paragraphs [ 0085 ] to [ 0087 ]).

The resulting styrene resin (hereinafter, sometimes referred to as "recycled polystyrene") exhibited excellent strength when the strength was evaluated by the following measurement method. When the strength of the polystyrene derived from naphtha is assumed to be 100, the strength of the polystyrene obtained by recycling the material is about 90. When the strength of the polystyrene derived from naphtha is set to 100, the strength of the regenerated polystyrene in the present invention has a lower limit of usually higher than 90, preferably 95 or higher, more preferably 97 or higher, and still more preferably 99 or higher, and an upper limit of usually 100 or lower, which is not particularly limited. These upper and lower limits may be arbitrarily combined. When the strength of the polystyrene derived from naphtha is set to 100, the strength of the regenerated polystyrene may be 100 or more. When the strength of the polystyrene derived from naphtha is set to 100 in the future, the strength of the regenerated polystyrene obtained by the present invention is usually more than 90 and 100 or less, preferably 95 to 100, more preferably 97 to 100, and still more preferably 99 to 100.

[ method for measuring polystyrene Strength ]

The strength of polystyrene can be evaluated by tensile breaking stress according to JIS K7161-1 and 2, or by flexural strength according to JIS K7171, for example. In the case of rubber-modified polystyrene, the impact strength of a beam can be evaluated according to JIS K7111-1.

The obtained regenerated polystyrene exhibits a good hue in which yellowness is suppressed when the hue is evaluated by the following measurement method. Specifically, the hue is evaluated by the yellowness (YI value) or the like. The larger the YI value is, the stronger the yellow color is, and the larger the negative value is, the stronger the blue color is. The YI value of the recycled polystyrene obtained in the present invention is lower than that of polystyrene obtained by recycling a material, and Δ YI, which is the difference between YI values, is usually 0.1 or more, preferably 0.3 or more, more preferably 0.5 or more, and further preferably 1.0 or more. There is no particular upper limit for Δ YI.

[ method for measuring hue of polystyrene ]

The hue of polystyrene can be measured, for example, according to JIS K7373.

< Multi-branched macromonomer >)

The hyperbranched macromonomer is used for imparting a hyperbranched structure to the copolymer.

The multi-branched macromonomer has a plurality of branches and a plurality of polymerizable double bonds at the end thereof.

The weight average molecular weight (Mw) of the multi-branched macromonomer is not particularly limited, but is preferably 1000 to 30000, more preferably 2000 to 10000.

[ GPC measurement ] the molecular weight of the multi-branched macromonomer (a 4) was measured by gel permeation chromatography (hereinafter, abbreviated as "GPC") using "HPLC8010" manufactured by Tosoh corporation under the conditions of column ShodexKF 802X 2+ KF803+ KF804, solvent THF, and flow rate 1.0 ml/min.

The content of the polymerizable double bond in the molecule of the multi-branched macromonomer is not particularly limited, but is preferably 1.0 to 5.0mmol/g, more preferably 1.5 to 3.5mmol/g.

One of the multi-branched macromonomers is a multi-branched macromonomer having a branched structure composed of an electron-withdrawing group and a saturated carbon atom in which all of 3 bonds other than the bond to the electron-withdrawing group are bonded to a carbon atom, and a double bond directly bonded to an aromatic ring.

The multi-branched macromonomer is preferably a multi-branched macromonomer having a repeating unit represented by the following general formula (I). The multi-branched macromonomer (m-1) is represented by AB ₂ Hyperbranched macromonomers derived from type monomers.

[ solution 1]

[ in the formula, Y ₁ Is selected from-CN, -NO ₂ 、-CONH ₂ 、-CON(R) ₂ 、-SO ₂ CH ₃ 、-P(＝O)(OR) ₂ (wherein R represents an alkyl group or an aryl group),

Y ₂ is arylene, -O-CO-or-NH-CO-,

z is selected from the group consisting of- (CH) ₂ ) _n O-、-(CH ₂ CH ₂ O) _n -、-(CH ₂ CH ₂ CH ₂ O) _n -a group of the group consisting of, and when Y ₂ is-O-CO-or-NH-CO-time Z represents- (CH) ₂ ) _n -、-(CH ₂ ) _n Ar-、-(CH ₂ ) _n O-Ar-、-(CH ₂ CH ₂ O) _n -Ar-, or- (CH) ₂ CH ₂ CH ₂ O) n-Ar- (wherein Ar is aryl)]。

Here, it is preferable that Y is ₂ For example, is selected fromArylene groups in the group consisting of,

[ solution 2]

Wherein, Y ₁ is-CN, Y ₂ Is phenylene. At Y ₂ In the case of phenylene, the binding position of Z may be any of ortho, meta or para positions, and is not particularly limited, but para is preferable. The number of repetitions n of Z is not particularly limited, but is preferably 1 to 12, more preferably 2 to 10, from the viewpoint of solubility in styrene.

The above multi-branched macromonomer (m-1) having a branched structure is obtained in the presence of a basic compound as follows: (1) So that 1 molecule has an active methylene group and an AB having a leaving group in nucleophilic substitution reaction of the active methylene group ₂ A multi-branched self-condensed polycondensate obtained by nucleophilic substitution of a monomer as a precursor; (2) The remaining unreacted active methylene group or methine group in the polycondensate is subjected to nucleophilic substitution reaction with a compound having a double bond directly bonded to the aromatic ring and a leaving group in nucleophilic substitution reaction of the active methylene group in 1 molecule.

Here, the leaving group in the nucleophilic substitution reaction of active methylene is halogen bonded to saturated carbon atom, -OS (= O) ₂ R (R represents an alkyl group or an aryl group) and the like, and specific examples thereof include a bromine, a chlorine, a methylsulfonyloxy group, a toluenesulfonyloxy group and the like.

The basic compound is preferably a strong base such as sodium hydroxide or potassium hydroxide, and is used as an aqueous solution during the reaction.

AB as leaving group in nucleophilic substitution reaction with active methylene and active methylene in 1 molecule ₂ Examples of the monomer include halogenated alkoxy-phenylacetonitriles such as bromoethoxy-phenylacetonitrile and chloromethylbenzyloxy-phenylacetonitrile, tosyloxy- (vinyloxy) -phenylacetonitrile and tosyloxy-bis (vinyloxy) -phenylacetonitrile having tosyloxy groupPhenyl acetonitriles of the group.

Representative examples of the compound having a leaving group in the nucleophilic substitution reaction of a double bond directly bonded to an aromatic ring and an active methylene group in 1 molecule include chloromethyl styrene and bromomethyl styrene.

The above-mentioned (1) is a reaction for synthesizing a polycondensate as a precursor, and (2) is a reaction for synthesizing a multi-branched macromonomer by introducing a double bond directly bonded to an aromatic ring into the precursor. (1) The reaction of (2) and the reaction of (3) may be carried out in the same reaction system, or may be carried out in the same reaction system. The molecular weight of the multi-branched macromonomer (m-1) can be controlled by changing the compounding ratio of the monomer to the basic compound.

As another preferable example of the multi-branched macromonomer, a multi-branched macromonomer having a branched structure formed by repeating structural units selected from an ester bond, an ether bond and an amide bond and an olefinic double bond at the end of the branch is preferable.

The multi-branched macromonomer having an ester bond as a repeating structural unit is obtained by introducing an ethylenic double bond such as a vinyl group or an isopropenyl group into a multi-branched polyester polyol having a molecular chain in which a carbon atom adjacent to a carbonyl group forming an ester bond of the molecular chain is a saturated carbon atom and all hydrogen atoms on the carbon atom are substituted. When an olefinic double bond is introduced into the multi-branched polyester polyol, the reaction can be carried out by esterification or addition reaction. The polyester polyols are commercially available from Perstorp corporation as "BoltornH20, H30, and H40".

The multi-branched polyester polyol may have a substituent introduced in advance to a part of the hydroxyl groups thereof through an ether bond or other bond, and a part of the hydroxyl groups thereof may be modified by an oxidation reaction or other reaction. In addition, a part of the hydroxyl groups of the multi-branched polyester polyol may be esterified in advance.

Typical examples of such a multi-branched macromonomer include: a monomer obtained by reacting a monocarboxylic acid having a saturated carbon atom as the carbon atom adjacent to the carboxyl group, having all of the hydrogen atoms on the carbon atom substituted, and having 2 or more hydroxyl groups with a compound having 1 or more hydroxyl groups to produce a multi-branched polymer, and then reacting the hydroxyl group as the terminal group of the polymer with an unsaturated acid such as acrylic acid or methacrylic acid, an isocyanate group-containing acrylic compound, or the like. A multi-branched polymer having an ester bond as a repeating structural unit is also described in "Angew. Chem. Int. Ed. Engl.29" p138 to 177 (1990) by Tamalia et al.

Examples of the compound having 1 or more hydroxyl groups include: hydroxyl-containing polymers produced by reacting a) aliphatic, alicyclic or aromatic diols, b) triols, c) tetrols, d) sugar alcohols such as sorbitol and mannitol, e) anhydrononane heptanol or dipentaerythritol, f) alpha-alkyl glucosides such as alpha-methyl glucoside, g) monofunctional alcohols such as ethanol and hexanol, h) hydroxyl groups of 1 or more alcohols selected from any of a) to g) with a molecular weight of up to 8000, and alkylene oxides or derivatives thereof.

Examples of the aliphatic diol, alicyclic diol and aromatic diol include 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, polytetrahydrofuran, dimethylolpropane, neopentyl propane, 2-propyl-2-ethyl-1, 3-propanediol, 1, 2-propanediol, 1, 3-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol; cyclohexanedimethanol, 1, 3-bis

Alkane-5, 5-dimethanol; 1, 4-xylyl dimethanol, 1-phenyl-1, 2-ethylene glycol, and the like.

Examples of the triol include trimethylolpropane, trimethylolethane, trimethylolbutane, glycerol, and 1,2, 5-hexanetriol.

Examples of the tetrols include pentaerythritol, ditrimethylolpropane, diglycerol, ditrimethylolethane, and the like.

Examples of the aromatic compound having 2 or more hydroxyl groups bonded to the aromatic ring include 1,3, 5-trihydroxybenzene, 1, 4-xylyl dimethanol, and 1-phenyl-1, 2-ethanediol.

Examples of monocarboxylic acids having a saturated carbon atom as the carbon atom adjacent to the carboxyl group, all of the hydrogen atoms of the carbon atom being substituted, and having 2 or more hydroxyl groups include dimethylolpropionic acid, α, α -bis (hydroxymethyl) butyric acid, α, α, α -tris (hydroxymethyl) acetic acid, α, α -bis (hydroxymethyl) valeric acid, and α, α -bis (hydroxymethyl) propionic acid. By using such a monocarboxylic acid, the ester decomposition reaction can be suppressed, and a multi-branched polyester polyol can be formed.

In addition, in the production of such a multi-branched polymer, a catalyst is preferably used, and examples of such a catalyst include dialkyltin oxide, halogenated dialkyltin, dialkyltin biscarboxylate, organotin compounds such as stannoxane, titanates such as tetrabutyltitanate, lewis acids, organic sulfonic acids such as p-toluenesulfonic acid, and the like.

Examples of the multi-branched macromonomer having an ether bond as a repeating structural unit include monomers obtained by reacting a compound having 1 or more hydroxyl groups with a cyclic ether compound having 1 or more hydroxyl groups to give a multi-branched polymer, and then reacting the hydroxyl groups as the terminal groups of the polymer with an unsaturated acid such as acrylic acid or methacrylic acid, an isocyanate group-containing acrylic compound, or a halogenated methylstyrene such as 4-chloromethylstyrene. Further, as a method for producing the multi-branched polymer, a method comprising reacting a compound having 1 or more hydroxyl groups with a compound having 2 or more hydroxyl groups and a halogen atom, -OSO ₂ OCH ₃ or-OSO ₂ CH ₃ The method of reacting the compound of (1) is also useful.

As the compound having 1 or more hydroxyl groups, the above-mentioned compounds can be used, and examples thereof include 3-ethyl-3- (hydroxymethyl) oxetane, 2, 3-epoxy-1-propanol, 2, 3-epoxy-1-butanol, 3, 4-epoxy-1-butanol and the like. The compound having 1 or more hydroxyl groups used in the Williamson ether synthesis method may be the above-mentioned compound, and is preferably an aromatic compound having 2 or more hydroxyl groups bonded to an aromatic ring. Typical examples of such compounds include 1,3, 5-trihydroxybenzene, 1, 4-xylyldimethanol, and 1-phenyl-1, 2-ethanediol.

In addition, the compound contains 2 or more hydroxyl groups and halogen atoms, -OSO ₂ OCH ₃ or-OSO ₂ CH ₃ Examples of the compound (2) include 5- (bromomethyl) -1, 3-dihydroxybenzene, 2-ethyl-2- (bromomethyl) -1, 3-propanediol, 2-methyl-2- (bromomethyl) -1, 3-propanediol, and 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propanediol.

In the production of the above-mentioned multi-branched polymer, a catalyst is usually preferably used, and examples of such a catalyst include BF ₃ Diethyl ether, FSO ₃ H、ClSO ₃ H、HClO ₄ And the like.

Examples of the multi-branched macromonomer having an amide bond as a repeating structural unit include multi-branched macromonomers having a structure in which an amide bond is repeated in the molecule through a nitrogen atom, and a typical multi-branched macromonomer is a Generation 2.0 (PAMAM dendrimer) manufactured by Dentoritech corporation.

The higher the number of double bonds directly bonded to the aromatic ring introduced into the multi-branched macromonomer, the higher the degree of branching of the multi-branched polystyrene as a copolymer with styrene. The Degree of Branching (DB) of the multi-branched macromonomer is defined by the following formula (3), and the range of the Degree of Branching (DB) is preferably 0.3 to 0.8.

DB = (D + L)/(D + T + L) · formula (3)

(wherein D represents the number of dendritic cells, L represents the number of linear cells, and T represents the number of terminal cells)

It is to be noted that D, L and T can be represented by ¹³ The active methylene group measured by C-NMR and the number of secondary, tertiary and quaternary carbon atoms derived from the reaction are determined, D corresponds to the number of quaternary carbon atoms, L corresponds to the number of tertiary carbon atoms, and T corresponds to the number of secondary carbon atoms.

The weight average molecular weight of the multi-branched polystyrene is preferably 1000 to 15000, more preferably 2000 to 5000, in order to control the weight average molecular weight of the multi-branched polystyrene to 1000 ten thousand or less.

The content of the double bond at the terminal position introduced into the multi-branched macromonomer is preferably from 0.1 mmol to 5.5 mmol, more preferably from 0.5 mmol to 3.5mmol, per 1g of the multi-branched macromonomer.

A styrene-based resin which is a mixture of a multi-branched polystyrene which is a copolymer of the multi-branched macromonomer and styrene and a linear polystyrene produced simultaneously is obtained by polymerizing the multi-branched macromonomer and styrene.

The blending ratio of the multi-branched macromonomer to styrene in the styrene resin is not particularly limited, but is preferably 50ppm to 1% by mass, more preferably 100ppm to 2000ppm by mass.

The weight average molecular weight of the styrene resin is not particularly limited, but is preferably in the range of 10 to 40 ten thousand as determined by GPC when the resin does not contain a multi-branched macromonomer, 15 to 70 ten thousand as determined by GPC-MALLS when the multi-branched macromonomer is used in combination, and more preferably in the range of 20 to 60 ten thousand from the viewpoint of productivity and processability. The styrene-based resin may be a single one or a mixture of a plurality of copolymers, and in the case of a mixture, the molecular weight of the mixture is preferably in the above range.

[ GPC-MALLS measurement ]

Note that the GPC-MALS measurement described above was carried out under conditions of Shodex HPLC, detector Wyatt Technology DAWNEOS, shodex RI-101, column Shodex KF-806 Lx 2, solvent THF, flow rate 1.0 ml/min. The analysis of GPC-MALLS measurement is performed by analysis software ASTRA of Wyatt corporation, and in addition to the weight average molecular weight, the slope of a molecular weight in a region of 25 to 1000 ten thousand in a log-log graph in which the molecular weight of the resin obtained by GPC-MALLS is plotted on the horizontal axis and the inertia radius is plotted on the vertical axis (the slope of an approximate straight line automatically calculated by the software is based only on the measured value of a linear portion obtained in the molecular weight range) is also included in the analysis of the styrene-based resin.

(styrene- (meth) acrylic acid copolymer)

The styrene- (meth) acrylic acid-based copolymer is 1 of the polymers obtained by the method for producing the polymer of the present invention.

The styrene- (meth) acrylic copolymer is obtained by copolymerizing a raw material of a polymer containing the regenerated styrene monomer of the present invention, (meth) acrylic monomer, and optionally other monomers. In other words, the styrene- (meth) acrylic copolymer in the present invention is a copolymer formed from a raw material of a polymer containing a regenerated styrene monomer, a (meth) acrylic monomer, and optionally other monomers.

In the present specification, the styrene- (meth) acrylic acid copolymer means a copolymer in which styrene accounts for more than 0 mass% and less than 98 mass% of the constituent components of the copolymer. The (meth) acrylic monomer may be contained in an amount of 2 mass% or more and less than 100 mass% of the remaining (meth) acrylic copolymer other than styrene.

The proportion of styrene in the styrene- (meth) acrylic copolymer is not particularly limited, and in the case of a molding resin, for example, it may be 50% by mass or more and less than 98% by mass, may be 70% by mass or more and less than 98% by mass, may be 85% by mass or more and less than 98% by mass, and may be 90% by mass or more and less than 98% by mass.

The proportion of styrene in the styrene- (meth) acrylic copolymer is not particularly limited, and in the case of an ink, for example, it may be 20 mass% or more and 50 mass% or less.

The proportion of styrene in the styrene- (meth) acrylic copolymer is not particularly limited, and may be, for example, 5 mass% or more and 50 mass% or less in the case of an adhesive or a coating agent.

The styrene constituting the styrene- (meth) acrylic copolymer may contain styrene other than styrene contained in the regenerated styrene monomer of the present invention. The ratio [ a/(a + B) ] of the styrene (a) and the other styrene (B) contained in the regenerated styrene monomer of the present invention in the styrene- (meth) acrylic copolymer is not particularly limited, and is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 100% by mass.

[ meth (acrylic) monomer ]

The (meth) acrylic monomer is not particularly limited as long as it is at least one of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester.

The acrylic acid ester and the methacrylic acid ester are preferably, for example, alkyl (meth) acrylates having an alkyl group or a substituted alkyl group having 1 to 6 carbon atoms. The substituted alkyl group herein means an alkyl group in which a part or all of hydrogen atoms of the alkyl group are substituted with a halogen atom, a hydroxyl group or the like, and examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like, and 2 or more kinds thereof may be used alone or in combination.

< other monomers >

The other monomer is not particularly limited, and examples thereof include styrene monomers other than styrene, acrylonitrile, methacrylonitrile, maleic anhydride, maleimide, core-substituted maleimide, and multi-branched macromonomers.

< styrene-based monomer >)

Examples of the styrenic monomer other than styrene include alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene, halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene, nitrostyrene, acetyl styrene, and methoxystyrene.

< Multi-branched macromonomer >

Examples of the multi-branched macromonomer include the multi-branched macromonomers described above.

The blending ratio of the multi-branched macromonomer to styrene in the styrene- (meth) acrylic copolymer is not particularly limited, and is preferably 50ppm to 1%, more preferably 100ppm to 2000ppm by mass.

The weight average molecular weight of the styrene- (meth) acrylic copolymer is not particularly limited, but is preferably in the range of 10 to 40 ten thousand as determined by GPC when a multi-branched macromonomer is not contained, or in the range of 15 to 70 ten thousand as determined by GPC-MALLS when a multi-branched macromonomer is used in combination, and more preferably in the range of 20 to 60 ten thousand from the viewpoint of productivity and processability.

[ GPC-MALLS assay ]

Incidentally, the aforementioned GPC-MALS measurement was carried out under conditions of Shodex HPLC, detector Wyatt Technology DAWNEOS, shodex RI-101, column Shodex KF-806 L.times.2, solvent THF, flow rate 1.0 ml/min. The analysis of GPC-MALLS measurement is performed by analysis software ASTRA of Wyatt corporation, and in addition to the weight average molecular weight, the slope of a molecular weight in a region of 25 to 1000 ten thousand in a log-log graph in which the molecular weight of the resin obtained from GPC-MALLS is plotted on the horizontal axis and the inertia radius is plotted on the vertical axis (the slope of an approximate straight line automatically calculated by the software based on only the measured value of a linear portion obtained in the molecular weight range) is also included in the analysis of the styrene-based resin.

(Polymer alloy)

The polymer alloy contains the polymer obtained by the method for producing a polymer of the present invention (hereinafter, may be referred to as "polymer of the present invention") and other polymers than the polymer, and further contains other components as necessary.

The polymer alloy is a mixture of 2 or more polymers in a molten state.

Examples of the other polymer include polyolefin, styrene-based elastomer, acrylic resin, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, polyester, polycarbonate, polyamide, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, polymethylpentene, polyvinyl alcohol, cycloolefin-based resin, polylactic acid, polybutylene succinate, polyacrylonitrile, polyethylene oxide, cellulose, polyimide, polyurethane, polyphenylene sulfide, polyphenylene ether, polyvinyl acetal, polybutadiene, polybutylene, polyamideimide, polyarylate, polyetherimide, polyetheretherketone, polyetherketone, polyethersulfone, polyketone, polysulfone, aramid, fluorine-based resin, polyacetal-based resin, and the like. They may also be modified.

The ratio of the polymer of the present invention to another polymer in the polymer alloy is not particularly limited, and may be 1/99 or more, 10/90 or more, 20/80 or more, and 30/70 or more in terms of a mass ratio (the polymer of the present invention/another polymer). The mass ratio (polymer of the present invention/other polymer) may be 99/1 or less, may be 90/10 or less, may be 80/20 or less, and may be 70/30 or less.

Examples of the other components include lubricants, plasticizers, inorganic fillers, colorants, heat stabilizers, antioxidants, ultraviolet absorbers, and anti-aging agents.

The following may be exemplified as the lubricant/plasticizer.

Examples thereof include: silicone oils such as dimethyl silicone and methylphenyl silicone; processing oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, vaseline, etc.; coal tar oils such as coal tar and coal tar pitch; fatty oils such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil, and the like; waxes such as tall oil, beeswax, carnauba wax, and lanolin; fatty acids such as ricinoleic acid, palmitic acid and stearic acid, or metal salts thereof; synthetic polymers such as petroleum resin, coumarone-indene resin, atactic polypropylene and the like; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; in addition, microcrystalline wax, liquid polybutadiene or a modified product thereof, or a hydride, liquid mercaptan, etc.

Examples of the inorganic filler include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, barium sulfate, aluminum sulfate, calcium sulfate, magnesium carbonate, phosphates such as calcium hydrogen phosphate, molybdenum disulfide, glass fiber, glass beads, fine pozzolan particles (Shirasu Balloon), graphite, alumina, hydrotalcite, zeolite, and the like.

The method for producing the polymer alloy is not particularly limited, and for example, a method of adding and mixing the respective components as appropriate, and then preparing the polymer alloy by dynamic heat treatment is exemplified.

The dynamic heat treatment here means kneading in a molten state. The dynamic heat treatment is preferably carried out in a non-open type apparatus such as a Banbury mixer, a kneader, a single-screw extruder or a twin-screw extruder, and is preferably carried out in an inert gas such as nitrogen gas.

In addition, a compatibilizing agent may be used in the manufacture of the polymer alloy.

(composition)

The composition of the present invention contains the polymer of the present invention, and further contains other components such as a colorant, water, and an organic solvent as required.

Examples of the composition include a coating agent, ink, and an adhesive.

The composition may be liquid or non-liquid.

The content of the polymer of the present invention in the coating agent is not particularly limited, and may be, for example, 5 to 90% by mass, 19 to 80% by mass, 20 to 80% by mass, or 30 to 70% by mass.

< coloring agent >

Examples of the colorant include organic and inorganic pigments and dyes used in general inks, paints, recording agents, and the like.

Examples of the organic pigment include azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene pigments, cyclic ketone pigments, quinacridone pigments, thioindigo pigments, and perylene pigments

Oxazine-based, isoindolinone-based, quinophthalone-based, azomethine azo-based, pyrrolopyrroledione-based, isoindoline-based pigments, and the like. Copper phthalocyanine is preferably used for the blue ink, and c.i. pigment No. yellow 83 is preferably used for the transparent yellow ink from the viewpoint of cost and light resistance.

Examples of the pigment c.i. number include Black (Black) 7, Y12, Y13, Y14, Y17, Y83, Y74, Y-154, Y180, R57: 1. r122, R48: 1. r48: 2. r48: 3. r53: 1. r146, R-150, R-166, R170, R184, R185, V19, V23, V32, O13, O16, O34, G7, G36, B15: 3. b15: 4. w6, and the like.

Examples of the inorganic pigment include carbon black, titanium oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, red iron oxide, aluminum, mica (mica), and the like. In terms of cost and coloring power, titanium oxide is preferably used for the white ink, carbon black is preferably used for the black ink, aluminum is preferably used for the gold or silver ink, and mica is preferably used for the pearl ink. The aluminum is in the form of powder or slurry, and is preferably used in the form of slurry from the viewpoint of handling and safety, and the floating type or non-floating type is suitably selected from the viewpoint of brightness and concentration. The colorant is preferably contained in an amount sufficient to secure the concentration and coloring power of the ink, that is, in a proportion of 1 to 50% by weight based on the total weight of the ink. Further, the coloring agent may be used alone or in combination of 2 or more.

The content of the colorant in the ink is not particularly limited, and is, for example, preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on the ink.

< Water >

The water may be pure water [ e.g., distilled water, ion-exchanged water, RO (Reverse Osmosis) water, etc. ], or may be tap water.

< organic solvent >

The organic solvent is not particularly limited, and examples thereof include a water-soluble solvent and a water-insoluble solvent.

In the present specification, the term "water-soluble solvent" means that the organic solvent and the same volume of pure water are gently stirred at 20 ℃ under 1 atmosphere, and the liquid mixture has a uniform appearance after the flow is stopped. On the other hand, the term "non-aqueous solvent" means that the mixture cannot maintain a uniform appearance after the flow of the solvent and the same volume of pure water are gently stirred at 20 ℃ under 1 atmosphere.

The water-soluble solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, and diethylene glycol methyl ether; ketones such as acetone; tetrahydrofuran, di

Ethers such as alkane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether.

Examples of the water-insoluble solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as hexane, heptane, octane, and the like; aromatic compounds such as benzene, toluene, xylene and cumene; and esters such as ethyl acetate and butyl acetate.

< coating agent >

The coating agent contains the polymer of the present invention, and further contains other components such as other polymers, water, and organic solvents, if necessary.

When a coating agent is used for imparting antifogging property, the coating agent contains the polymer of the present invention and an antifogging agent, and further contains other components such as a hydrophilic polymer, water, and an organic solvent as necessary.

The antifogging agent has a function of imparting antifogging property by improving wettability of a layer (coating layer) obtained from the coating agent.

Examples of the antifogging agent include nonionic antifogging agents and amphoteric antifogging agents.

The nonionic antifogging agent is not particularly limited, and examples thereof include sucrose fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene block copolymers, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene polyglycerin fatty acid esters, fatty acid alkanolamides, and the like. Among them, sucrose fatty acid esters, polyglycerol fatty acid esters, and sorbitan fatty acid esters are preferably used.

The amphoteric antifogging agent is not particularly limited, and examples thereof include alkylbetaines such as lauryl dimethylaminoacetic acid betaine and stearyl dimethylaminoacetic acid betaine: fatty acid amide propyl betaines such as cocamidopropyl betaine; alkylimidazoles such as 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline betaine; amino acids such as sodium lauroyl glutamate; amine oxides such as lauryl dimethylamine N-oxide and oleyldimethylamine N-oxide.

The content of the antifogging agent in the coating agent is not particularly limited, but is preferably 5% by mass or more, and more preferably 10 to 50% by mass, based on the nonvolatile component of the coating agent. It is preferable that the content of the antifogging agent is 5% by mass or more because high antifogging property can be obtained. Further, if the content of the antifogging agent is 50% by mass or less, the reduction in oil resistance can be suppressed or prevented, which is preferable.

The hydrophilic polymer has a function of imparting high oil resistance and antifogging property by being used in combination with the polymer of the present invention and the antifogging agent.

In the present specification, the term "hydrophilic polymer" refers to a water-soluble polymer other than the polymer of the present invention. The term "polymer" means a molecule which is composed of a molecule characterized by a sequence (arrangement) of 1 or more kinds of monomer units and contains more than half of molecules of at least 3 or more kinds of monomer units.

In one embodiment, the hydrophilic polymer includes a polymer obtained by polymerizing a hydrophilic monomer and, if necessary, another monomer; natural polymers or derivatives thereof.

The hydrophilic monomer is not particularly limited, and examples thereof include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and a sulfonic group (-SO) ₃ H) Monomers, monomers containing basic nitrogen atoms, vinyl ether monomers, monomers having a hydrophilic polymer, and the like.

Examples of the natural polymer or a derivative thereof include, but are not particularly limited to, alkyl celluloses such as methyl cellulose, ethyl cellulose, and propyl cellulose; hydroxyalkyl cellulose such as hydroxyethyl cellulose (HEC) and hydroxypropyl cellulose; hydroxyalkyl alkylcelluloses such as hydroxyethyl methylcellulose and hydroxypropyl methylcellulose; carboxyalkyl celluloses such as carboxymethyl cellulose and carboxyethyl cellulose; alginic acid; pectin; starch; hyaluronic acid; sodium chondroitin sulfate; chondroitin heparin; agar; acacia gum; dextrin, and the like.

Among the above, the hydrophilic polymer preferably contains at least 1 selected from the group consisting of a polyvinyl alcohol polymer, a polyvinyl pyrrolidone polymer, and a natural polymer or a derivative thereof, and more preferably contains a polyvinyl alcohol polymer and/or a polyvinyl pyrrolidone polymer from the viewpoint of improving adhesion to a substrate.

The content of the hydrophilic polymer in the coating agent is not particularly limited, but is preferably 10 to 80% by mass, and more preferably 30 to 60% by mass, based on the nonvolatile components of the coating agent. It is preferable that the content of the hydrophilic polymer is 10% by mass or more because high antifogging durability can be obtained. On the other hand, if the content of the hydrophilic polymer is 80% by mass or less, the decrease in oil resistance can be prevented or suppressed, which is preferable.

The coating agent can be applied to a wide variety of surfaces. An example of the use of the coating agent will be described.

The coating agent is useful, for example, for surface coating of substrates for food packaging containers. Examples of the substrate include a styrene resin sheet or film, a polyolefin resin sheet or film, a polyester resin sheet or film, and a laminate thereof. Styrenic resin sheets or films can also be formed from the polymers of the present invention.

The coating agent is used for surface coating of a plastic film such as a PET (polyethylene terephthalate) film. The plastic film may be used as a light diffusion film of a backlight unit to achieve an increase in brightness of the liquid crystal display.

Examples of the plastic film include a polyester film. Examples of the polyester used for the polyester film include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1, 4-cyclohexylenedimethylene terephthalate), and polyethylene-2, 6-naphthalate, and a copolymer thereof or a blend thereof with other resins in a small proportion.

< ink >

The ink contains the polymer of the present invention and a colorant, and further contains other components such as a pigment dispersant, water, and an organic solvent as required.

The ink is, for example, a printing ink.

The ink may be, for example, a water-based ink or an ink containing no water (solvent-based ink).

Examples of the other component include nitrocellulose. The pigment dispersibility and the drying property are improved by using the nitrocotton. The content of the nitrocellulose in the ink is not particularly limited, and is preferably 1 to 10% by mass.

Examples of other components include resins generally used in gravure printing and flexographic printing inks. Specific examples thereof include cellulose acetate butyrate resin, cellulose acetate propionate resin, chlorinated polyolefin resin, nitrocellulose resin, polyurethane resin, ketone resin, polyvinyl butyral resin, epoxy resin, ethylene vinyl acetate resin, and a copolymer resin of vinyl chloride and vinyl isobutyl ether.

When the ink is a water-based ink, water is used as a base, and an alcohol such as methanol, ethanol, isopropanol, or n-propanol may be used in combination as an aqueous solvent. The mixing ratio is water: the alcohol content is preferably 100.

When the ink is an aqueous ink, for example, the polymer of the present invention constitutes the core of the core-shell type emulsion resin. As the shell, for example, acrylic resin can be cited.

The glass transition temperature of the polymer of the present invention constituting the core is not particularly limited, but is preferably 50 to 80 ℃. The glass transition temperature of the acrylic resin constituting the shell is not particularly limited, and is preferably 60 to 80 ℃. The water-based ink containing the core-shell type emulsion resin is excellent in heat resistance and moldability, and is suitable as a water-based gravure ink for polystyrene trays.

Heat-shrinkable labels for beverage containers based on gravure printing mainly use shrinkable styrene films, shrinkable polyester films, shrinkable polyvinyl chloride films, and the like. Among these, the shrink styrene film lacks solvent resistance, and therefore an ink containing 50 mass% or more of an alcohol solvent is preferable for printing.

The alcohol solvent is preferably 1 selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol, for example. In particular, ethanol, 1-propanol, and 2-propanol are preferable from the viewpoints of drying rate, odor, and safety to human body.

When the ink is applied to a polystyrene film, it is preferable that the alcohol-based solvent is contained in an amount of 50 mass% or more based on the total solvent from the viewpoint of solubility in the film, and that the alcohol-based solvent is 10 mass% or less based on the total solvent, and that the ester-based solvent is 50 mass% or less based on the total solvent, such as aromatic hydrocarbon (toluene, xylene, etc.), aliphatic hydrocarbon (n-hexane, etc.), alicyclic hydrocarbon (cyclohexane, etc.), ketone (acetone, methyl ethyl ketone, etc.). Among them, a mixed solvent of ethyl acetate and isopropyl alcohol in a mass ratio of 20/80 to 50/50 (ethyl acetate/isopropyl alcohol) is particularly preferable.

In the case of using the ink for a polyolefin film, it is also preferable that the aromatic hydrocarbon, the aliphatic hydrocarbon, and the alicyclic hydrocarbon are 10 mass% or less and the ester is 50 mass% or less in all the solvents, from the viewpoint of solubility in the film.

The thickness of the printed layer formed by the ink is not particularly limited, but is preferably 0.1 to 5.0 μm, more preferably 0.1 to 2.0 μm, by printing or coating in a dry state.

The printing and coating method is not particularly limited, and examples thereof include gravure printing, flexographic printing, screen printing, and the like.

As the gravure printing, forward and reverse gravure printing methods can be applied. As the gravure coater, there are a natural reverse extrusion coater, a natural reverse roll coater, a natural roll coater, a reverse roll coater, and the like, and a forward gravure coater system can be preferably used.

< adhesive agent >

The adhesive contains the polymer of the present invention, and further contains other components such as other resins, curing agents, and organic solvents as necessary.

The adhesive is, for example, a laminating adhesive composition used for manufacturing a composite film of a packaging material mainly used for foods, pharmaceuticals, detergents, etc., by laminating the adhesive on various plastic films, metal vapor-deposited films, aluminum foils, etc.

As such an adhesive, for example, a two-pack curable adhesive containing the polymer of the present invention, a polymer polyol and a polyisocyanate; a one-pack adhesive comprising an acrylic resin, a urethane resin, and an ethylene-vinyl acetate copolymer. These adhesives may be solvent-based, solvent-free, water-based, or alcohol-based adhesives, if necessary.

The polymer polyol of the two-component curable adhesive is not particularly limited, and examples thereof include polymer polyols selected from polyester polyols, polyether polyols, polyester (polyurethane) polyols, polyether (polyurethane) polyols, polyesteramide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, polyurethane polyols, polyols of copolymers of monomers having unsaturated double bonds, castor seed oil, and mixtures thereof.

Examples of the polyisocyanate include organic compounds having at least 2 isocyanate groups in the molecule.

Examples of the polyisocyanate include polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, 1, 5-naphthalene diisocyanate, and triphenylmethane triisocyanate; and polyisocyanate derivatives (modified products) such as adducts of these polyisocyanates, biuret products of these polyisocyanates, and isocyanurate products of these polyisocyanates.

The polyisocyanate functions as a curing agent, and may be appropriately selected and used, and may be aromatic or aliphatic. Examples of the polyisocyanate preferably used include polyisocyanates such as Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), and diphenylmethane diisocyanate (MDI).

The curing agent exerts its performance only by the polyisocyanate, but by positively using the polyisocyanate in combination with the epoxy resin, it is possible to impart higher hydrolysis resistance to the cured coating film.

The mixing ratio of the polymer polyol and the polyisocyanate is preferably an equivalent ratio of the solid hydroxyl group equivalent (a) of the polymer polyol (A) to the solid isocyanate equivalent (B) of the polyisocyanate (B) [ (a)/(B) ], of 1.0 to 5.0, more preferably 1.2 to 3.0.

The adhesive can be prepared, for example, by preparing a main agent premix in which components other than the curing agent are blended in advance, and then mixing the main agent premix with the curing agent.

Examples of the one-pack type adhesive include an adhesive composed of polyurethane and a copolymer of monomers having an unsaturated double bond. In particular, in the case of a film lacking solvent resistance, a one-pack type aqueous urethane adhesive, an alcohol-soluble urethane adhesive, or an aqueous adhesive comprising a copolymer of a monomer having an unsaturated double bond containing a carboxyl group and a sulfonic acid group is preferable. In addition, the adhesive may be an aqueous adhesive obtained by emulsion polymerization using a surfactant.

The adhesive can be applied to various substrates and dried to form a cured coating film having adhesion on the substrate. The amount of the base material to be coated is not particularly limited, but is preferably from 0.5 to 20g/m in view of imparting excellent weather resistance to the base material in a small amount ² Wherein 1 to 10g/m ² Selecting the range of (1). For the coating, for example, a gravure coater or a dimple can be usedPlate coaters, reverse coaters, bar coaters, roll coaters, die coaters, and the like.

Examples of the substrate include paper, synthetic resin films obtained from olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), polyvinyl chloride resins, fluorine resins, poly (meth) acrylic resins, carbonate resins, polyamide resins, polyimide resins, polyphenylene ether resins, polyphenylene sulfide resins, and polyester resins, and metal foils such as copper foils and aluminum foils. The thickness of the base material is not particularly limited, and may be selected from, for example, 10 to 400 μm, and the application to a base material having a softening temperature of 180 ℃ or lower of 30 to 80 μm is most suitable from the viewpoints that the coating can be performed in a small amount, the drying can be performed at a low temperature for a short time, the base material is not warped, the elasticity is not weakened, and the excellent adhesion can be exhibited, and the excellent weather resistance can be imparted.

(sheet)

The sheet of the present invention is formed using at least 1 selected from the polymer alloy of the present invention and the composition of the present invention.

For example, the sheet of the present invention is formed using a composition containing the polymer of the present invention. Alternatively, for example, the sheet of the present invention is formed using the polymer alloy of the present invention. Hereinafter, the "composition" and the "polymer alloy of the present invention" may be collectively referred to as "sheet material".

The composition may contain other resins and various additives in addition to the polymer of the present invention.

Examples of the various additives include plasticizers, antistatic agents, antioxidants, ultraviolet absorbers, lubricants, antiblocking agents, and heat stabilizers.

Examples of the sheet include an unstretched sheet, a biaxially stretched sheet, and a foamed sheet.

< unstretched sheet >

The unstretched sheet can be produced, for example, by melt-extruding pellets of a sheet material in an extruder, melt-extruding the pellets into a sheet shape using a T-die, and cooling the sheet using a cooling roll or the like. The cooling temperature is preferably 70 to 90 ℃.

< biaxially stretched sheet >

The biaxially stretched sheet is obtained by melt extrusion with an extruder and then longitudinal and transverse biaxial stretching with a stretcher. For example, first, a sheet material is supplied to an extruder, and is melt-extruded into a sheet shape by a T-die. At this time, casting is performed so that the sheet before stretching has a predetermined thickness. Then, the sheet is cooled to a temperature at which biaxial stretching can be performed, for example, 110 to 150 ℃, and stretched in the longitudinal direction (flow direction) and the transverse direction (direction crossing the flow direction).

The stretching method may be a method in which a sheet material is melt-extruded to form a sheet, and then simultaneously biaxially stretched or sequentially biaxially stretched. In the case of sequential biaxial stretching, generally, the longitudinal stretching treatment is performed first, followed by the transverse stretching. In particular, biaxially stretched styrene-based sheets are longitudinally stretched using rolls and then transversely stretched using a tenter. The stenter method has the advantages of wide product and high production rate.

As the longitudinal stretching method using rolls, there are a method of rotating a low-speed roll and a high-speed roll in the same direction to smoothly pass and stretch a resin and a method of rotating a low-speed roll and a high-speed roll in the opposite direction to alternately pass and stretch a resin, and any combination of single-stage or multi-stage, smooth, or alternate stretching may be employed.

The stretching magnification varies depending on the purpose, and is usually 1.5 to 15 times, more preferably 4 to 10 times, in terms of area magnification. The draw ratio in the flow direction in the sequential drawing is 1.2 to 5 times, preferably 1.5 to 3.0 times, and the draw ratio in the direction crossing the flow direction is 1.2 to 5 times, preferably 1.5 to 3.0 times. The stretching ratio in each direction of the simultaneous biaxial stretching is 1.5 to 5 times. In addition, the temperature conditions in this case are preferably set so that the orientation relaxation stress measured according to ASTM D-1504 becomes 0.2 to 2.0MPa, more preferably 0.4 to 1.0 MPa. A range of 0.4 to 1.0MPa is more preferable because not only the fracture properties of the resulting sheet are good, but also the moldability of the sheet itself is extremely good.

The thickness of the biaxially stretched sheet is preferably 0.1 to 0.5mm. The biaxially stretched sheet may be laminated with the same or different thermoplastic resins by coextrusion, dry lamination, or the like, as necessary. Further, the biaxially stretched sheet may be coated with an antifogging agent, a coating agent, or the like, as necessary.

< foamed sheet >

In the case of producing a foamed sheet, an extruded foamed sheet can be produced by a general foam molding method in which a sheet material is impregnated with a foaming agent, then supplied to an extruder, heated to be melted and kneaded, and then extruded from a circular die, a T-die, or the like, while foaming is performed.

As the foaming agent, a general-purpose foaming material can be used. Examples thereof include lower hydrocarbons such as propane, butane, pentane and hexane, halogenated hydrocarbons such as methyl chloride, methylene chloride, trichlorofluoromethane and dichlorodifluoromethane, and carbon dioxide. In the case of a low expansion ratio by a normal processing operation using an extruder, chemical foaming using a sodium bicarbonate-based foaming agent that generates carbon dioxide when heated is preferable.

Further, in order to control the amount and size of cells to be foamed, an inorganic compound may be used as a nucleating agent. Preferable inorganic compounds include talc.

The temperature at the time of melt-kneading the material of the sheet material is preferably in the range of 180 to 260 ℃, and is preferably 180 to 230 ℃ from the viewpoints of preventing thermal degradation of the sheet material and preventing carbon dioxide generation efficiency when a sodium bicarbonate-based foaming agent is used.

For stable foam molding, the die temperature of a circular die, a T-die, or the like is preferably in the range of 120 to 150 ℃.

The ratio in the production of the foamed sheet is not particularly limited, but is preferably 2 to 50 times from the viewpoint of balance between maintenance of mechanical strength and weight reduction and moldability by foaming.

The thickness of the foamed sheet is not particularly limited, but is preferably 0.5 to 6.0mm from the viewpoints of ease of handling when a molded article is obtained by secondary processing and strength as a molded articleThe range is more preferably 0.7 to 4.0 mm. The bulk density is preferably 0.02 to 0.50g/cm from the viewpoint of strength ³ The range of (1).

The use of the sheet of the present invention is not particularly limited, and the sheet can be widely used for, for example, food packaging containers, building materials, home electric appliances, sundries, and the like.

(Membrane material)

The film material of the present invention uses at least 1 selected from the polymer alloy of the present invention and the composition of the present invention.

The film material of the present invention is formed using a composition containing the polymer of the present invention. Alternatively, the film material of the present invention is formed using the polymer alloy of the present invention. Hereinafter, the "composition" and the "polymer alloy of the present invention" may be collectively referred to as "film material raw material".

Examples of the film material include an unstretched film, a biaxially stretched film, and a uniaxially stretched film, and for example, the film material can be produced by melting pellets of a film material in an extruder, and then forming a film by a T-die or an inflation method. In the case of the T die method, longitudinal stretching is performed using a speed difference of a roll, and transverse stretching is performed using a tenter, thereby obtaining a biaxially stretched film.

(laminated body)

The laminate of the present invention has at least 1 selected from the sheet of the present invention and the film of the present invention, and further has other configurations such as a printing layer and a resin film as necessary.

The laminate is obtained by, for example, laminating a film or a sheet for improving mechanical strength, chemical resistance, and the like to one or both surfaces of at least 1 selected from the sheet of the present invention and the film of the present invention. Specifically, the sheet or the film is obtained by thermally laminating a polystyrene-based blown film on at least one of the front surface side and the back surface side of the sheet or the film, or by bonding an olefin-based film (CPP) using an adhesive.

The adhesive used is not particularly limited, and may be, for example, the adhesive of the present invention or a known adhesive. The adhesive preferably contains a component of biological origin.

The laminate may have a printed layer formed of a printing ink on at least one of the front side and the back side or in the middle of at least 1 selected from the sheet of the present invention and the film of the present invention. The printing ink is not particularly limited, and may be, for example, the ink of the present invention or a known ink.

From the reduction of CO ₂ From the viewpoint of the present invention, the raw materials of the ink, the adhesive and the coating agent used in the present invention preferably contain a biologically derived component and a renewable raw material. Further, by using a copolymer containing styrene and formed of unsaturated double bonds, the efficiency of chemical regeneration can be improved.

The laminate is obtained by, for example, laminating a film or a sheet for improving mechanical strength, chemical resistance, and the like to one or both surfaces of at least 1 selected from the sheet of the present invention and the film of the present invention. If necessary, a coating layer for blocking oxygen, water vapor, chemicals, an adhesive may be used.

An example of the use of the laminate is described below.

The laminate comprises a foamed polystyrene sheet, a printing layer and a polystyrene film in this order. The laminate can be obtained, for example, as follows: after a printed film is obtained by forming a printed layer on the surface of a polystyrene film in advance with a printing ink, the printed film is laminated on the surface of a foamed polystyrene sheet by thermal lamination. Here, the expanded polystyrene sheet is a sheet of the present invention.

An example of the use of the laminate is a shrink label for a bottle made of polyethylene terephthalate.

The laminate comprises the film material of the present invention and a printing layer. The laminate is obtained by forming a printed layer with printing ink on the surface of the film material of the present invention. Such a laminate is wound around the outer side surface of a polyethylene terephthalate bottle and is releasably adhered to the bottle by shrinkage.

The use of the laminate of the present invention is not particularly limited, and the laminate can be widely used for, for example, food packaging containers, building materials, household electric appliances, miscellaneous goods, and the like.

(molded article)

The molded article of the present invention is obtained by molding at least 1 selected from the sheet of the present invention, the film of the present invention, and the laminate of the present invention.

The molded article is obtained by, for example, thermoforming the sheet of the present invention, the film of the present invention, or the laminate of the present invention. Examples of the thermoforming method include a hot plate contact heating molding method, a vacuum pressure air molding method, a plunger assist molding method, and the like, and particularly, indirect heating molding using an infrared heater as a heat source can be preferably used.

The surface and the back of the molded article may be bonded with a film or a sheet for the purpose of improving mechanical strength, chemical resistance, and the like. Specifically, a polystyrene blown film may be thermally laminated, or an olefin-based film (CPP) may be laminated using an adhesive. Further, the film or sheet may be simultaneously bonded in the production line of foam molding.

Examples of the molded article include various containers such as a tray, a bowl-shaped container, a bottomed cylindrical or bottomed prismatic container, and a lidded container such as a container for natto, the tray having a shape of a perfect circle, an ellipse, a semicircle, a polygon, a sector, or the like in a plan view; a lid attached to the container body, and the like.

The use of these containers is preferably for food, for example. That is, the molded article is preferably a food packaging container.

The molded article can be used for parts of household appliances and appliances; various parts of OA equipment such as copying machines, printers, facsimiles, and personal computers; IC vector-journal; parts of medical instruments; blister packs, and the like.

The energy consumption in the production of a monomer, a polymer, or a processed product using the same can be determined by the amount of electricity used in the production,Various fuels and the like are converted into heat for comparison. In addition, regarding CO in the production ₂ The discharge amount may be obtained by multiplying the respective usage amounts of electric power, various fuels, and the like used in the production by CO for each fuel type published by economic industry province and environmental province, for example ₂ Coefficient of discharge, calculating CO ₂ The discharge amount is calculated by summing up the discharge amounts.

Examples

The present invention will be described in further detail with reference to examples below, but the scope of the present invention is not limited to these examples.

Preparation example 1 Synthesis of Multi-branched macromonomer (Mm-1)

< Synthesis of Multi-branched polyether polyol >

In a 2L flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 50.5g of ethoxylated pentaerythritol (5 moles of ethylene oxide-added pentaerythritol) and BF were charged at room temperature ₃ 1g of diethyl ether solution (50%) was heated to 110 ℃. 450g of 3-ethyl-3- (hydroxymethyl) oxetane was slowly added thereto over 25 minutes while controlling the heat generation caused by the reaction. After the exothermic digestion, the reaction mixture was further stirred at 120 ℃ for 3 hours and then cooled to room temperature. The weight average molecular weight of the obtained multi-branched polyether polyol was 3000, and the hydroxyl value was 530mgKOH/g.

< Synthesis of Multi-branched polyether having methacryloyl group and acetyl group >

50g of the multi-branched polyether polyol obtained in the above-mentioned < Synthesis of Multi-branched polyether polyol >, 13.8g of methacrylic acid, 150g of toluene, 0.06g of hydroquinone, and 1g of p-toluenesulfonic acid were charged into a reactor equipped with a stirrer, a thermometer, a Dean-Stark decanter equipped with a condenser, and a gas introduction tube, and the mixed solution was stirred and heated under normal pressure while blowing nitrogen gas containing 7% oxygen at a rate of 3 ml/min. The heating amount was adjusted so that the amount of distillate into the decanter became 30g per 1 hour, and heating was continued until the amount of dehydration reached 2.9g.

After the reaction, the mixture was cooled once, 36g of acetic anhydride and 5.7g of sulfamic acid were added thereto, and the mixture was stirred at 60 ℃ for 10 hours. Then, in order to remove the remaining acetic acid and hydroquinone, the mixture was washed 4 times with 50g of a 5% aqueous solution of sodium hydroxide, 1 time with 50g of a 1% aqueous solution of sulfuric acid, and 2 times with 50g of water. To the obtained organic layer was added 0.02g of methoquinone, and the solvent was distilled off under reduced pressure while introducing 7% oxygen, to obtain 60g of a multi-branched polyether having an isopropenyl group and an acetyl group. The weight average molecular weight of the obtained multi-branched polyether was 3900, and the introduction rates of isopropenyl and acetyl groups in the multi-branched polyether polyol were 30% and 62%, respectively.

Preparation example 2 Synthesis of Multi-branched macromonomer (Mm-2)

< Synthesis of Multi-branched polyester polyol having methacryloyl group and acetyl group >

In a reaction vessel equipped with a 7% oxygen introduction tube, a thermometer, a Dean-Stark decanter equipped with a condenser, and a stirrer, "Boltorn H20"10g, dibutyltin oxide 1.25g, methyl methacrylate 100g having an isopropenyl group as the functional group (B), and hydroquinone 0.05g were charged, and 7% oxygen was blown into the mixed solution at a rate of 3 ml/min while heating with stirring. The amount of heating was adjusted so that the amount of distillate to the decanter became 15 to 20g per 1 hour, the distillate in the decanter was taken out 1 time per 1 hour, and an amount equivalent thereto of methyl methacrylate was added and reacted for 4 hours.

After completion of the reaction, methyl methacrylate was distilled off under reduced pressure, and 10g of acetic anhydride and 2g of sulfamic acid were added to cap the remaining hydroxyl groups, followed by stirring at room temperature for 10 hours. Sulfamic acid was removed by filtration, acetic anhydride and acetic acid were distilled off under reduced pressure, and then the residue was dissolved in 70g of ethyl acetate and washed 4 times with 20g of a 5% aqueous sodium hydroxide solution in order to remove hydroquinone. Further, the mixture was washed 2 times with 20g of a 7% aqueous sulfuric acid solution and 2 times with 20g of water. To the obtained organic layer was added 0.0045g of methoquinone, and the solvent was distilled off under reduced pressure while introducing 7% oxygen to obtain 11g of a multi-branched polyester having isopropenyl and acetyl groups. The obtained multi-branched polyester had a weight average molecular weight of 3000 and a number average molecular weight of 2100, and the isopropenyl and acetyl groups introduced into the multi-branched polyester polyol were 55% and 36%, respectively.

(example 1)

Regenerated styrene monomer was produced according to the scheme shown in FIG. 1.

The used polystyrene product was recovered, and then pulverized and granulated. The pellets of waste polystyrene 1t were put into a thermal decomposition apparatus using a microwave.

The reaction temperature in the thermal decomposition apparatus was set to 350 ℃, and thermal decomposition treatment was performed under steam purge using silicon carbide as a catalyst in an amount of 2 mass% based on the waste polystyrene.

As a result, 600kg of styrene monomer was obtained (yield: 60%). The purity of the purified regenerated styrene monomer is close to 95 percent.

Example 2 styrene resin (A-1)

A mixed solution of 90 parts of the regenerated styrene monomer obtained in example 1 and 10 parts of toluene was prepared, and tert-butyl peroxybenzoate was further added as an organic peroxide in an amount of 150ppm based on styrene, and the bulk polymerization was continuously carried out under the following conditions by using an apparatus shown in FIG. 2.

Supply amount of mixed solution: 9 l/h

Reaction temperature in the stirred reactor (102): 132 deg.C

Reaction temperature in the circulating polymerization line (I): 138 deg.C

Reaction temperature in the non-circulating polymerization line (II): 140-160 DEG C

Reflux ratio: r = F1/F2=6

The mixed solution obtained by polymerization was heated to 220 ℃ by a heat exchanger, volatile components were removed under a reduced pressure of 50mmHg, and the resultant was pelletized to obtain a styrene resin (A-1) of the present invention. The strength and hue of the produced styrene resin A-1 were evaluated by the methods described below. In addition, the energy consumption in the production of regenerated styrene monomer and polymer was 8MJ/kg.

Example 3 styrene resin (A-2)

A styrene-based resin (A-2) was obtained in the same manner as in example 2, except that the multi-branched macromonomer (Mm-1) of production example 1 was added to the mixed solution of example 2 in an amount of 600ppm relative to styrene. The energy consumption in the manufacture of recycled styrene monomer and polymer was 9MJ/kg.

Example 4 styrene resin (A-3)

A styrene-based resin (A-3) was obtained in the same manner as in example 3, except that the multi-branched macromonomer (Mm-2) of production example 2 was used in place of the multi-branched macromonomer (Mm-1) of example 3. The energy consumption in the production of recycled styrene monomer and polymer was 9MJ/kg.

Example 5 styrene resin (A-4)

A mixed solution of 100 parts of the regenerated styrene monomer obtained in example 1, 8 parts of Asaprene 700A produced as a polybutadiene by Asahi chemical synthesis and 8 parts of ethylbenzene was prepared, and 500ppm of 2, 4-diphenyl-4-methyl-1-pentene as a chain transfer agent, 150ppm of t-butyl peroxybenzoate as a polymerization initiator and a monofunctional organic peroxide, and 1.5 parts of mineral oil were added to 100 parts of styrene, and then bulk polymerization was continuously carried out under the following conditions using an apparatus shown in FIG. 2.

Supply amount of mixed solution: 12L/hr

Reaction temperature of the stirred reactor (102): 135 deg.C

Reaction temperature of the circulating polymerization line (I): 135 deg.C

Reaction temperature of the non-circulating polymerization line (II): 140-160 DEG C

Reflux ratio: r = F1/F2=6

The mixed solution obtained by the polymerization was heated to 220 ℃ by a heat exchanger, and after volatile components were removed under a reduced pressure of 50mmHg, the mixed solution was pelletized to obtain styrene-based resin (A-4) of the present invention. The energy consumption in the manufacture of recycled styrene monomer and polymer was 10MJ/kg.

Example 6 styrene resin (A-5)

A styrene-based resin (A-5) was obtained in the same manner as in example 5, except that 300ppm of the multi-branched macromonomer (Mm-1) of production example 1 relative to styrene was added to the mixed solution of example 5. The energy consumption in the production of recycled styrene monomer and polymer was 11MJ/kg.

Comparative example 1

A styrene-based resin was obtained in the same manner as in example 2, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 2. The energy consumption in the manufacture of styrene monomer and polymer was 16MJ/kg.

Comparative example 2

A styrene-based resin was obtained in the same manner as in example 3, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 3. The energy consumption in the manufacture of styrene monomer and polymer was 17MJ/kg.

Comparative example 3

A styrene-based resin was obtained in the same manner as in example 4, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 4. The energy consumption in the production of styrene monomer and polymer was 17MJ/kg.

Comparative example 4

A styrene-based resin was obtained in the same manner as in example 5, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 5. The energy consumption in the manufacture of styrene monomer and polymer was 18MJ/kg.

Comparative example 5

A styrene-based resin was obtained in the same manner as in example 6, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 6. The energy consumption in the manufacture of styrene monomer and polymer was 19MJ/kg.

Example 7 styrene- (meth) acrylic acid copolymer (B-1)

A styrene- (meth) acrylic copolymer (B-1) was obtained in the same manner as in example 2, except that the mixed solution in example 2 was changed to 87 parts of the regenerated styrene monomer, 3 parts of methacrylic acid and 10 parts of toluene. The energy consumption in the production of recycled styrene monomer and polymer was 10MJ/kg.

Example 8 styrene- (meth) acrylic acid copolymer (B-2)

A styrene- (meth) acrylic copolymer (B-2) was obtained in the same manner as in example 7, except that the multi-branched macromonomer (Mm-1) of production example 1 was added in an amount of 400ppm based on the total amount of styrene and methacrylic acid to the mixed solution of example 7. The energy consumption in the manufacture of recycled styrene monomer and polymer was 10MJ/kg.

Example 9 styrene- (meth) acrylic acid copolymer (B-3)

A styrene- (meth) acrylic copolymer (B-3) was obtained in the same manner as in example 8, except that the multi-branched macromonomer (Mm-2) of production example 2 was used in place of the multi-branched macromonomer (Mm-1) of example 8. The energy consumption in the manufacture of recycled styrene monomer and polymer was 10MJ/kg.

Example 10 styrene- (meth) acrylic acid copolymer (B-4)

A styrene- (meth) acrylic copolymer (B-4) was obtained in the same manner as in example 2, except that the mixed solution in example 2 was changed to 87 parts of the regenerated styrene monomer, 3 parts of butyl acrylate and 10 parts of toluene. The energy consumption in the manufacture of recycled styrene monomer and polymer was 10MJ/kg.

Example 11 styrene- (meth) acrylic acid copolymer (B-5)

A styrene- (meth) acrylic copolymer (B-5) was obtained in the same manner as in example 10, except that the multi-branched macromonomer (Mm-1) of production example 1 was added to the mixed solution of example 10 in an amount of 600ppm based on the total amount of styrene and butyl acrylate. The energy consumption in the manufacture of recycled styrene monomer and polymer was 10MJ/kg.

Example 12 styrene- (meth) acrylic acid copolymer (B-6)

A styrene- (meth) acrylic copolymer (B-6) was obtained in the same manner as in example 11, except that the multi-branched macromonomer (Mm-2) of production example 2 was used in place of the multi-branched macromonomer (Mm-1) of example 11. The energy consumption in the manufacture of recycled styrene monomer and polymer was 10MJ/kg.

Comparative example 6

A styrene- (meth) acrylic copolymer was obtained in the same manner as in example 7, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 7. The energy consumption in the manufacture of styrene monomer and polymer was 18MJ/kg.

Comparative example 7

A styrene- (meth) acrylic copolymer was obtained in the same manner as in example 8, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 8. The energy consumption in the manufacture of styrene monomer and polymer was 18MJ/kg.

Comparative example 8

A styrene- (meth) acrylic copolymer was obtained in the same manner as in example 9, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 9. The energy consumption in the manufacture of styrene monomer and polymer was 18MJ/kg.

Comparative example 9

A styrene- (meth) acrylic copolymer was obtained in the same manner as in example 10, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 10. The energy consumption in the manufacture of styrene monomer and polymer was 18MJ/kg.

Comparative example 10

A styrene- (meth) acrylic copolymer was obtained in the same manner as in example 11, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 11. The energy consumption in the manufacture of styrene monomer and polymer was 18MJ/kg.

Comparative example 11

A styrene- (meth) acrylic copolymer (B-6) was obtained in the same manner as in example 12, except that a petroleum-derived styrene monomer was used instead of the regenerated styrene monomer used in example 12. The energy consumption in the manufacture of styrene monomer and polymer was 18MJ/kg.

As is clear from the above examples and comparative examples, the styrene-based resin and styrene- (meth) acrylic copolymer obtained by polymerizing the recycled styrene monomer of the present invention can significantly reduce the energy consumption in production.

Comparative example 12 styrene resin (C-1)

100 parts by mass of the used styrene resin (A-1) was melt-kneaded at a cylinder temperature of 220 ℃ using a twin-screw kneading extruder, and the strands were cooled with water and pelletized to obtain styrene resin (C-1).

The tensile breaking stress of the styrenic resin (C-1) obtained by recycling the material was measured at 45MPa, while the tensile breaking stress of the styrenic resin (A-1) was measured at 50MPa, and Δ YI obtained by subtracting the YI of (A-1) from the YI of (C-1) was 0.6.

Comparative example 13 styrene resin (C-2)

A styrene-based resin (C-2) was obtained by melt-kneading 100 parts by mass of the used styrene-based resin (A-2) in the same manner as in comparative example 12.

The tensile breaking stress of the styrenic resin (C-2) obtained by recycling the material was measured at 45MPa, while the tensile breaking stress of the styrenic resin (A-2) was measured at 50MPa, and Δ YI obtained by subtracting the YI of (A-2) from the YI of (C-2) was 0.6.

Comparative example 14 styrene resin (C-3)

A styrene-based resin (C-3) was obtained by melt-kneading 100 parts by mass of the used styrene-based resin (A-3) in the same manner as in comparative example 12.

The tensile breaking stress of the styrenic resin (C-3) obtained by recycling the material was measured at 45MPa, while the tensile breaking stress of the styrenic resin (A-3) was measured at 50MPa, and Δ YI obtained by subtracting the YI of (A-3) from the YI of (C-3) was 0.6.

Comparative example 15 styrene resin (C-4)

A styrene-based resin (C-4) was obtained by melt-kneading 100 parts by mass of the used styrene-based resin (A-4) in the same manner as in comparative example 12.

The measured value of the impact strength of a simple beam of a styrene-based resin (C-4) obtained by recycling the material was 12kJ/m ² And the impact strength of the styrenic resin (A-4) was measured at 14kJ/m ² The Δ YI obtained by subtracting the YI value of (A-4) from the YI value of (C-4) was 0.5.

Comparative example 16 styrene resin (C-5)

A styrene-based resin (C-5) was obtained by melt-kneading 100 parts by mass of the used styrene-based resin (A-5) in the same manner as in comparative example 12.

The measured value of the impact strength of a simple beam of a styrene-based resin (C-5) obtained by recycling the material was 13kJ/m ² And the impact strength of the styrenic resin (A-5) measured as a simple beam was 15kJ/m ² Δ YI obtained by subtracting the YI value of (A-5) from the YI value of (C-5) was 0.4.

Comparative example 17 styrene- (meth) acrylic acid copolymer (D-1)

100 parts by mass of the used styrene- (meth) acrylic copolymer (B-1) was melt-kneaded in the same manner as in comparative example 12 to obtain a styrene- (meth) acrylic copolymer (D-1).

The measured value of tensile breaking stress of the styrene- (meth) acrylic copolymer (D-1) obtained by recycling the material was 45MPa, the measured value of tensile breaking stress of the styrene- (meth) acrylic copolymer (B-1) was 51MPa, and Δ YI obtained by subtracting the YI value of (B-1) from the YI value of (D-1) was 0.5.

Comparative example 18 styrene- (meth) acrylic acid copolymer (D-2)

100 parts by mass of the used styrene- (meth) acrylic copolymer (B-2) was melt-kneaded in the same manner as in comparative example 12 to obtain a styrene- (meth) acrylic copolymer (D-2).

The measured value of tensile breaking stress of the styrene- (meth) acrylic acid-based copolymer (D-2) obtained by regeneration of the material was 46MPa, and the measured value of tensile breaking stress of the styrene- (meth) acrylic acid-based copolymer (B-2) was 51MPa, and Δ YI obtained by subtracting the YI value of (B-2) from the YI value of (D-2) was 0.4.

Comparative example 19 styrene- (meth) acrylic acid copolymer (D-3)

100 parts by mass of the used styrene- (meth) acrylic copolymer (B-3) was melt-kneaded in the same manner as in comparative example 12 to obtain a styrene- (meth) acrylic copolymer (D-3).

The styrene- (meth) acrylic copolymer (D-3) obtained by recycling the material had a tensile stress at break of 46MPa, while the styrene- (meth) acrylic copolymer (B-3) had a tensile stress at break of 51MPa, and Δ YI obtained by subtracting the YI of (B-3) from the YI of (D-3) was 0.4.

Comparative example 20 styrene- (meth) acrylic acid copolymer (D-4)

100 parts by mass of the used styrene- (meth) acrylic copolymer (B-4) was melt-kneaded in the same manner as in comparative example 12 to obtain a styrene- (meth) acrylic copolymer (D-4).

The tensile breaking stress of the styrene- (meth) acrylic copolymer (D-4) obtained by recycling the material was measured at 45MPa, the tensile breaking stress of the styrene- (meth) acrylic copolymer (B-4) was measured at 50MPa, and Δ YI obtained by subtracting the YI of (B-4) from the YI of (D-4) was 0.5.

Comparative example 21 styrene- (meth) acrylic acid copolymer (D-5)

100 parts by mass of the used styrene- (meth) acrylic copolymer (B-5) was melt-kneaded in the same manner as in comparative example 12 to obtain styrene- (meth) acrylic copolymer (D-5).

The styrene- (meth) acrylic copolymer (D-5) obtained by recycling the material had a tensile stress at break of 46MPa, while the styrene- (meth) acrylic copolymer (B-5) had a tensile stress at break of 50MPa, and Δ YI obtained by subtracting the YI of (B-5) from the YI of (D-5) was 0.4.

Comparative example 22 styrene- (meth) acrylic acid copolymer (D-6)

100 parts by mass of the used styrene- (meth) acrylic copolymer (B-6) was melt-kneaded in the same manner as in comparative example 12 to obtain a styrene- (meth) acrylic copolymer (D-6).

The measured value of tensile breaking stress of the styrene- (meth) acrylic acid-based copolymer (D-6) obtained by recycling the material was 46MPa, while the measured value of tensile breaking stress of the styrene- (meth) acrylic acid-based copolymer (B-6) was 50MPa, and Δ YI obtained by subtracting the YI value of (B-6) from the YI value of (D-6) was 0.4.

Example 13 foam sheet (E-1)

99 parts of the styrene resin (A-1) obtained in example 2 and 1 part of talc were melt-kneaded at 230 ℃ using an extruder, and 1 part of liquefied butane was forced into the extruder to obtain a foamed sheet (E-1) having a thickness of 2 mm.

Example 14 film Material (F-1)

The styrene resin (A-3) obtained in example 4 was subjected to film formation by inflation method to obtain a styrene film material (F-1) having a thickness of 25 μm.

(example 15) laminate

The styrene-based film material (F-1) obtained in example 8 was subjected to corona treatment, and solvent-based ink containing an acrylic resin was gravure-printed so that the dry film thickness became 1 μm, thereby obtaining a printed film. The printed film and a styrene-based film material (F-1) were laminated with a two-pack curable adhesive comprising a polyol and a polyisocyanate to obtain a laminated film.

(example 16) food tray

The laminated film obtained in example 9 was thermally laminated at 180 ℃ with the foamed sheet (E-1) having a thickness of 2mm obtained in example 7 to obtain a laminated sheet (S-1) for molding. The sheet was molded using a vacuum molding machine in which an indirectly heated heater was set at 300 ℃ to obtain a food tray (T-1).

Example 17 foam sheet (E-2)

Polystyrene (P-1) was obtained in the same manner as in example 7, except that the mixed solution in example 7 was changed to 90 parts of regenerated styrene monomer and 10 parts of toluene. 99 parts of this polystyrene (P-1) and 1 part of talc were melt-kneaded at 230 ℃ using an extruder, and 1 part of liquefied butane was forced into the extruder to obtain a foamed sheet (E-2) having a thickness of 3 mm.

Example 18 film Material (F-2)

The styrene- (meth) acrylic acid copolymer (B-6) was blown into a film to obtain a film (F-2) having a thickness of 25 μm.

Example 19 coating agent (C-1)

[ method for producing coating composition ]

512 parts of water and 10 parts of a surfactant were charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux vessel, and the reaction vessel was saturated with nitrogen gas. After the temperature in the reaction vessel was raised to 50 ℃,2 parts of potassium persulfate and 2 parts of sodium metabisulfite, which are polymerization initiators, were added to dissolve the components uniformly, and then a monomer solution comprising 250 parts of butyl acrylate, 65 parts of butyl methacrylate, 200 parts of a regenerated styrene monomer, 5 parts of acrylic acid and 5 parts of 2-hydroxyethyl methacrylate was added dropwise over 4 hours. After further aging at 60 ℃ for 1 hour, the mixture was cooled and adjusted to a pH of 8.0 to 9.0 with aqueous ammonia, whereby a styrene- (meth) acrylic copolymer (B-7) having a solid content of 51% and a viscosity of 600 mPas was obtained. 0.1 part of a leveling agent was added thereto to obtain an aqueous coating agent (C-1).

Example 20 adhesive (Ad-1)

[ method for producing laminating adhesive composition ]

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 512 parts of water and 10 parts of a surfactant were charged and saturated with nitrogen gas in the same manner as in example 9. After the temperature in the reaction vessel was raised to 50 ℃,2 parts of potassium persulfate and 2 parts of sodium metabisulfite, which are polymerization initiators, were added and uniformly dissolved, and then a monomer solution comprising 350 parts of butyl acrylate, 10 parts of methyl methacrylate, 150 parts of a regenerated styrene monomer, 5 parts of acrylic acid, 5 parts of acrylamide and 5 parts of 2-hydroxyethyl methacrylate was added dropwise over 4 hours. After further 1 hour of heating at 60 ℃ for aging, the mixture was cooled and adjusted to a pH of 8.0 to 9.0 with aqueous ammonia, whereby an aqueous adhesive (Ad-1) having a solid content of 51% and a viscosity of 500 mPas was obtained.

Example 21 ink (I-1)

[ method for producing ink composition ]

To a stainless steel tank, 40 parts of an aqueous blue pigment base, 40 parts of the styrene- (meth) acrylic acid copolymer (B-7) synthesized in example 9, 0.1 part of a defoaming agent, 2 parts of wax, 2 parts of isopropyl alcohol, and 15.9 parts of water were added, and stirred for 30 minutes to obtain an aqueous ink (I-1).

Example 22 food tray (T-2)

100 parts of the aqueous ink (I-1) was diluted with a mixed solvent of water/ethanol =4/6, and the ink viscosity was adjusted to 16 to 18 seconds with zeien cup # 3. The film material (F-1) obtained in example 8, which had a thickness of 25 μm after the corona treatment, was gravure-printed with the adjusted ink so that the dry film thickness became 1 μm, to obtain a printed film. The printed film was thermally laminated with a foamed sheet (E-2) having a thickness of 3mm by applying heat of 180 ℃ to obtain a laminated sheet (S-2) for molding. The sheet was molded using a vacuum molding machine in which an indirectly heated heater was set at 300 ℃, to obtain a tray for food (T-2).

Example 23 food tray (T-3)

The printed surface of the printed film of example 22 was coated with an aqueous adhesive (Ad-1) and laminated with a film material (F-2). The laminated film was heat laminated and vacuum-molded in the same manner as in example 22 to obtain a food tray (T-3).

Example 24 food tray (T-4)

100 parts of the aqueous coating agent (C-1) was diluted with a mixed solvent of water/ethanol =4/6, and the ink viscosity was adjusted to 16 to 18 seconds with zeien cup # 3. The ink was gravure-printed on a film material (F-2) having a thickness of 25 μm after corona treatment so that the dry film thickness became 2 μm, to obtain a coating film. The coated film was thermally laminated with a foamed sheet (E-2) having a thickness of 3mm by applying heat of 180 ℃ to obtain a laminated sheet (S-3) for molding. The sheet was molded using a vacuum molding machine in which an indirectly heated heater was set at 300 ℃, to obtain a tray for food (T-4).

Description of the symbols

1 waste polystyrene products; 2 regenerating styrene monomer; 10, steam; 11 slurry composition; 12 clarifying the slurry; 13 solid matter (coke/inorganic); 14 a monomer oil component; 15 gas flame; 16 benzene/toluene/ethylbenzene; 17 dimer/other (alpha-methylstyrene); 101 plunger pump; 102 a stirred reactor; 103 gear pump; 104 a tubular reactor; 105 a tubular reactor; 106 tubular reactor; 107 gear pumps; 108 a tubular reactor; 109 a tubular reactor; a 110 tubular reactor; 111 a gear pump; a thermal decomposition device; b, a separation device; c, a condenser; d a first distillation column; e a second distillation column; f, a condenser; i a recycle polymerization line; II non-circulating polymerization line.

Claims

1. A regenerated styrene monomer, characterized in that it is a product obtained by thermal decomposition treatment of a waste polystyrene product, and contains styrene.

2. The regenerated styrene monomer according to claim 1, which contains at least 1 selected from the group consisting of an inorganic substance, an aromatic compound, a cyclohexadiene-based compound and a cyclohexene-based compound.

3. A styrene resin, which is a polymer formed from a raw material of a polymer containing the regenerated styrene monomer according to claim 1 or 2.

4. A styrene-based resin according to claim 3, which is obtained by graft-polymerizing a rubber-like polymer in a continuous phase comprising a homopolymer of styrene containing the styrene contained in the regenerated styrene monomer and dispersing the polymer in particles.

5. A styrene resin according to claim 3 or 4, wherein a raw material of said polymer comprises a multi-branched macromonomer.

6. A polymer alloy comprising a styrenic resin according to any one of claims 3 to 5 and a polymer other than the styrenic resin.

7. A composition comprising a styrenic resin according to any one of claims 3 to 5.

8. The composition of claim 7, which is a coating agent.

9. The composition of claim 7, which is an ink.

10. The composition of claim 7 which is an adhesive.

11. A sheet comprising at least 1 selected from the group consisting of the polymer alloy according to claim 6 and the composition according to claim 7.

12. A film material comprising at least 1 selected from the polymer alloy according to claim 6 and the composition according to claim 7.

13. A laminate characterized by having at least 1 selected from the sheet material according to claim 11 and the film material according to claim 12.

14. A molded article obtained by molding at least 1 selected from the sheet according to claim 11, the film according to claim 12, and the laminate according to claim 13.

15. Shaped body according to claim 14, which is a food packaging container.

16. A styrene- (meth) acrylic copolymer characterized by being a copolymer formed from a raw material containing a polymer of the regenerated styrene monomer according to any one of claims 1 to 2 and a (meth) acrylic monomer.

17. A polymer alloy comprising the styrene- (meth) acrylic copolymer according to claim 16 and a polymer other than the styrene- (meth) acrylic copolymer.

18. A composition comprising the styrene- (meth) acrylic copolymer according to claim 16.

19. The composition of claim 18, which is a coating agent.

20. The composition of claim 18, which is an ink.

21. The composition of claim 18, which is an adhesive.

22. A sheet comprising at least 1 selected from the group consisting of the polymer alloy according to claim 17 and the composition according to claim 18.

23. A film material comprising at least 1 selected from the polymer alloy according to claim 17 and the composition according to claim 18.

24. A laminate comprising at least 1 selected from the sheet of claim 22 and the film of claim 23.

25. A molded article obtained by molding at least 1 selected from the sheet according to claim 22, the film according to claim 23, and the laminate according to claim 24.

26. The shaped body according to claim 25, which is a food packaging container.

27. A method for producing a polymer, characterized by comprising polymerizing a raw material of a polymer containing a regenerated styrene monomer which is a product obtained by a thermal decomposition treatment of a waste polystyrene product and contains styrene.

28. The method for producing a polymer according to claim 27, wherein the polymerization comprises continuously reacting a mixture of raw materials containing the polymer in 2 or more reaction tanks.