JP5996954B2 - Polyester resin composition and use thereof - Google Patents

Description

  The present invention relates to a polyester resin composition and use thereof.

Polymers obtained by condensation typified by polyester resins are used in various fields such as bottles, sheets and films because of their excellent mechanical strength. In particular, polyethylene terephthalate (hereinafter sometimes referred to as pet), which is a polyester resin, is excellent in mechanical properties and chemical properties. Therefore, pet fibers and pet films that have improved crystallization and mechanical strength by stretching orientation. It is widely used for PET bottles by stretch blow molding.
However, all of these processing methods achieve strength improvement by stretching orientation using the crystallinity of pet resin, and melt viscosity is very low for extrusion molding other than processing methods by these stretching. The fact is that little attention has been paid to the reason that the drawdown during extrusion is large.

In Japan, a law concerning the separate collection and promotion of re-commercialization related to containers and packaging has been enforced since April 2000. In order to achieve the objectives of this law, in recent years, there has been an active movement to collect and reuse plastics for the purpose of reducing environmental burdens. Increasing year by year. The main uses of recycled PET resin are egg-packed sheets, clothes, carpet fibers, etc., while the amount of recycled PET resin recovered has increased, but the reuse of sheets and fibers has remained flat. It is becoming.
Therefore, at present, in order to expand the use of recycled pet resin, development of new products and molded products made from recycled polyester resin (hereinafter sometimes referred to as recycled pet resin) is required. Pet resins are inherently low in melt viscosity and melt tension, and are therefore suitable for molded products with small diameters and small cross-sectional areas such as fibers and films.

However, with PET resin, in general, in order to obtain a molded product having a large diameter and a large cross-sectional area (especially an extrusion molded product), the melt tension is too low to cause a drawdown phenomenon, and a molded product having a desired size is obtained. There is no problem. In addition, even in vacuum forming using a PET resin sheet prepared by extrusion, uneven thickness unevenness due to a drawdown phenomenon is likely to occur. The reason why such a molded product cannot be obtained with pet resin is that pet resin inherently has low melt viscosity and low melt tension. Many recycled PET resins have undergone a thermal history more than new non-recycled PET resins, and the hydrolysis of the resin has progressed, so the melt viscosity and melt tension are lower than new PET resins. Development of new molded product applications is extremely difficult.
Therefore, conventionally, as a method for improving (increasing) the melt viscosity and melt tension of pet resin and recycled pet resin, a method of blending a polymer having an epoxy group (see, for example, Patent Document 1 and Patent Document 2), epoxy A method of blending a group-containing compound and an organic alkali metal salt (for example, see Patent Document 3 and Patent Document 4) has been proposed.

According to the methods described in Patent Document 1 and Patent Document 2, it is possible to improve (increase) the melt viscosity and melt tension of the polyester resin and improve drawdown during molding.
However, in the above method, the reaction between the epoxy group-containing compound and the polyester resin may be insufficient depending on the conditions. Therefore, it is necessary to add a large amount of the epoxy group-containing compound in the resin composition. In this case, there is a problem that a cross-linked product of the polyester resin and the epoxy group-containing compound is generated during melt-kneading in the extruder, and appearance defects of molded products such as fish eyes are likely to occur.

According to the methods described in Patent Document 3 and Patent Document 4, the reactivity with the polyester resin is enhanced by using an epoxy group-containing compound and an organic alkali metal salt in combination. However, depending on the conditions, there arises a problem that the viscosity of the thermoplastic resin composition is lowered.
In addition, as a new processing technique using recycled pet resin, as recycled plastic resin, styrenic elastomer modifier and / or acrylic modifier (B) as impact resistance improver, and melt viscosity improver It is known to extrude a recycled PET resin composition containing an acrylic polyethylene terephthalate (PTFE) processing aid (C) and a chemical foaming agent as a foaming agent (D) (see Patent Document 5). However, with the exception of this example, there has been almost no proposal. When this recycled pet resin composition is used as a raw material for a profile extrusion molding machine having a large cross-sectional area, the cooling efficiency at the center of the product is lowered, so that the strength is reduced due to the occurrence of bubble communication, and sink marks are generated. It may occur, and the improvement of moldability was insufficient. In addition, when a chemical foaming agent is used as a foaming agent to obtain a high expansion ratio, an acrylic as a melt viscosity improver is used to prevent bubble breakage in the vicinity of the surface of the molded product and connection of bubbles inside the molded product. It is necessary to add a large amount of system PTFE processing aid. However, orientation on the surface of the molded product from which the acrylic PTFE processing aid is obtained may reduce the paintability and adhesiveness of the molded product.

Japanese Patent No. 2675718 International Publication No. 03/066704 International Publication No. 01/094433 JP 2004-155968 A JP 2003-192816 A

  The object of the present invention is to produce a polyester resin molded article by molding which has a good dimensional stability, excellent surface properties, has closed cells inside, and is lightweight despite containing a recycled polyester resin. It is providing the polyester-type resin composition which can be performed. Moreover, it aims at providing the polyester-type resin molding excellent in dimensional stability.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved by a composition in which a specific dimensional stability-imparting agent is blended with a recycled polyester resin, and have reached the present invention. .
That is, the polyester-based resin composition according to the present invention is a composition containing a regenerated polyester resin and a dimensional stability imparting agent, and the dimensional stability imparting agent is a carboxyl group-containing monomer as a monomer component. And a heat-expandable microsphere composed of an outer shell made of a thermoplastic resin obtained by polymerizing a polymerizable component containing a nitrile monomer and a foaming agent contained therein and vaporized by heating. Ri, weight ratio of the mixture of the carboxyl group-containing monomer and said nitrile monomer is the monomer components is 80 wt% or more, a carboxyl group-containing monomer and said nitrile group monomer The ratio of the carboxyl group-containing monomer in the mixture of monomers is 30 to 90% by weight .

The weight ratio of the dimensional stability imparting agent is preferably 0.01 to 30% by weight.
The thermally expandable microsphere preferably contains a metal belonging to Groups 1 and 2 of the periodic table.

The thermally expandable microsphere preferably has an expansion start temperature of 200 ° C. or higher .
The thermally expandable microspheres are preferably surface-treated with an organic compound containing a metal belonging to Groups 3 to 12 of the periodic table.

It is preferable to further contain a melt viscosity modifier.
The polyester-based resin molded product of the present invention is a molded product formed by molding the above-described polyester-based resin composition.

The molding is preferably profile extrusion molding, and the area (extrusion cross-sectional area) of the cut surface perpendicular to the extrusion direction is preferably 10 cm ² or more.
The polyester resin molding is preferably a building material.
It is preferable that the polyester-based resin molded product has closed cells therein and an average cell diameter is in the range of 10 to 150 μm.

Although the polyester resin composition of the present invention contains a regenerated polyester resin, a polyester resin molded article having good dimensional stability and excellent surface properties can be produced by molding.
The polyester resin molded product of the present invention has good dimensional stability and excellent surface properties despite containing the recycled polyester resin.

  The polyester resin composition of the present invention is a composition containing a regenerated polyester resin and a dimensional stability imparting agent. Here, the dimensional stability imparting agent is composed of an outer shell made of a thermoplastic resin obtained by polymerizing a polymerizable component containing a carboxyl group-containing monomer, and a foaming agent encapsulated therein and vaporized by heating. It is a thermally expansible microsphere comprised. First, the thermally expandable microsphere will be described in detail.

<Thermal expandable microsphere that is a dimensional stability imparting agent>
The dimensional stability imparting agent exerts an effect of imparting dimensional stability to the obtained molded product when a polyester-based resin composition containing the recycled polyester resin is molded to produce a polyester-based resin molded product. In particular, when a polyester-based resin composition is extruded using a profile extrusion machine having a large cross-sectional area, the effect of suppressing the occurrence of sink marks is large, and the dimensional stability of a molded product having a large cross-sectional area obtained by molding is high. Especially excellent.
The dimensional stability imparting agent is a thermally expandable microsphere composed of an outer shell made of a thermoplastic resin and a foaming agent encapsulated in the outer shell and vaporized by heating. The thermoplastic resin is a copolymer obtained by polymerizing a polymerizable component including a monomer component containing a carboxyl group-containing monomer as an essential component (that is, a polymerizable component including a carboxyl group-containing monomer). Composed of coalescence.

It is preferable that the thermally expandable microspheres contain a metal belonging to Groups 1 and 2 of the periodic table because the dimensional stability of the polyester resin molded product obtained by molding the polyester resin composition is improved. Here, when the metal which belongs to periodic table 1-2 group is contained in the outer shell which consists of thermoplastic resins, the heat resistance of a thermoplastic resin increases and it is preferable at the point of dimensional stability.
Examples of metals belonging to Groups 1 and 2 of the periodic table include potassium, sodium, magnesium, calcium, and the like. Among these, sodium, magnesium and the like are preferable because the dimensional stability effect is enhanced.

As content of the metal which belongs to periodic table 1-2 group, for example, 0.5-20 weight% is preferable with respect to a thermally expansible microsphere, It is further more preferable in it being 2-10 weight%, and a dimensional stability effect Becomes higher.
As described later, the thermally expandable microspheres containing metals belonging to Groups 1 and 2 of the periodic table use, for example, an aqueous dispersion medium containing an electrolyte such as sodium chloride when manufacturing the thermally expandable microspheres. Or can be produced by polymerization in the presence of sodium hydroxide.

The heat-expandable microspheres are surface-treated with an organic compound containing a metal belonging to Group 3 to 12 of the periodic table (hereinafter, sometimes referred to as a metal-containing organic compound), thereby comprising a thermoplastic resin. If a cross-linked structure of a metal is formed in the vicinity of the outer surface of the outer shell, heat resistance is improved, which is preferable in terms of dimensional stability.
The average particle size of the thermally expandable microsphere is not particularly limited, but is preferably 1 to 100 μm, more preferably 2 to 80 μm, still more preferably 3 to 60 μm, and particularly preferably 5 to 50 μm. When the average particle size is smaller than 1 μm, the expansion performance of the thermally expandable microspheres is lowered, and the dimensional stability when the polyester resin composition is molded may be lowered. On the other hand, when the average particle diameter is larger than 100 μm, when the polyester resin composition is molded, the bubble diameter of the hollow fine particles obtained by the expansion of the thermally expandable microspheres becomes large, and the polyester resin molding obtained by molding There is a possibility that the surface property of the object is lowered.

  The coefficient of variation CV of the particle size distribution of the heat-expandable microspheres is not particularly limited, but is preferably 35% or less, more preferably 30% or less, and particularly preferably 25% or less. The variation coefficient CV is calculated by the following calculation formulas (1) and (2).

(Wherein, s is the standard deviation of the particle size, <x> is an average particle size, x _i is the i-th particle diameter, n is the number of particles.)
The expansion start temperature (Ts1) of the thermally expandable microsphere is not particularly limited, but is preferably 160 ° C. or higher, more preferably 200 ° C. or higher, further preferably 220 ° C. or higher, particularly preferably 230 ° C. or higher, and most preferably 240. It is above ℃. On the other hand, the upper limit of the expansion start temperature is preferably 300 ° C. When the expansion start temperature is less than 160 ° C., the heat resistance is low, the expansion performance of the thermally expandable microspheres is decreased, and the dimensional stability when the polyester resin composition is molded may be decreased. On the other hand, when the expansion start temperature exceeds 300 ° C., the heat resistance is too high, and when the polyester resin composition is molded, sufficient expansion performance may not be obtained, and dimensional stability may be lowered.

  The maximum expansion ratio of the thermally expandable microsphere is not particularly limited, but is preferably 30 times or more, more preferably 45 times or more, still more preferably 56 times or more, particularly preferably 59 times or more, and further preferably 62 times or more. , Most preferably 65 times or more, and most preferably 80 times or more. On the other hand, the upper limit of the maximum expansion ratio is preferably 200 times. When the maximum expansion ratio is less than 30 times, sufficient dimensional stability may not be obtained in a polyester resin molded product obtained by molding a polyester resin composition.

The foaming agent constituting the thermally expandable microsphere is not particularly limited as long as it is a substance that is vaporized by heating. Examples of the blowing agent include propane, (iso) butane, (iso) pentane, (iso) hexane, (iso) heptane, (iso) octane, (iso) nonane, (iso) decane, (iso) undecane, ( Hydrocarbons having 3 to 13 carbon atoms such as iso) dodecane and (iso) tridecane; hydrocarbons having 13 to 20 carbon atoms such as (iso) hexadecane and (iso) eicosane; pseudocumene, petroleum ether, initial boiling point 150 Hydrocarbons such as petroleum fractions such as normal paraffin and isoparaffin having a distillation range of ˜260 ° C. and / or a distillation range of 70 to 360 ° C .; their halides; fluorine-containing compounds such as hydrofluoroethers; tetraalkylsilanes; The compound etc. which decompose | disassemble and produce | generate a gas can be mentioned. These foaming agents may be used alone or in combination of two or more. The foaming agent may be linear, branched or alicyclic, and is preferably aliphatic.
A foaming agent is a substance that is vaporized by heating, but if a substance having a boiling point below the softening point of a thermoplastic resin is included as a foaming agent, a vapor pressure sufficient for expansion at the expansion temperature of the thermally expandable microspheres is obtained. It is preferable because it can be generated and a high expansion ratio can be imparted. In this case, a substance having a boiling point not higher than the softening point of the thermoplastic resin and a substance having a boiling point higher than the softening point of the thermoplastic resin may be included as a foaming agent.

Further, when a substance having a boiling point higher than the softening point of the thermoplastic resin is included as the foaming agent, the ratio of the substance having a boiling point higher than the softening point of the thermoplastic resin to the foaming agent is not particularly limited, but preferably Is 95% by weight or less, more preferably 80% by weight or less, further preferably 70% by weight or less, particularly preferably 65% by weight, particularly more preferably 50% by weight or less, and most preferably less than 30% by weight. When the ratio of the substance having a boiling point exceeding the softening point of the thermoplastic resin exceeds 95% by weight, the maximum expansion temperature is increased, but the expansion ratio is decreased, and when used as a foaming agent for the heat insulating layer, the heat insulating property is decreased. Sometimes.
There is another way of thinking about the foaming agent, and hydrocarbons having 12 or more carbon atoms (hereinafter sometimes referred to as hydrocarbons a) may be essential. Hydrocarbon a is essential when the thermally expandable microspheres are surface-treated with a metal-containing organic compound, or when a crosslinked structure is formed by a metal near the outer surface of the outer shell made of a thermoplastic resin. It is preferable that

The carbon number of the hydrocarbon a is preferably 14 or more, more preferably 16 or more. Moreover, the upper limit of the carbon number of the hydrocarbon a is preferably 25. The hydrocarbon a may be linear, branched or alicyclic, and is preferably aliphatic. Examples of the hydrocarbon a include linear hydrocarbons such as dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nanodecane, eicosan, heneicosan, docosan, tricosan, tetracosan, pentacosan; isododecane, 3-methylundecane, Isotridecane, 4-methyldodecane, isotetradecane, isopentadecane, isohexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane, isooctadecane, isonanodecane, 2,6,10,14-tetra Methylpentadecane, isoeicosane, 2,2,4,4,6,6,8,8,10-nonamethylundecane, isoheneicosane, isodocosane, isotricosane, isotetracosane, isopentacosane, etc. Branched hydrocarbons: cyclododecane, cyclotridecane, hexylcyclohexane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane, pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane, etc. A hydrocarbon etc. can be mentioned. These hydrocarbons a may be used alone or in combination of two or more.
It is preferable that the hydrocarbon a used as the foaming agent is composed of two or more types because it becomes thermally expandable microspheres having a sufficient expansion ratio.

When the blowing agent further contains a hydrocarbon having 3 to 11 carbon atoms (hereinafter sometimes referred to as hydrocarbon b) together with the hydrocarbon a, the thermally expandable microspheres are heated at a temperature lower than the expansion start temperature. Is preferable because the expansion start temperature can be lowered without reducing the expansion ratio.
The carbon number of the hydrocarbon b is preferably 4 to 10, more preferably 5 to 8. The hydrocarbon b may be linear, branched or alicyclic, and is preferably aliphatic. Examples of the hydrocarbon b include hydrocarbons such as (iso) butane, (iso) pentane, (iso) hexane, (iso) heptane, (iso) octane, (iso) nonane, and (iso) decane. it can. These hydrocarbons b may be used alone or in combination of two or more.

In addition to hydrocarbon a and hydrocarbon b, the foaming agent may contain halides of hydrocarbon a and hydrocarbon b; fluorine-containing compounds such as hydrofluoroether; other foaming agents such as tetraalkylsilane. Good. These foaming agents may be linear, branched, or alicyclic. The weight ratio of hydrocarbon a in the foaming agent is not particularly limited, but is preferably 5% by weight or more of the foaming agent, more preferably Is 10% by weight or more, particularly preferably 30% by weight or more, and most preferably 60% by weight or more. When the weight ratio of the hydrocarbon a is less than 5% by weight with respect to the foaming agent, the expansion coefficient of the thermally expandable microsphere is high, but the maximum expansion temperature may be lowered.

When the blowing agent further contains hydrocarbon b, the weight ratio of hydrocarbon b is not particularly limited, but is preferably 15% by weight or more, more preferably 30% by weight or more, particularly preferably 50% by weight of the blowing agent. Above, most preferably 60% by weight or more. The upper limit of the weight ratio of hydrocarbon b is preferably 95% by weight. When the weight ratio of the hydrocarbon b is more than 95% by weight with respect to the foaming agent, the expansion coefficient of the thermally expandable microsphere is high, but the maximum expansion temperature may be lowered.
The encapsulating rate of the foaming agent encapsulated in the heat-expandable microspheres is not particularly limited, but is preferably 1 to 60% by weight, preferably 3 to 50% by weight, more preferably based on the weight of the heat-expandable microspheres. Is 8 to 40% by weight, particularly preferably 10 to 30% by weight.

Next, the thermoplastic resin is composed of a copolymer obtained by forming a shell of thermally expandable microspheres and polymerizing a polymerizable component.
The polymerizable component is a component that becomes a copolymer that is a thermoplastic resin that forms an outer shell by polymerization. The polymerizable component is a component which essentially includes a monomer component and may contain a crosslinking agent, and contains a carboxyl group-containing monomer as a monomer component as an essential component.

The monomer component generally includes a component called a (radical) polymerizable monomer having one polymerizable double bond. The monomer component requires a carboxyl group-containing monomer.
The carboxyl group-containing monomer is not particularly limited as long as it has one or more free carboxyl groups per molecule, but unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, and cinnamic acid. Acid; unsaturated dicarboxylic acid such as maleic acid, itaconic acid, fumaric acid, citraconic acid, chloromaleic acid; anhydride of unsaturated dicarboxylic acid; monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, fumaric acid And unsaturated dicarboxylic acid monoesters such as monoethyl, monomethyl itaconate, monoethyl itaconate and monobutyl itaconate. These carboxyl group-containing monomers may be used alone or in combination of two or more. In the carboxyl group-containing monomer, some or all of the carboxyl groups may be neutralized during polymerization or after polymerization. Among the carboxyl group-containing monomers, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and itaconic acid are preferable, acrylic acid and methacrylic acid are more preferable, and methacrylic acid is particularly preferable because of high gas barrier properties. Hereinafter, acrylic acid or methacrylic acid may be collectively referred to as (meth) acrylic acid, and (meth) acryl means acrylic or methacrylic.

The monomer component may include a carboxyl group-containing monomer as an essential component, and one or more other monomer components may be used in combination. Other monomer components are not particularly limited. For example, nitrile monomers such as acrylonitrile, methacrylonitrile, and fumaronitrile; vinyl halide monomers such as vinyl chloride; halogenation such as vinylidene chloride Vinylidene monomers; vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl butyrate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc. (Meta) Acu Luric acid ester monomers; (meth) acrylamide monomers such as acrylamide, substituted acrylamide, methacrylamide, and substituted methacrylamide; maleimide monomers such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, α -Styrene monomers such as methyl styrene; Ethylene unsaturated mono-olefin monomers such as ethylene, propylene and isobutylene; Vinyl ether monomers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl methyl ketone Examples thereof include vinyl ketone monomers such as N-vinyl carbazole, N-vinyl monomers such as N-vinyl pyrrolidone, and vinyl naphthalene salts.
Monomer components include nitrile monomers, (meth) acrylic acid ester monomers, styrene monomers, vinyl ester monomers, acrylamide monomers, and vinylidene halide monomers. It is preferable to further include at least one selected.

From the viewpoint that the weight ratio of the carboxyl group-containing monomer increases the heat resistance and solvent resistance of the thermally expandable microspheres, and lowers the expansion start temperature when heat treatment is performed at a temperature lower than the expansion start temperature. Preferably it is 10 to 90 weight% with respect to a monomer component, More preferably, it is 30 to 90 weight%, More preferably, it is 40 to 90 weight%, Especially preferably, it exceeds 51.2 weight% and 90 weight% The most preferred is 53 to 90% by weight. When the carboxyl group-containing monomer is less than 10% by weight, the heat resistance and solvent resistance are insufficient, and the expansion start temperature and the maximum expansion temperature are lowered. Furthermore, when the heat treatment is performed at a temperature lower than the expansion start temperature, the expansion start temperature may not be sufficiently lowered. When the carboxyl group-containing monomer is more than 90% by weight, the expansion performance of the thermally expandable microspheres may be lowered.
When the monomer component further contains a nitrile monomer, it is preferable because the gas barrier property of the thermoplastic resin constituting the outer shell is improved.

When the nitrile monomer is included as an essential component, the weight ratio of the mixture of the carboxyl group-containing monomer and the nitrile monomer is preferably 50% by weight or more with respect to the monomer component, more preferably It is 60% by weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.
At this time, the mixing ratio of the carboxyl group-containing monomer in the mixture of the carboxyl group-containing monomer and the nitrile monomer is preferably 10 to 90% by weight, more preferably 30 to 90% by weight, still more preferably. It is 40 to 90% by weight, particularly preferably more than 51.2% by weight and 90% by weight or less, and most preferably 53 to 90% by weight. When the mixing ratio is less than 10% by weight, the heat resistance and solvent resistance are not sufficiently improved, and the expansion start temperature and the maximum expansion temperature are lowered. Furthermore, when the heat treatment is performed at a temperature lower than the expansion start temperature, the expansion start temperature may not be sufficiently lowered. When the carboxyl group-containing monomer is more than 90% by weight, the expansion performance of the thermally expandable microspheres may be lowered.

When the monomer component contains a vinylidene chloride monomer, gas barrier properties are improved. Moreover, when the monomer component contains a (meth) acrylic acid ester monomer and / or a styrene monomer, the thermal expansion characteristics can be easily controlled. When the monomer component contains a (meth) acrylamide monomer, the heat resistance is improved.
The weight ratio of at least one selected from vinylidene chloride, (meth) acrylic acid ester monomer, (meth) acrylamide monomer, and styrene monomer is preferably 50 wt. %, More preferably less than 30% by weight, particularly preferably less than 10% by weight. If it is contained in an amount of 50% by weight or more, the heat resistance may be lowered.

The monomer component may contain a monomer that reacts with the carboxyl group of the carboxyl group-containing monomer. When the monomer component further contains a monomer that reacts with a carboxyl group, the heat resistance is further improved, and the expansion performance at a high temperature is improved. Examples of the monomer that reacts with the carboxyl group include N-methylol (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, vinyl glycidyl ether, and propenyl. Glycidyl ether, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. Can be mentioned. The weight ratio of the monomer that reacts with the carboxyl group is preferably 0.1 to 10% by weight, more preferably 3 to 5% by weight, based on the monomer component.
The polymerizable component may or may not contain a polymerizable monomer (crosslinking agent) having two or more polymerizable double bonds in addition to the monomer component. By polymerizing using a crosslinking agent, a decrease in the retention rate (encapsulation retention rate) of the encapsulated foaming agent at the time of thermal expansion is suppressed, and thermal expansion can be effectively performed.

Although it does not specifically limit as a crosslinking agent, For example, aromatic divinyl compounds, such as divinylbenzene; Allyl methacrylate, triacryl formal, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, PEG # 200 di (meth) acrylate, PEG # 600 di (meth) acrylate, trimethylolpropane trimethacrylate, pentaerythrul Examples include di (meth) acrylate compounds such as tall tri (meth) acrylate, dipentaerythritol hexaacrylate, and 2-butyl-2-ethyl-1,3-propanediol diacrylate. These crosslinking agents may be used alone or in combination of two or more.
The amount of the crosslinking agent is not particularly limited, but is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, and particularly preferably 0. More than 2 parts by weight and less than 1 part by weight. The amount of the crosslinking agent may be 0 part by weight or more and less than 0.1 part by weight with respect to 100 parts by weight of the monomer component.

The weight ratio of the carboxyl group-containing monomer in the polymerizable component increases the heat resistance and solvent resistance of the resulting heat-expandable microspheres, and the expansion start temperature when heat treatment is performed at a temperature lower than the expansion start temperature. From the viewpoint of lowering, it is preferably 10% by weight or more, more preferably 30% by weight or more, further preferably 40% by weight or more, particularly preferably more than 50% by weight, and most preferably 53% by weight or more. The upper limit of the weight ratio is preferably 90% by weight. When the weight ratio is less than 10% by weight, the heat resistance and solvent resistance are insufficient, and the expansion start temperature and the maximum expansion temperature are lowered. Furthermore, when the heat treatment is performed at a temperature lower than the expansion start temperature, the expansion start temperature may not be sufficiently lowered. If the weight ratio of the carboxyl group-containing monomer is more than 90% by weight, the expansion ratio may decrease.
The heat-expandable microspheres are preferably surface-treated with a metal-containing organic compound. By this surface treatment, a crosslinked structure of metal is formed in the vicinity of the outer surface of the outer shell made of the thermoplastic resin. This metal cross-linked structure is based on chemical bonds such as covalent bonds (including coordination bonds) between the anionic carboxylate group derived from the carboxyl group-containing monomer and contained in the thermoplastic resin, and the metal. It is considered that the structure is formed by This structure is preferably a cross-linked structure (metal cross-linked structure) in which a plurality of carboxylate groups are linked through a metal. When the metal is A and the electronic valence is p, the crosslinked structure is represented, for example, as (—COO) _p A. Here, when p is 2, it is represented as (—COO) ₂ A, that is, —COO—A—OCOC—. The cross-linked structure of the metal is not easily destroyed by washing the thermally expandable microspheres with water.

Examples of the metal forming the cross-linked structure include metals belonging to Groups 3 to 12 of the periodic table. Examples of such metals include group 3 metals such as scandium, ytterbium and cerium; group 4 metals such as titanium, zirconium and hafnium; group 5 metals such as vanadium, niobium and tantalum; 6 such as chromium, molybdenum and tungsten. Group metals; Group 7 metals such as manganese and rhenium; Group 8 metals such as iron, ruthenium and osmium; Group 9 metals such as cobalt and rhodium; Group 10 metals such as nickel and palladium; Group 11 such as copper, silver and gold Metal: Group 12 metals such as zinc and cadmium can be exemplified. These metals may be used alone or in combination of two or more. The above metal classification is “Chemical and Education” published by the Chemical Society of Japan, Volume 54, No. 4 (2006), and the “Periodic Table of Elements (2005)” (2006 The Chemical Society of Japan atomic weight) Subcommittee).
Among these metals, transition metals (metals belonging to Groups 3 to 11) are preferred, metals belonging to Groups 4 to 10 are more preferred, and metals belonging to Groups 4 to 5 are particularly preferred.

Examples of transition metals include scandium, ytterbium, cerium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, nickel, palladium, copper , Silver, gold and the like. Among these, scandium, ytterbium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, silver, and the like are preferable, and periodic table 4 such as titanium, zirconium, and vanadium. Transition metals belonging to ˜5 periods are more preferable from the viewpoint of improving heat resistance. When it is not a transition metal, the improvement of heat resistance may be insufficient.
The valence number of the metal is not particularly limited, but is preferably 2 to 5 valence, more preferably 3 to 5 valence, and particularly preferably 4 to 5 valence in terms of crosslinking efficiency per metal atom. When the valence number is monovalent, the solvent resistance and water resistance of the thermally expandable microsphere may be lowered. Moreover, the crosslinking efficiency may fall that it is 6 or more.

Regarding the above metal, the combination of metal species and valence number thereof is zinc (II), cadmium (II), aluminum (III), vanadium (III), ytterbium (III), titanium from the viewpoint of improving heat resistance. (IV), zirconium (IV), lead (IV), cerium (IV), vanadium (V), niobium (V), tantalum (V) and the like are preferable.
When the metal contained in the thermally expandable microspheres contains a metal belonging to Group 3-12 of the periodic table, the weight ratio is preferably 0.05 to 15% by weight of the thermally expandable microspheres, more preferably 0. 10 to 7% by weight, more preferably 0.13 to 5% by weight, further preferably 0.14 to 3% by weight, more preferably 0.15 to 1.5% by weight, and particularly preferably 0.16 to 0%. 0.8% by weight, most preferably 0.20 to 0.54% by weight. If the weight ratio of the metal belonging to Group 3-12 of the periodic table is less than 0.05% by weight, the heat resistance may not be improved sufficiently. On the other hand, when the weight ratio of the metal exceeds 15% by weight, the outer shell becomes stiff and the maximum expansion ratio may be lowered. When the metal contained in the thermally expansible microsphere includes a metal belonging to the periodic table group 3 to 11, when including a metal belonging to the periodic table group 4 to 10, or when including a metal belonging to the periodic table group 4 to 5 However, it is preferable that the weight ratio is the above-described weight ratio.
The surface treatment of the metal-containing organic compound will be described in detail in the method for producing thermally expandable microspheres described below, but is not limited to the following method.

<Method for producing thermally expandable microsphere that is a dimensional stability imparting agent>
The method for producing thermally expandable microspheres is a step of polymerizing a polymerizable component in an aqueous dispersion medium in which an oily mixture containing a polymerizable component and a foaming agent described above is dispersed (hereinafter referred to as a polymerization step). A manufacturing method including:
In the polymerization step, it is preferable to polymerize the polymerizable component in the presence of the polymerization initiator using an oily mixture containing a polymerization initiator.

Although there is no limitation in particular as a polymerization initiator, A peroxide, an azo compound, etc. can be mentioned.
Examples of the peroxide include diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-octyl peroxydicarbonate, and dibenzyl peroxydicarbonate. Peroxydicarbonates such as t-butyl peroxypivalate, t-hexyl peroxypivalate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-butylperoxy 3,5,5-trimethyl Examples thereof include peroxyesters such as hexanoate; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide.

Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4- Dimethylvaleronitrile), 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), and the like. These polymerization initiators may be used alone or in combination of two or more. As the polymerization initiator, an oil-soluble polymerization initiator soluble in the monomer component is preferable. Among the polymerization initiators, peroxydicarbonate is preferable. When the polymerization initiator includes other initiators together with peroxydicarbonate, the proportion of peroxydicarbonate in the polymerization initiator is preferably 60% by weight or more.
Although there is no limitation in particular about the quantity of a polymerization initiator, it is preferable in it being 0.3-8.0 weight part with respect to 100 weight part of said monomer components.

In the polymerization step, the oily mixture may further contain a chain transfer agent and the like.
The aqueous dispersion medium is a medium mainly composed of water such as ion exchange water in which the oily mixture is dispersed. Although there is no limitation in particular about the usage-amount of an aqueous dispersion medium, it is preferable to use 100-1000 weight part aqueous dispersion medium with respect to 100 weight part of polymeric components.

The aqueous dispersion medium may further contain an electrolyte. Examples of the electrolyte include sodium chloride, magnesium chloride, calcium chloride, sodium sulfate, magnesium sulfate, ammonium sulfate, and sodium carbonate. These electrolytes may be used alone or in combination of two or more. Although there is no limitation in particular about content of an electrolyte, it is preferable to contain 0.1-50 weight part with respect to 100 weight part of aqueous dispersion media.
An aqueous dispersion medium is a water-soluble 1,1-substituted compound having a structure in which a hydrophilic functional group selected from a hydroxyl group, a carboxylic acid (salt) group, and a phosphonic acid (salt) group and a hetero atom are bonded to the same carbon atom , Potassium dichromate, alkali metal nitrite, metal (III) halide, boric acid, water-soluble ascorbic acids, water-soluble polyphenols, water-soluble vitamin Bs and water-soluble phosphonic acids (salts) It may contain at least one water-soluble compound. In addition, the water solubility in this invention means the state which melt | dissolves 1g or more per 100g of water.

The amount of the water-soluble compound contained in the aqueous dispersion medium is not particularly limited, but is preferably 0.0001 to 1.0 part by weight, more preferably 0.0003 to 100 parts by weight of the polymerizable component. 0.1 parts by weight, particularly preferably 0.001 to 0.05 parts by weight. If the amount of the water-soluble compound is too small, the effect of the water-soluble compound may not be sufficiently obtained. Moreover, when there is too much quantity of a water-soluble compound, a polymerization rate may fall or the residual amount of the polymeric component which is a raw material may increase.
The aqueous dispersion medium may contain a dispersion stabilizer and a dispersion stabilization auxiliary agent in addition to the electrolyte and the water-soluble compound.

The dispersion stabilizer is not particularly limited, and examples thereof include tricalcium phosphate, magnesium pyrophosphate, calcium pyrophosphate obtained by a metathesis generation method, colloidal silica, alumina sol, and the like. These dispersion stabilizers may be used alone or in combination of two or more.
The blending amount of the dispersion stabilizer is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymerizable component.

The dispersion stabilizing aid is not particularly limited, and examples thereof include a polymer type dispersion stabilizing aid, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant. Mention may be made of activators. These dispersion stabilizing aids may be used alone or in combination of two or more.
The aqueous dispersion medium is prepared, for example, by blending water (ion-exchanged water) with a water-soluble compound and, if necessary, a dispersion stabilizer and / or a dispersion stabilizing aid. The pH of the aqueous dispersion medium at the time of polymerization is appropriately determined depending on the type of the water-soluble compound, the dispersion stabilizer, and the dispersion stabilization aid.

In the polymerization step, polymerization may be performed in the presence of sodium hydroxide, sodium hydroxide and zinc chloride.
In the polymerization step, the oily mixture is emulsified and dispersed in an aqueous dispersion medium so that spherical oil droplets having a predetermined particle diameter are prepared.

Examples of the method for emulsifying and dispersing the oily mixture include, for example, a method of stirring with a homomixer (for example, manufactured by Tokushu Kika Kogyo Co., Ltd.) and the like, and a static dispersion device such as a static mixer (for example, manufactured by Noritake Engineering Co., Ltd.). And general dispersion methods such as a method using a film, a membrane emulsification method, and an ultrasonic dispersion method.
Next, suspension polymerization is started by heating the dispersion in which the oily mixture is dispersed as spherical oil droplets in the aqueous dispersion medium. During the polymerization reaction, it is preferable to stir the dispersion, and the stirring may be performed so gently as to prevent, for example, floating of the monomer and sedimentation of the thermally expandable microspheres after polymerization.

Although superposition | polymerization temperature is freely set by the kind of polymerization initiator, Preferably it is 30-100 degreeC, More preferably, it controls in the range of 40-90 degreeC. The time for maintaining the reaction temperature is preferably about 0.1 to 20 hours. Although there is no limitation in particular about the superposition | polymerization initial pressure, it is the range of 0-5.0 MPa by gauge pressure, More preferably, it is the range of 0.1-3.0 MPa.
Next, the thermally expandable microsphere, which is surface-treated with a metal-containing organic compound or has a cross-linked structure formed of a metal in the vicinity of the outer surface of the outer shell made of a thermoplastic resin, for example, Thermally expandable microspheres composed of a copolymer obtained by polymerizing a polymerizable component containing a carboxyl group-containing monomer with a thermoplastic resin as the outer shell (for example, thermally expandable microspheres obtained in the polymerization process) Sphere) as a raw material microsphere, and is obtained by performing the following surface treatment process. In the following description of the surface treatment process, the raw material microspheres include, for example, thermally expandable microspheres obtained in the polymerization process.

A surface treatment process is a process of surface-treating with a metal containing organic compound with respect to raw material microsphere. The surface treatment is a treatment of bringing the raw material microspheres into contact with the metal-containing organic compound. The surface treatment here does not originally intend to physically attach the metal-containing organic compound to the outer surface of the outer shell of the raw material microspheres. The purpose of the surface treatment is, for example, a crosslinked structure (metal crosslinked structure) by linking anionic carboxylate groups contained in the thermoplastic resin that forms the outer shell of the raw material microspheres via a metal. Is chemically formed. The heat resistance is improved by forming the metal bridge structure in the vicinity of the outer surface of the outer shell. The crosslinking efficiency means the formation efficiency of metal crosslinking.
The metal-containing organic compound is not particularly limited, but is preferably water-soluble from the viewpoint of surface treatment efficiency. The metal contained in the metal-containing organic compound is as described above.

The metal-containing organic compound is preferably a compound having at least one bond represented by the following general formula (1) and / or a metal amino acid compound.
M-O-C (1)
(However, M is a metal atom belonging to Groups 3 to 12 of the periodic table, and carbon atom C is bonded to oxygen atom O, and in addition to oxygen atom O, only hydrogen atom and / or carbon atom is bonded.)
First, the compound having at least one bond represented by the general formula (1) will be described in detail.

-Compound having at least one bond represented by the general formula (1)-
The bond between the metal atom and the oxygen atom represented by the general formula (1) (the bond between MO) may be either an ionic bond or a covalent bond (including a coordination bond). preferable.
When the compound having at least one bond represented by the general formula (1) is a compound having a metal-alkoxide bond and / or a metal-aryloxide bond, it has high solvent resistance and is stable in a wide range of high temperatures. Expansion performance can be imparted to thermally expandable microspheres. Hereinafter, for the sake of simplicity, “metal-alkoxide bond and / or metal-aryl oxide bond” will be referred to as “MO bond”, and “compound having metal-alkoxide bond and / or metal-aryl oxide bond” will be referred to as “ It may be described as “MO compound”.

The MO compound is a compound having at least one metal-alkoxide bond or metal-aryloxide bond. MO compounds include metal-O—C═O bond (metal-acylate bond), metal-OCON bond (metal-carbamate bond), metal = O bond (metal oxy bond), and the following general formula (2) (formula R ¹ and R ² are organic groups which may be the same or different from each other.) Further, it has a bond to a metal which is not an MO bond, such as a metal-acetylacetonate bond shown in the above. You may do it. M represents a metal.

As is apparent from the above, the MO bond and the metal-O—C═O bond (metal-acylate bond) are different concepts, and the metal-O—C═O bond (metal-acylate bond) has an MO. There is no binding.
The MO compound is classified into, for example, the following four compounds (1) to (4).

Compound (1):
Compound (1) is a metal alkoxide and a metal aryloxide, for example, a compound represented by the following chemical formula (A).
M (OR) _n (A)
(However, M represents a metal; n is a valence number of the metal M; R is a hydrocarbon group having 1 to 20 carbon atoms, and each n hydrocarbon group is the same or different. It may be linear, branched or cyclic.)

In compound (1), M (metal) and n (valence number) are as described above.
R may be aliphatic or aromatic, and may be saturated or unsaturated. R may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, allyl, n-decyl, tridecyl, stearyl. Group, an aliphatic hydrocarbon group such as a cyclopentyl group; an aromatic hydrocarbon group such as a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

  Examples of the compound (1) include zinc (II) alkoxides such as diethoxy zinc and diisopropoxy zinc; aluminum (III) alkoxides such as aluminum triisopropoxide and aluminum triethoxide; vanadium triethoxide and vanadium triiso Vanadium (III) alkoxides such as propoxide; Titanium (IV) such as tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra normal propoxy titanium, tetra normal butoxide titanium, tetrakis (2-ethylhexyloxy) titanium, tetraphenoxy titanium ) Alkoxide; tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetranormalpropoxyzirconium, tetranor Zirconium (IV) alkoxides such as rubutoxyzirconium, tetrakis (2-ethylhexyloxy) zirconium, tetraphenolatezirconium; tetramethoxycerium, tetraethoxycerium, tetraisopropoxycerium, tetranormalpropoxycerium, tetranormalbutoxycerium, tetrakis ( Cerium (IV) alkoxides such as 2-ethylhexyloxy) cerium and tetraphenolate cerium; trimethoxyoxyvanadium, triethoxyoxyvanadium, tri (n-propoxy) oxyvanadium, isopropoxyoxyvanadium, tri (n-butoxide) oxy Alkoxyoxyvanadium (V) such as vanadium, isobutoxyoxyvanadium; others, tantalum, manganese, co Belt, the metal of the metal alkoxide such as copper and the like.

Compound (2):
The compound (2) is an oligomer or polymer of the compound (1) and is generally obtained by condensing the compound (1). Compound (2) is, for example, a compound represented by the following chemical formula (B). The chemical formula (B) shows a partially hydrolyzed structure.
RO [-M (OR) ₂ O-] _x-1 R (B)
(However, M and R are the same as chemical formula (A); x is an integer of 2 or more.)

The molecular weight of the compound (2) is not particularly limited, but the number average molecular weight is preferably 200 to 5000, particularly preferably 300 to 3000. If the number average molecular weight is less than 200, the crosslinking efficiency may be low. On the other hand, if the number average molecular weight exceeds 5000, it may be difficult to control the degree of crosslinking.
Examples of the compound (2) include titanium alkoxy polymers and titanium alkoxy dimers that satisfy x = 2 to 15 in the chemical formula (B).

Specific examples of the compound (2) include, for example, titanium methoxy polymers such as hexamethyl dititanate and octamethyl trititanate; titanium ethoxy polymers such as hexaethyl dititanate and octaethyl trititanate; hexaisopropyl dititanate and octaisopropyl tritate. Titanium propoxy polymer such as titanate, hexanormal propyl dititanate, octa normal propyl trititanate, etc .; Titanium butoxy polymer such as hexabutyl dititanate, octabutyl trititanate, etc .; Titanium phenoxy polymer such as hexaphenyl dititanate, octaphenyl trititanate; hydroxy titanium stearate (formula: _i-C 3 _{H 7} O _{[Ti (OH) (OCOC 17 H} 35) O ] _{n -i-C} 3 _{H 7)} or the like Al of Kishichitan - acylate polymer; titanium methoxy dimer, titanium ethoxy dimer, titanium butoxy dimer, and titanium alkoxy dimers such as titanium phenoxy dimer.

Compound (3):
Compound (3) is a metal chelate compound having an MO bond. In the compound (3), a ligand compound having at least one MO bond and having at least one electron donating group selected from a hydroxyl group, a keto group, a carboxyl group and an amino group is coordinated to M Metal chelate compound. The ligand compound may have at least one electron donating group, but preferably has 2 to 4 electron donating groups. Compound (3) may have a plurality of MO bonds, M, and a ligand compound.
The ligand compound is not particularly limited, and examples thereof include alkanolamines, carboxylic acids, hydroxycarboxylic acids (salts), β-diketones, β-ketoesters, diols and amino acids.

Examples of alkanolamines include ethanolamine, diethanolamine, and triethanolamine.
Examples of carboxylic acids include acetic acid and the like.

Examples of hydroxycarboxylic acids (salts) include glycolic acid, lactic acid, malic acid, citric acid, tartaric acid, salicylic acid, and salts thereof.
Examples of β-diketone include acetylacetone and the like.

Examples of the β-ketoester include ethyl acetoacetate and the like.
Examples of diols include ethylene glycol, diethylene glycol, 3-methyl-1,3-butanediol, triethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, and 1,5-pentanediol. Hexylene glycol, octylene glycol and the like.

  Examples of the compound (3) in which the ligand compound is an alkanolamine include, for example, titanium tetrakis (diethanolaminate), isopropoxytitanium tris (diethanolamate), diisopropoxytitanium bis (diethanolaminate), triisopropoxytitanium mono ( Diethanolaminate), dibutoxytitanium bis (diethanolamate), titanium tetrakis (triethanolamate), dimethoxytitanium bis (triethanolamate), diethoxytitanium bis (triethanolamate), isopropoxytitanium tris (triethanolamate) , Diisopropoxytitanium bis (triethanolamate), triisopropoxytitanium mono (triethanolamate), di-n-butoxytitanium Alkanolamine-alkoxytitanium chelate compounds such as tris (triethanolaminate); zirconium tetrakis (diethanolaminate), isopropoxyzirconium tris (diethanolamate), diisopropoxyzirconium bis (diethanolaminate), triisopropoxyzirconium mono (diethanolamin ), Dibutoxyzirconium bis (diethanolaminate), zirconium tetrakis (triethanolamate), dimethoxyzirconium bis (triethanolamate), diethoxyzirconium bis (triethanolamate), isopropoxyzirconium tris (triethanolaminate) Nate), diisopropoxyzirconium bis (triethanolamate), tri Alkanolamine-alkoxyzirconium chelate compounds such as sopropoxyzirconium mono (triethanolaminate) and di-n-butoxyzirconium bis (triethanolaminate); cerium tetrakis (diethanolaminate), isopropoxycerium tris (diethanolaminate), Diisopropoxycerium bis (diethanolamate), triisopropoxycerium mono (diethanolamate), dibutoxycerium bis (diethanolamate), cerium tetrakis (triethanolamate), dimethoxycerium bis (triethanolamate), diethoxy Cerium bis (triethanolaminate), isopropoxycerium tris (triethanolamate), diisopro Examples thereof include alkanolamine-alkoxycerium chelate compounds such as poxycerium bis (triethanolamate), triisopropoxycerium mono (triethanolamate), and di-n-butoxycerium bis (triethanolamate).

  Examples of the compound (3) in which the ligand compound is a hydroxycarboxylic acid (salt) include, for example, titanium lactate, dihydroxy titanium bis (lactate), dihydroxy titanium bis (lactate) monoammonium salt, dihydroxy titanium bis (lactate) diammonium salt, Hydroxycarboxylic acid (salt) -alkoxytitanium chelate compound such as dihydroxytitanium bis (glycolate), titanium lactate ammonium salt; zirconium lactate, monohydroxyzirconium tris (lactate), dihydroxyzirconium bis (lactate), dihydroxyzirconium bis (lactate) mono Ammonium salt, dihydroxyzirconium bis (lactate) diammonium salt, dihydroxyzirconium bis (glycolate), di Hydroxycarboxylic acid (salt) -alkoxyzirconium chelate compounds such as ammonium lactate ammonium salt; cerium lactate, monohydroxycerium tris (lactate), dihydroxycerium bis (lactate), dihydroxycerium bis (lactate) monoammonium salt, dihydroxycerium bis Examples thereof include hydroxycarboxylic acid (salt) -alkoxycerium chelate compounds such as (lactate) diammonium salt, dihydroxycerium bis (glycolate), and cerium lactate ammonium salt.

Examples of the compound (3) in which the ligand compound is a β-diketone include alkoxy zinc-β-diketone chelate compounds such as zinc acetylacetonate; β-diketone-alkoxyaluminum chelate compounds such as aluminum acetylacetonate; vanadium Β-diketone-alkoxyvanadium chelate compounds such as acetylacetonate; titanium tetrakis (acetylacetonate), dimethoxytitanium bis (acetylacetonate), diethoxytitanium bis (acetylacetonate), diisopropoxytitanium bis (acetylacetate), dinormal Propoxytitanium bis (acetylacetonate), dibutoxytitanium bis (acetylacetonate), titanium tetrakis (2,4-hexanedionate), titanium tetrakis (3,5-he Β-diketone chelate-alkoxytitanium compounds such as Tandionato; dihydroxyzirconium bis (acetylacetonate), zirconium tetrakis (acetylacetonate), tributoxyzirconium mono (acetylacetonate), dibutoxyzirconium bis (acetylacetonate), Β-diketone-alkoxyzirconium chelate compounds such as monobutoxyzirconium tris (acetylacetonate); dihydroxycerium bis (acetylacetonate), cerium tetrakis (acetylacetonate), tributoxycerium mono (acetylacetonate), dibutoxycerium Β-diketone-alkoxycerium chelates such as bis (acetylacetonate) and monobutoxycerium tris (acetylacetonate) Compounds and the like.
Examples of the compound (3) in which the ligand compound is a β-ketoester include β-ketoester-alkoxytitanium chelate compounds such as diisopropoxytitanium bis (ethylacetoacetate); dibutoxyzirconium bis (ethylacetoacetate) and the like Examples include β-ketoester-alkoxyzirconium chelate compounds.

Examples of the compound (3) in which the ligand compound is a β-diketone and β-ketoester include alkoxytitanium-β-diketone and β-ketoester such as monobutoxytitanium mono (acetylacetonate) bis (ethylacetoacetate) Chelate compounds; β-diketones such as monobutoxyzirconium mono (acetylacetonate) bis (ethylacetoacetate) and β-ketoester-alkoxyzirconium chelate compounds; monobutoxycerium mono (acetylacetonate) bis (ethylacetoacetate) Examples include β-diketone and β-ketoester-alkoxycerium chelate compound.
Examples of the compound (3) in which the ligand compound is a diol include alkoxy titanium-diol chelate compounds such as dioctyloxy titanium bis (octylene glycolate).
The compound (3) may be a metal chelate compound in which the ligand compound is coordinated to a metal atom such as tantalum, manganese, cobalt, copper, or the like, or a derivative thereof.

Compound (4):
The compound (4) is a compound having at least one MO bond and metal-acylate bond.
Compound (4) is, for example, a compound represented by the following chemical formula (C).
M (OCOR ¹ ) _nm (OR) _m (C)
(However, M, n, and R are the same as chemical formula (A); R ¹ is the same as R, but may be the same or different; m is 1 ≦ m ≦ (n−1). Is a positive integer that satisfies.)

Compound (4) may be obtained by condensation of the compound represented by chemical formula (C).
Examples of the compound (4) include alkoxytitanium-acylate compounds such as tributoxyzirconium monostearate; alkoxyzirconium-acylate compounds such as tributoxyzirconium monostearate; alkoxycerium-acylate compounds such as tributoxycerium monostearate Etc.

-Metal amino acid compounds-
The metal-containing organic compound may be a metal amino acid compound. The metal amino acid compound is an amino acid chelate metal compound obtained by a reaction between a metal salt belonging to Groups 3 to 12 of the periodic table and amino acids shown below.
Amino acids include not only amino acids having an amino group (—NH ₂ ) and a carboxyl group (—COOH) in the same molecule, but also iminos such as proline and hydroxyproline having an imino group (—NH) instead of an amino group. Also includes acids. The amino acid is usually an α-amino acid, but may be a β, γ, δ or ω-amino acid.

Amino acids include amino acid derivatives such as those in which one or two hydrogen atoms of the amino group of the amino acid are substituted, and complexes chelated with nitrogen of the amino acid amino group and oxygen of the carboxyl group.
The pH of amino acids is preferably 1-7.

Examples of amino acids include dihydroxymethyl glycine, dihydroxyethyl glycine, dihydroxypropyl glycine, dihydroxybutyl glycine, glycine, alanine, valine, leucine, isoleucine, serine, histidine, threonine, glycylglycine, 1-aminocyclopropane carboxylic acid 1-aminocyclohexanecarboxylic acid, 2-aminocyclohexanehydrocarboxylic acid, and the like. Among these, dihydroxyethyl glycine, glycine, serine, threonine, and glycylglycine are preferable from the viewpoint of crosslinking efficiency.
As a metal salt belonging to Groups 3-12 of the periodic table that reacts with the amino acids, basic zirconyl chloride is preferred. As a commercial item of a metal amino acid compound, for example, ORGATICS ZB-126 (manufactured by Matsumoto Pharmaceutical Co., Ltd.) and the like can be mentioned.

Among the above metal-containing organic compounds, dioctyloxy titanium bis (octylene glycolate), titanium butoxy dimer, titanium tetrakis (acetylacetonate), diisopropoxy titanium bis (ethyl acetoacetate), diisopropoxy titanium bis (triethanolaminate) ), Dihydroxytitanium bis (lactate), dihydroxytitanium bis (lactate) monoammonium salt, zirconium tetrakis (acetylacetonate), dihydroxytitanium bis (lactate) diammonium salt, triisopropoxyoxyvanadium, reaction product of zirconium chloride and aminocarboxylic acid (Orugatics ZB-126) and the like are preferable in terms of heat resistance improvement efficiency and handling properties.
In the surface treatment step, the molar ratio of the metal-containing organic compound (the number of moles of the metal-containing organic compound / the number of moles of the carboxyl group-containing monomer as the raw material of the raw material microspheres) is not particularly limited, but is preferably 0. 0.001 to 1.0, more preferably 0.005 to 0.5, still more preferably 0.007 to 0.3, particularly preferably 0.009 to 0.15, and most preferably 0.009 to 0.06. It is. When the molar ratio of the metal-containing organic compound is less than 0.001, there is little effect of improving heat resistance, and the expansion performance may be deteriorated when exposed to a high temperature environment for a long time. On the other hand, when the molar ratio of the metal-containing organic compound exceeds 1.0, the outer shell of the thermally expandable microspheres becomes too strong and the expansion performance is lowered, and the polyester resin obtained by molding the polyester resin composition In a molded product, sufficient dimensional stability may not be obtained, and moldability may deteriorate.

The surface treatment step is not particularly limited as long as it is a treatment step for bringing the raw material microspheres into contact with the metal-containing organic compound. However, it is preferable to mix the raw material microspheres and the metal-containing organic compound with the aforementioned aqueous dispersion medium. . Accordingly, the metal-containing organic compound is preferably water-soluble.
When the surface treatment step is performed in an aqueous dispersion medium, the weight ratio of the raw material microspheres to the dispersion mixture containing the raw material microspheres, the metal-containing organic compound and the aqueous dispersion medium is preferably 1 to 50% by weight, more preferably 3%. -40% by weight, more preferably 5-35% by weight. When the weight ratio of the raw material microspheres is less than 1% by weight, the processing efficiency may be lowered. On the other hand, when the weight ratio of the raw material microspheres exceeds 50% by weight, the processing may be nonuniform.

The weight ratio of the metal-containing organic compound in the dispersion mixture is not particularly limited as long as it can be uniformly treated, but is preferably 0.1 to 20% by weight, and more preferably 0.5 to 15% by weight. When the weight ratio of the metal-containing organic compound is less than 0.1% by weight, the treatment efficiency may be lowered. On the other hand, when the weight ratio of the metal-containing organic compound is more than 20% by weight, the treatment may be nonuniform.
Moreover, the aqueous dispersion medium used for the surface treatment is usually an aqueous dispersion medium used for the preparation of the raw material microspheres or an aqueous dispersion medium containing newly prepared water, but if necessary, methanol, ethanol and Alcohols such as propanol; aliphatic hydrocarbons such as hexane, isooctane and decane; hydroxycarboxylic acids such as glycolic acid, lactic acid, malic acid, citric acid and salicylic acid and salts thereof (for example, lithium salt, sodium salt, potassium salt, ammonium) Salts, amine salts, etc.); ethers such as tetrahydrofuran, dialkyl ethers and diethyl ether; surfactants; may contain other components such as antistatic agents.

In the surface treatment step, the heat-expandable microspheres may be produced using the polymerization liquid containing the raw material microspheres obtained in the polymerization step as it is. In addition, a series of isolation operations such as filtration and washing are performed on the polymerization solution obtained in the polymerization step, and if necessary, the raw material microspheres are once separated from the polymerization solution, followed by a surface treatment step. Thermally expandable microspheres may be manufactured.
When the aqueous dispersion medium contains other components, for example, the surface treatment step can be performed by the following methods A) to D).

A) Method of mixing component 1 containing other components and raw material microspheres and component 2 containing metal-containing organic compound B) Component 1 containing metal-containing organic compound and raw material microspheres and component containing other components 2) Method 2 of mixing other components and component 1 containing a metal-containing organic compound and component 2 containing raw material microspheres D) Component 1 containing raw material microspheres and other components Method of simultaneously mixing component 2 and component 3 containing a metal-containing organic compound (at least one of the above components 1 to 3 contains water. Two or three components may contain water) .)
The surface treatment step may be performed by a method other than that described above, for example, the following methods 1) and 2).

1) Surface treatment on moistened raw material microspheres (wet cake-like raw material microspheres) The raw material microspheres, the metal-containing organic compound, and the aqueous dispersion medium are contained (uniformly), and the weight ratio of the raw material microspheres is A mixture that is preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 70% by weight or more is prepared, and the aqueous dispersion medium is removed by operations such as airflow drying or heat drying under reduced pressure to perform thermal expansion. To obtain sex microspheres.
2) Surface treatment on (almost) dried raw material microspheres A metal-containing organic compound is added to dried raw material microspheres in which the weight ratio of the raw material microspheres is preferably 90% by weight or more, preferably 95% by weight or more. After uniformly mixing, the volatile matter may be removed by heating to such an extent that it does not expand to obtain thermally expandable microspheres. At this time, the raw material microspheres may be left stationary, stirred, or fluidized in the air using a fluidized bed or the like. The addition of the metal-containing organic compound is preferably performed by uniformly spraying the metal-containing organic compound or the liquid containing the metal-containing organic compound with a spray or the like.

Although there is no limitation in particular about the processing temperature in a surface treatment process, Preferably it is the range of 40-150 degreeC. The time for maintaining this treatment temperature is preferably about 0.1 to 20 hours.
Although there is no limitation in particular about the pressure in a surface treatment process, Preferably it is the range of 0-5.0 MPa by a gauge pressure.

In the surface treatment step, the heat-expandable microspheres obtained by the surface treatment are usually separated from the aqueous dispersion medium by operations such as suction filtration, centrifugation, and centrifugal filtration. Furthermore, the thermally expandable microspheres can be obtained in a dry state by an operation such as air-drying and drying under reduced pressure by heating the liquid-containing cake of thermally expandable microspheres obtained after the separation. In addition, when surface-treating by the method of said 1) and 2), operation may be abbreviate | omitted suitably.
The amount of metal (for example, metal belonging to Group 3-12 of the periodic table) contained in the thermally expandable microsphere increases before and after the surface treatment process. The weight ratio of the amount of metal increased by the surface treatment step to the amount of metal contained in the thermally expandable microspheres after the surface treatment step is usually 10% by weight or more, preferably 60% by weight or more, more preferably 70% by weight. % Or more, more preferably 80% by weight, particularly preferably 90% by weight or more, and most preferably 95% by weight or more. If it is less than 10% by weight, the entire outer shell becomes rigid and does not show good expansion performance, and sufficient dimensional stability cannot be obtained in a polyester resin molded product obtained by molding a polyester resin composition. May decrease.

<Recycled polyester resin>
The recycled polyester resin is not particularly limited, and examples thereof include a recycled resin made of polyethylene terephthalate and recycled from a plastic bottle or the like used as a container for soft drinks. Examples of the recycled polyester resin include a flaked recycled polyester resin obtained by washing and pulverizing a polyester resin molded product such as a used waste plastic bottle with a washing and pulverizing apparatus, and then drying by heat drying and dehumidification. Examples thereof include pelletized recycled polyester resin obtained by melting and pelletizing recycled polyester resin. Since the pelletized recycled polyester resin is obtained by heat-treating the flaky recycled polyester resin, the hydrolysis of the polyester resin may proceed and the quality may be lowered. It is preferable to use a flaky recycled polyester resin.
Since the flaky recycled polyester resin is made from waste PET bottles or the like, many of them are in the form of a fine sheet.

The average thickness of the flaky recycled polyester resin is not particularly limited, but is preferably in the range of 50 to 2000 μm, more preferably 100 to 700 μm. If the average thickness of the flaky recycled polyester resin is outside the above range, the molten state of the polyester-based resin composition may become nonuniform during molding.
The size (length × width) of the flaky recycled polyester resin is not particularly limited, but is preferably (1-50 mm) × (1-50 mm), more preferably (3-20 mm) × (3-20 mm). It is. If the size of the flaky recycled polyester resin is outside the above range, the supply of the recycled polyester resin may become unstable during molding, which is not preferable.

<Polyester resin composition>
The polyester-based resin composition is a composition containing a regenerated polyester resin and a dimensional stability imparting agent.
The weight ratio of the recycled polyester resin in the polyester resin composition is not particularly limited, but is preferably 70 to 99.9% by weight, more preferably 80 to 99.5% by weight in the polyester resin composition, Particularly preferred is 85 to 99% by weight, and most preferred is 90 to 98% by weight. When the weight ratio of the recycled polyester resin is less than 70% by weight, the strength of the molded product using the polyester resin composition may be lowered, which is not preferable. On the other hand, when the weight ratio of the recycled polyester resin exceeds 99.9% by weight, the dimensional stability may be lowered.

The weight ratio of the dimensional stability imparting agent in the polyester-based resin composition is not particularly limited, but is preferably 0.01 to 30% by weight, more preferably 0.5 to 20% by weight in the polyester-based resin composition. %, Particularly preferably 1 to 15% by weight, most preferably 2 to 10% by weight. When the weight ratio of the dimensional stability imparting agent is less than 0.01% by mass, the dimensional stability may be lowered. On the other hand, when the weight ratio of the dimensional stability imparting agent is more than 30% by mass, the strength of the molded product using the polyester resin composition may be lowered.
It is preferable that the polyester resin composition further contains a melt viscosity modifier. The melt viscosity modifier is not particularly limited as long as it is a compound that can suppress a rapid decrease in melt viscosity when the polyester resin composition is molded. When the melt viscosity modifier is a polymer having a melting point (Vicat softening point when it is difficult to measure the melting point) of 10 to 120 ° C., a rapid decrease in melt viscosity can be suppressed, and the polyester resin composition contains It is preferable because of its high dispersibility. When the melt viscosity modifier is a polymer and its melting point (Vicat softening point when the melting point is difficult to measure) exceeds 120 ° C., the dispersibility may be deteriorated and the melt viscosity adjusting ability may be lowered. On the other hand, when the melt viscosity modifier is a polymer and its melting point (Vicat softening point when the melting point is difficult to measure) is less than 10 ° C., the polyester resin composition may be difficult to handle.

The melt viscosity modifier is, for example, a polymer modified with an unsaturated carboxylic acid compound, and a polymer such as polyethylene or polystyrene modified with an unsaturated carboxylic acid compound such as glycidyl (meth) acrylate is particularly preferable. . Here, the unsaturated carboxylic acid compound used for modification is preferably 0.1 to 20% by weight of the polymer modified with the unsaturated carboxylic acid compound.
Examples of the polymer modified with the unsaturated carboxylic acid compound include 1) a random copolymer with the unsaturated carboxylic acid compound and other monomers, and 2) an unsaturated carboxylic acid as a base polymer serving as a trunk. A graft polymer obtained by grafting a polymer chain formed from a compound as a branch can be given.

As an unsaturated carboxylic acid compound, unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, and maleic anhydride, its anhydride, its ester, etc. can be mentioned, for example.
Examples of the random copolymer include a copolymer of an unsaturated carboxylic acid compound and ethylene. Here, the unsaturated carboxylic acid compound is preferably acrylic acid or methacrylic acid. Specific examples of the random copolymer include, for example, ethylene-methyl acrylate copolymer (EMA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene- N-butyl acrylate copolymer (EnBA), ethylene-glycidyl methacrylate copolymer (EGMA), ethylene-n-butyl acrylate-glycidyl methacrylate copolymer (EnBAGMA), ethylene-ethyl acrylate-maleic anhydride copolymer Examples thereof include a copolymer such as a polymer.

In addition, when the random copolymer is an unsaturated carboxylic acid compound among the random copolymers described above, the —COOH group contained in the random copolymer is a —COOM group (M is a metal ) May be an ionomer neutralized in (1). Here, examples of the metal M include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as magnesium, calcium and strontium; and other metals such as zinc, copper, cobalt and nickel. The degree of neutralization of the random copolymer is preferably 20 to 90 mol%.
Next, examples of the base polymer constituting the graft polymer include polyethylene, ethylene-propylene copolymer rubber (EPR), propylene-ethylene copolymer rubber (PER), and ethylene-butene copolymer rubber (EBR). ), Ethylene-propylene-diene terpolymer rubber (EPDM) and other ethylene polymers; SBS, SEBS, SIS, SEPS and other block polymers such as styrene polymers. As the unsaturated carboxylic acid compound grafted to the base polymer, maleic anhydride and the like are preferable.

Among the melt viscosity modifiers described above, from the viewpoint of compatibility with the recycled polyester resin, ethylene-glycidyl methacrylate copolymer (EGMA); ethylene-n-butyl acrylate-glycidyl methacrylate copolymer (EnBAGMA) An ethylene-ethyl acrylate-maleic anhydride copolymer; an ionomer obtained by neutralizing an ethylene-unsaturated carboxylic acid copolymer with a metal ion; an aromatic dicarboxylic acid polyester elastomer; a styrenic polymer (SBS, A modified product obtained by grafting a block polymer of SEBS, SIS, SEPS, etc.) with maleic anhydride or the like is preferable.
The weight ratio of the melt viscosity modifier is not particularly limited, but is preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, and particularly preferably 3 to 20 parts by weight with respect to 100 parts by weight of the recycled polyester resin. Parts, most preferably 4 to 15 parts by weight. If the weight ratio of the melt viscosity modifier is outside the above range, the melt viscosity control ability may be insufficient.

The polyester-based resin composition may be a known hindered phenol-based, sulfur-based, phosphorous-based antioxidant or the like as necessary; a hindered amine-based, triazole-based, benzophenone-based, benzoate-based, nickel-based, salicyl-based, etc. Light stabilizers; molecular weight regulators such as peroxides; organic and inorganic nucleating agents; neutralizing agents; antacids; antibacterial agents; fluorescent brighteners; glass fibers, carbon fibers, silica fibers, alumina Inorganic fibrous materials such as fibers; wood powder; flame retardant; lubricant; colorant; carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, wollastonite, oxidation It may further contain inorganic fillers such as iron, titanium oxide, zinc oxide, alumina, calcium carbonate, barium carbonate; hydrolysis inhibitors; antistatic agents and the like.
The method for producing the polyester resin composition is not particularly limited as long as it is a method of blending the regenerated polyester resin and the thermally expandable microsphere that is a dimensional stability imparting agent, but the dispersion of the polyester resin composition is not limited. In order to enhance the property, it is preferable to use thermally expandable microspheres that have been wetted with a liquid compound. The liquid compound is not particularly limited as long as it is compatible with the polyester-based resin and does not inhibit the expansion performance of the thermally expandable microsphere. For example, ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol Examples thereof include polyfunctional epoxy compounds such as A diglycidyl ether, and glycol compounds such as ethylene glycol, trimethylene glycol, tetramethylene glycol, and hexamethylene glycol.

In the said manufacturing method, when mix | blending recycled polyester resin and thermally expansible microsphere, the masterbatch containing thermally expansible microsphere may be prepared previously, and the masterbatch and recycled polyester resin may be mix | blended.
The raw material resin used in the preparation of the masterbatch is not particularly limited as long as it has good compatibility with the polyester resin and does not hinder the expansion performance of the thermally expandable microspheres. For example, the above-mentioned used as a melt viscosity modifier Polymers modified with an unsaturated carboxylic acid compound described in detail above, ethylene copolymers such as ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer; low density polyethylene, high density polyethylene, polypropylene, Polyolefin resins such as polybutene, polyisobutylene, polystyrene, polyterpene; styrene copolymers such as styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer; polyester elastomers, styrene elastomers, olefin elastomers, etc. It may be mentioned thermoplastic resin elastomer. The master batch is preferably prepared at a temperature not higher than the expansion start temperature of the thermally expandable microsphere.

  The polyester resin composition expands when heated, but the expansion conditions can be set as appropriate. The expansion ratio before and after the expansion of the polyester resin composition is preferably 1.5 times or more, more preferably 1.5 to 5 times, particularly preferably 1.7 to 4 times, and most preferably 1.8 to 3 times. It is. When the expansion ratio of the polyester resin composition is less than 1.5 times, the dimensional stability may be insufficient. On the other hand, when the expansion ratio of the polyester resin composition is larger than 5 times, the effect of dimensional stability can be sufficiently obtained, but the strength may be greatly impaired.

<Polyester resin molding>
The polyester resin molded product is formed by molding the polyester resin composition described above. There are no particular limitations on the molding method, and examples thereof include known resin molding methods such as injection molding, blow molding, profile extrusion molding, molding with an extruder equipped with a T-die, and vacuum molding. Among these moldings, injection molding and profile extrusion molding are preferable, and profile extrusion molding is more preferable in terms of excellent dimensional stability.
In the case where the molding is profile extrusion molding, in the polyester resin molded product, the area of the cut surface perpendicular to the extrusion direction (extrusion cross-sectional area) is preferably 10 cm ² or more, more preferably 20 cm ² or more, particularly preferably 30 cm ² or more. It is. The upper limit with preferable extrusion cross-sectional area is 500 cm < ² >. When the extrusion cross-sectional area exceeds the above range, the dimensional stability may be lowered.

The polyester-based resin molded article usually has closed cells inside and is excellent in dimensional stability. The average cell diameter of the closed cells is not particularly limited, but is preferably 10 to 150 μm, more preferably 30 to 120 μm, and most preferably 40 to 100 μm. If the average cell diameter is less than 10 μm, the effect of dimensional stability may be reduced. On the other hand, when the average cell diameter exceeds 150 μm, the strength of the polyester resin molded product may be greatly reduced, or the surface properties of the polyester resin molded product may be deteriorated when closed cells are present near the surface. .
There are no particular restrictions on the use of the polyester resin molded product, but, for example, molded products obtained by injection molding include various containers, trash cans, road cones, etc .; obtained by blow molding and T-die extrusion molding. Examples of molded products include film raw materials such as bags and various printing films, and sheet raw materials for packaging materials such as egg packs. Molded products obtained by profile extrusion include handrails and floor materials. Examples include building materials.
Among these uses, when used for building materials, especially building materials such as handrails and flooring materials having a large extrusion cross-sectional area, the effect of a dimensional stability imparting agent is easily obtained, which is preferable.

  Examples of the present invention will be specifically described below. The present invention is not limited to these examples. In the following Examples and Comparative Examples, “%” means “% by weight” unless otherwise specified. Prior to the examples, production examples of thermally expandable microspheres and regenerated polyester resins which are dimensional stability-imparting agents will be shown. Hereinafter, the heat-expandable microsphere may be referred to as “microsphere” for simplicity.

[Measurement of average particle size and particle size distribution]
A laser diffraction particle size distribution analyzer (HEROS & RODOS manufactured by SYMPATEC) was used. The dispersion pressure of the dry dispersion unit was 5.0 bar and the degree of vacuum was 5.0 mbar, measured by a dry measurement method, and the D50 value was taken as the average particle size.

[Measurement of moisture content of microspheres]
As a measuring apparatus, a Karl Fischer moisture meter (MKA-510N type, manufactured by Kyoto Electronics Industry Co., Ltd.) was used for measurement.

[Measurement of encapsulation rate of foaming agent enclosed in microspheres]
1.0 g of microspheres were placed in a stainless steel evaporation dish having a diameter of 80 mm and a depth of 15 mm, and the weight (W ₁ ) was measured. 30 ml of DMF was added and dispersed uniformly. After standing at room temperature for 24 hours, the weight (W ₂ ) after drying under reduced pressure at 130 ° C. for 2 hours was measured. The encapsulation rate (CR) of the foaming agent is calculated by the following formula.
CR (wt%) = (W ₁ −W ₂ ) (g) /1.0 (g) × 100− (water content) (wt%)
(In the formula, the moisture content is measured by the above method.)

[Weight ratio of periodic table group 3-12 metal in microsphere]
0.1 g of microspheres and 5 ml of nitric acid (made by Wako Pure Chemical Industries, Ltd. for measuring harmful metals) are added to a quartz container, and a microwave wet decomposition apparatus (Multiwave manufactured by Anton Paar) is used under the conditions shown below. Steps 1 to 4 were sequentially performed to perform microwave wet decomposition treatment.
Process 1: Process for 4 minutes at an output of 300 W Process 2: Start processing at an output of 400 W, and increase the output to 600 W over 6 minutes (output increase rate: 33.3 W / min) Process 3: Process at an output of 700 W , And increase the output to 800 W over 30 minutes (output increase rate: 3.3 W / min) and process step 4: Cooling process for 20 minutes without applying output

  Next, using the sample obtained by the above decomposition treatment, the ICP emission spectrometer (ICPS-8100 manufactured by Shimadzu Corporation) is used to measure the content of the Group 3-12 metal of the periodic table in the sample. The weight ratio (weight%) of the periodic table group 3-12 metal contained in the whole was computed. The weight ratio of the periodic table group 12 metal was also calculated separately. In the following table, when it was below the detection limit (usually less than about 100 ppm), it was described as ND. In Examples and Comparative Examples, only metal species derived from the metal-containing organic compound or metal compound used were detected.

[Measurement of expansion start temperature (Ts) and maximum expansion temperature (Tmax)]
As a measuring device, DMA (DMA Q800 type, manufactured by TA instruments) was used. Place 0.5 mg of microspheres in an aluminum cup with a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, and place an aluminum lid (diameter 5.6 mm, thickness 0.1 mm) on top of the microsphere layer. Samples were prepared. The sample height was measured in a state where a force of 0.01 N was applied to the sample with a pressurizer from above. In a state where a force of 0.01 N was applied by the pressurizer, heating was performed from 20 ° C. to 350 ° C. at a rate of temperature increase of 10 ° C./min, and the displacement of the pressurizer in the vertical direction was measured. The displacement start temperature in the positive direction was defined as the expansion start temperature (Ts), and the temperature when the maximum displacement was indicated was defined as the maximum expansion temperature (Tmax).

[Calculation of expansion ratio of recycled PET resin moldings]
The density (D1) of the recycled pet resin molded product was measured by a liquid immersion method using a precision hydrometer AX200 (manufactured by Shimadzu Corporation). The theoretical density (D2) of the component obtained by removing the dimensional stability imparting agent from the recycled PET resin molded product was calculated, and the expansion ratio was calculated by the following equation using D1 and D2.
Expansion ratio (times) = D2 / D1

[Production Example 1]
A mixture obtained by adding 150 g of sodium chloride, 40 g of colloidal silica which is 20% by weight of silica active ingredient, 1.0 g of polyvinylpyrrolidone and 0.5 g of 5% aqueous solution of ethylenediaminetetraacetic acid and 4Na salt to 600 g of ion-exchanged water, was obtained. Was adjusted to 2.8 to 3.2 to prepare an aqueous dispersion medium.
Separately, 30 g of acrylonitrile, 100 g of methacrylonitrile, 170 g of methacrylic acid, 0.2 g of 1,9-nonanediol diacrylate, 0.3 g of trimethylolpropane trimethacrylate, 80 g of isooctane and di-sec- of 50% active ingredient. An oily mixture was prepared by mixing 8 g of a butyl peroxydicarbonate-containing solution.

  The aqueous dispersion medium and the oily mixture were mixed, and the obtained mixed liquid was dispersed with a homomixer (TK machine manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare a suspension. The suspension was transferred to a pressure reactor having a capacity of 1.5 liters, and purged with nitrogen. Then, the initial reaction pressure was 0.5 MPa, and polymerization was performed at a polymerization temperature of 60 ° C. for 20 hours while stirring at 80 rpm. While stirring at room temperature, 15 g of a diisopropoxy titanium bis (triethanolaminate) -containing liquid containing 80% of the active ingredient as a metal-containing organic compound was added to the polymerization liquid obtained after the polymerization. The obtained dispersion mixture was transferred to a pressure reactor (capacity: 1.5 liters), purged with nitrogen, brought to a treatment initial pressure of 0.5 MPa, and treated at 80 ° C. for 5 hours while stirring at 80 rpm. The obtained treated product was filtered and dried to obtain thermally expandable microspheres (microspheres). The physical properties are shown in Table 1.

[Production Example 2]
Bottles made of materials other than polyester resin (polyethylene terephthalate) were removed from a used bottle group mainly composed of plastic bottles for beverages and the like collected and collected by general consumers using X-rays. Next, the obtained PET bottle group was washed with a weak alkaline aqueous solution, and then washed and ground with a washing and grinding apparatus using water. Next, after separating resin pieces other than pet resin and metal pieces using the difference in specific gravity, flaky recycled polyester resin was obtained by heat drying.
The shape of the obtained flaky recycled polyester resin was about 8 mm square, and the average thickness was 300 μm. The intrinsic viscosity was 0.75 dL / g. The intrinsic viscosity was measured by dissolving 1 g of recycled pet resin flake sample in 100 mL of hexafluoroisopropanol solvent and measuring at 30 ° C.

[Example 1]
A polyester resin composition was prepared by uniformly mixing 97 parts by weight of the flaky recycled polyester resin obtained in Production Example 2 and 3 parts by weight of the thermally expandable microspheres obtained in Production Example 1. Next, the polyester resin composition was subjected to profile extrusion using a single screw extruder with a vent (screw diameter φ65 mm) to produce a polyester resin molded product. The molding temperature at the time of profile extrusion was 240 ° C., and the die shape was a rectangle having a width of 150 mm × height of 20 mm (extrusion cross-sectional area of 30 cm ² ).
The density of the obtained polyester resin molded product was measured. The cross-section of the polyester resin molded product was observed to evaluate the bubble shape. Furthermore, the dimensional stability and surface property of the polyester resin molded product were evaluated. The bubble shape, dimensional stability and surface properties were evaluated based on the following evaluation criteria. The results are shown in Table 2.

(Bubble shape)
The polyester resin molded product was cut, and the shape of bubbles in the cross section was observed with an electron microscope.
○: Independent bubbles and small variation in bubble size.
X: Many communication bubbles are confirmed, and the bubble size is largely varied.

(Dimensional stability)
○: The polyester resin molded product has no shrinkage and the same cross-sectional area as the die.
X: Shrinkage is confirmed in the central part of the polyester resin molded product.

[Surface property]
○: The surface of the polyester resin molded product is smooth and rough skin is not confirmed.
X: Skin roughness due to foam breakage is confirmed on the surface of the polyester resin molded product.

[Examples 2-4 and Comparative Examples 1-2]
In Example 1, a polyester resin molded product was prepared and evaluated in the same manner as in Example 1 except that the dimensional stability imparting agent and the melt viscosity modifier used as necessary were changed as shown in Table 1. . The results are shown in Table 2, respectively.
In Comparative Example 1, the melt viscosity of the polyester resin composition during extrusion molding was too low to be molded.

As is clear from the results in Table 2, according to the polyester resin composition of the present invention, the polyester resin molded article has good dimensional stability, excellent surface properties, and has closed cells inside and is lightened. Can be molded. In particular, a profile extrusion molded product having an extrusion cross-sectional area of 10 cm ² or more is excellent in dimensional stability and suitable as a building material.
In Tables 1 and 2, the abbreviations shown in Table 3 are used.

Claims (9)

A composition containing a recycled polyester resin and a dimensional stability imparting agent,
The dimensional stability-imparting agent includes an outer shell made of a thermoplastic resin obtained by polymerizing a polymerizable component containing a carboxyl group-containing monomer and a nitrile monomer as a monomer component, and is encased therein and heated. heat-expandable microspheres der comprised of a blowing agent which vaporizes by is,
The weight ratio of the mixture of the carboxyl group-containing monomer and the nitrile monomer is 80% by weight or more based on the monomer component,
The ratio of the carboxyl group-containing monomer in the mixture of the carboxyl group-containing monomer and the nitrile monomer is 30 to 90% by weight,
Polyester resin composition.   The polyester resin composition according to claim 1, wherein a weight ratio of the dimensional stability imparting agent is 0.01 to 30% by weight.   The polyester-type resin composition of Claim 1 or 2 in which the said thermally expansible microsphere contains the metal which belongs to the periodic tables 1-2 group. The polyester-type resin composition in any one of Claims 1-3 whose expansion start temperature of the said thermally expansible microsphere is 200 degreeC or more .   The polyester resin composition according to any one of claims 1 to 4, wherein the thermally expandable microsphere is surface-treated with an organic compound containing a metal belonging to Groups 3 to 12 of the periodic table.   The polyester resin composition according to claim 1, further comprising a melt viscosity modifier.   A polyester resin molded product obtained by molding the polyester resin composition according to claim 1. The polyester resin molded product according to claim 7, wherein the molding is profile extrusion molding, and an area (extrusion cross-sectional area) of a cut surface perpendicular to the extrusion direction is 10 cm ² or more.   The polyester resin molded product according to claim 7 or 8, which is a building material.