WO2018012415A1

WO2018012415A1 - Resin composition and use thereof

Info

Publication number: WO2018012415A1
Application number: PCT/JP2017/024888
Authority: WO
Inventors: 勝志三木; 直哉太野垣
Original assignee: 松本油脂製薬株式会社
Priority date: 2016-07-15
Filing date: 2017-07-07
Publication date: 2018-01-18
Also published as: JPWO2018012415A1; JP7189768B2

Abstract

The purpose of the present invention is to provide: a resin composition from which a resin molded article having excellent production stability and weight reduction efficiency can be produced; and a use of the resin composition. The resin composition comprises hollow particles (A) and an organic base resin (B), wherein each of the hollow particles (A) is an expanded body of a thermally expandable microsphere, the thermally expandable microsphere is composed of a shell part made from a thermoplastic resin and a foaming agent enclosed in the shell part and capable of being vaporized by heating, and the volume proportion (P) of air in the hollow particles (A) is 30% or more wherein the total volume of the hollow particle (A) is 100%.

Description

Resin composition and use thereof

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

Hollow particles such as plastic balloons are used as lightweight fillers such as clay, paint, and adhesive. The purpose of blending these lightweight fillers is to reduce costs by saving environmental measures and resin components (Patent Document 1).
Such a plastic balloon is obtained by inflating thermally expandable microspheres having a structure in which a thermoplastic resin is used as an outer shell and a foaming agent is enclosed therein. The thermally expandable microsphere is generally called a thermally expandable microcapsule. As the thermoplastic resin, a vinylidene chloride copolymer, an acrylonitrile copolymer, an acrylate copolymer, or the like is 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 not been sufficiently improved in resistance to load due to external pressure during mixing and filling in the production process of the resin composition.
Patent Document 3 discloses hollow fine particles obtained by heating and foaming thermally expandable microcapsules 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 that it is blended into lightweight cement products. However, even with these hollow fine particles, the improvement of the resistance of the hollow particles against the load caused by external pressure is insufficient.

International Publication No. 97/05201 US Pat. No. 3,615,972 Japanese Unexamined Patent Publication No. 2004-131361

An object of the present invention is to provide a resin composition capable of producing a resin molded product excellent in production stability and weight reduction efficiency and its use.

As a result of intensive studies by the inventors, the resin composition containing the hollow particles (A) in which the volume ratio of the air amount has a specific value improves the resistance of the hollow particles to a load due to external pressure, and the mixing and filling steps As a result, the present inventors have found that a resin molded body excellent in production stability and weight reduction 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 encased in a shell made of a thermoplastic resin and heated. The expandable body of thermally expandable microspheres composed of a foaming agent that vaporizes when the volume ratio (P) of the amount of air contained in the hollow particles (A) is the total volume 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 satisfies 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) A paint composition, an adhesive composition or a resin clay.

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 a step (1) of obtaining thermally expandable microspheres comprising an outer shell made of a thermoplastic resin and a foaming agent encapsulated therein and vaporized by heating; The step (2) of obtaining the hollow particles (a) by thermally expanding the thermally expandable microspheres, and aging the hollow particles (a) at a temperature in the range of −10 to 80 ° C. to obtain the hollow particles (A). Including the step (3) of obtaining 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 entire hollow particles (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 becomes possible to produce a resin molded article excellent in production stability and light 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 with a dry-type thermal expansion method.

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

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

As a method for producing the hollow particles (A), a step (1) of producing thermally expandable microspheres comprising an outer shell made of a thermoplastic resin and a foaming agent encapsulated therein and vaporized by heating. The step (2) of obtaining the hollow particles (a) by thermally 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 to 80 ° C. A production method including the step (3) of aging in the range of obtaining hollow particles (A) can be mentioned. Step (1) may be referred to as a polymerization step, step (2) as an expansion step, and step (3) as an aging step.

(Polymerization process)
The polymerization step refers to a step (1) for producing thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent encapsulated therein and vaporized by heating. Examples of the polymerization step include 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 foaming agent is not particularly limited as long as it is a substance that is vaporized by heating. 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; (iso) hexadecane, (iso) eicosane and the like having more than 13 carbon atoms Examples of the hydrocarbon include 20 or less. 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 ° C. If a hydrocarbon having a boiling point exceeding 60 ° C. is used, the hollow particles (A) may be crushed 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 the outer shell of the thermally expandable microsphere by polymerization. The polymerizable component is a component which essentially includes a monomer component and may contain a crosslinking agent.
The monomer component generally includes a component called a (radical) polymerizable monomer having one polymerizable double bond.

From 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 particles contain a nitrile monomer When comprised, it is preferable from the outstanding holding | maintenance property of the foaming agent included in the hollow particle (A) and (a).
Examples of nitrile monomers include acrylonitrile (AN), methacrylonitrile (MAN), and fumaronitrile.

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. When the weight ratio of the nitrile monomer is less than 20% by weight, the retention of the foaming agent included in the hollow particles (A) and (a) is poor, and the foaming agent may be released gradually.
When the nitrile monomer is essentially acrylonitrile (AN) and methacrylonitrile (MAN), the thermally expanded microcapsules and the hollow particles (A) and (a) that are the raw materials of the hollow particles (A) and (a) This is preferable because of the excellent retention of the encapsulating foaming agent.

The polymerizable component may contain a monomer other than the nitrile monomer as the monomer component.
The monomer other than the nitrile monomer is not particularly limited. For example, vinyl halide monomers such as vinyl chloride; vinylidene halide monomers 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 anhydrides such as maleic acid, itaconic acid and fumaric acid Monomers: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meta ) Acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzine (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 monomers such as phenylmaleimide and N-cyclohexylmaleimide; styrene monomers such as styrene and α-methylstyrene; ethylenically unsaturated monoolefin 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-vinyl carbazole and N-vinyl pyrrolidone; vinyl naphthalene salts, etc. Can be mentioned. In addition, (meth) acryl means acryl or methacryl.

Polymerizable components include (meth) acrylic acid ester monomers, carboxyl group-containing monomers, styrene monomers, vinyl ester monomers, acrylamide monomers, maleimide monomers, and vinylidene chloride. It is preferable that at least one selected from the group consisting of
When the polymerizable component contains a nitrile monomer and a (meth) acrylic acid ester monomer, it is preferable from the viewpoints of retention of the foaming agent in the heat-expandable microsphere and heat resistance.

The polymerizable component may contain a polymerizable monomer (crosslinking agent) having two or more polymerizable double bonds in addition to the monomer component. By polymerizing using a cross-linking agent, a decrease in the retention rate of the encapsulated foaming agent at the time of thermal expansion is suppressed, and thermal expansion can be effectively performed.

The crosslinking agent is not particularly limited. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, allyl methacrylate, triacryl 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, trime Roll propane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. 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. 3 to 0.9 parts by weight, most preferably 0.5 to 0.8 parts by weight.
Polymerization of the polymerizable component may be performed using a polymerization initiator, and an oil-soluble polymerization initiator is preferable.

In the polymerization step, the oily mixture may further contain a chain transfer agent and the like.
The aqueous dispersion medium is a medium mainly composed of water such as ion-exchanged water in which the oily mixture is dispersed, 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 that it can be arbitrarily mixed with water. The amount of the aqueous dispersion medium to be 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, and sodium carbonate. These electrolytes may be used alone or in combination of two or more. The content of the electrolyte is not particularly limited, but is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the aqueous dispersion medium.

An aqueous dispersion medium is a water-soluble 1,1-substituted compound having a structure in which a hydrophilic functional group selected from a hydroxyl group, a carboxylic acid (salt) group, and a phosphonic acid (salt) group and a hetero atom are bonded to the same carbon atom , Potassium dichromate, alkali metal nitrite, metal (III) halide, boric acid, water-soluble ascorbic acids, water-soluble polyphenols, water-soluble vitamin Bs and water-soluble phosphonic acids (salts) It may contain at least one water-soluble compound. In addition, the water solubility in this invention means the state which melt | dissolves 1g or more per 100g of water.

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

The aqueous dispersion medium may contain a dispersion stabilizer and a dispersion stabilization auxiliary agent in addition to the electrolyte and the water-soluble compound.
The dispersion stabilizer is not particularly limited. For example, colloidal silica, colloidal calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, ferric hydroxide, calcium sulfate, barium sulfate, calcium oxalate, metasilicic acid. Calcium, calcium carbonate, barium carbonate, magnesium carbonate, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, etc. phosphates, calcium pyrophosphate, aluminum pyrophosphate, pyrophosphates such as zinc pyrophosphate, difficulties such as alumina sol The dispersion stabilizer of a water-soluble inorganic compound can be mentioned. These dispersion stabilizers may be used alone or in combination of two or more.
The amount of the dispersion stabilizer is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymerizable component.

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

Examples of the method for emulsifying and dispersing the oily mixture include, for example, a method of stirring with a homomixer (for example, manufactured by Tokushu Kika Kogyo Co., Ltd.) and the like, and a static dispersion device such as a static mixer (for example, manufactured by Noritake Engineering Co., Ltd.). And general dispersion methods such as a method using a film, a membrane emulsification method, and an ultrasonic dispersion method.
Next, suspension polymerization is started by heating the dispersion in which the oily mixture is dispersed as spherical oil droplets in the aqueous dispersion medium. During the polymerization reaction, it is preferable to stir the dispersion, and the stirring may be performed so gently as to prevent, for example, floating of the monomer and sedimentation of the thermally expandable microspheres after polymerization.
The polymerization temperature is freely set depending on the kind of the polymerization initiator, but is preferably 30 to 100 ° C., more preferably 40 to 90 ° C., particularly preferably 45 to 80 ° C., and most preferably 50 to 75 ° C. Be controlled. The time for maintaining the reaction temperature is preferably about 0.1 to 20 hours. The initial polymerization pressure is not particularly limited, but is 0 to 5.0 MPa, more preferably 0.1 to 3.0 MPa in terms of gauge pressure.

(Expansion process)
The expansion step refers to a step (2) in which the thermally expandable microspheres obtained in the step (1) are heated and expanded to obtain hollow particles (a). The expansion step is not particularly limited as long as it is a step in which the thermally expandable microspheres are heated and expanded, and may be either a dry heating expansion method or a wet heating expansion method.
Examples of the dry heating expansion method include the method described in JP-A-2006-213930, particularly the internal injection method. As another dry heating expansion method, there is a method described in JP-A-2006-96963. Examples of the wet heating expansion method include the method described in JP-A-62-201231.
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 particles are composed of an outer shell and a hollow portion surrounded by the outer shell. The hollow particles have 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 gas and may be in a liquefied state. Usually, the hollow part is preferably one large hollow part, but there may be a plurality of hollow parts.

A hollow particle (a) is an expanded body of the above-mentioned thermally expandable microsphere, which is not aged or insufficiently aged. The aging will be described in detail in the aging process. The hollow particles (a) can be obtained by heating and expanding the heat-expandable microspheres and then cooling to room temperature. An air concentration gradient is generated inside and outside the hollow portion of the hollow particles immediately after cooling, and a negative pressure state is caused by the low air content in the hollow portion of the hollow particles. Therefore, it has a distorted shape or is weak against external pressure. When such a hollow particle (a) is used for a lightweight filler for a resin composition, the hollow particle (a) is easily deformed, crushed or ruptured, and the foaming agent leaks. The efficiency of reducing the weight of the object and its molded body may be lowered.
The volume ratio (P) of the amount of air contained in the hollow particles (a) is less than 30% when the entire volume of the hollow particles is 100%. The method for measuring the volume ratio (P) will be described in the aging step.

(Aging process)
The aging step refers to a step (3) in which the hollow particles (a) obtained in the step (2) are aged at a temperature of −10 to 60 ° C. to obtain the hollow particles (A). The aging period is described below. In general, aging means storing a substance for a certain period of time under appropriate conditions in order to obtain the necessary properties of the substance. As described above, in the hollow particles (a) obtained in the step (2), the inside of the hollow portion has a lower air concentration than 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 against external pressure. Aging in the present invention means gradually taking air in the air into the hollow part, eliminating the air concentration gradient inside and outside the hollow part, adjusting the balance between the internal pressure and the external pressure of the particles, and improving the resistance to external pressure. It means to make it. Specifically, the hollow particles (a) obtained in the step (2) are stored at a temperature in the range of −10 to 60 ° C. (hereinafter, this temperature is referred to as aging temperature) for a certain period.

Whether or not the hollow part of the hollow particles is in a negative pressure state (whether or not the hollow particles are aged) can be confirmed, for example, by the following method.
As one method, the degree of ripening can be confirmed by calculating the amount of air taken into the hollow particles. For example, the hollow particles can be stored in a sealed container 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 entire container decreases, it means that the air in the container is taken into the hollow particles. Depending on the aging conditions, the sealed container may expand.
Another method includes a method of measuring the amount of air or 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., and particularly preferably 5 ˜35 ° C., most preferably 10-30 ° C. When the aging temperature is less than −10 ° C., the hollow particles are not sufficiently restored, and are deformed, crushed or ruptured due to external factors, and the foaming agent leaks. On the other hand, when the aging temperature is higher than 80 ° C., the foaming agent is gradually released, and it is deformed or crushed due to external factors.

During 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 entire volume of the hollow particles (a) is 100% (that is, If it is a period which becomes said hollow particle (A)), it will not specifically limit. The aging period can be determined according to the aging temperature (T) (° C.). When ripening at the ripening temperature (T) (° C.), the ripening period (Q) (time) preferably satisfies the following formula (I).
Q ≧ 62 × e ^−0.03T (I)
If the aging period does not satisfy the above formula (I), the internal pressure and the external pressure of the hollow particles are not balanced, and the foaming agent leaks due to deformation, crushing, or rupture due to external factors. The upper limit of the aging period is not particularly limited as long as the effect of aging is exhibited, but the period is about 8 weeks. After aging, it can be further stored for a period during which the quality of the hollow particles (A) can be maintained.

The hollow particles (a) obtained by the dry heat expansion method are powders and are aged in the powder state. Similarly, in the case of hollow particles (A1) to which a fine particle filler to be described later is attached, they are aged in a powder state. On the other hand, the hollow particles (a) obtained by the wet heating expansion method have a hollow particle composition containing water and are aged in the state of a hollow particle composition containing water. The weight ratio of water in the hollow particle composition is not particularly limited, and is preferably 99% by weight or less, more preferably 84% by weight or less, particularly preferably 49% by weight or less, and most preferably 30 parts by weight or less. . If ripening is carried out in a sealed state with too few voids other than hollow particles, ripening may not proceed well even at a predetermined temperature and for a predetermined time.

The hollow shell (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 (almost) spherical and have a hollow portion corresponding to a large cavity inside. If the shape of the hollow particles is exemplified by familiar articles, a soft tennis ball can be mentioned.
The hollow part is (substantially) spherical and is in contact with the inner surface of the outer shell. The hollow portion is basically filled with gas and may be in a liquefied state. Usually, the hollow part is preferably one large hollow part, but there may be a plurality of hollow parts.

The hollow particles (A) used in the resin composition of the present invention are the above-mentioned expanded bodies of thermally expandable microspheres, and the volume ratio (P) of the amount of air contained in the hollow particles (A) is hollow particles ( A) When the total volume is 100%, it means 30% or more. By using such hollow particles (A), the effect of the present application can be exhibited. When the volume ratio (P) is less than 30%, the hollow particles are deformed by external factors, crushed, or ruptured and the foaming agent leaks. The volume ratio (P) is preferably 35 to 99%, more preferably 40 to 98%, still more preferably 45 to 95%, and particularly preferably 50 to 90%.
The method for measuring the volume ratio (P) of the amount of air contained in the hollow particles is shown in the following examples. The amount of air contained in the hollow particles can be determined from the amount of collected gas and the oxygen concentration in the gas. In addition to the galvanic cell type, there are zirconia type and magnetic type as the oxygen concentration measurement method, but the galvanic cell type can be measured without error even in flammable gas, while the zirconia type and magnetic type are If flammable gas is included, the measurement error increases, which is not preferable.

The hollow particles (A) are preferably those in which the volume ratio (Z) of the intake air amount with respect to the hollow particles is in a certain range from the viewpoint of further exerting the effect of the present application. In the volume ratio (Z), the volume of the container sealed in a state containing the hollow particles of volume (V) and air is defined as (Y1), and the volume of the container after standing under a certain condition is defined as (Y2). Sometimes, it is represented by the following formula. The specific measurement method of the volume ratio (Z) of the intake air amount with respect to the hollow particles is shown in the following examples.
Volume ratio of intake air amount 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, and further preferably −0.02 ≦ (Z). ≦ 0.02.

The foaming agent retention of the hollow particles (A) is preferably 85% or more, more preferably 90% or more, particularly preferably 95% or more, and most preferably 97%. When 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 during the production of the resin composition, so that the effect as a lightweight filler is reduced. There is. The measuring method of the foaming agent retention of the hollow particles (A) is shown in the following examples.
You may use a hollow particle (A) for a resin composition as a hollow particle composition containing water. The weight ratio of water in the hollow particle composition is not particularly limited, and is preferably 99% by weight or less, more preferably 84% by weight or less, particularly preferably 49% by weight or less, and most preferably 30 parts by weight or less. . If the weight ratio of water in 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 from 5 to 130 μm, most preferably from 7 to 120 μm. When D50 is outside this range, the weight reduction efficiency may deteriorate when used in a resin composition.

The true specific gravity of the hollow particles (A) is not particularly limited, but is preferably 0.01 to 0.5, more preferably 0.012 to 0.49, still more preferably 0.04 to 0.49, particularly Preferably it is 0.1 to 0.48, most preferably 0.31 to 0.47. If the true specific gravity is less than 0.01, the strength of the hollow shell of the hollow particles (A) is reduced due to the thinness, and the hollow particles (A) are broken when the resin composition is mixed, resulting in a reduction in weight reduction efficiency. There are things to do. On the other hand, when the true specific gravity exceeds 0.5, the lightening effect corresponding to the amount to be blended is low, which is uneconomical.

As shown in FIG. 1, the hollow particles (A) may be further composed of a fine particle filler adhered to the outer surface of the outer shell. Hereinafter, the hollow particles (A) to which the fine particle filler is attached may be referred to as “hollow particles (A1)” for the sake of simplicity. Here, the term “adhesion” simply means that the fine particle fillers (6 and 7) are adsorbed on the outer surface of the outer shell 5 of the hollow particle (A1) 4, and the outer shell in the vicinity of the outer surface may be removed. This means that the thermoplastic resin constituting the resin may be softened or melted by heating, and the fine particle filler may sink into the outer surface of the outer shell of the hollow particles (A1) and be fixed. The particle shape of the fine particle filler may be indefinite or spherical.
The true specific gravity of the hollow particles (A1) is not particularly limited, but is preferably 0.01 to 0.5, more preferably 0.03 to 0.4, still more preferably 0.05 to 0.35. Particularly preferred is 0.07 to 0.3, and most preferred is 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 greater than 0.5, the effect of lowering the specific gravity is reduced. Therefore, when the resin composition is prepared using the hollow particles (A1), the amount added is increased. May be uneconomical.

The ratio between the average particle diameter of the fine particle filler and the average particle diameter of the hollow particles (A1) (average particle diameter of the fine particle filler / average particle diameter of the hollow particles (A1)) is from the viewpoint of the adhesion of the fine particle 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, and most preferably 0.2.
Various particles can be used as the fine particle filler, and any of inorganic and organic materials may be used. Examples of the shape of the fine particles include spherical shapes, needle shapes, plate shapes, and irregular shapes.

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 is preferably 0.001 to 30 μm, more preferably 0.005 to 25 μm, and particularly preferably 0.01 to 20 μm. It is. Within this range, as will be described later, the mixing property becomes good when the hollow particles (A1) are produced.
The average particle diameter of the fine particle filler here is the particle diameter of the fine particle filler measured by a laser diffraction method. If the particle size of the fine particle filler is in the micron order, it indicates primary particles. However, nano-order fine particles are often aggregated and act as an aggregate in the order of micron. The average particle size was calculated as a unit.

Examples of inorganic substances 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 .; in the periodic table of elements, metals in groups 1 to 16 (zinc, aluminum, molybdenum, tungsten, zirconium, barium, 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 elements (titanium oxide, oxidation) 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 hydroxide (aluminum hydroxide, gold hydroxide, magnesium hydroxide, etc.), metal sulfide ( Copper sulfide, sodium sulfide, lead sulfide, nickel sulfide, platinum sulfide, etc.), metal halide (calcium fluoride, tin fluoride, potassium fluoride, etc.), metal carbide (calcium carbide, titanium carbide, iron carbide, sodium carbide, etc.) ), Metal nitride (aluminum nitride, chromium nitride, germanium nitride, cobalt nitride, etc.), metal carbonate (calcium carbonate (light calcium carbonate), calcium bicarbonate, sodium bicarbonate (bicarbonate), iron carbonate, etc.), metal sulfate Salt (aluminum sulfate, cobalt sulfate, sodium hydrogen sulfate, copper sulfate, nickel sulfate, ), Other metal salts (titanates (barium titanate, magnesium titanate, potassium titanate, etc.), borates (aluminum borate, zinc borate, etc.), phosphates (calcium phosphate, sodium phosphate, phosphoric acid) Magnesium compounds, etc.), aluminates (yttrium aluminate, etc.), nitrates (sodium nitrate, iron nitrate, lead nitrate, etc.)) and the like.

Inorganic substances constituting the fine particle filler are also synthetic calcium carbonate, ferrite, zeolite, silver ion supported zeolite, zirconia, alum, lead zirconate titanate, alumina fiber, cement, zonotlite, silicon oxide (silica, silicate, glass, (Including glass fiber), silicon nitride, silicon carbide, silicon sulfide, carbon black, carbon nanotube, graphite, activated carbon, bamboo charcoal, charcoal, fullerene, and the like.

Examples of organic substances constituting the fine particle filler include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, vinyl benzoic acid; esters thereof, amides, nitriles; styrene, methylstyrene, Emulsion polymerization, leap, using vinyl aromatics such as ethylstyrene and chlorostyrene, divinyl compounds having two or more vinyl groups such as divinylbenzene and trimethylolpropane, etc., using a crosslinking agent as necessary Examples thereof include organic resins obtained by polymerization using a free polymerization method, a dispersion polymerization method, a suspension polymerization method, a miniemulsion polymerization method, or the like.
Organic substances constituting the fine particle filler are sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, nitrocellulose, hydroxypropyl cellulose, sodium alginate, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide. It may be a resin, nylon resin, silicone resin, urethane resin, polyethylene resin, polypropylene resin, fluorine resin, or the like.

When the fine particle filler is composed of an organic material, it is better not to soften. In the case of softening, fusion may occur when producing the hollow particles (A1) to which fine particles further adhere, and problems such as deterioration in yield may occur. The softening temperature of the organic substance depends on the temperature at which the hollow particles (A1) are produced, but is preferably 80 to 300 ° C, more preferably 90 to 290 ° C, and further preferably 100 to 280 ° C. The softening temperature of the organic substance is preferably 10 ° C. or more higher than the process temperature.
The inorganic substance or 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, etc., or may be untreated.

As a method for producing the hollow particles (A1), for example, the step (1) for producing thermally expandable microspheres and a step of mixing the obtained thermally expandable microspheres and a fine particle filler (simply referred to as a mixing step). And the mixture obtained in the mixing step is heated to a temperature above the softening point of the thermoplastic resin to expand the thermally expandable microspheres (corresponding to step (2) above), and the fine particle filling A manufacturing method comprising: a step of attaching an agent to the outer surface of the outer shell (attachment step); and the step (3) of obtaining hollow particles (A1) by aging the hollow particles (a) to which the fine particle filler is attached. Can be mentioned.

The mixing step is a step of mixing the thermally expandable microspheres and the fine particle filler.
The weight ratio of the fine particle filler and the thermally expandable microsphere in the mixing step (fine particle filler / thermally expandable microsphere) is not particularly limited, but is preferably 90/10 to 60/40, more preferably 85. / 15 to 65/35, particularly preferably 80/20 to 70/30. When the fine particle filler / heat-expandable microsphere (weight ratio) is larger than 90/10, the true specific gravity of the hollow particles (A1) is increased, and the effect of lowering the specific gravity may be reduced. On the other hand, when the fine particle filler / heat-expandable microsphere (weight ratio) is smaller than 60/40, the true specific gravity of the hollow particles (A1) is lowered, 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, such as a container and a stirring blade. Moreover, you may use the powder mixer which can perform a general rocking | swiveling or stirring. Examples of the powder mixer include a powder mixer that can perform rocking stirring or stirring, such as a ribbon mixer and a vertical screw mixer. In recent years, super mixers (manufactured by Kawata Co., Ltd.), high-speed mixers (manufactured by Fukae Co., Ltd.), and Newgram Machines (Seishin Co., Ltd.), which are efficient and multifunctional powder mixers by combining stirring devices Product), SV mixer (manufactured by Shinko Environmental Solution Co., Ltd.), and the like.
In the attaching step, the mixture containing the thermally expandable microspheres and the fine particle filler obtained in the mixing step is heated to a temperature above the softening point of the thermoplastic resin constituting the outer shell of the thermally expandable microsphere. It is a process. In the attaching step, the thermally expandable microspheres are expanded and the fine particle 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 mixed drying apparatus. The function of the mixing type drying apparatus is not particularly limited, but it is preferable to be able to adjust the temperature and disperse and mix the raw materials, and optionally equipped with a decompression device and a cooling device for speeding up drying. Although there is no limitation in particular as an apparatus used for a heating, For example, a Ladige mixer (made by Matsubo Co., Ltd.), solid air (Hosokawa Micron Co., Ltd.), etc. can be mentioned.
Although the heating temperature condition depends on the type of thermally expandable microsphere, it is preferable to set the optimum expansion temperature, preferably 60 to 250 ° C., more preferably 70 to 230 ° C., further preferably 80 to 220 ° C. Particularly preferred is 100 to 200 ° C, and most preferred is 120 to 180 ° C.

[Organic base resin (B)]
The resin composition of the present invention essentially contains an organic base resin (B). It does not specifically limit as organic base resin (B), Resin used for a coating composition, an adhesive composition, and resin clay is mentioned. Examples thereof include acrylic resin, polyvinyl chloride resin (PVC), urethane resin, epoxy resin, polyvinyl alcohol, vinyl acetate resin, ethylene / vinyl acetate copolymer resin, and rubber. Among these, acrylic resin is preferable from the viewpoint of environment.

As the acrylic resin, for example, a polymer of acrylic acid alkyl ester (alkyl as methyl, ethyl, butyl, 2-ethylhexyl, etc.) or methacrylic acid alkyl ester (alkyl as methyl, ethyl, butyl, lauryl, stearyl, etc.), or Examples include acrylic resins containing copolymers with other acrylic monomers.

Examples of the polyvinyl chloride resin (PVC) include a homopolymer of polyvinyl chloride, a copolymer (copolymer) made of vinyl chloride, vinyl acetate, and the like.

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

The 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, for example, polyoxyalkylene polyol (PPG), polyether polyol modified, polyether polyol containing polytetramethylene ether glycol; condensed polyester polyol, lactone polyester polyol, polyester polyol containing polycarbonate diol; polybutadiene Polyol polyols; Polyolefin polyols: Polyether polyols: Acrylonitrile alone or a mixed monomer of acrylonitrile and at least one selected from the group of styrene, acrylamide, acrylate ester, methacrylate ester and vinyl acetate is polymerized or graft polymerized And polymer polyols.

Examples of the polyisocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-cyclohexane. 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 -Cyclohexane diisocyanate, 1,4-bis (isocyanate methyl) cyclohexane, 1,3-bis (isocyanate methyl) Chlohexane, 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) and the like. These may be used alone or in combination of two or more.
(2) Next, the terminal NCO-containing urethane prepolymer is reacted with a suitable blocking agent (usually 0.9 to 1.5 equivalents of blocking agent per 1 mol of the former NCO), and free NCO
To obtain a target blocked urethane prepolymer (in particular, at least a part of the polyol preferably contains the polymer 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, 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 maleic imide; 2-ethylimidazole, 2- Imidazoles such as ethyl-4-methylimidazole; Lactams such as 2-pyrrolidone and ε-caprolactam; Acetoxime, methylethylketoxime, cyclohexanone oxime, acetoaldoxy Ketones such as oximes or oximes of aldehydes; other examples include ethyleneimine and bisulfite. These may be used alone or in combination of two or more.

Specific examples of the blocked urethane prepolymer include, for example, polypropylene glycol having an excess polyisocyanate compound reacted with TDI and / or HDI, and then reacted with methyl ethyl ketoxime as a blocking agent.

The blocked polyisocyanate compound can be obtained by blocking the free NCO of the polyisocyanate compound exemplified in the production of the terminal NCO-containing urethane prepolymer with the above-mentioned blocking agent. Specific examples of the blocked isocyanate compound include a polyisocyanate compound obtained by reacting TDI and / or HDI with methylethylketoxime 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, and silicone rubber.

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

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

The true specific gravity of the resin composition is preferably 0.3 to 1.4, more preferably 0.4 to 1.3, still more preferably 0.5 to 1.2, and particularly preferably 0.6 to 1.1. Preferably, 0.7 to 0.95 is most preferable. If it is less than 0.3, the weight ratio of the hollow particles becomes high, so that the adhesion performance or the molding performance may be lowered. If it exceeds 1.4, the effect of weight reduction 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, and still more preferably 1.0 to 15% with respect to the entire 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, the weight ratio of the hollow particles is high, so that the adhesion performance or the molding performance may be deteriorated.

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

When the resin composition of the present invention contains a plasticizer (C), for example, the intermolecular force is weakened, and the glass transition temperature of the organic base resin (B) is lowered to give flexibility, elasticity, adhesiveness, and the like. It is preferable because both workability such as spray coating and physical performance are improved.
Examples of the plasticizer (C) include di (2-ethylhexyl) phthalate, butyl benzyl phthalate (high polarity plasticizer), dinonyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate, diundecyl phthalate, diheptyl phthalate, butyl Phthalic acid esters such as phthalyl butyl glycolate and isononyl benzyl phthalate; Aliphatic dibasic acid esters such as dioctyl adipate, didecyl adipate and dioctyl sebacate; polyoxyethylene glycol dibenzoate, polyoxypropylene glycol dibenzoate, etc. Polyglycol benzoate; trimellitic acid ester; pyromellitic acid ester; phosphoric acid ester such as tributyl phosphate and tricresyl phosphate; 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. Of these, phthalates are preferred from the viewpoint 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 based on the entire composition, 25 More preferred is ˜45% by weight. If it is less than 15% by weight, the coating film becomes too hard and the effect of the present application may not be obtained. If it exceeds 60% by weight, the fluidity of the coating film becomes too high, and the coating film formation may not be sufficient.

The resin composition of the present invention is not particularly limited, but is preferably a coating composition, an adhesive composition or a resin clay from the viewpoint of easily exerting the effect of the present application. The paint is not particularly limited, and examples thereof include automotive paints such as underbody coating agents and vibration control paints; architectural paints such as heat insulating paints, exterior wall paints, and waterproof paints. Adhesives include body sealers, hemming adhesives, structural adhesives, spot sealers, mastic adhesives, sheet metal reinforcements and other automotive adhesives; exterior wall sealants, tile adhesives, dirt adhesives, etc. And the like.
Although it does not specifically limit as resin clay, There exists a lightweight clay etc. which are used in education fields, such as a handicraft field, an art field, and a school teaching material.

The resin composition according to the present invention comprises a filler (calcium carbonate, silicic acid, silicate, carbon black, talc, kaolin, silica, water, depending on the application such as a coating composition, an adhesive composition, and a resin clay. 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.), stabilizers [2,6-di-t-butyl-4-methylphenol, 2.2-methylene-bis (4-methyl-6-t-butylphenol), dibutyldithiocarbamine Nickel acid, lead stabilizer, barium / zinc stabilizer, calcium / zinc stabilizer, organotin compound, etc.] Curing 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 adhesive component.
The adhesive component is not particularly limited as long as it is a component capable of adhering between an object, a one-component polyurethane adhesive component, a two-component polyurethane adhesive component, a one-component modified silicone adhesive component, Examples include a two-component modified silicone adhesive component, a one-component polysulfide adhesive component, a two-component polysulfide adhesive component, and an acrylic adhesive component. 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 modified silicone adhesive component, and a two-component modified silicone adhesive component.

The one-pack type polyurethane adhesive component contains an isocyanate group-containing urethane prepolymer as a curing component. The isocyanate group-containing urethane prepolymer expresses adhesiveness when the isocyanate group reacts with moisture in the air and is crosslinked and cured.
As a one-component type polyurethane adhesive component, for example, Penguin Seal 999 (manufactured by Sunstar Giken) and the like are commercially available.

Next, the two-component polyurethane adhesive component is composed of two combinations of a urethane prepolymer (hereinafter also referred to as A1) and a curing agent such as polyol (hereinafter also referred to as A2). In the two-component type polyurethane adhesive component, A1 and A2 are mixed to express adhesiveness by crosslinking and curing.
As the two-component polyurethane adhesive component, for example, penguin seal PU9000 typepeNB (manufactured by Sunstar Giken), Hamatite UH-30 (manufactured by Yokohama Rubber Co., Ltd.), bond PU seal (manufactured by Konishi Co., Ltd.) and the like are commercially available. .

The one-component type modified silicone adhesive component exhibits adhesiveness when the crosslinkable silyl group-containing resin reacts with moisture in the air and is crosslinked and cured. Examples of the one-component type modified silicone adhesive component include sealant 45 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH780 sealant (manufactured by Dow Corning Toray), penguin seal 2505 (manufactured by Sunstar Giken Co., Ltd.), hamatite SS-310 ( Yokohama Rubber Co., Ltd.) are commercially available.
Next, the two-component type modified silicone adhesive component includes a siloxane polymer (hereinafter also referred to as B1) and a curing agent such as a curing agent such as an organic tin compound (hereinafter also referred to as B2). Adhesiveness is developed by mixing and reacting. Examples of the two-component type modified silicone adhesive component include two-component sealant 74 (manufactured by Shin-Etsu Chemical Co., Ltd.), SE792 sealant (manufactured by Dow Corning Toray), penguin seal SR2520 (manufactured by Sunstar Giken Co., Ltd.), and hamatite silicone 70. (Manufactured by Yokohama Rubber Co., Ltd.), Bond MS seal (manufactured by Konishi Co., Ltd.) and the like are commercially available.

The one-component type polysulfide adhesive component contains a liquid polysulfide resin as a curing component, and is blended with a peroxide of an alkali or alkaline earth metal such as BaO ₂ and CaO ₂ as a latent curing agent. It reacts with moisture in the air and generates adhesiveness. As the one-component type polysulfide adhesive component, for example, Topcol SP (manufactured by Toray Fine Chemical Co., Ltd.), Hamatite PS-ONE (manufactured by Yokohama Rubber Co., Ltd.), etc. are commercially available.
The two-component type polysulfide adhesive component includes a base composed of a sulfide polymer (hereinafter sometimes referred to as C1) and a curing agent (hereinafter also referred to as C2) including a metal peroxide such as PdO ₂ . Adhesiveness is generated by mixing. As the two-component type polysulfide adhesive component, for example, Penguin Seal PS169N (manufactured by Sunstar Giken), Hamatite SC-M500 (manufactured by Yokohama Rubber) and the like are commercially available.

The acrylic adhesive component is made of an acrylate polymer emulsion, and adhesiveness is generated by evaporation of moisture. Examples of the acrylic adhesive component are commercially available under a trade name such as Penguin Seal 1250 (manufactured by Sunstar Giken).
The weight ratio of the hollow particles (A) and the adhesive component (hollow particles (A) / adhesive component) blended in the resin composition is not particularly limited, but is preferably 0.0005 to 0.30, more preferably Is 0.001 to 0.20, particularly preferably 0.01 to 0.1. When the hollow particles (A) / adhesive component (weight ratio) is smaller than 0.0005, the amount of the 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. On the other hand, when the hollow particle (A) / adhesive component (weight ratio) is larger than 0.30, the amount of the adhesive component is too small, and the function as the adhesive composition may be remarkably deteriorated. Here, the adhesive component means the total amount of A1 and A2 in the case of a two-component polyurethane adhesive component, and means the total amount of B1 and B2 in the case of a two-component modified silicone adhesive component, In the case of a two-component type polysulfide adhesive component, it means the total amount of C1 and C2.
The degree of elongation of the cured product obtained from the adhesive composition is large, and the cured product is not easily destroyed when deformed by an external force or the like.

When the resin composition of the present invention is a resin clay, it contains polyvinyl alcohol as the hollow particles (A) and the organic base resin (B).
The saponification degree of the polyvinyl alcohol used in the present invention is preferably from 70 to 99 mol%, more preferably from 80 to 90 mol%, still more preferably from 85 to 90 mol%. When the degree of saponification is within this range, workability during modeling 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 even more preferably 10 to 45 mPa · s. When the viscosity of the polyvinyl alcohol is within this range, workability at the time of modeling becomes good.

The blending amount of polyvinyl alcohol in the resin clay is preferably in the range of 2 to 15% by weight, more preferably in the range of 5 to 12% by weight based on the entire resin clay. When the blending amount of polyvinyl alcohol is less than 2% by weight, the adhesiveness (plasticity, extensibility) at the time of molding deteriorates, and when it exceeds 15% by weight, the clay becomes hard, and workability and hand feeling when modeling with clay, etc. The physical properties may deteriorate.
When polyvinyl alcohol is blended in a gel state with a gelling agent, it is desirable in that a clay with “koshi” can be obtained. Examples of the gelling agent include bow glass (sodium sulfate), potassium alum (alum), boric acid, borax and the like. The blending amount is preferably 2 to 15 parts by weight, 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. Examples of the vinyl acetate resin include polyvinyl acetate, polymodified vinyl acetate, ethylene vinyl acetate copolymer resin, vinyl acetate / versaic acid vinyl copolymer resin, vinyl acetate / acrylic acid copolymer, vinyl acetate / acrylic acid ester copolymer Examples thereof include a vinyl acetate / methacrylic acid copolymer, a vinyl acetate / methacrylic acid ester copolymer, a vinyl acetate / acrylamide copolymer, and a vinyl acetate / diene copolymer. This vinyl acetate resin is used in the form of a powder or an emulsion, but usually is often used in the form of an emulsion. When used in the form of an emulsion, it is desirable to use one containing 50% or more of the vinyl acetate resin component.
The vinyl acetate resin used in the present invention preferably has a 59% aqueous solution viscosity at 30 ° C. of 1,000 to 150,000 mPa · s. The vinyl acetate-based resin imparts plasticity to the resin clay and maintains the shape of the shaped article after shaping and drying.

A vinyl acetate resin to which a plasticizer is added is preferable. Examples of the plasticizer include dibutyl phthalate. 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 the plasticizer is preferably 1.5 to 7% by weight (expressed in dry weight), particularly 2 to 5% by weight, based on the entire resin clay. The mixing ratio of the polyvinyl acetate resin containing polyvinyl alcohol and the plasticizer is preferably 10: 7 to 10: 3 by weight. If the blending ratio of the vinyl acetate resin containing the plasticizer exceeds 7, the clay may become sticky and the formability may be impaired. If it is less than 3, the clay tends to be damaged by the 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 highly polymerized polymer having an ether group in the middle and a hydroxyl group at the 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. The viscosity of a 2.0 wt% aqueous solution at 25 ° C. is preferably 100 to 2000 mPa · s, particularly 200 to 700 mPa · s (measured with a rotational viscometer). The melting point is preferably 65 to 67 ° C. The physical properties of polyethylene oxide are excellent in compatibility with hollow particles, polyvinyl alcohol, and vinyl acetate resin. Polyethylene oxide improves the plasticity and extensibility of clay during modeling of the clay, and improves the adhesion of the clay to reduce adhesion to the hand and make the modeling work comfortable. The blending amount is preferably 0.5 to 1.5% by weight (expressed in dry weight) with respect to the entire resin clay. When the blending amount of the polyethylene oxide is less than 0.5% by weight, the extensibility and surface smoothness of the resulting clay are preferable, and when it exceeds 1.5% by weight, the clay sticks to the hand during modeling. There is a fear.

In addition to the above, carboxymethylcellulose salt, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, natural polymer guar gum, and guar gum derivatives can be added to the resin clay of the present invention. These improve clay extensibility, surface smoothness, and texture, and the blending amount thereof is preferably 0.5 to 1.5% by weight based on the entire resin clay.
In addition to 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 has an effect of preventing shrinkage. Examples of the fiber powder include powdered pulp, vinylon fiber, powdered cotton, and pulverized sheet pulp. Natural fibers and synthetic fibers having a fiber powder length of 0.5 to 5.5 mm, particularly 1 to 3 mm are desirable. The blending amount is preferably 0.5 to 4% by weight based on the total weight of the clay.
In addition to the above, a moisturizing agent can be added to the clay of the present invention. Examples of the humectant include liquid paraffin, sorbitol, polyethylene glycol, propylene glycol and the like. The amount of the humectant is preferably 0.5 to 1.5% by weight based on the entire resin clay. The blending amount of water is preferably 50 to 80% by weight, more preferably 60 to 75% by weight, based on the entire resin clay.

The method for producing the resin composition of the present invention comprises the above-mentioned step (1), step (2) and step (3), the hollow particles (A) obtained in step (3) and the organic base resin (B). The process (4) of mixing is included. As a process (4), when hollow particles (A) and organic base resin (B) are mix | blended and other components, such as a plasticizer (C), are further contained, these components are mix | blended, and it is conventionally well-known. A step of batch mixing using a means (for example, a planetary mixer) may be mentioned.

(Molded product)
The molded product of the present invention is obtained by molding the above resin composition. More specifically, when the resin composition of the present invention is an adhesive composition or a coating composition, the molded product of the present invention is obtained by applying the resin composition to an object, drying and curing. .
More specifically, the resin composition can be applied to various undercoating surfaces applied to various metal (particularly steel) surfaces, but can be advantageously applied particularly to cationic electrodeposition coating surfaces. The coating amount of the resin composition on the painted surface is preferably 200 to 2,000 g / m 2, and the coating film thickness is preferably 0.2 to 20 mm from the viewpoint of physical properties of the coating film. Examples of the coating method include brush coating, roller coating, and airless spray coating.
Further, after the coating, a heat treatment is performed. In this case, the temperature is preferably 110 to 200 ° C., more preferably 120 to 180 ° C., from the viewpoint of curability of the resin composition. The heat treatment time is preferably 8 to 60 minutes from the viewpoint of curability of the resin composition.

The molded article has a true specific gravity when the resin composition is treated at 120 ° C. for 10 minutes as D1, and a true specific gravity when the resin composition is treated at 140 ° C. for 20 minutes as D2.
Preferably 0.85 <(D2 / D1) <1.1 is satisfied,
More preferably, 0.87 <(D2 / D1) <1.07 is satisfied,
More preferably, 0.89 <(D2 / D1) <1.04 is satisfied,
It is particularly preferable that 0.91 <(D2 / D1) ≦ 1.0 is satisfied.
If it is 0.85 or less, the surface smoothness may be lowered, and the adhesion performance may be lowered. In 1.1 or more, there is a possibility that the adhesion performance may be deteriorated due to the reduction of closed cells constituted by hollow particles, the influence of fine holes and voids caused by the leakage of the inclusion agent, or a very lightweight molded product May not be obtained.

The molded product of the present invention formed by molding the resin composition of the present invention is firmly bonded to the metal painted surface and is lightweight. Therefore, the molded product of the present invention has excellent underbody coating materials, sealing materials, and hemming adhesives for various industrial uses such as adhesives, sealants, paints, etc., especially for automobile bodies that have been subjected to cationic electrodeposition coating in the automotive industry. When used as an agent, structural adhesive, spot sealer, mastic adhesive, sheet metal reinforcement, and body sealer, it can contribute to an automobile having excellent strength, light weight and excellent fuel efficiency.

The present invention is described in detail in the following examples and comparative examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, “%” means “% by weight”, and “parts” means “parts by weight”.
Below, the manufacture example and comparative manufacture example of the thermally expansible microsphere used as the raw material of a hollow particle are shown first, Then, the Example and comparative example of the resin composition containing a hollow particle are shown. The physical properties of thermally expandable microspheres and hollow particles were measured in the following manner, and the performance was further evaluated.

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

[Measurement of moisture content of thermally expandable microspheres]
The measurement was performed using a Karl Fischer moisture meter (MKA-510N type, manufactured by Kyoto Electronics Industry Co., Ltd.).

[Measurement of encapsulation 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. 30 ml of acetonitrile was added and dispersed uniformly, left at room temperature for 30 minutes, then heated at 120 ° C. for 2 hours, and the weight (W ₂ ) after drying was measured. The encapsulation rate of the foaming agent is calculated by the following formula.
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 encapsulation rate of foaming 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. Acetonitrile 30ml added and dispersed uniformly, after standing at room temperature for 30 minutes and weighed (W ₂₎ after heating was dried 2 hours at 120 ° C.. The encapsulation rate of the foaming agent is calculated by the following formula.
Inclusion rate (G) = (W ₁ −W ₂ ) (g) /0.20 (g) × 100− (water content) (% by weight)
(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 thermally expandable microspheres and hollow particles was measured by the following measuring method.
The true specific gravity was measured by an immersion method (Archimedes method) using isopropyl alcohol in an atmosphere having an environmental temperature of 25 ° C. and a relative humidity of 50%.
Specifically, the volumetric flask having a capacity of 100 cc was emptied and dried, and the weight of the volumetric flask (WB ₁ ) was weighed. After the weighed volumetric flask was accurately filled with isopropyl alcohol to the meniscus, the weight (WB ₂ ) of the volumetric flask filled with 100 cc of isopropyl alcohol was weighed.

Further, the volumetric flask with a capacity of 100 cc was emptied and dried, and the weight of the volumetric flask (WS ₁ ) was weighed. The weighed volumetric flask was filled with about 50 cc of particles, and the weight (WS ₂ ) of the volumetric flask filled with the particles was weighed. Then, the filled volumetric flask particles were weighed weight after filling exactly the isopropyl alcohol to the meniscus to avoid air bubbles are (WS _3). Then, the obtained WB ₁ , WB ₂ , WS ₁ , WS ₂ and WS ₃ were introduced into the following equation, and the true specific gravity (d) of the particles was calculated.
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 particles.

[Volume ratio of intake air volume to hollow particles (Z)]
Place 300 ml of hollow particles in the following aluminum container. In order to measure the volume of a prescribed amount of hollow particles, the weight obtained by the following formula may be measured.
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: Lamidip AL-18) having no gas permeability in an atmosphere having an environmental temperature of 25 ° C. and a relative humidity of 50% is used. The aluminum container does not expand or contract the aluminum film itself due to an increase or decrease in the internal volume, but the shape of the bag is deformed.
Next, the opening is sealed by heat welding so that the volume of the aluminum container is about 900 ml. Using an immersion method (Archimedes method), the volume (Y1) (ml) of the sealed aluminum container is measured. The sealed aluminum container is allowed to stand for 7 days in an atmosphere having an environmental temperature of 25 ° C. and a relative humidity of 50%. After the period, 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 with respect to the hollow particles was calculated by the following formula.
Volume ratio of intake air amount to hollow particles (Z) = (Y1-Y2) / 300
<Aging criteria>
(Z) <− 0.2: ×
−0.2 ≦ (Z) <− 0.05: Δ
−0.05 ≦ (Z) ≦ 0.05: ◎
0.05 <(Z) ≦ 0.2: ○
0.2 <(Z) ≦ 1: △
1 <(Z): ×

[Volume ratio of air content in hollow particles (P)]
The hollow particles W (g) are put in a 1 L container, filled with DMF (dimethylformamide), and sealed. The container 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 oxygen concentration in the gas. The amount of air in the collected gas was calculated by the following formula.
Air volume in collected gas (V) = V1 × C / 20.9
Collected gas volume (V1) (ml)
Oxygen concentration in gas (C) (volume%)
The volume ratio (P) of the amount of air contained in the hollow particles was calculated by the following formula. The volume ratio (P) is a ratio when the volume of the entire hollow particles (A) is 100%.
Volume ratio (P) (%) of the amount of air contained in the hollow particles = V × d × 100 / W
Weight of hollow particles: W (g)
True specific gravity of hollow particles: d (g / cc)
<Aging criteria>
(P) <10: ×
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) in which the specific gravity cup was filled with the resin composition was measured and calculated.
dpo = (Ws−We) / 100 (g / cc)

[Measurement of true specific gravity of molded product]
The true specific gravity of the molded product was measured in a solid specific gravity measurement mode using a Shimadzu top plate electronic analysis balance AX200 (manufactured by Shimadzu Corporation).

[Production Example 1]
In 600 g of ion-exchanged water, 100 g of sodium chloride, 40 g of colloidal silica having an active silica content of 20% by weight, 2 g of polyvinylpyrrolidone and carboxymethylated polyethyleneimines (CMPEI; substituted alkyl group: —CH ₂ COONa, substitution rate) : 80%, weight average molecular weight: 50,000) was added, and then the pH of the resulting mixture was adjusted to 2.8 to 3.2 to prepare an aqueous dispersion medium. Note that CMPEI is the same as that described in paragraph 0140 of the pamphlet of International Publication No. 2008/142849.
Separately, 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 blowing agent, 50 g of isopentane, and 70% pure 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 resulting mixture was dispersed with a homomixer (Primix Co., TK homomixer) at a rotational speed of 12000 rpm for 2 minutes to prepare a suspension. The suspension was transferred to a 1.5 liter pressurized reactor and purged with nitrogen. The initial reaction pressure was 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 were evaluated and are shown in Table 1.

[Production Examples 2 to 5]
In Production Examples 2 to 5, thermal expansion microspheres were obtained by polymerization in the same manner as in Example 1 except that the reaction conditions in Example 1 were changed as shown in Table 1. 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, substituted alkyl group substitution rate: 80%, weight average molecular weight: 50,000). In addition, it is described as carboxymethylated polyethyleneimine / Na salt.
PVP: polyvinylpyrrolidone AN: acrylonitrile MAN: methacrylonitrile IBX: isobornyl methacrylate VCl ₂ : vinylidene chloride MMA: methyl methacrylate TMP: trimethylolpropane trimethacrylate EDMA: diethylene glycol dimethacrylate OPP: di-2-ethylhexyl peroxydicarbonate (Purity 70%)
Colloidal silica (average particle diameter 11 nm, specific surface area 260 m ² / g, colloidal silica effective concentration 20% by weight dispersion)

The hollow particles (a) before aging are produced by a wet heating expansion method described in JP-A-62-201231, and the hollow particles (A) and the hollow particles (A) and the comparative examples 1 to 4 are used 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 heating expansion method described in JP-A-62-201231, this slurry is fed from a slurry introduction tube to a foaming tube (diameter 16 mm, volume 120 ml, made of SUS304TP) at a flow rate of 5 L / min, and further steam ( (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 from the protruding portion of the foamed tube, mixed with cooling water (water temperature 15 ° C.), and cooled to 50-60 ° C. The cooled slurry was dehydrated with a centrifugal dehydrator to obtain a hollow particle composition containing 10% by weight of the wet hollow particles (a) (that is, containing 90% by weight of water).
The obtained hollow particles (a) were aged at 40 ° C. for 24 hours to obtain a hollow particle composition containing 10% by weight of the hollow particles (A). The volume ratio (Z) of the intake air amount with respect to the hollow particles and the volume ratio (P) of the air amount contained in the hollow particles were measured. The evaluation results are shown in Table 2.

Using a universal mixer, 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 are mixed. Mixing for 5 minutes gave a lightweight resin clay. When the aging is sufficient, the hollow particles are not crushed and are sufficiently lightened, and a light-weight resin clay without stickiness can be obtained. The results of 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 the resin clay specific gravity actually obtained with respect to theoretical specific gravity, it computed with the following formula.
Specific gravity increase rate (%) = (resin clay specific gravity / theoretical specific gravity−1) × 100

For stickiness evaluation of resin clay, when creating a plastic image using the obtained clay, whether or not the clay adheres well and exhibits good formability without sticking to the hand evaluated.
○: The clay does not adhere to the hand and the clay adheres well.
Δ: adheres to the hand, but clay also adheres.
X: It adheres to a hand and clay hardly sticks.

[Examples 2 and 3 and Comparative Examples 1 to 4]
In Examples 2 and 3 and Comparative Examples 1 to 4, as shown in Table 2, in Example 1, except that the heat-expandable microspheres, composition, conditions, and the like were changed, respectively, as in Example 1, A lightweight resin clay was obtained. The physical properties are shown in Table 2.

As can be seen from Table 2, in Examples 1 to 3, since sufficient aging treatment was performed until the resin composition was used as a lightweight filler, the inside and outside of the hollow particles (A) There is no air concentration gradient, and there is almost no air intake into the hollow particles (A). Thereby, it is confirmed that the hollow particles have sufficient resistance to the load due to external pressure during mixing and filling in the production process of the resin composition, and the effects of the present application are obtained.
On the other hand, when the aging period is inadequate (Comparative Examples 1 to 4), when used as a lighter filler for the resin composition, the hollow particles are broken due to mixing or loading due to external pressure during filling in the production process. Therefore, the resin composition greatly deviates from the theoretical specific gravity at the time of designing the resin composition, and the lightening effect becomes insufficient, and the effect of the present application is not obtained.

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

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

(Explanation of foaming process part)
As shown in FIG. 2, the foaming process section was installed in the downstream portion of the dispersion nozzle (11), with a gas introduction pipe (not shown) provided with a dispersion nozzle (11) at the outlet and disposed in the center. An impingement plate (12), an overheating prevention cylinder (10) arranged around the gas introduction pipe with a gap, and a hot air nozzle (8) arranged around the overheating prevention cylinder (10) with an interval Is provided. In this foaming process section, a gas fluid (13) containing thermally expandable microspheres is caused to flow in the direction of the arrow in the gas introduction tube, and in the space formed between the gas introduction tube and the overheating prevention cylinder (10). The gas flow (14) for improving the dispersibility of the thermally expandable microspheres and preventing the overheating of the gas introduction pipe and the collision plate is flowed in the direction of the arrow, 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 flows in the direction of the arrow. Here, the hot air flow (15), the gas fluid (13), and the gas flow (14) are usually flows in the same direction. A refrigerant flow (9) flows in the direction of the arrow inside the overheating prevention cylinder (10) for cooling.

(Manufacturing equipment operation)
In the jetting process, the gaseous fluid (13) containing the thermally expandable microspheres is flowed through a gas introduction pipe provided with a dispersion nozzle (11) at the outlet and installed inside the hot air flow (15), and the gaseous fluid (13). From the dispersion nozzle (11).
In the dispersion step, the gas fluid (13) is caused to collide with the collision plate (12) installed downstream of the dispersion nozzle (11), so that the thermally expandable microspheres are uniformly dispersed in the hot air flow (15). To be operated. Here, the gaseous fluid (13) exiting from the dispersion nozzle (11) is guided toward the collision plate (12) together with the gas flow (14) and collides with it.
In the expansion step, the dispersed thermally expandable microspheres are heated and expanded above the expansion start temperature in the hot air flow (15). Thereafter, the obtained hollow particles are recovered by passing them through a cooling part.

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

(Manufacture of molded products)
The resin composition obtained above was applied to an electrodeposition coating plate (thickness 2 mm), and a molded product was obtained by heat treatment at 140 ° C. for 20 minutes. The 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, in Example 4, the same procedure as in Example 4 was performed except that the heat-expandable microspheres, foaming temperature, aging conditions, etc. were changed. A resin composition and a molded product were obtained. The physical properties are shown in Table 3.

As can be seen from Table 3, in Examples 4 and 5, sufficient aging treatment was performed until the resin composition was used as a lighter filler for the resin composition. There is no air concentration gradient, and there is almost no air intake into the hollow particles (A). Thereby, it is confirmed that the hollow particles have sufficient resistance to a load due to an external pressure assumed when the resin composition is used, and the effect of the present application is obtained.
On the other hand, when the aging period is insufficient (Comparative Examples 5 and 6), when used as a lighter filler for the resin composition, the hollow particles are broken by a load due to external pressure assumed when the resin composition is used. Thus, the effect of reducing the weight of the resin composition is insufficient, and the effect of the present application is not obtained.

Example 6
20 parts by weight of the heat-expandable microspheres obtained in Production Example 3 (softening point of the thermoplastic resin constituting the outer shell: 109 ° C.) and calcium carbonate (White White SB Red, manufactured by Bihoku Powdered Industries Co., Ltd.); Laser 80 parts by weight of an average particle diameter by a diffraction method of about 1.8 μm) was added to a separable flask and mixed. Next, the temperature was raised to 130 ° C. over 5 minutes with stirring to obtain a hollow particle (a) before ripening with a fine particle filler attached thereto.
The resulting hollow particles (a) were aged at 10 ° C. for 60 hours to obtain hollow particles (A). The volume ratio (Z) of the intake air amount with respect to the hollow particles and the volume ratio (P) of the air amount contained in the hollow particles were measured. The evaluation results are shown in Table 4.

[Adhesive composition]
80 parts by weight of a two-component polyurethane adhesive component curing agent component (Bond UP Seal Gray, manufactured by Konishi Co., Ltd.), 3.8 parts by weight of hollow particles (A) as a modifier for the adhesive composition, After adding 2 parts by weight of hydrocarbon (Idemitsu Kosan Co., Ltd., IP-2835), the mixture was stirred and mixed at 50 ° C for 30 minutes using a planetary mixer (Inoue Seisakusho, PLM-50), then degassed under reduced pressure. 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 (%) = (curing agent 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 polyurethane adhesive component base material (Bond UP Seal Gray, manufactured by Konishi Co., Ltd.) and a premixed mixture were added to a conditioning mixer (Sinky Co., Ltd.). , AR-360), the mixture was stirred and defoamed at 500 rpm rotation and 2000 rpm revolution for 150 seconds to obtain an adhesive composition. The obtained adhesive composition was cured and cured under conditions of 23 ° C. and 50% RH for 3 days, and further under conditions of 50 ° C. and 50% RH for 3 days, 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, in Example 6, the same procedure as in Example 6 was performed except that the heat-expandable microspheres, foaming temperature, aging conditions, etc. were changed. A resin composition and a molded product were obtained. The physical properties are shown in Table 4.

As can be seen from Table 4, in Examples 6 and 7, sufficient aging treatment was performed until the resin composition was used as a lighter filler for the resin composition. There is no air concentration gradient, and there is almost no air intake into the hollow particles (A). Thereby, it is confirmed that the hollow particles have sufficient resistance to the load due to external pressure during mixing and filling in the production process of the resin composition, and the effects of the present application are obtained.
On the other hand, when the aging period is insufficient (Comparative Examples 7 and 8), when used as a lighter filler for the resin composition, the hollow particles are broken by a load due to external pressure during mixing or filling in the production process. Therefore, the resin composition greatly deviates from the theoretical specific gravity at the time of designing the resin composition, and the lightening 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 Fine particle filler (adsorbed state)
7 Fine particle filler (indented and fixed state)
8 Hot Air Nozzle 9 Refrigerant Flow 10 Overheating Prevention Tube 11 Dispersion Nozzle 12 Colliding Plate 13 Gas Fluid Containing Thermally Expandable Microspheres 14 Gas Flow 15 Hot Air Flow

Claims

A resin composition containing hollow particles (A) and an organic base resin (B),
The hollow particle (A) is an expanded body of thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent encapsulated therein and 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 entire 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 coating composition, an adhesive composition or a resin clay.
A molded product obtained by molding the resin composition according to any one of claims 1 to 3.
A step (1) of obtaining thermally expandable microspheres composed of an outer shell made of a thermoplastic resin and a foaming agent encapsulated therein and vaporized by heating;
(2) obtaining the hollow particles (a) by thermally expanding the thermally expandable microspheres;
Aging the hollow particles (a) at a temperature in the range of −10 to 80 ° C. to obtain hollow particles (A) (3);
Including the step (4) of mixing the obtained hollow particles (A) and the organic base resin (B),
The volume ratio (P) of the amount of air contained in the hollow particles (A) is 30% or more when the volume of the entire hollow particles (A) is 100%.
A method for producing a resin composition.