JPWO2018012415A1 - Resin composition and use thereof - Google Patents

Abstract

An object of the present invention is to provide a resin composition and its use which can produce a resin molded product excellent in production stability and lightening efficiency. The resin composition contains hollow particles (A) and an organic base resin (B), and the hollow particles (A) are contained in an outer shell made of a thermoplastic resin and are contained therein and are vaporized by heating. An expandable body of thermally expandable microspheres composed of a foaming agent, wherein the volume ratio (P) of the amount of air contained in the hollow particles (A) makes the total volume of the hollow particles (A) 100%. When it is over 30%.

Description

  The present invention relates to a resin composition and its use.

Hollow particles such as plastic balloons have been used as lightening fillers for clays, paints, adhesives and the like. The purpose of blending these lightening fillers is cost reduction due to environmental measures and saving of resin components (Patent Document 1).
Such a plastic balloon has a thermoplastic resin as an outer shell and is obtained by expanding thermally expandable microspheres having a structure in which a foaming agent is enclosed. The thermally expandable microspheres are generally referred to as thermally expandable microcapsules. As the thermoplastic resin, a vinylidene chloride copolymer, an acrylonitrile copolymer, an acrylic ester copolymer and the like are usually used. Moreover, hydrocarbons, such as isobutane and isopentane, are mainly used as a foaming agent (refer patent document 2).

However, these lightweight fillers have insufficient improvement in the resistance to the load due to external pressure at the time of mixing and filling in the production process of the resin composition.
In addition, Patent Document 3 has a hollow particle formed by heating and foaming a thermally expandable microcapsule having an outer shell formed of a polymer obtained from a specific monomer and a crosslinking agent and having an expansion ratio of 20 to 100 times. It is described to be formulated into lightweight cement products. However, even with this hollow particle, the improvement of the resistance of the hollow particle to the load by the external pressure is insufficient.

WO 97/05201 U.S. Pat. No. 3,615,972 Japanese Patent Application Laid-Open No. 2004-131361

  An object of the present invention is to provide a resin composition and its use which can produce a resin molded product excellent in production stability and lightening efficiency.

  As a result of intensive investigations conducted by the inventor, the resin composition containing hollow particles (A) having a specific volume ratio of air content improves the resistance of the hollow particles to external pressure load, and the mixing and filling process. The present invention has been found out that the resin molded product having excellent production stability and lightening efficiency can be produced.

  That is, the resin composition of the present invention contains hollow particles (A) and an organic base resin (B), and the hollow particles (A) are contained in an outer shell made of a thermoplastic resin and contained therein and heated. And the expansion ratio of the amount of air contained in the hollow particles (A) is the expansion of the whole of the hollow particles (A). When the volume is 100%, it is 30% or more.

It is preferable that the resin composition of the present invention further satisfy at least one selected from the following 1) to 2).
1) The volume-based cumulative 50% particle diameter (D50) of the hollow particles (A) is 1 to 300 μm.
2) paint compositions, adhesive compositions or resin clays.

The molded product of the present invention is obtained by molding the above resin composition.
The method for producing a resin composition of the present invention comprises the step (1) of obtaining thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent which is contained therein and is vaporized by heating. The step of obtaining the hollow particles (a) by heating and expanding the thermally expandable microspheres (2), and ripening the hollow particles (a) at a temperature of -10 to 80 ° C to obtain the hollow particles (A) And the step (4) of mixing the obtained hollow particles (A) and the organic base resin (B), and the volume ratio of the amount of air contained in the hollow particles (A) ( P) is 30% or more when the volume of the whole hollow particle (A) is 100%.

  By using the resin composition of the present invention or the resin composition obtained by the production method of the present invention, it is possible to produce a resin molded product excellent in production stability and weight reduction efficiency.

It is an example of the schematic diagram of a hollow particle (A). It is the schematic of the foaming process part of the manufacturing apparatus for manufacturing a hollow particle by the dry heating expansion method.

  The resin composition of the present invention contains hollow particles (A) and an organic base resin (B). The details will be described below.

[Hollow particles (A)]
Hollow particles (A) are an essential component of the resin composition of the present invention. The hollow particles (A) are expandable bodies of thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent which is contained therein and is vaporized by heating, and the hollow particles (A) When the volume ratio (P) of the amount of air contained in the hollow particle (A) is 100%, the volume ratio (P) is 30% or more. The hollow particle (A) will be described by way of an example of its production method.

  As a method of producing hollow particles (A), a step (1) of producing thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent contained therein and vaporized by heating C., the step of obtaining the hollow particles (a) by heating and expanding the thermally expandable microspheres obtained in the step (1), and the hollow particles (a) obtained in the step (2) at a temperature of -10.degree. The production method may include the step (3) of ripening in the range of to obtain hollow particles (A). In addition, a process (1) may be called a superposition | polymerization process, a process (2) may be called expansion | swelling process, and a process (3) may be called an aging process.

(Polymerization process)
The polymerization step refers to the step (1) of producing thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent contained therein and vaporized by heating. As the polymerization step, there is mentioned a step of dispersing an oily mixture containing a polymerizable component and a foaming agent in an aqueous dispersion medium, and polymerizing the polymerizable component.
The blowing agent is not particularly limited as long as it is a substance which is vaporized by heating, and for example, propane, (iso) butane, (iso) pentane, (iso) hexane, (iso) heptane, (iso) octane, ( Hydrocarbons having 3 to 13 carbon atoms such as iso) nonane, (iso) decane, (iso) undecane, (iso) dodecane, (iso) tridecane, and the like; and having more than 13 carbon atoms such as (iso) hexadecane and (iso) eicosane 20 or less hydrocarbons etc. can be mentioned. These foaming agents may be used alone or in combination of two or more.
The blowing agent is preferably a hydrocarbon having a boiling point of less than 60.degree. When a hydrocarbon having a boiling point of more than 60 ° C. is used, crushing of the hollow particles (A) may occur during mixing of the resin composition, and a sufficient weight reduction rate may not be obtained.

The polymerizable component is a component that becomes a thermoplastic resin that forms an outer shell of thermally expandable microspheres by polymerization. A polymerizable component is a component which makes a monomer component essential and may contain a crosslinking agent.
The monomer component generally includes a component called as a (radical) polymerizable monomer having one polymerizable double bond.

A thermoplastic resin obtained by polymerizing a polymerizable component in which the monomer component is a nitrile monomer, the polymerizable component contains a nitrile monomer, and the hollow particle contains a nitrile monomer The composition is preferable because it is excellent in the retention of the blowing agent contained in the hollow particles (A) and (a).
Examples of nitrile monomers include acrylonitrile (AN), methacrylonitrile (MAN), fumaronitrile and the like.

The weight ratio of the nitrile monomer in the polymerizable component is not particularly limited, but is preferably 20% by weight or more, more preferably 40% by weight or more, and particularly preferably 60% by weight or more. The upper limit of the weight ratio of the nitrile monomer is preferably 100% by weight. If the weight ratio of the nitrile monomer is less than 20% by weight, the retention of the foaming agent contained in the hollow particles (A) and (a) may be poor, and the foaming agent may be slowly released.
When the nitrile monomer essentially comprises acrylonitrile (AN) and methacrylonitrile (MAN), thermally expanded microcapsules and hollow particles (A) and (a), which are raw materials of hollow particles (A) and (a), can be used. It is preferable because it is excellent in the retention of the blowing agent contained therein.

The polymerizable component may contain a monomer other than a nitrile monomer as a monomer component.
The monomer other than the nitrile monomer is not particularly limited. For example, a vinyl halide monomer such as vinyl chloride; a vinylidene halide monomer such as vinylidene chloride; vinyl acetate, propionic acid Vinyl ester monomers such as vinyl and vinyl butyrate; Carboxyl group-containing monomers such as (meth) acrylic acid, ethacrylic acid, crotonic acid and cinnamic acid; Carboxylic acid anhydrides such as maleic acid, itaconic acid and fumaric acid Monomer; 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 monomers such as (meth) acrylate and 2-hydroxyethyl (meth) acrylate; (meth) acrylamide monomers such as acrylamide, substituted acrylamide, methacrylamide and substituted methacrylamide; N- Maleimide based monomers such as phenyl maleimide and N-cyclohexyl maleimide; Styrene based monomers such as styrene and α-methyl styrene; Ethylenically unsaturated monoolefin based monomers such as ethylene, propylene and isobutylene; Vinyl methyl ether, Vinyl ether monomers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketone monomers such as vinyl methyl ketone; N-vinyl monomers such as N-vinylcarbazole and N-vinyl pyrrolidone; vinyl naphthalene salts etc. It can be mentioned. (Meth) acrylic means acrylic or methacrylic.

The polymerizable component includes (meth) acrylate monomers, carboxyl group-containing monomers, styrene monomers, vinyl ester monomers, acrylamide monomers, maleimide monomers, and vinylidene chloride It is preferable to further include at least one selected from
It is preferable that the polymerizable component contains a nitrile monomer and a (meth) acrylic acid ester monomer from the viewpoint of the retention of the foaming agent in the thermally expandable microspheres and the heat resistance.

  The polymerizable component may contain, in addition to the above-mentioned monomer components, a polymerizable monomer (crosslinking agent) having two or more polymerizable double bonds. By polymerization using a crosslinking agent, a temporal decrease in retention of the contained foaming agent at the time of thermal expansion can be suppressed, and thermal expansion can be performed effectively.

  The crosslinking agent is not particularly limited. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, allyl methacrylate, triacrylic formal, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, PEG # 200 di (meth) acrylate, PEG # 400 di (meth) acrylate, PEG # 600 di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethyl Triol propane tri (meth) acrylate, EO modified trimethylol propane tri (meth) acrylate, glycerin di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned. 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, particularly preferably 0.1 to 1 part by weight, per 100 parts by weight of the monomer component. 3 to 0.9 parts by weight, most preferably 0.5 to 0.8 parts by weight.
The polymerization of the polymerizable component may be carried out using a polymerization initiator, and an oil-soluble polymerization initiator is preferred.

In the polymerization step, the oily mixture may further contain a chain transfer agent and the like.
The aqueous dispersion medium is a medium containing water as a main component, such as ion-exchanged water, for dispersing the oily mixture, and may further contain an alcohol such as methanol, ethanol or propanol, or a hydrophilic organic solvent such as acetone. . The hydrophilicity in the present invention means being in a state of being freely miscible with water. The amount of the aqueous dispersion medium used is not particularly limited, but it is preferable to use 100 to 1000 parts by weight of the aqueous dispersion medium with respect to 100 parts by weight of the polymerizable component.

  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, sodium carbonate and the like. These electrolytes may be used alone or in combination of two or more. The content of the electrolyte is not particularly limited, but preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the aqueous dispersion medium.

  The 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 nitrites, metal (III) halides, 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 the present invention, water solubility means that 1 g or more is dissolved in 100 g of water.

  The amount of the water-soluble compound contained in the aqueous dispersion medium is not particularly limited, but preferably 0.0001 to 1.0 parts by weight, more preferably 0.0003 to 100 parts by weight with respect to 100 parts by weight of the polymerizable component. The amount is 0.1 parts by weight, particularly preferably 0.001 to 0.05 parts by weight. When the amount of the water soluble compound is too small, the effect of the water soluble compound may not be sufficiently obtained. In addition, when the amount of the water-soluble compound is too large, the polymerization rate may be decreased, or the residual amount of the polymerizable component as the raw material may be increased.

The aqueous dispersion medium may contain, in addition to the electrolyte and the water-soluble compound, a dispersion stabilizer and a dispersion stabilizer adjuvant.
The dispersion stabilizer is not particularly limited, but, for example, colloidal silica, colloidal calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, ferric hydroxide, calcium sulfate, barium sulfate, calcium borate, metasilicate Phosphate such as calcium, calcium carbonate, barium carbonate, magnesium carbonate, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium pyrophosphate, pyrophosphate such as aluminum pyrophosphate, zinc pyrophosphate, alumina sol etc Dispersion stabilizers of water-soluble inorganic compounds can be mentioned. These dispersion stabilizers may be used alone or in combination of two or more.
The compounding amount of the dispersion stabilizer is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymerizable component.

The dispersion stabilizing adjuvant is not particularly limited, and, for example, a polymer type dispersion stabilizing adjuvant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, an interface such as a nonionic surfactant, etc. Activators can be mentioned. These dispersion stabilizing adjuvants may be used alone or in combination of two or more.
The aqueous dispersion medium is prepared, for example, by mixing a water-soluble compound and, if necessary, a dispersion stabilizer and / or a dispersion stabilizer adjuvant with water (ion-exchanged water). The pH of the aqueous dispersion medium at the time of polymerization is appropriately determined depending on the types of the water-soluble compound, the dispersion stabilizer, and the dispersion stabilizer adjuvant.

As a method of emulsifying and dispersing the oily mixture, for example, a method of stirring with a homomixer (for example, manufactured by Tokushu Kika Kogyo Co., Ltd.) or a static dispersing device such as a static mixer (for example, manufactured by Noritake Engineering Co., Ltd.) And dispersion methods such as a membrane emulsification method and an ultrasonic dispersion method.
Then, suspension polymerization is initiated by heating the dispersion in which the oily mixture is dispersed in the aqueous dispersion medium as spherical oil droplets. During the polymerization reaction, it is preferable to stir the dispersion, and the stirring may be carried out, for example, to such an extent that the floating of the monomer and the sedimentation of the thermally expandable microspheres after polymerization can be prevented.
The polymerization temperature is freely set according to the type of polymerization initiator, but is preferably in the range of 30 to 100 ° C., more preferably 40 to 90 ° C., particularly preferably 45 to 80 ° C., most preferably 50 to 75 ° C. It is controlled. The time for maintaining the reaction temperature is preferably about 0.1 to 20 hours. The initial pressure of polymerization is not particularly limited, but it is in the range of 0 to 5.0 MPa, more preferably 0.1 to 3.0 MPa in gauge pressure.

(Inflating process)
The expansion step refers to the step (2) of heat-expanding the thermally expandable microspheres obtained in the step (1) to obtain hollow particles (a). The expansion step is not particularly limited as long as it is a step of thermally expanding thermally expandable microspheres, but any of a dry thermal expansion method and a wet thermal expansion method may be used.
As a dry-type heating expansion method, the method described in Unexamined-Japanese-Patent No. 2006-213930, especially the internal injection method can be mentioned. Moreover, as another dry-type thermal expansion method, there is a method described in JP-A-2006-96963. As a wet thermal expansion method, there is a method described in JP-A-62-201231 and the like.
The temperature at which the thermally expandable microspheres are heated and expanded is preferably 60 to 350 ° C.

  The hollow particle (a) has an outer shell made of a thermoplastic resin. The hollow particle is composed of an outer shell and a hollow portion surrounded by the outer shell. The hollow particle has a hollow portion corresponding to a large cavity inside. The hollow portion is in contact with the inner surface of the outer shell. The hollow portion is basically filled with a gas and may be in a liquefied state. The hollow portion is usually preferably one large hollow portion, but a plurality of hollow portions may be present.

The hollow particles (a) are expansion bodies of the above-mentioned thermally expandable microspheres, which are not matured or those which are insufficiently matured. Aging will be described in detail in the aging step. The hollow particles (a) can be obtained by heating and expanding the above-mentioned thermally expandable microspheres and then cooling them to room temperature. An air concentration gradient is generated inside and outside the hollow portion of the hollow particle immediately after the cooling, and a negative pressure state occurs because the air content in the hollow portion of the hollow particle is low. Therefore, it has a distorted shape or is weak to external pressure. When such hollow particles (a) are used as a lightweight filler for a resin composition, the hollow particles (a) may be easily deformed, crushed, or ruptured to cause the foaming agent to leak, and the resin composition The weight reduction efficiency of the object and its molded body is lowered.
The volume ratio (P) of the amount of air contained in the hollow particles (a) is less than 30% when the volume of the whole hollow particles is 100%. The method of measuring the volume fraction (P) will be described in the ripening step.

(Aging process)
The ripening step refers to the step (3) of ripening the hollow particles (a) obtained in the step (2) at a temperature of -10 to 60 ° C. to obtain hollow particles (A). The ripening period is described below. In general, ripening refers to storage of a substance under appropriate conditions for a certain period of time in order to obtain the property required of the substance. As described above, in the hollow particles (a) obtained in the step (2), the air concentration in the hollow portion is lower than that in the outside, and the hollow portion of the hollow particles is in a negative pressure state. Therefore, it has a distorted shape or is weak to external pressure. The term "aging" in the present invention means that air in the atmosphere is gradually taken into the hollow part, thereby eliminating the concentration gradient of air inside and outside the hollow part, balancing the internal pressure and external pressure of the particles, and improving the resistance to external pressure. It means to let it go. Specifically, the hollow particles (a) obtained in the step (2) are stored at a temperature of -10 to 60 ° C (hereinafter, this temperature is referred to as a ripening temperature) for a certain period of time.

It can be confirmed, for example, by the following method as to whether or not the hollow portion of the hollow particle is in a negative pressure state (whether or not the hollow particle is matured).
As one method, the degree of ripening can be confirmed by calculating the amount of air taken into the hollow particles. For example, hollow particles can be stored in a sealed container in a state containing air, and the amount of air taken into the hollow particles can be calculated from the volume change of the sealed container. When the volume of the whole container decreases, it means that the air in the container is taken inside the hollow particles. Depending on the aging conditions, the sealed container may expand.
Another method is a method of measuring the amount of air or the amount of oxygen contained in the hollow particles.

  The aging temperature of the hollow particles (a) is in the range of -10 to 80 ° C, preferably -10 to 60 ° C, more preferably -5 to 50 ° C, still more preferably 0 to 40 ° C, particularly preferably 5 It is -35 ° C, most preferably 10-30 ° C. When the aging temperature is less than -10 ° C, the hollow particles are not sufficiently restored, and may deform, collapse or rupture due to an external factor to cause the foaming agent to leak. On the other hand, when the aging temperature is higher than 80 ° C., controlled release of the foaming agent occurs, and deformation or crushing occurs due to external factors.

In the aging period of the hollow particles (a), the volume ratio (P) of the amount of air contained in the hollow particles (a) is 30% or more when the volume of the whole hollow particles (a) is 100% (that is, It will not be limited especially if it is a period which becomes the above-mentioned hollow particle (A). The aging period can be determined according to the aging temperature (T) (° C.). In the case of ripening at the ripening temperature (T) (° C.), the ripening period (Q) (hour) preferably satisfies the following formula (I).
Q ≧ 62 × e ^{−0.03 T} (I)
When the aging period does not satisfy the above-mentioned formula (I), the internal pressure and the external pressure of the hollow particles are not balanced, and the foaming agent may be deformed or crushed or ruptured due to an external factor. The upper limit of the ripening period is not particularly limited as long as the effect of ripening is exhibited, but the period is about 8 weeks. After aging, it is also possible to store for a period of time in which the quality of the hollow particles (A) can be maintained.

  The hollow particles (a) obtained by the dry thermal expansion method are powder, and are aged in the form of powder. Also in the case of the hollow particles (A1) to which the fine particle filler described later adheres, it is similarly aged in the form of powder. On the other hand, the hollow particles (a) obtained by the wet thermal expansion method become a hollow particle composition containing water, and are aged in the state of the hollow particle composition containing water. The weight ratio of water to the hollow particle composition is not particularly limited, and is preferably 99 wt% or less, more preferably 84 wt% or less, particularly preferably 49 wt% or less, most preferably 30 wt% or less . When aging is performed in a sealed state and in a state in which there are too few voids other than hollow particles, aging may not proceed well even at a predetermined temperature and for a predetermined time.

The hollow particle (A) has an outer shell made of a thermoplastic resin. The hollow particles (A) are preferably composed of an outer shell and a hollow portion surrounded by the outer shell. The hollow particles (A) are (approximately) spherical and have hollows corresponding to large cavities inside. A soft tennis ball can be mentioned if the shape of a hollow particle is illustrated with a familiar article.
The hollow portion is (approximately) spherical and is in contact with the inner surface of the outer shell. The hollow portion is basically filled with a gas and may be in a liquefied state. The hollow portion is usually preferably one large hollow portion, but a plurality of hollow portions may be present.

The hollow particles (A) used in the resin composition of the present invention are the expansion bodies of the above-mentioned thermally expandable microspheres, and the volume ratio (P) of the amount of air contained in the hollow particles (A) A) When the total volume is 100%, it means 30% or more. By using such hollow particles (A), the effects of the present invention can be exhibited. When the volume ratio (P) is less than 30%, the hollow particles may be deformed, crushed or ruptured by an external factor to cause the foaming agent to leak. The volume fraction (P) is preferably 35 to 99%, more preferably 40 to 98%, still more preferably 45 to 95%, particularly preferably 50 to 90%.
The measuring method of the volume ratio (P) of the amount of air contained in a hollow particle is shown in the following Example. The amount of air contained in the hollow particles can be quantified from the amount of gas collected and the oxygen concentration in the gas. The measurement method of the oxygen concentration is not limited to the galvanic cell type, but there are the zirconia type and the magnetic type. However, while the galvanic cell type can be measured without any error even in the flammable gas, the zirconia type and the magnetic type are The inclusion of the flammable gas is not preferable because the measurement error becomes large.

The hollow particles (A) preferably have a volume ratio (Z) of the amount of air taken in to the hollow particles within a certain range from the viewpoint of exerting the effect of the present invention. The volume ratio (Z) is the volume of the container sealed in a state containing hollow particles of volume (V) and air as (Y1) and the volume of the container after standing under certain conditions as (Y2) When, it says what is shown by the following formula. The specific measuring method of the volume ratio (Z) of the intake air quantity with respect to a hollow particle is shown in the following Example.
Volume ratio of the amount of air taken in to hollow particles (Z) = (Y1-Y2) / V
The volume ratio (Z) is preferably −0.05 ≦ (Z) ≦ 0.2, more preferably −0.05 ≦ (Z) ≦ 0.05, still more preferably −0.02 ≦ (Z) It is ≦ 0.02.

The retention of the foaming agent in the hollow particles (A) is preferably 85% or more, more preferably 90% or more, particularly preferably 95% or more, and most preferably 97%. If the foaming agent retention is less than 85%, the mechanical strength of the hollow particles (A) is weak, and the hollow particles (A) are easily crushed at the time of production of the resin composition, so the effect as a lightweight filler is lowered. There is. The measuring method of the foaming agent retention of a hollow particle (A) is shown in the following Example.
The hollow particles (A) may be used in the resin composition as a hollow particle composition containing water. The weight ratio of water to the hollow particle composition is not particularly limited, and is preferably 99 wt% or less, more preferably 84 wt% or less, particularly preferably 49 wt% or less, most preferably 30 wt% or less . When the weight ratio of water to the hollow particle composition is too large, it may not be uniformly dispersed when mixed with other components constituting the resin composition.

  The volume based cumulative 50% particle diameter (D50) of the hollow particles (A) is not particularly limited, but is preferably 1 to 300 μm, more preferably 2 to 200 μm, still more preferably 3 to 150 μm, particularly preferably Is 5 to 130 μm, most preferably 7 to 120 μm. When D50 is out of this range, the weight reduction efficiency may be deteriorated when it is used for the resin composition.

  The true specific gravity of the hollow particles (A) is not particularly limited, but preferably 0.01 to 0.5, more preferably 0.012 to 0.49, still more preferably 0.04 to 0.49, particularly It is preferably 0.1 to 0.48, and most preferably 0.31 to 0.47. When the true specific gravity is less than 0.01, the strength of the hollow particle (A) is reduced due to the thin thickness of the shell of the hollow particle (A), and the hollow particle (A) is broken when the resin composition is mixed, and the weight reduction efficiency is lowered. There is something to do. On the other hand, when the true specific gravity exceeds 0.5, the weight reduction effect commensurate with the amount to be blended is low and it is uneconomical.

The hollow particles (A) may further be composed of a fine particle filler attached to the outer surface of the outer shell, as shown in FIG. Hereinafter, the hollow particles (A) to which the particulate filler is attached may be referred to as "hollow particles (A1)" for the sake of simplicity. The adhesion referred to here may simply be a state 6 in which the particulate filler (6 and 7) is adsorbed on the outer surface of the outer shell 5 of the hollow particle (A1) 4, and the outer shell near the outer surface It means that the thermoplastic resin to be configured may be softened or melted by heating, and the fine particle filler may be embedded in the outer surface of the outer shell of the hollow particle (A1) and be fixed. The particle shape of the particulate filler may be amorphous or spherical.
The true specific gravity of the hollow particles (A1) is not particularly limited, but preferably 0.01 to 0.5, more preferably 0.03 to 0.4, and still more preferably 0.05 to 0.35. , Particularly preferably 0.07 to 0.3, most preferably 0.1 to 0.25. When the true specific gravity of the hollow particles (A1) is smaller than 0.01, the durability may be lowered. On the other hand, when the true specific gravity of the hollow particles (A1) is larger than 0.5, the effect of lowering the specific gravity becomes low, so when preparing the resin composition using the hollow particles (A1), the addition amount thereof becomes large. It may be uneconomical.

The ratio of the average particle size of the particulate filler to the average particle size of the hollow particles (A1) (average particle size of the particulate filler / average particle size of the hollow particles (A1)) is from the viewpoint of adhesion of the particulate filler It is preferably 1 or less, more preferably 0.8 or less, more preferably 0.6 or less, particularly preferably 0.4 or less, most preferably 0.2.
As the fine particle filler, various ones can be used, and either inorganic or organic material may be used. The shape of the fine particles may, for example, be spherical, needle-like, plate-like or amorphous.

The average particle size of the fine particle filler is appropriately selected depending on the hollow particle body to be used, and is not particularly limited, but preferably 0.001 to 30 μm, more preferably 0.005 to 25 μm, particularly preferably 0.01 to 20 μm It is. When it is in this range, as described later, the mixing property becomes good when the hollow particles (A1) are produced.
The average particle size of the particulate filler as referred to herein is the particle size of the particulate filler measured by a laser diffraction method. If the particle size of the fine particle filler is micron order, it refers to primary particles, but in many cases the nano order particles etc. are aggregated, and since they act as aggregates of substantially micron order, the aggregated secondary particles 1 The average particle size was calculated as a unit.

  Examples of the inorganic substance constituting the fine particle filler include limestone (heavy calcium carbonate), quartz, silica (silica), wollastonite, gypsum, asbestos, apatite, magnetite, zeolite, clay (montmorillonite, saponite, hectorite, beidellite, Minerals such as stevensite, nontronite, vermiculite, halloysite, talc, mica, mica, etc .; Group 1 to 16 metals (zinc, aluminum, molybdenum, tungsten, zirconium, barium, etc.) in the periodic table of the elements Manganese, cobalt, calcium, gold, silver, chromium, titanium, iron, platinum, copper, lead, nickel, etc.) and alloys thereof; metal oxides of groups 1 to 16 in the periodic table of the elements (titanium oxide, oxide Zinc, aluminum oxide, chromium oxide, manganese oxide, Molybdenum oxide, tungsten oxide, vanadium oxide, tin oxide, iron oxide (including magnetic iron oxide), indium oxide etc., metal hydroxides (aluminum hydroxide, gold hydroxide, magnesium hydroxide etc.), metal sulfides Copper sulfide, sodium sulfide, lead sulfide, nickel sulfide, platinum sulfide etc., metal halides (calcium fluoride, tin fluoride, potassium fluoride etc.), metal carbides (calcium carbide, titanium carbide, iron carbide, sodium carbide etc.) ), Metal nitrides (aluminum nitride, chromium nitride, germanium nitride, cobalt nitride etc.), metal carbonates (calcium carbonate (light calcium carbonate), calcium hydrogencarbonate, sodium hydrogencarbonate (sodium bicarbonate), iron carbonate etc.), metal sulfates Salts (aluminum sulfate, cobalt sulfate, sodium hydrogensulfate, copper sulfate, nickel sulfate, burrs sulfate And other metal salts (titanate (barium titanate, magnesium titanate, potassium titanate etc.), borates (aluminium borate, zinc borate etc.), phosphates (calcium phosphate, sodium phosphate, phosphate) Examples thereof include metal compounds such as magnesium), aluminates (yttrium aluminate etc.), and nitrates (sodium nitrate, iron nitrate, lead nitrate etc.) and the like.

  The inorganic substance constituting the fine particle filler may also be synthetic calcium carbonate, ferrite, zeolite, silver ion-loaded zeolite, zirconia, alum, lead zirconate titanate, alumina fiber, cement, sonotolite, silicon oxide (silica, silicate, glass, Glass fibers may be included, silicon nitride, silicon carbide, silicon sulfide, carbon black, carbon nanotubes, graphite, activated carbon, bamboo charcoal, charcoal, fullerene, and the like.

Examples of the organic substance constituting the particulate filler include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, vinylbenzoic acid, esters thereof, amides, nitriles, styrene, methylstyrene, Emulsion polymerization method, leap using a crosslinking agent, if necessary, using vinyl aromatics such as ethylstyrene and chlorostyrene, and divinyl compounds having two or more vinyl groups such as divinylbenzene and trimethylolpropane as monomers. Organic resin etc. which were obtained by polymerizing by the free polymerization method, the dispersion polymerization method, the suspension polymerization method, the mini-emulsion polymerization method etc. are mentioned.
The organic substance constituting the particulate filler is sodium carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, nitrocellulose, hydroxypropylcellulose, sodium alginate, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide It may be resin, nylon resin, silicone resin, urethane resin, polyethylene resin, polypropylene resin, fluorine resin, or the like.

If the particulate filler is composed of organic matter, it is better not to soften. When softened, fusion may occur during production of the hollow particles (A1) to which fine particles further adhere, which may cause problems such as deterioration in yield. The softening temperature of the organic matter depends on the temperature at the production of the hollow particles (A1), but is preferably 80 to 300 ° C., more preferably 90 to 290 ° C., and still more preferably 100 to 280 ° C. The softening temperature of the organic substance is also preferably 10 ° C. or more higher than the process temperature.
The inorganic substance and the organic substance constituting the fine particle filler may be treated with a surface treatment agent such as a silane coupling agent, paraffin wax, fatty acid, resin acid, urethane compound, fatty acid ester or the like, or may be untreated.

  As a method for producing hollow particles (A1), for example, the step (1) of producing thermally expandable microspheres, and the step of mixing the obtained thermally expandable microspheres with a fine particle filler (simply referred to as mixing step) And heating the mixture obtained in the mixing step to a temperature above the softening point of the thermoplastic resin to expand the thermally expandable microspheres (corresponding to the above step (2)) and filling the fine particles Manufacturing method including the step of attaching the agent to the outer surface of the outer shell (adhesion step) and the step (3) of ripening the hollow particles (a) to which the fine particle filler is attached to obtain the hollow particles (A1) Can be mentioned.

The mixing step is a step of mixing the thermally expandable microspheres and the particulate filler.
The weight ratio of the fine particle filler to the thermally expandable microspheres (fine particle filler / thermally expandable microspheres) in the mixing step is not particularly limited, but preferably 90/10 to 60/40, more preferably 85. / 15 to 65/35, particularly preferably 80/20 to 70/30. When the ratio of fine particle filler to thermally expandable microspheres (weight ratio) is larger than 90/10, the true specific gravity of the hollow particles (A1) may be large, and the low specific gravity effect may be small. On the other hand, when the ratio of fine particle filler to thermally expandable microspheres (weight ratio) is smaller than 60/40, the true specific gravity of the hollow particles (A1) may be low, and handling such as dusting may be deteriorated.

There is no limitation in particular as an apparatus used for a mixing process, It can carry out using the apparatus provided with the very simple mechanism of a container and a stirring blade. Moreover, you may use the powder mixer which can perform general rocking | fluctuation or stirring. As a powder mixer, the powder mixer which can perform rocking | stirring stirring or stirring, such as a ribbon type mixer and a vertical screw type mixer, can be mentioned, for example. In recent years, super mixers (manufactured by Kawata Co., Ltd.) and high speed mixers (manufactured by Fukae Co., Ltd.), which are efficient multi-functional powder mixers by combining stirring devices, Newgram Machine (Seishin Co., Ltd.) , SV mixer (manufactured by Shinko Environmental Solution Co., Ltd.) or the like may be used.
The adhesion step heats the mixture containing the thermally expandable microspheres and the particulate filler obtained in the mixing step to a temperature above the softening point of the thermoplastic resin constituting the shell of the thermally expandable microspheres. It is a process. In the attaching step, the thermally expandable microspheres are expanded and the particulate filler is attached to the outer surface of the outer shell.

Heating may be performed using a general contact heat transfer type or direct heating type mixing type drying apparatus. The function of the mixing-type drying device is not particularly limited, but it is preferable to have a temperature-controllable ability to disperse and mix the raw materials, and a decompression device and a cooling device to accelerate drying in some cases. The apparatus used for heating is not particularly limited, and examples thereof include a Loedige mixer (manufactured by Matsubo Co., Ltd.), Solid Air (Hosokawa Micron Co., Ltd.), and the like.
The temperature condition for heating depends on the type of thermally expandable microspheres, but the optimum expansion temperature is preferably 60 to 250 ° C., more preferably 70 to 230 ° C., still more preferably 80 to 220 ° C. The temperature is particularly preferably 100 to 200 ° C, most preferably 120 to 180 ° C.

[Organic base resin (B)]
The resin composition of the present invention essentially comprises the organic base resin (B). It does not specifically limit as organic base resin (B), Resin used for a coating composition, adhesive composition, and resin clay is mentioned. For example, acrylic resin, polyvinyl chloride resin (PVC), urethane resin, epoxy resin, polyvinyl alcohol, vinyl acetate resin, ethylene / vinyl acetate copolymer resin, rubber, etc. may be mentioned. Among them, acrylic resin is preferable from the environmental point of view.

  As an acrylic resin, for example, a polymer of alkyl acrylate (alkyl as methyl, ethyl, butyl, 2-ethylhexyl etc.) or alkyl methacrylate (alkyl as methyl, ethyl butyl, lauryl, stearyl etc), or The acrylic resin etc. which contain a copolymer with other acrylic type monomers are mentioned.

  Examples of polyvinyl chloride resin (PVC) include homopolymers of polyvinyl chloride and copolymers (copolymers) made of vinyl chloride, vinyl acetate and the like.

  Examples of urethane resins include blocked urethane prepolymers and blocked polyisocyanate compounds.

The above-mentioned blocked urethane prepolymer can be produced, for example, according to the following procedure.
(1) First, a polyol and an excess polyisocyanate compound are reacted to obtain a terminal NCO-containing urethane prepolymer.
Examples of the polyol include polyoxyalkylene polyol (PPG), polyether polyol modified product, polyether polyol including polytetramethylene ether glycol; condensation polyester polyol, lactone polyester polyol, polyester polyol including polycarbonate diol, polybutadiene Polyol; Polyolefin type polyol; Polymerization or graft polymerization of acrylonitrile alone or a mixed monomer of acrylonitrile and at least one selected from the group consisting of styrene, acrylamide, acrylic ester, methacrylic ester and vinyl acetate among polyether polyols Polymer polyols and the like.

As the polyisocyanate compound, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-cyclo Pentane diisocyanate, 1,6-hexane diisocyanate (HDI), 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2, 6 Cyclohexanediisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) silane Chlorohexane, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), crude MDI, 2,4- or 2,6 -Tolylene diisocyanate (TDI), 4,4 '-toluidine diisocyanate, dianidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,3- or 1, 4- xylylene diisocyanate, ω, ω'-diisocyanate-1, 4-diethylbenzene, isophorone diisocyanate (IPDI), etc. are mentioned. These may be used alone or in combination of two or more.
(2) Next, a terminal NCO-containing urethane prepolymer is reacted with a suitable blocking agent (usually, 0.9 to 1.5 equivalents of blocking agent are reacted per mole of the former NCO) to give free NCO
Are blocked to obtain the desired blocked urethane prepolymer (in particular, one in which the above-mentioned polymer polyol is contained in at least a part of the above-mentioned polyol).
Examples of the blocking agent include alcohols such as methanol, ethanol, propanol, butanol and isobutanol; phenols such as phenol, cresol, xylenol, p-nitrophenol and alkylphenol; methyl malonate, ethyl malonate and dimethyl malonate Active methylene compounds such as diethyl malonate, ethyl acetoacetate, methyl acetoacetate and acetylacetone; Acid amides such as acetamide, acrylamide and acetanilide; Acid imides such as succinimide and maleinimide; 2-ethyl imidazole, 2- Imidazoles such as ethyl-4-methylimidazole; Lactams such as 2-pyrrolidone and ε-caprolactam; Acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, acetoaldoxy And oximes of ketones or aldehydes, and the like; and other ethyleneimines, bisulfites and the like. These may be used alone or in combination of two or more.

  As a specific example of the above-described blocked urethane prepolymer, for example, one obtained by reacting TDI and / or HDI as an excess polyisocyanate compound with polypropylene glycol and then reacting methyl ethyl ketoxime as a blocking agent can be mentioned.

  The blocked polyisocyanate compound can be obtained by blocking the free NCO of the polyisocyanate compound exemplified in the preparation of the terminal NCO-containing urethane prepolymer described above with the above-mentioned blocking agent. Specific examples of the blocked isocyanate compound include, for example, those obtained by reacting TDI and / or HDI as a polyisocyanate compound with methyl ethyl ketoxime as a blocking agent.

The epoxy resin is not particularly limited, and examples thereof include glycidyl ether type, glycidyl ester type, glycidyl amine type and alicyclic type.
The rubber type is not particularly limited, and examples thereof include chloroprene rubber type, styrene butadiene type, nitrile rubber type, natural rubber, silicone rubber and the like.

  These organic base resins (B) are usually secondary particles in which primary particles and / or primary particles are aggregated, and the particle size thereof is preferably 0.1 to 100 μm. Moreover, these organic base resins (B) may be used individually by 1 type, and may use 2 or more types together.

[Resin composition and method for producing resin composition]
The resin composition of the present invention essentially comprises hollow particles (A) and an organic base resin (B).

  0.3-1.4 are preferable, as for the true specific gravity of the said resin composition, 0.4-1.3 are more preferable, 0.5-1.2 are more preferable, 0.6-1.1 are especially preferable. Preferably, 0.7 to 0.95 is most preferred. If it is less than 0.3, the weight proportion of the hollow particles will be high, and the adhesion performance or the molding performance may be lowered. If it exceeds 1.4, the weight reduction effect may be insufficient.

  The weight ratio of the hollow particles (A) to the resin composition is preferably 0.1 to 30% by weight, more preferably 0.5 to 25% by weight, still more preferably 1.0 to 15%, based on the whole composition. % By weight, particularly preferably 1.4 to 10% by weight. If it is less than 0.1% by weight, the effect on weight reduction may be insufficient. If it exceeds 30% by weight, adhesion performance or molding performance may be lowered due to the high proportion by weight of the hollow particles.

  The weight ratio of the organic base resin (B) to the resin composition of the present invention is preferably 5 to 65% by weight, more preferably 10 to 55% by weight, still more preferably 15 to 45% with respect to the whole composition. It is weight%. If it is less than 5% by weight, excellent adhesion performance may not be obtained, and if it exceeds 65% by weight, mechanical properties, thermal properties and other properties of the molded article may not be obtained.

When the resin composition of the present invention contains a plasticizer (C), for example, it reduces the intermolecular force and lowers the glass transition temperature of the organic base resin (B) to impart flexibility, elasticity, adhesiveness and the like. It is preferable in order to improve both the workability such as spray application and the physical performance.
As a plasticizer (C), for example, di (2-ethylhexyl) phthalate, butyl benzyl phthalate (high polar plasticizer), dinonyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate, diundecyl phthalate, diheptyl phthalate, butyl Phthalates such as phthalyl butyl glycolate and isononyl benzyl phthalate; Aliphatic dibasic esters such as dioctyl adipate, didecyl adipate and dioctyl sebacate; polyoxyethylene glycol dibenzoate, polyoxypropylene glycol dibenzoate and the like Polyglycol benzoic acid ester; trimellitic acid ester; pyromellitic acid ester; phosphoric acid esters such as tributyl phosphate and tricresyl phosphate; alkyl substituted diphe Le, alkyl-substituted terphenyl, partially hydrogenated alkyl terphenyl, aromatic process oils, hydrocarbons such as pine oil, and the like. These may be used alone or in combination of two or more. Among them, phthalic acid ester is preferable in terms of cost and versatility.

  When the resin composition of the present invention contains a plasticizer (C), the weight ratio of the plasticizer (C) in the resin composition of the present invention is preferably 15 to 60% by weight with respect to the whole composition, 25 -45 wt% is more preferred. If the amount is less than 15% by weight, the coating film may be too hard, and the effect of the present invention may not be obtained. If it exceeds 60% by weight, the flowability of the coating film may be too high, and the film formation may not be sufficient.

The resin composition of the present invention is not particularly limited, but is preferably a paint composition, an adhesive composition or a resin clay from the viewpoint that the effect of the present invention is easily exhibited. The paint is not particularly limited, and examples thereof include automotive paints such as underbody coat agents and antivibration paints; architectural paints such as heat insulating paints, paints for outer walls, waterproof paints and the like; Adhesives include automotive seal adhesives such as body sealers, hemming adhesives, structural adhesives, spot sealers, mastic adhesives, sheet metal reinforcing agents, etc .; sealing agents for outer walls, adhesives for tiles, adhesives for soil, etc. Adhesives for construction; and the like.
The resin clay is not particularly limited, and examples thereof include lightweight clays used in the field of handicrafts, art, and education such as school teaching materials.

  The resin composition according to the present invention can be used as a filler (calcium carbonate, silicic acid, silicate, carbon black, talc, kaolin, silica, water, etc. depending on the application such as a paint composition, adhesive composition, resin clay, etc. Aluminum oxide, antimony trioxide, ferrites, barium titanate, mica, alumina, iron oxide etc., hygroscopic agent (calcium oxide, molecular sieves etc.), thixotropic agent (organic bentonite, fumed silica, aluminum stearate), Metal soaps, castor oil derivatives, etc., Stabilizer [2,6-di-t-butyl-4-methylphenol, 2.2-methylene-bis (4-methyl-6-t-butylphenol), dibutyldithiocarbamine Acid nickel, lead-based stabilizers, barium and zinc-based stabilizers, calcium and zinc-based stabilizers, organotin compounds, etc.], Accelerator (dibutyltin dilaurate, lead octylate, etc. bismuth octylate), a solvent which does not dissolve the latent curing agent (high boiling hydrocarbon solvent) may be added by appropriately selecting the epoxy resin and the like.

The case where the resin composition of the present invention is an adhesive composition will be described. An adhesive composition is a composition containing the said hollow particle (A) and organic base resin (B) used as an adhesion component.
The adhesive component is not particularly limited as long as it is an component capable of adhering between objects, but there is no limitation on one-component polyurethane adhesive component, two-component polyurethane adhesive component, one-component type modified silicone adhesive component, A two-component type modified silicone adhesive component, a one-component type polysulfide adhesive component, a two-component type polysulfide adhesive component, an acrylic adhesive component, etc. may be mentioned. The adhesive component is preferably at least one selected from a one-component polyurethane adhesive component, a two-component polyurethane adhesive component, a one-component type modified silicone adhesive component, and a two-component type modified silicone adhesive component.

The polyurethane adhesive component of the one-pack type contains an isocyanate group-containing urethane prepolymer as a curing component. The isocyanate group-containing urethane prepolymer reacts with water in the air to exhibit adhesiveness by crosslinking and curing.
As a one-component polyurethane adhesive component, for example, Penguin Seal 999 (manufactured by Sun Star Giken Co., Ltd.) is commercially available.

Next, a two-component type polyurethane adhesive component consists of two combinations of a urethane prepolymer (hereinafter sometimes referred to as A1) and a curing agent such as a polyol (hereinafter referred to as A2). In the two-component polyurethane adhesive component, adhesion is exhibited by crosslinking and curing by mixing A1 and A2.
As a two-component polyurethane adhesive component, for example, Penguin Seal PU 9000 type NB (manufactured by Sun Star Giken), Hamatight UH-30 (manufactured by Yokohama Rubber Co., Ltd.), Bond PU seal (manufactured by Konishi Co., Ltd.), etc. are commercially available. .

The one-pack type modified silicone adhesive component is one that exhibits adhesiveness by the crosslinkable silyl group-containing resin reacting with moisture in the air to crosslink and cure. As a modified silicone adhesive component of one-component type, for example, sealant 45 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH 780 sealant (manufactured by Toray Dow Corning), penguin seal 2505 (manufactured by Sunstar Giken Co., Ltd.), Hamatight SS-310 Yokohama Rubber Co., Ltd.) are commercially available.
Next, the two-component type modified silicone adhesive component comprises a siloxane polymer (hereinafter sometimes referred to as B1) and a curing agent such as a curing agent such as an organic tin compound (hereinafter sometimes referred to as B2). Adhesion is expressed by mixing and reacting. As a modified silicone adhesive component of two-pack type, for example, two-component sealant 74 (manufactured by Shin-Etsu Chemical Co., Ltd.), SE 792 sealant (manufactured by Toray Dow Corning), Penguin Seal SR 2520 (manufactured by Sunstar Giken Co., Ltd.), Hamatite silicone 70 (Yokohama rubber company make), Bond MS seal (Konishi company make) etc. are commercially available.

The one-component polysulfide adhesive component contains a liquid polysulfide resin as a curing component, to which a peroxide of an alkali or alkaline earth metal such as BaO ₂ or CaO ₂ is blended as a latent curing agent, It reacts with moisture in the air to generate adhesion. As a one-component type polysulfide adhesive component, for example, Topcor SP (manufactured by Toray Fine Chemical Co., Ltd.), Hamatight PS-ONE (manufactured by Yokohama Rubber Co., Ltd.), etc. are commercially available.
The two-component type polysulfide adhesive component is a base (hereinafter sometimes referred to as C1) made of a sulfide polymer, and a curing agent containing a metal peroxide such as PdO ₂ (hereinafter sometimes referred to as C2). The adhesion is generated by mixing the For example, Penguin Seal PS169N (manufactured by Sun Star Giken Co., Ltd.), Hamatight SC-M500 (manufactured by Yokohama Rubber), etc. are commercially available as the two-component type polysulfide adhesive component.

The acrylic adhesive component is composed of an acrylic ester polymer emulsion, and adhesion is generated by evaporation of water. The acrylic adhesive component is commercially available, for example, under the trade name of Penguin Seal 1250 (manufactured by Sun Star Giken Co., Ltd.).
The weight ratio of the hollow particles (A) to the adhesive component (hollow particles (A) / adhesive component) blended in the resin composition is not particularly limited, but preferably 0.0005 to 0.30, more preferably Is from 0.001 to 0.20, particularly preferably from 0.01 to 0.1. When hollow particles (A) / adhesion component (weight ratio) is smaller than 0.0005, the amount of hollow particles (A) added is too small, and the effect of improving the elongation of the cured product of the resin composition is diminished There is a possibility of On the other hand, when the hollow particle (A) / adhesion component (weight ratio) is larger than 0.30, the amount as the adhesive component is too small, and the function as the adhesive composition may be significantly reduced. Here, the adhesive component means the total amount of A1 and A2 in the case of the two-component type polyurethane adhesive component, and means the total amount of B1 and B2 in the case of the two-component type modified silicone adhesive component, In the case of a two-component type polysulfide adhesive component, the total amount of C1 and C2 is meant.
The elongation of the cured product obtained from the adhesive composition is large, and the cured product is unlikely to be broken when it is deformed by an external force or the like.

When the resin composition of the present invention is resin clay, it contains hollow particles (A) and polyvinyl alcohol as the organic base resin (B).
70-99 mol% is preferable, as for the saponification degree of the polyvinyl alcohol used for this invention, 80-90 mol% is more preferable, and 85-90 mol% is further more preferable. When the degree of saponification is within this range, the workability at the time of shaping is good.
The viscosity of the polyvinyl alcohol used in the present invention is preferably 2 to 60 mPa · s in a 4% aqueous solution at 20 ° C., more preferably 4 to 50 mPa · s, and still more preferably 10 to 45 mPa · s. When the viscosity of polyvinyl alcohol is in this range, the workability at the time of shaping becomes good.

The content of polyvinyl alcohol in the resin clay is preferably in the range of 2 to 15% by weight of the entire resin clay, and more preferably in the range of 5 to 12% by weight. If the blending amount of polyvinyl alcohol is less than 2% by weight, the adhesiveness (plasticity, extensibility) at the time of shaping is deteriorated, and if it exceeds 15% by weight, the clay becomes hard and the workability at the time of shaping with clay, touch etc. Physical properties of may deteriorate.
Polyvinyl alcohol is desirable in that it can be incorporated into a gel by means of a gelling agent and a clay having a "stiffness" can be obtained. Examples of the gelling agent include sodium sulfate (sodium sulfate), potassium alum (alum), oxalic acid, borax and the like. The compounding amount is preferably 2 to 15 parts by weight, and more preferably 8 to 15 parts by weight with respect to 100 parts by weight of polyvinyl alcohol.

The resin clay of the present invention may contain a vinyl acetate resin. The vinyl acetate resin is, for example, polyvinyl acetate, poly-modified vinyl acetate, ethylene vinyl acetate copolymer resin, vinyl acetate / vinyl versatate copolymer, vinyl acetate / acrylic acid copolymer, vinyl acetate / acrylic ester copolymer Examples include coalescence, vinyl acetate / methacrylic acid copolymer, vinyl acetate / methacrylic acid ester copolymer, vinyl acetate / acrylamide copolymer, vinyl acetate / diene copolymer, and the like. The vinyl acetate resin is used in the form of powder or emulsion, but usually it is often used in the form of emulsion. When used in the form of an emulsion, it is desirable to use one containing 50% or more of a vinyl acetate resin component.
As a vinyl acetate resin used for this invention, that whose 59-% aqueous solution viscosity in 30 degreeC is 1,000-150,000 mPa * s is preferable. The vinyl acetate resin imparts plasticity to the resin clay and retains the shape of the shaped article after shaping and drying.

  It is preferable that a plasticizer be added to the vinyl acetate resin. Examples of the plasticizer include dibutyl phthalate and the like. The blending amount of the plasticizer is desirably 4 to 10% by weight based on the weight of the vinyl acetate resin emulsion. The blending amount of the vinyl acetate resin containing a plasticizer is preferably 1.5 to 7% by weight (expressed as dry weight), particularly preferably 2 to 5% by weight, based on the whole resin clay. The blending ratio of polyvinyl alcohol and vinyl acetate resin containing a plasticizer is preferably 10: 7 to 10: 3 by weight. If the compounding ratio of the vinyl acetate resin containing a plasticizer exceeds 7, the clay may become sticky and the formability may be impaired, and if it is less than 3, it tends to be easily broken due to external pressure after drying.

  The resin clay of the present invention may contain polyethylene oxide. Polyethylene oxide is a polymer obtained by ring-opening polymerization of ethylene oxide, and is a water-soluble high-polymer having an ether group at the middle and a hydroxyl group at an end. The polyethylene oxide used in the present invention preferably has a viscosity average molecular weight of about 300,000 to 1,200,000, particularly 600,000 to 800,000. It is preferable that the viscosity of a 2.0 wt% aqueous solution at 25 ° C. is 100 to 2000 mPa · s, particularly 200 to 700 mPa · s (measured by a rotational viscometer). Moreover, as for melting | fusing point, the thing of 65-67 degreeC is desirable. Polyethylene oxide having the above-mentioned physical properties is excellent in compatibility with hollow particles, polyvinyl alcohol and vinyl acetate resin. Polyethylene oxide improves the plasticity and extensibility of clay at the time of shaping of clay, and also improves the tackiness of clay to reduce adhesion to the hand and makes shaping work comfortable. The compounding amount is preferably 0.5 to 1.5% by weight (represented by dry weight) with respect to the entire resin clay. If the blending amount of polyethylene oxide is less than 0.5% by weight, the extensibility and surface smoothness of the clay at the time of shaping of the obtained clay are preferable, and if it exceeds 1.5% by weight, sticky hand clings at the time of shaping There is a fear.

To the resin clay of the present invention, in addition to those described above, carboxymethylcellulose salts, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, natural high molecular guar gum, guar gum derivatives can be added. These improve the extensibility of the clay, improve the surface smoothness, and improve the texture, and the blending amount thereof is preferably 0.5 to 1.5% by weight with respect to the entire resin clay.
Besides the above, fiber powder can be added to the resin clay of the present invention. The fiber powder enhances the shape retention after shaping and drying, and exhibits a shrinkage preventing effect. As the above-mentioned fiber powder, powder pulp, vinylon fiber, powder cotton, those obtained by crushing sheet pulp and the like can be exemplified. It is preferable to use natural fibers or synthetic fibers having a fiber powder length of 0.5 to 5.5 mm, particularly 1 to 3 mm. As a compounding quantity, 0.5 to 4 weight% of the clay total weight is preferable.
In addition to the above, a humectant can be added to the clay of the present invention. As the moisturizer, liquid paraffin, sorbitol, polyethylene glycol, propylene glycol and the like can be mentioned. As for the compounding quantity of a moisturizer, 0.5-1.5 weight% is preferable with respect to the whole resin clay. As a compounding quantity of water, 50-80 weight% is preferable with respect to the whole resin clay, and 60-75 weight% is more preferable.

  The method for producing a resin composition of the present invention comprises the steps (1), (2) and (3), and the hollow particles (A) and the organic base resin (B) obtained in the step (3). And a step of mixing (4). In the step (4), the hollow particles (A) and the organic base resin (B) are blended, and when the plasticizer (C) and other components are further contained, these components are blended, and conventionally known The process of carrying out package mixing using a means (for example, planetarium mixer) is mentioned.

[Molded article]
The molded product of the present invention is obtained by molding the above-mentioned resin composition. More specifically, when the resin composition of the present invention is an adhesive composition or a paint composition, the molded article of the present invention is obtained by applying the resin composition to an object, drying and curing it. .
More specifically, although the above resin composition can be applied to various undercoating surfaces applied to various metal (particularly steel materials) surfaces, it can be advantageously applied particularly to a cationic electrodeposition coating surface. The application amount of the resin composition to the coated surface is preferably 200 to 2,000 g / m 2, and the applied film thickness is preferably 0.2 to 20 mm from the viewpoint of coating film physical properties. Coating methods include brush coating, roller coating, airless spray coating, and the like.
Moreover, although heat treatment is performed after application, the temperature in that case is preferably 110 to 200 ° C., more preferably 120 to 180 ° C. from the viewpoint of the curability of the resin composition. The heat treatment time is preferably 8 to 60 minutes from the viewpoint of the curability of the resin composition.

The molded product has a true specific gravity D1 when the resin composition is treated at 120 ° C. for 10 minutes, and a true specific gravity D2 when the resin composition is treated at 140 ° C. for 20 minutes.
It is preferable to satisfy 0.85 <(D2 / D1) <1.1,
It is more preferable to satisfy 0.87 <(D2 / D1) <1.07,
It is further preferable to satisfy 0.89 <(D2 / D1) <1.04,
It is particularly preferable to satisfy 0.91 <(D2 / D1) ≦ 1.0.
If it is 0.85 or less, the surface smoothness may be reduced, and the adhesion performance may be reduced. In 1.1 or more, the decrease in the number of closed cells constituted by hollow particles and the influence of fine holes and voids generated due to the inclusion agent leakage may cause a decrease in adhesion performance or a very lightweight molded product May not be obtained.

  The molded article of the present invention obtained by molding the resin composition of the present invention adheres firmly to a metal-coated surface and is lightweight. Therefore, the molding of the present invention is an adhesive, a sealant, a paint, etc. An excellent underbody coating material, sealing material and adhesion for hemming of automobile bodies subjected to cationic electrodeposition coating in various industrial applications, particularly in the automobile industry. When used as an agent, a structural adhesive, a spot sealer, a mastic adhesive, a sheet metal reinforcing material and a body sealer, it can contribute to an automobile which is excellent in strength, light in weight and excellent in fuel consumption.

The present invention will be described in detail by the following examples and comparative examples, but the present invention is not limited thereto. In the following, “%” means “% by weight” and “part” means “part by weight” unless otherwise noted.
In the following, first, production examples and comparative production examples of thermally expandable microspheres as a raw material of hollow particles are shown, and then examples and comparative examples of resin compositions containing hollow particles are shown. The physical properties of the thermally expandable microspheres and hollow particles were measured in the following manner to further evaluate the performance.

[Measurement of particle size and particle size distribution]
A laser diffraction type particle size distribution analyzer (manufactured by SYMPATEC, HEROS & RODOS) was used. The dispersion pressure of the dry dispersion unit was 5.0 bar, and the degree of vacuum was measured by dry measurement at 5.0 mbar.
The volume-based cumulative particle diameter means the diameter of particles to a predetermined ratio of the cumulative distribution of all particles accumulated from the smaller side in volume order.
The laser diffraction type particle size distribution measuring device measures the distribution of cumulative particle diameter on a volume basis in principle, and the measurement value of the cumulative 50% particle diameter (D50) on a volume basis can be confirmed by software of the measuring device.
The cumulative particle diameter based on the number means the diameter of particles of a predetermined number ratio of distribution accumulated by arranging all particles in order of particles and integrating from the smaller side. The cumulative particle diameter on a number basis can be converted from the cumulative particle diameter on a volume basis by software of the measuring apparatus.

[Measurement of moisture content of thermally expandable microspheres]
As a measuring apparatus, it measured using a Karl-Fisher moisture meter (MKA-510N type | mold, the Kyoto Electronic Industry Co., Ltd. make).

[Measurement of inclusion rate of foaming agent enclosed in thermally expandable microspheres]
1.0 g of thermally expandable 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. After 30 ml of acetonitrile was uniformly dispersed and allowed to stand at room temperature for 30 minutes, it was heated at 120 ° C. for 2 hours and the weight after drying (W ₂ ) was measured. The inclusion rate of the blowing agent is calculated by the following equation.
Inclusion rate (% by weight) = (W ₁ −W ₂ ) (g) /1.0 (g) × 100 − (water content) (% by weight)
(In the formula, the moisture content is measured by the above method.)

[Measurement of inclusion rate of blowing agent enclosed in hollow particles]
0.20 g of hollow particles 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. After 30 ml of acetonitrile was uniformly dispersed and allowed to stand at room temperature for 30 minutes, it was heated at 120 ° C. for 2 hours and the weight after drying (W ₂ ) was measured. The inclusion rate of the blowing agent is calculated by the following equation.
Inclusion rate (G) = (W _1- W ₂ ) (g) / 0.20 (g) x 100-(water content) (wt%)
(In the formula, the moisture content is measured by the above method.)

[Measurement of true specific gravity of thermally expandable microspheres and hollow particles]
The true specific gravity of the thermally expandable microspheres and hollow particles was measured by the following measurement method.
The true specific gravity was measured by an immersion method (Archimedes method) using isopropyl alcohol in an atmosphere at an environmental temperature of 25 ° C. and a relative humidity of 50%.
Specifically, a 100 cc volumetric flask was emptied, and after drying, the volumetric flask weight (WB ₁ ) was weighed. After exactly filling the weighed measuring flask with isopropyl alcohol to the meniscus, the weight (WB ₂ ) of the filled measuring flask with 100 cc of isopropyl alcohol was weighed.

In addition, a 100 cc volumetric flask was emptied and dried, and then the weight of the volumetric flask (WS ₁ ) was weighed. The weighed measuring flask was filled with about 50 cc of particles, and the weight (WS ₂ ) of the filled measuring flask was weighed. Then, in the particle-filled measuring flask, the weight (WS ₃ ) after exactly filling the isopropyl alcohol into the meniscus without bubbles was weighed. Then, the obtained WB ₁ , WB ₂ , WS ₁ , WS ₂ and WS ₃ were introduced into the following equation to calculate the true specific gravity (d) of the particles.
d (d _b ) = {(WS ₂ −WS ₁ ) × (WB ₂ −WB ₁ ) / 100} / {(WB ₂ −WB ₁ ) − (WS ₃ −WS ₂ )}
Above, the true specific gravity was calculated using hollow particles as the particles.

[Volume ratio of intake air amount to hollow particles (Z)]
300 ml of hollow particles are put into the following aluminum container. In order to determine the volume of hollow particles of a specified amount, it is sufficient to measure the weight obtained by the following formula.
Weight of hollow particles (W) (g) = volume of hollow particles (V) (ml) × true specific gravity of hollow particles (d) (g / cc)
Aluminum container: An aluminum container (maximum capacity 1.4 L, film thickness: 114 μm: Ramizip AL-18) which does not have gas permeability under an atmosphere of environmental temperature 25 ° C. and relative humidity 50% is used. Although the said aluminum container does not expand-contract the film itself of aluminum by the increase or decrease in internal volume, the shape of a bag deform | transforms.
Next, the opening is sealed by heat welding so that the volume of the aluminum container is about 900 ml. Using a liquid immersion method (Archimedes method), measure the volume (Y1) (ml) of the sealed aluminum container. The sealed aluminum container is allowed to stand for 7 days under an atmosphere of environmental temperature 25 ° C. and relative humidity 50%. After the period has elapsed, the volume (Y2) (ml) of the sealed aluminum container is measured using the immersion method (Archimedes method). The volume ratio (Z) of the intake air amount to the hollow particles was calculated by the following equation.
Volume ratio of the amount of air taken in to hollow particles (Z) = (Y1-Y2) / 300
<Maturity evaluation criteria>
(Z) <-0.2: x
−0.2 ≦ (Z) <− 0.05: Δ
−0.05 ≦ (Z) ≦ 0.05: ◎
0.05 <(Z) ≦ 0.2: ○
0.2 <(Z) ≦ 1: Δ
1 <(Z): x

[Volume ratio of air contained in hollow particles (P)]
The hollow particles W (g) are placed in a 1 L container, and the container is filled with DMF (dimethylformamide) and sealed. The above-mentioned vessel is heated at 90 ° C. for 12 hours, and the generated gas is collected by a modification of the water displacement method using DMF. The amount of gas collected by the water displacement method is measured, and the oxygen concentration in the gas is measured with an oxygen gas sensor (model: PS-2126A, measurement method: galvanic cell type). The amount of air contained in the hollow particles can be quantified from the amount of gas collected and the concentration of oxygen in the gas. The amount of air in the collected gas was calculated by the following equation.
Amount of air in collected gas (V) = V1 × C / 20.9
Amount of collected gas (V1) (ml)
Oxygen concentration in gas (C) (vol%)
The volume ratio (P) of the amount of air contained in the hollow particles was calculated by the following equation. The said volume ratio (P) turns into a ratio when the volume of the whole hollow particle (A) is made into 100%.
Volume fraction (P) (%) of the amount of air contained in the hollow particles = V x d x 100 / W
Weight of hollow particles: W (g)
True specific gravity of hollow particles: d (g / cc)
<Maturity evaluation criteria>
(P) <10: x
10% ≦ (P) <30%: Δ
30% ≦ (P) <50%: ○
50% ≦ (P): ◎
[Measurement of true specific gravity of resin composition]
The true specific gravity (dpo) of the resin composition was measured using an Elcometer 1800 stainless steel specific gravity cup (100 ml).
The mass We (g) of the empty specific gravity cup was measured, and the mass Ws (g) of the specific gravity cup filled with the resin composition was measured and calculated.
dpo = (Ws-We) / 100 (g / cc)

[Measurement of true specific gravity of molding]
The true specific gravity of the molded product was measured in a solid specific gravity measurement mode using Shimadzu Ushido Electronic Analysis Balance AX200 (manufactured by Shimadzu Corporation).

Production Example 1
100 g of sodium chloride, 40 g of colloidal silica having an active ingredient content of 20% by weight, 600 g of ion-exchanged water, 2 g of polyvinyl pyrrolidone and carboxymethylated polyethyleneimines (CMPEI; substituted alkyl group: -CH ₂ COONa, substitution ratio After adding 0.1 g of 80%, weight average molecular weight: 50,000, the pH of the obtained mixture was adjusted to 2.8 to 3.2 to prepare an aqueous dispersion medium. The CMPEI is the same as that described in paragraph 0140 of WO 2008/142849.
Apart from this, 150 g of acrylonitrile, 100 g of methacrylonitrile, 15 g of isobornyl methacrylate, 0.5 g of diethylene glycol dimethacrylate, 30 g of isobutane as a foaming agent, 50 g of isopentane, and 70% purity of di-2-ethylhexylperoxydi An oily mixture was prepared by mixing 3 g of carbonate. The aqueous dispersion medium and the oily mixture were mixed, and the obtained mixed solution was dispersed at a rotation number of 12000 rpm for 2 minutes with a homomixer (manufactured by Primix, TK homomixer) to prepare a suspension. The suspension was transferred to a pressure reactor of 1.5 liter capacity and purged with nitrogen, and then the reaction initial pressure was adjusted to 0.5 MPa, and the polymerization reaction was carried out at a polymerization temperature of 55 ° C. for 20 hours while stirring at 80 rpm. After polymerization, the polymerization product was filtered and dried to obtain thermally expandable microspheres, the physical properties of which were evaluated, and are shown in Table 1.

[Production Examples 2 to 5]
In Production Examples 2 to 5, polymerization was carried out in the same manner as in Example 1 except that the reaction conditions were changed as shown in Table 1 in Example 1, to obtain thermally expandable microspheres. Furthermore, the physical properties were evaluated and are shown in Table 1.

In Table 1 above, the following abbreviations are used:
CMPEI: polyethyleneimines (substituted alkyl group: -CH ₂ COONa, substitution rate of substituted alkyl group: 80%, weight average molecular weight: 50,000). In addition, it is described also as carboxymethylated polyethylene imine and Na salt.
PVP: polyvinyl pyrrolidone AN: acrylonitrile MAN: methacrylonitrile IBX: isobornyl methacrylate VCl ₂ : vinylidene chloride MMA: methyl methacrylate TMP: trimethylolpropane trimethacrylate EDMA: diethylene glycol dimethacrylate OPP: di-2-ethylhexylperoxydicarbonate (Purity 70%)
Colloidal silica (average particle diameter 11 nm, specific surface area 260 m ² / g, effective concentration of colloidal silica 20% by weight dispersion)

  The hollow particles (a) before ripening are produced by a wet heating expansion method described in JP-A-62-201231, and hollow particles (A) and hollow particles (A) and comparative examples 1 to 4 as in Examples 1 to 3 and Comparative Examples 1 to 4 below. A resin composition was prepared and evaluated.

Example 1
An aqueous dispersion (slurry) containing 5% by weight of the thermally expandable microspheres obtained in Production Example 1 was prepared. According to the wet thermal expansion method described in JP-A-62-201231, this slurry is fed from a slurry introduction pipe into a foam pipe (diameter 16 mm, volume 120 ml, made of SUS304TP) so as to exhibit a flow rate of 5 L / min. Temperature: 147 ° C., pressure: 0.3 MPa) was supplied from the steam introduction pipe, mixed with the slurry, and wet heated and expanded. The slurry temperature (foaming temperature) after mixing was adjusted to 115 ° C.
The obtained slurry containing hollow particles was allowed to flow out of the foam tube protrusion, mixed with cooling water (water temperature 15 ° C.), and cooled to 50 to 60 ° C. The cooled slurry liquid was dewatered by a centrifugal dehydrator to obtain a hollow particle composition (that is, containing 90% by weight of water) containing 10% by weight of the moistened hollow particles (a).
The obtained hollow particles (a) were aged at 40 ° C. for 24 hours to obtain a hollow particle composition containing 10% by weight of hollow particles (A). The volume ratio (Z) of the amount of air taken in to the hollow particles and the volume ratio (P) of the amount of air contained in the hollow particles were measured. The evaluation results are shown in Table 2.

Using a universal mixer, mixing 840 parts by weight of the hollow particle composition containing the above hollow particles (A), 200 parts by weight of polyvinyl alcohol, 840 parts by weight of vinyl acetate, 20 parts by weight of boric acid, and 1000 parts by weight of water Mix for 5 minutes to obtain a lightweight resin clay. When the aging is sufficient, the hollow particles are not crushed and the weight is sufficiently reduced, and a lightweight resin clay free from stickiness is obtained. The results of the physical property evaluation of the obtained hollow particles (A) and lightweight resin clay are shown in Table 2.
About the specific gravity increase rate of resin clay specific gravity actually obtained with respect to theoretical specific gravity, it computed by the following Formula.
Specific gravity increase rate (%) = (Resin clay specific gravity / theoretical specific gravity-1) × 100

As for tackiness evaluation of resin clay, when a figure is made using the obtained clay, whether or not the clay adheres well to each other without adhering to the hand and exhibits good formability or not evaluated.
○: Not adhering to hand, clay adheres well.
Δ: Hand adheres, but clays adhere to each other.
X: It adheres to the hand and clays hardly stick together.

[Examples 2 and 3 and Comparative Examples 1 to 4]
Examples 2 and 3 and Comparative Examples 1 to 4 are the same as Example 1 except that the thermally expandable microspheres, the composition, the conditions, and the like are changed as shown in Table 2 in Example 1. I got a lightweight resin clay. Physical properties are shown in Table 2.

As can be seen from Table 2, in Examples 1 to 3, sufficient aging treatment was applied before it was used as a lightweight filler for the resin composition, so the hollow particles (A) inside and outside The concentration gradient of air disappears, and the amount of air taken into the hollow particles (A) is almost zero. Thereby, it is confirmed that the hollow particles have sufficient resistance to the load due to the external pressure at the time of mixing and filling in the production process of the resin composition, and the effect of the present invention is obtained.
On the other hand, when the aging period is insufficient (Comparative Examples 1 to 4), when used as a lightweight filler for the resin composition, the hollow particles are broken due to the load due to external pressure during mixing or filling in the production process. As a result, a large deviation from the theoretical specific gravity at the time of design of the resin composition occurs, and the weight reduction effect becomes insufficient, and the effect of the present application is not obtained.

  The hollow particles (a) before ripening are produced by a dry heating expansion method described in JP-A-2006-213930, and hollow particles (A) and a resin as in Examples 4 to 6 and Comparative Examples 5 to 7 below. The composition was prepared and evaluated.

Example 4
(Production of hollow particles (a) by dry thermal expansion method)
The internal injection method described in JP-A-2006-213930 was adopted as the dry heating expansion method. Specifically, hollow particles (a) were produced using the thermally expandable microspheres obtained in Production Example 4 according to the following procedure using the production apparatus provided with the foaming step shown in FIG. .

(Description of the foaming process part)
As shown in FIG. 2, the foaming process part is provided with a gas introduction pipe (not numbered) provided at the outlet with a dispersion nozzle (11) at the outlet and disposed at the downstream part of the dispersion nozzle (11) A collision plate (12), an overheat prevention cylinder (10) arranged at intervals around the gas introduction pipe, and a hot air nozzle (8) arranged at intervals around the overheat prevention cylinder (10) Equipped with In this foaming step, a gas fluid (13) containing thermally expandable microspheres is flowed in the direction of the arrow in the gas introduction tube, and in the space formed between the gas introduction tube and the overheat prevention cylinder (10) The gas flow (14) for improving the dispersibility of the thermally expandable microspheres and for preventing the overheating of the gas introduction pipe and the collision plate is made to flow in the arrow direction, and further, the overheating prevention cylinder (10) and the hot air nozzle In the space formed between (8), a hot air flow for thermal expansion is flowed in the arrow direction. Here, the hot air flow (15), the gas fluid (13) and the gas flow (14) are usually flows in the same direction. In the inside of the overheat prevention cylinder (10), a refrigerant flow (9) is flowed in the arrow direction for cooling.

(Operation of manufacturing equipment)
In the injection step, a gaseous fluid (13) containing thermally expandable microspheres is allowed to flow through a gas introduction pipe provided with a dispersion nozzle (11) at the outlet and installed inside a hot air flow (15), Is jetted from the dispersion nozzle (11).
In the dispersing step, the gaseous fluid (13) is caused to collide with the collision plate (12) installed at the downstream portion of the dispersing nozzle (11) so that the thermally expandable microspheres are uniformly dispersed in the hot air flow (15). Operated by Here, the gaseous fluid (13) exiting from the dispersing nozzle (11) is guided with the gas flow (14) towards the collision plate (12) and collides with it.
In the expansion step, the dispersed thermally expandable microspheres are heated and expanded in the hot air stream (15) above the expansion start temperature. Thereafter, the obtained hollow particles are collected by, for example, passing through the cooling portion.

(Inflated conditions and results)
Using the manufacturing apparatus shown in FIG. 2, as expansion conditions, the raw material supply amount 0.8 kg / min, the raw material dispersed gas amount 0.35 m3 / min, the hot air flow rate 8.0 m3 / min, the hot air temperature 290 ° C., and before ripening Hollow particles (a) were obtained.
The obtained hollow particles (a) were aged at 30 ° C. for 36 hours to obtain hollow particles (A). The volume ratio (Z) of the amount of air taken in to the hollow particles and the volume ratio (P) of the amount of air contained in the hollow particles were measured. The evaluation results are shown in Table 3.
(Production of resin composition)
1.4% by weight of the obtained hollow particles (A) (14 parts by weight), 37.6% by weight of a PVC resin (376 parts by weight) as an organic base resin, diisononyl phthalate (220 parts by weight) as a plasticizer (C) 22% by weight, 37.0% by weight of calcium carbonate (370 parts by weight) as a filler, and 2% by weight of a barium / zinc stabilizer (AC-290: manufactured by Adeka) (20 parts by weight) as a stabilizer The resin composition (specific gravity 0.75) was obtained.
It was 0.76 when specific gravity of the resin composition after pressure-processing the obtained resin composition for 30 minutes of pressure 5MPa in a pressure cylinder was measured. At this time, the specific gravity increase rate by pressure treatment was calculated by the following formula about the specific gravity increase rate of the resin composition by pressure treatment.
Specific gravity increase rate (%) = (Specific gravity of resin composition after pressure / Specific gravity of resin composition before pressure-1) × 100

(Manufacturing of moldings)
The resin composition obtained above was applied to an electrodeposition coated plate (thickness: 2 mm), and a heat treatment was performed at 140 ° C. for 20 minutes to obtain a molded product. Physical properties are shown in Table 3.

[Example 5 and Comparative Examples 5 and 6]
In Example 5 and Comparative Examples 5 and 6, as shown in Table 3, the same procedure as in Example 4 is carried out except that the thermally expandable microspheres, the foaming temperature, the condition relating to aging, etc. are respectively changed. The resin composition and the molded product were obtained. Physical properties are shown in Table 3.

As can be seen from Table 3, in Examples 4 and 5, sufficient aging treatment was applied before being used as a weight saving filler of the resin composition, so the hollow particles (A) were treated at the inside and the outside. The concentration gradient of air disappears, and the amount of air taken into the hollow particles (A) is almost zero. Thereby, it is confirmed that the hollow particles have sufficient resistance to the load due to the external pressure assumed when using the resin composition, and the effect of the present invention is obtained.
On the other hand, when the aging period is insufficient (Comparative Examples 5 and 6), when used as a lightweight filler for the resin composition, the hollow particles are broken due to the load caused by the external pressure assumed when using the resin composition. As a result, the weight reduction effect of the resin composition is insufficient, and the effect of the present invention is not obtained.

[Example 6]
20 parts by weight of the thermally expandable microspheres (the softening point of the thermoplastic resin constituting the outer shell: 109 ° C.) obtained in Production Example 3 and calcium carbonate (Whiten SB red manufactured by Bihoku Powder Co., Ltd .; laser; 80 parts by weight of an average particle diameter of about 1.8 μm according to a diffraction method was added to and mixed with a separable flask. Next, the temperature was raised to a heating temperature of 130 ° C. over 5 minutes while stirring to obtain hollow particles (a) before aging to which the fine particle filler was attached.
The obtained hollow particles (a) were aged at 10 ° C. for 60 hours to obtain hollow particles (A). The volume ratio (Z) of the amount of air taken in to the hollow particles and the volume ratio (P) of the amount of air contained in the hollow particles were measured. The evaluation results are shown in Table 4.

[Adhesive composition]
To 80 parts by weight of a curing agent component of a two-component polyurethane adhesive component (bond UP seal gray, manufactured by Konishi), 3.8 parts by weight of hollow particles (A) as a modifier for an adhesive composition, After adding 2 parts by weight of a hydrocarbon (manufactured by Idemitsu Kosan Co., Ltd., IP-2835) and stirring and mixing for 30 minutes at 50 ° C. using a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd., PLM-50) A polyurethane adhesive curing agent composition was obtained. The specific gravity of the obtained polyurethane adhesive curing agent composition (curing agent composition) was measured, and the specific gravity increase rate of the actually obtained curing agent composition relative to the theoretical specific gravity was calculated by the following equation. The results are shown in Table 4.
Specific gravity increase rate (%) = (hardener composition specific gravity / theoretical specific gravity-1) × 100

  Subsequently, 85.8 parts by weight of the curing agent composition and 20 parts by weight of a base component (bond UP seal gray, made by Konishi) of polyurethane adhesive component are added and premixed into a conditioning mixer (made by Shinky Co., Ltd.) , AR-360), and degassing by stirring for 150 seconds at 500 rpm and 2000 rpm for revolution, to obtain an adhesive composition. The resulting adhesive composition was cured by curing for 3 days under conditions of 23 ° C. and 50% RH, and further for 3 days under conditions of 50 ° C. and 50% RH, and then the specific gravity of the cured molded article was measured. The results are shown in Table 4.

[Example 7 and Comparative Examples 7 and 8]
In Example 7 and Comparative Examples 7 and 8, as shown in Table 3, the same procedure as in Example 6 is carried out except that the thermally expandable microspheres, the foaming temperature, the condition concerning ripening, etc. are respectively changed. The resin composition and the molded product were obtained. Physical properties are shown in Table 4.

As can be seen from Table 4, in Examples 6 and 7, sufficient aging treatment was applied before being used as a weight saving filler of the resin composition, so the hollow particles (A) were treated at the inside and the outside. The concentration gradient of air disappears, and the amount of air taken into the hollow particles (A) is almost zero. Thereby, it is confirmed that the hollow particles have sufficient resistance to the load due to the external pressure at the time of mixing and filling in the production process of the resin composition, and the effect of the present invention is obtained.
On the other hand, when the aging period is insufficient (Comparative Examples 7 and 8), when used as a lightweight filler for the resin composition, the hollow particles are broken due to the load due to external pressure during mixing or filling in the production process. As a result, a large deviation from the theoretical specific gravity at the time of design of the resin composition occurs, and the weight reduction effect becomes insufficient, and the effect of the present application is not obtained.

  The resin composition of the present invention can be suitably used for paints, adhesives, and resin clays.

4 Hollow particles (A1)
5 Outer shell 6 Particulate filler (in the adsorbed state)
7 Particulate filler (inset and fixed)
Reference Signs List 8 hot air nozzle 9 refrigerant flow 10 overheat preventing cylinder 11 dispersion nozzle 12 collision plate 13 gas fluid containing thermally expandable microspheres 14 gas flow 15 hot air flow

Claims (5)

A resin composition comprising hollow particles (A) and an organic base resin (B),
The hollow particle (A) is an expandable body of thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent which is contained therein and is vaporized by heating.
The volume ratio (P) of the amount of air contained in the hollow particles (A) is 30% or more when the volume of the whole hollow particles (A) is 100%.
Resin composition.   The resin composition according to claim 1, wherein the volume-based cumulative 50% particle diameter (D50) of the hollow particles (A) is 1 to 300 μm.   The resin composition according to claim 1 or 2, which is a paint composition, an adhesive composition or a resin clay.   A molded article obtained by molding the resin composition according to any one of claims 1 to 3. Obtaining thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent contained therein and vaporized by heating, (1)
A step (2) of thermally expanding the thermally expandable microspheres to obtain hollow particles (a);
Ripening the hollow particles (a) at a temperature in the range of −10 to 80 ° C. to obtain hollow particles (A);
Mixing the obtained hollow particles (A) with the organic base resin (B), and (4)
The volume ratio (P) of the amount of air contained in the hollow particles (A) is 30% or more when the volume of the whole hollow particles (A) is 100%.
Method for producing a resin composition.

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