JP2015143331A - Modifier for adhesive composition and adhesive composition comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modifier for adhesive composition which makes it possible to offer high elongation when it is blended as a component of an adhesive composition, and provide an adhesive composition comprising the modifier for adhesive composition.SOLUTION: A modifier for adhesive composition comprises a resin particle 1 comprising a resin particle 1 body and wax adhering to the resin particle 1 body. Preferably the resin particle 1 is one which also has fine particles 4, 5 adhering thereto. In the modifier for adhesive composition, the resin particle 1 is a hollow particle B or a solid particle.

Description

  The present invention relates to an adhesive composition modifier and an adhesive composition containing the same.

Inorganic fillers such as calcium carbonate and hollow particles such as plastic balloons and glass balloons are used as modifiers for adhesive compositions used mainly for building materials. The purpose of blending these modifiers is to improve the thixotropy of the adhesive composition and workability such as sagging prevention with inorganic fillers (Patent Document 1), while with hollow particles, environmental measures and adhesive components This is a cost reduction due to saving (Patent Document 2), and both are now indispensable fillers for adhesive compositions.
However, by blending these modifiers, the viscosity of the adhesive composition increases and the adhesive component tends to decrease, and the elongation, which is one of the important physical properties of the cured adhesive composition, decreases. In recent years, these problems have surfaced. In other words, the elongation means the flexibility of the adhesive composition after curing. That is, it is a physical property that is a measure of whether or not a bonded object (for example, a building or glass) can withstand displacement after construction. If the elongation is low, there is a possibility that the adhesive component breaks and loses the function as the adhesive component, or the object is destroyed. Therefore, high elongation is required for the cured product of the adhesive composition.

  Patent document 3 is mentioned as what paid attention to the elongation of the hardened | cured material of adhesive composition among the research of the said modifier. In Patent Document 3, elongation is improved by blending hollow particles coated with tacky treated fine particles into an adhesive composition. However, the present situation is that further improvement in elongation is desired.

Japanese Patent Laid-Open No. 11-349846 International Publication No. 97/05201 JP 2010-275453 A

  An object of the present invention is to provide an adhesive composition modifier that exhibits a high elongation when cured as a component of the adhesive composition, and an adhesive composition modifier. It is providing the adhesive composition containing a material.

As a result of intensive studies, the present inventor has found that the above-mentioned problems can be solved by a specific modifier for adhesive composition, and has reached the present invention.
That is, the modifier for an adhesive composition of the present invention comprises resin particles composed of a resin particle body and a wax attached to the resin particle body.

It is preferable that this modifier for adhesive composition further satisfies at least one constituent requirement of the following (1) to (5).
(1) The weight ratio of the wax is 0.1 to 30% by weight of the entire resin particles.
(2) The resin particles are resin particles to which fine particles further adhere.
(3) The weight ratio of the fine particles is 40 to 90% by weight of the entire resin particles.
(4) The resin particle body is a hollow body.
(5) The resin particle body is a solid body.
The adhesive composition of the present invention includes an adhesive component and the adhesive composition modifier.

The adhesive component is a one-component polyurethane adhesive component, a two-component polyurethane adhesive component, a one-component modified silicone adhesive component, a two-component modified silicone adhesive component, a one-component polysulfide adhesive component, a two-component type. The polysulfide adhesive component and at least one selected from an acrylic adhesive component are preferable.
The method for producing resin particles of the present invention comprises a wax mixing step of mixing thermally expandable microspheres and wax, and the wax mixture obtained in the wax mixing step is brought to a temperature equal to or higher than the expansion start temperature of the thermally expandable microspheres. And an expansion step for heating.

The wax mixing step is preferably a step of further mixing fine particles.
In another method for producing resin particles of the present invention, thermally expandable microspheres and wax are mixed and heated to a temperature lower than the expansion start temperature of the thermally expandable microspheres to obtain wax-attached thermally expandable microspheres. A wax adhering step, a fine particle mixing step of mixing the wax-adhering thermally expandable microspheres and fine particles, and the fine particle mixture obtained in the fine particle mixing step is heated to a temperature equal to or higher than an expansion start temperature of the thermally expandable microspheres. And an expansion step.
In the above production method, the thermally expandable microsphere is preferably a microsphere composed essentially of an outer shell made of a thermoplastic resin and a foaming agent contained therein, and the resin particles are modified for an adhesive composition. Good material.

When the modifier for adhesive composition of the present invention is blended as a component of the adhesive composition, the cured product of the adhesive composition exhibits high elongation.
Since the adhesive composition of this invention contains the modifier for adhesive compositions of this invention, the hardened | cured material of the adhesive composition shows high elongation.
The method for producing resin particles of the present invention can produce resin particles efficiently.

FIG. 2 is an example of a cross-sectional view of a hollow particle (hollow particle B) that is a resin particle as a modifying material for an adhesive composition and is composed of a hollow main body and wax and fine particles attached to the hollow main body.

[Basic structure of modifier for adhesive composition]
The modifier for adhesive composition is composed of resin particles composed of a resin particle body and wax attached to the outer surface of the resin particle body.
The average particle size (volume average particle size) of the resin particles is not particularly limited because it can be freely designed according to the use, but is preferably 0.1 to 1000 μm, more preferably 0.3 to 500 μm, More preferably, it is 0.5-300 micrometers, Most preferably, it is 0.8-200 micrometers.

The resin particle body is not limited as long as it is composed of a resin, but the resin is preferably a thermoplastic resin, and adhesion of fine particles described later is facilitated. When the resin particles are hollow particles, the adhesive composition It is possible to achieve the weight reduction of the battery relatively easily.
The thermoplastic resin is not particularly limited. For example, nitrile monomer; carboxyl group-containing monomer; vinylidene chloride; vinyl acetate; (meth) acrylic acid ester monomer; styrene monomer; A resin obtained by (co) polymerizing an acrylamide monomer; a radical polymerizable monomer such as a maleimide monomer. The thermoplastic resin constituting the resin particle body is preferably a thermoplastic resin constituting the outer shell of the thermally expandable microsphere described in detail below. Specific examples of the radical polymerizable monomer will also be described in detail below.

The average particle diameter of the resin particle main body is not particularly limited, but is preferably 0.1 to 1000 μm, more preferably 0.3 to 500 μm, particularly preferably 0.5 to 300 μm, and most preferably 0.8 to 200 μm.
The resin particles that are the modifier for the adhesive composition are composed of a resin particle body and a wax attached thereto. Wax suppresses chemical interaction between the adhesive component and the resin particle body in the adhesive composition, and improves the elongation of the adhesive composition after curing. it is conceivable that.

Examples of the wax include animal waxes such as beeswax and spermaceti; plant waxes such as wood wax, rice bran wax, kauna barrow and candelilla wax; mineral waxes such as montan wax, ozokerite, ceresin and oil shell; magnesium stearate, stearic acid Metal soaps such as lithium; petroleum waxes such as paraffin wax and microcrystalline wax; synthetic waxes such as polyethylene wax, polypropylene wax, hydrogenated castor oil, fatty acid amide, and fatty acid ester; and oxidized waxes and compounded waxes of these waxes It is done. The wax may be selected in accordance with the physical properties of the resin particle body to be coated. Among these, paraffin wax, microcrystalline wax, polyethylene wax, and the like are preferable. These waxes are chemically stable and are exerted by the wax that suppresses the occurrence of chemical interaction between the adhesive component and the resin particle body in the adhesive composition. It is easier to obtain the action.
There is no particular limitation on the melting point of the wax. As the wax, for example, one that is solid at 20 to 200 ° C. can be used. However, the glass transition point of the resin particle body, the production temperature of the resin particle, and thermally expandable microspheres as the raw material of the resin particle are used. When using, it is necessary to select the wax after sufficiently considering the temperature of the expansion process.

The weight ratio of the wax in the entire resin particles is not particularly limited, but is preferably 0.1 to 30% by weight, more preferably 0.2 to 25% by weight, still more preferably 0.3 to 20% by weight, Particularly preferred is 0.5 to 15% by weight. When the weight ratio of the wax is less than 0.1% by weight of the total resin particles, when the adhesive composition modifier is blended in the adhesive composition, a high elongation is obtained in the cured product of the composition. It may not be possible. On the other hand, when the weight ratio of the wax exceeds 30% by weight of the whole resin particles, the resin particles are aggregated and fused, and the fluidity of the resin particles is lowered, so that the uniform dispersibility in the adhesive composition is lowered. there's a possibility that.
It is preferable that the resin particles are resin particles in which fine particles further adhere to the resin particle main body because aggregation and fusion of the resin particles hardly occur and the dispersibility and handling properties of the adhesive composition are improved. Here, the adhesion of the fine particles may be a state where the fine particles are simply adsorbed on the outer surface of the resin particle main body, and the thermoplastic resin near the outer surface of the resin particle main body is melted by heating, and the resin particle main body It may be in a state in which fine particles have sunk into the outer surface and are fixed.

Various particles can be used as the fine particles, and any of inorganic materials 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 diameter of the fine particles is appropriately selected depending on the resin 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. . Within this range, as will be described later, the mixing property becomes good when the resin particles are produced.

Here, the average particle diameter of the fine particles is the particle diameter of the fine particles measured by a laser diffraction method. If the particle size of the fine particles is on the order of micron, it indicates primary particles, but nano-order fine particles are often agglomerated and act as aggregates in the order of micron, so the aggregated secondary particles are regarded as one unit. The average particle size was calculated.
Examples of inorganic substances constituting the fine particles include limestone (heavy calcium carbonate), quartz, silica (silica), wollastonite, gypsum, asbestos, apatite, magnetite, zeolite, clay (montmorillonite, saponite, hectorite, beidellite, and steven. Minerals such as site, nontronite, vermiculite, halloysite, talc, mica, mica, etc .; in the periodic table of elements, metals of group 1 to group 16 (zinc, aluminum, molybdenum, tungsten, zirconium, barium, manganese, Cobalt, calcium, gold, silver, chromium, titanium, iron, platinum, copper, lead, nickel, etc.) and alloys thereof; in the periodic table of the elements, metal oxides of groups 1 to 16 (titanium oxide, zinc oxide, Aluminum oxide, chromium oxide, manganese oxide, molybdenum oxide Buden, 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 (sulfide) Copper, sodium sulfide, lead sulfide, nickel sulfide, platinum sulfide, etc.), metal halides (calcium fluoride, tin fluoride, potassium fluoride, etc.), metal carbides (calcium carbide, titanium carbide, iron carbide, sodium carbide, etc.) , Metal 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.), sulfate metal salt (Aluminum sulfate, cobalt sulfate, sodium hydrogen sulfate, copper sulfate, nickel sulfate, barium sulfate, etc. , Other metal salts (titanates (barium titanate, magnesium titanate, potassium titanate, etc.), borates (aluminum borate, zinc borate, etc.), phosphates (calcium phosphate, sodium phosphate, magnesium phosphate, etc.) And metal compounds such as aluminate (yttrium aluminate, etc.) and nitrate (sodium nitrate, iron nitrate, lead nitrate, etc.).

The inorganic substances that make up the fine particles 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, glass fiber) Silicon nitride, silicon carbide, silicon sulfide, carbon black, carbon nanotubes, graphite, activated carbon, bamboo charcoal, charcoal, fullerene, and the like.
Examples of organic substances constituting the fine particles include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, vinyl benzoic acid; esters thereof, amides, nitriles; styrene, methylstyrene, ethylstyrene. , Vinyl aromatics such as chlorostyrene, divinyl compounds having two or more vinyl groups such as divinylbenzene and trimethylolpropane, etc. as monomers, using a crosslinking agent as necessary, emulsion polymerization, leap free weight Examples thereof include organic resins obtained by polymerization using a combination method, a dispersion polymerization method, a suspension polymerization method, a miniemulsion polymerization method, or the like.

Organic substances constituting the fine particles 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 resin, Nylon resin, silicone resin, urethane resin, polyethylene resin, fluorine resin, and the like may be used.
When the fine particles are composed of organic matter, it is better not to soften. In the case of softening, fusion may occur when producing resin particles to which fine particles further adhere, and problems such as deterioration in yield may occur. The softening temperature of the organic matter depends on the temperature at which the resin particles 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 resin particles may be hollow particles or solid particles. Hollow particles are preferred because they are lightweight. On the other hand, solid particles have a higher degree of freedom in selecting the particle size and the heating temperature when producing solid particles compared to hollow particles. For this reason, solid particles are preferable because the types of wax that can be selected are increased.
Here, when the resin particles are hollow particles, the resin particle main body is a hollow main body. On the other hand, when the resin particles are solid particles, the resin particle main body is a solid main body.

Although the modifier for adhesive composition of the present invention is composed of resin particles, the structure thereof can be classified into the following two, for example, when the particles are hollow particles.
1) Resin particles composed of hollow particles A composed of a hollow body and wax adhered to the hollow body 2) Consisting of hollow bodies B composed of a hollow body and wax and fine particles adhered to the hollow body Resin particles

On the other hand, although the modifier for adhesive composition of the present invention is composed of resin particles, when it is solid particles, its structure can be classified into the following two, for example.
1) Resin particles comprising solid particles A composed of a solid body and wax adhering to the solid body 2) Consisting of solid bodies and wax and fine particles adhering to the solid body Resin Particles Consisting of Solid Particles B In the following, first, the hollow particles A and B and their production methods will be described.

[Hollow particles A and B]
The hollow particle A is composed of a hollow main body as a resin particle main body and a wax attached to the hollow main body. A hollow main body is comprised from the outer shell part which consists of thermoplastic resins, and the hollow part enclosed in it. Wax adheres to the outer surface of the outer shell of the hollow body. Generally, the thickness of the wax attached to the outer surface of the outer shell is smaller than the thickness of the outer shell.
As shown in FIG. 1, for example, the hollow particle B (1) is composed of a hollow main body as a resin particle main body, wax attached to the hollow main body, and fine particles attached to the hollow main body. A hollow main body is comprised from the outer shell part (2) which consists of thermoplastic resins, and the hollow part (3) enclosed by it. The wax adheres to the outer surface of the outer shell of the hollow body (not shown). The fine particles (4 and 5) are attached to the outer surface of the outer shell of the hollow body. Similar to the hollow particle A, the hollow particle B generally has a smaller thickness of the wax attached to the outer surface of the outer shell than the thickness of the outer shell. Accordingly, the wax is not shown in FIG. The wax may be attached to the fine particles attached to the outer surface of the outer shell portion.

The true specific gravity of the hollow particles A is 0.001 to 0.50, preferably 0.002 to 0.40, more preferably 0.003 to 0.20, and particularly preferably 0.005 to 0,10. Most preferably, it is 0.01-0,07. When the true specific gravity is smaller than 0.001, the uniform dispersibility may be lowered when blended as a component of the adhesive composition. On the other hand, when the true specific gravity is greater than 0.50, when blended as a component of the adhesive composition, the effect of lowering the specific gravity is reduced, so that the amount of hollow particles A added is increased, which is uneconomical. There is.
The true specific gravity of the hollow particles B is 0.01 to 0.65, preferably 0.02 to 0.55, more preferably 0.03 to 0.45, and particularly preferably 0.04 to 0.40. Most preferably, it is 0.05-0.35. When the true specific gravity is smaller than 0.01, the uniform dispersibility may be lowered when blended as a component of the adhesive composition. On the other hand, when the true specific gravity is larger than 0.65, when blended as a component of the adhesive composition, the effect of lowering the specific gravity is reduced, so that the amount of hollow particles B added is large, which is uneconomical. There is.

The average particle diameter (volume average particle diameter) of the hollow particles A and B is not particularly limited because it can be freely designed according to the application, but is usually 0.1 to 1000 μm, preferably 0.3 to 500 μm. More preferably, the thickness is 0.5 to 300 μm, and particularly preferably 0.8 to 200 μm.
The water content of the hollow particles A and B is usually 5% by weight or less, preferably 4% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less. When the amount of water exceeds 5% by weight, there is a possibility of affecting the curing of the adhesive component shown below.

As shown in FIG. 1, the hollow main body constituting the hollow particles A and B includes an outer shell portion and a hollow portion surrounded by the outer shell portion. The hollow body is (substantially) spherical and has a hollow portion corresponding to a large cavity inside. If the shape of the hollow body is exemplified by familiar articles, a soft tennis ball can be mentioned. The hollow body generally has a small hardness and true specific gravity, but the hollow particles B have sufficient hardness and a large true specific gravity because the fine particles adhere to the outer surface of the outer shell portion.
The average particle size of the hollow body is not particularly limited, but is preferably 0.1 to 1000 μm, more preferably 0.3 to 500 μm, particularly preferably 0.5 to 300 μm, and most preferably 0.8 to 200 μm. It is.

Although there is no limitation in particular about true specific gravity of a hollow main body, Usually, it is 0.001-0.40, Preferably it is 0.002-0.35, More preferably, it is 0.01-0.30. When the true specific gravity of the hollow body is smaller than 0.001, durability and uniform dispersibility in the adhesive composition may be lowered. On the other hand, when the true specific gravity of the hollow main body is larger than 0.30, the effect of lowering the specific gravity is lowered, so that the amount of hollow particles A and B added is increased, which may be uneconomical.
The outer shell part constituting the hollow body is made of a thermoplastic resin, is surrounded by the outer surface and the inner surface, has no end part, and has a continuous shape. The thickness of the outer shell, that is, the distance between the outer surface and the inner surface is preferably uniform, but may be non-uniform.

The average thickness of the outer shell portion is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm, and particularly preferably 0.15 to 1 μm. When the average thickness of the outer shell is smaller than 0.01 μm, the durability may be lowered. On the other hand, when the average thickness of the outer shell is larger than 10 μm, the elasticity may be lowered. The average thickness of the outer shell is the average thickness of the outer shell calculated from the average particle diameter of the entire hollow body.
The ratio of the average thickness of the outer shell part to the average particle diameter of the hollow body (average thickness of the outer shell part / average particle diameter of the hollow body) is not particularly limited, but is preferably 0.0005 to 0.1, Preferably it is 0.0010-0.7, Most preferably, it is 0.0015-0.5. If the average thickness of the outer shell / the average particle diameter of the hollow body is outside the range of 0.0005 to 0.1, the hollow particles A and B may not exhibit elasticity.

The hollow portion constituting the hollow body is (almost) spherical and is in contact with the inner surface of the outer shell portion. The hollow portion is basically filled with a gas obtained by vaporizing the foaming agent described in detail below, and a part of the foaming agent may be in a liquefied state. All or part of the blowing agent may be replaced with another gas such as air. There may be a plurality of hollow portions in the hollow main body, but it is usually preferable that there is one large hollow portion as shown in FIG.
The wax constituting the hollow particles A and B has been described in detail above, but the weight ratio of the wax to the hollow body (wax / hollow body, hereinafter sometimes referred to as wax weight ratio) is not particularly limited. , Preferably 0.0015 to 3.5, more preferably 0.010 to 2.0, and particularly preferably 0.025 to 1.0. When the wax weight ratio is larger than 3.5, the hollow particles may aggregate and the uniform dispersibility in the adhesive composition may be reduced. On the other hand, when the wax weight ratio is smaller than 0.0015, the elongation of the cured product of the adhesive composition may be lowered.

The fine particles constituting the hollow particle B have been described in detail above, but the ratio of the average particle diameter of the fine particles to the average particle diameter of the hollow main body (average particle diameter of the fine particles / average particle diameter of the hollow main body) is From the viewpoint of adhesion to the surface, it is preferably 1.0 or less, more preferably 0.8 or less, and particularly preferably 0.6 or less.
The weight ratio between the fine particles and the hollow main body (fine particles / hollow main body, hereinafter sometimes referred to as fine particle weight ratio) is not particularly limited, but is preferably 0.65 to 9.5, more preferably 1.0 to 7 .5, particularly preferably 1.5 to 5.5. When the fine particle weight ratio is larger than 9.5, the true specific gravity of the hollow particles B becomes large, and the effect of reducing the specific gravity may not be exhibited. On the other hand, when the fine particle weight ratio is smaller than 0.65, the surface coating of the fine particles becomes insufficient, and the production stability may be lacking.

[Method for producing hollow particle A]
The method for producing hollow particles A includes a wax mixing step of mixing thermally expandable microspheres and wax, and heating the wax mixture obtained in the wax mixing step to a temperature equal to or higher than the expansion start temperature of the thermally expandable microspheres. And an expansion step.

(Wax mixing process)
The wax mixing step is a step of mixing thermally expandable microspheres and wax.
The weight ratio of the wax and the heat-expandable microspheres in the mixing step (wax / heat-expandable microsphere) is not particularly limited, but is preferably 0.0015 to 3.5, more preferably 0.010 to 2. 0, particularly preferably 0.025 to 1.0. When the wax / heat-expandable microsphere (weight ratio) is larger than 3.5, the hollow particles A may aggregate in the next expansion step, and the uniform dispersibility may be lowered in the adhesive composition. On the other hand, when the wax / heat-expandable microsphere (weight ratio) is smaller than 0.0015, the elongation of the cured product of the resulting adhesive composition may be low.

The wax used in the wax mixing step is as described above.
Thermally expandable microspheres are microspheres composed essentially of an outer shell made of a thermoplastic resin and a foaming agent encapsulated in the outer shell. The property that the whole sphere expands by heating).

The foaming agent is not particularly limited as long as it has a boiling point equal to or lower than the softening point of the thermoplastic resin. For example, hydrocarbons having 1 to 12 carbon atoms and their halides; fluorine-containing compounds; tetraalkylsilanes; Examples thereof include a compound that thermally decomposes by heating amide or the like to generate a gas. These foaming agents may be used alone or in combination of two or more. In the following description, the inclusion substance and the foaming agent may be used synonymously.
Examples of the hydrocarbon having 1 to 12 carbon atoms include propane, cyclopropane, propylene, normal butane, isobutane, cyclobutane, normal pentane, cyclopentane, isopentane, neopentane, normal hexane, isohexane, cyclohexane, heptane, cycloheptane, and octane. , Hydrocarbons such as isooctane, cyclooctane, 2-methylpentane, 2,2-dimethylbutane, and petroleum ether. These hydrocarbons may be linear, branched or alicyclic, and are preferably aliphatic.

The heat-expandable microsphere is composed of, for example, a thermoplastic resin obtained by polymerizing a monomer mixture containing a radical polymerizable monomer, and by appropriately blending and polymerizing a polymerization initiator in the monomer mixture. The outer shell of the thermally expandable microsphere can be formed.
The radical polymerizable monomer is not particularly limited as long as it is a monomer having one carbon-carbon double bond. For example, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, Nitrile monomers such as fumaronitrile; carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid; vinylidene chloride; vinyl acetate; methyl (meth) acrylate, ethyl (meta ) Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, β-carboxyethyl acrylate, etc. (Meth) acrylic acid Stealic monomers; styrene monomers such as styrene, α-methylstyrene, chlorostyrene; acrylamide monomers such as acrylamide, substituted acrylamide, methacrylamide, and substituted methacrylamide; N-phenylmaleimide, N- ( And maleimide monomers such as 2-chlorophenyl) maleimide, N-cyclohexylmaleimide, and N-laurylmaleimide. As for the carboxyl group-containing monomer, some or all of the carboxyl groups may be neutralized during polymerization.

These radically polymerizable monomers may be used alone or in combination of two or more. Among these, the monomer mixture is at least one radical polymerizable selected from nitrile monomers, (meth) acrylate monomers, styrene monomers, vinyl acetate, and vinylidene chloride. A monomer mixture containing monomers is preferred. In particular, the monomer mixture is preferably a monomer mixture containing a nitrile monomer as an essential component because heat resistance can be imparted. The weight ratio of the nitrile monomer is preferably 80% by weight or more, more preferably 90% by weight or more, particularly preferably 95% by weight or more, considering heat resistance with respect to the monomer mixture. It is.
The monomer mixture may contain a polymerizable monomer (crosslinking agent) having two or more polymerizable double bonds in addition to the radical polymerizable monomer. By polymerizing using a crosslinking agent, the content of aggregated microspheres contained in the thermally expandable microspheres is reduced, and the decrease in the retention rate (encapsulation retention rate) of the encapsulated foaming agent after thermal expansion is suppressed. Can be effectively thermally expanded.

The weight ratio of the cross-linking agent is not particularly limited, and the cross-linking agent may be omitted. However, in consideration of the degree of cross-linking, the retention rate of the foaming agent included in the outer shell, heat resistance and thermal expansion, Preferably it is 0.001 to 5 weight% with respect to a body mixture, More preferably, it is 0.003 to 3 weight%.
There is no limitation in particular about a polymerization initiator, A well-known polymerization initiator can be used. The polymerization initiator is preferably an oil-soluble polymerization initiator that is soluble in the radical polymerizable monomer.

Thermally expansible microspheres can be manufactured using various methods used in a conventionally known method for manufacturing thermally expandable microcapsules. That is, a monomer mixture that contains a radically polymerizable monomer and may optionally contain a crosslinking agent, a polymerization initiator, and a foaming agent are mixed, and the resulting mixture is mixed with an appropriate dispersion stabilizer or the like. And suspension polymerization in an aqueous suspension.
Although superposition | polymerization temperature is freely set by the kind of polymerization initiator, Preferably it is 40-100 degreeC, More preferably, it is 45-90 degreeC, Most preferably, it controls in the range of 50-85 degreeC. The initial polymerization pressure is 0 to 5.0 MPa, more preferably 0.1 to 3.0 MPa, and particularly preferably 0.2 to 2.0 MPa in terms of gauge pressure.

The average particle diameter of the heat-expandable microsphere is not particularly limited because it can be designed freely according to the use, and is preferably 1 to 100 μm, more preferably 2 to 80 μm, and particularly preferably 5 to 60 μm. is there.
The thermal expansion start temperature of the thermally expandable microsphere depends on the type of the thermally expandable microsphere, but is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and most preferably 100 ° C. or higher. . When the thermal expansion start temperature is less than 60 ° C., there is a possibility that the thermally expandable microspheres will expand unexpectedly in the wax mixing step or the following wax adhesion step. A method for measuring the thermal expansion start temperature will be described in Examples.

  In the wax mixing step, the apparatus used for mixing the thermally expandable microspheres and the wax is not particularly limited, and can be performed using an apparatus having a 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 capable of performing rocking stirring or stirring such as a ribbon type mixer and a vertical screw type mixer. In recent years, super mixers (made by Kawata) and high-speed mixers (made by Fukae), Newgram machines (made by Seishin Enterprises), which are efficient and multifunctional powder mixers by combining stirring devices, An SV mixer (manufactured by Shinko Environmental Solution Co., Ltd.) or the like may be used.

(Expansion process)
The expansion step is a step of heating the wax mixture containing the heat-expandable microspheres and wax obtained in the wax mixing step to a temperature equal to or higher than the expansion start temperature of the heat-expandable microspheres. In the expansion step, the thermally expandable microspheres are expanded and wax is attached to the outer surface of the obtained hollow body. The adhesion of the wax here may be a state where the wax is adsorbed on the outer surface of the hollow body, or a state where the wax covers the outer surface of the hollow body. The wax is preferably coated uniformly, but may be coated in a patchy state.
The process temperature in the expansion process may be equal to or higher than the expansion start temperature of the thermally expandable microsphere, but the melting point of the wax selected at this time is a temperature lower by 5 ° C. or more than the temperature of the expansion process of the thermally expandable microsphere. Preferably, the wax adheres like a film to the outer surface of the hollow particle A, and it becomes easy to coat uniformly, and the elongation of the cured product of the adhesive composition is easily improved. On the other hand, if the melting point of the wax is higher than the temperature of 5 ° C. lower than the temperature of the expansion process of the heat-expandable microspheres, the wax melts but the adhesion to the heat-expandable microspheres is part of the heat-expandable microspheres May be biased.

Moreover, although the temperature of the expansion | swelling process of a thermally expansible microsphere is based also on the kind of thermally expansible microsphere, it is 80-300 degreeC, for example, Preferably it is 90-280 degreeC, More preferably, it is 100-270 degreeC. .
The heating in the expansion step may be performed using a general contact heat transfer type or direct heating type mixing dryer. 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. The apparatus used for heating is not particularly limited, and examples thereof include a Ladige mixer (manufactured by Matsubo) and solid air (manufactured by Hosokawa Micron).

[Method for producing hollow particle B (part 1)]
The method for producing the hollow particles B is a case where in the wax mixing step of the method for producing the hollow particles A, fine particles are further mixed together with the thermally expandable microspheres and the wax.
In the method for producing hollow particles B, the weight ratio of the fine particles and the thermally expandable microspheres in the wax mixing step (particulate / thermally expandable microspheres, hereinafter sometimes referred to as the fine particle weight ratio) is not particularly limited, but preferably Is 0.65 to 9.5, more preferably 1.0 to 7.5, and particularly preferably 1.5 to 5.5. When the fine particle weight ratio is larger than 9.5, the true specific gravity of the hollow particles increases, and the effect of lowering the specific gravity may be reduced. On the other hand, when the fine particle weight ratio is smaller than 0.65, the surface coating of the fine particles becomes insufficient, and the production stability may be lacking.

[Method for producing hollow particle B (part 2)]
Another method for producing hollow particles B is to mix thermally expandable microspheres and wax and heat to a temperature lower than the expansion start temperature of the thermally expandable microspheres to obtain wax-attached thermally expandable microspheres. A step of mixing the wax-adhering thermally expandable microspheres and the fine particles, and an expansion step of heating the fine particle mixture obtained in the fine particle mixing step to a temperature equal to or higher than the expansion start temperature of the thermally expandable microspheres. The manufacturing method including these.

(Wax adhesion process)
In the wax attaching step, the heat-expandable microspheres and the wax are mixed, and the resulting mixture is heated to a temperature not lower than the melting point of the wax and lower than the expansion start temperature of the heat-expandable microspheres to melt the wax, Is a process of obtaining wax-attached thermally expandable microspheres attached to the outer surface of the thermally expandable microspheres.
The adhesion of the wax here may be in a state where the wax is adsorbed on the outer surface of the thermally expandable microsphere, or in a state where the wax covers the outer surface of the thermally expandable microsphere. The wax is preferably coated uniformly, but may be coated in a patchy state.

The description of the weight ratio of the wax and the heat-expandable microsphere in the wax adhesion step is the same as the description of the weight ratio of the wax and the heat-expandable microsphere described in the wax mixing step of the method for producing the hollow particle A, The explanation can be applied here as it is.
In addition, the description of the apparatus used in the wax adhering process and the fine particle mixing process described below is also the apparatus used for mixing the heat-expandable microspheres and the wax described in the wax mixing process of the hollow particle A manufacturing method. This description is the same as that described above and can be applied here as it is.

The process temperature in the wax adhering step is preferably lower than the expansion start temperature of the thermally expandable microspheres in order to avoid the expansion of the thermally expandable microspheres and the formation of a hollow body in this step. More preferably, the temperature is 10 ° C. or more lower than the expansion start temperature of the microspheres. In addition, the process temperature in the wax adhesion process is such that wax-adhesive thermally expandable microspheres in which wax is uniformly adhered to the thermally expandable microspheres are prepared, and the resulting hollow particles B are blended as components of the adhesive composition. In this case, since a high elongation can be obtained, the temperature is preferably higher than the melting point of the wax, and more preferably 5 ° C. or more higher than the melting point of the wax. On the other hand, if the process temperature is lower than a temperature higher by 5 ° C. than the melting point of the wax, the wax melts, but the adhesion to the thermally expandable microspheres may be biased to some thermally expandable microspheres.
The process temperature in the wax adhesion process is not particularly limited, but is preferably 20 to 200 ° C., more preferably 30 to 190 ° C., and still more preferably 40 to 180, although it depends on the type of thermally expandable microspheres and wax. ° C.

(Particle mixing process)
The fine particle mixing step is a step of obtaining a fine particle mixture by mixing the wax-adhesive thermally expandable microspheres and fine particles obtained in the wax adhesion step.
The description of the weight ratio of the fine particles and the thermally expandable microspheres in the fine particle mixing step is the description of the weight ratio of the fine particles and the thermally expandable microspheres described in the wax mixing step of the hollow particle B production method (Part 1). The explanation is also applicable here as it is.

(Expansion process)
The expansion step is a step of obtaining hollow particles B by heating the fine particle mixture obtained in the fine particle mixing step to a temperature equal to or higher than the expansion start temperature of the thermally expandable microspheres. In this expansion step, the thermally expandable microspheres are thermally expanded, and fine particles are attached to the outer surface of the resulting hollow body.
The description of the process temperature and apparatus in this expansion process is the same as the description of the expansion temperature and apparatus described in the expansion process of the hollow particle A manufacturing method, and the description can be applied here as it is.
Next, the solid particles A and B and the production method thereof will be described.

[Solid particles A and B]
The solid particles A are composed of a solid main body as a resin particle main body and a wax attached to the solid main body. If the solid main body of the solid particles A is made of a resin, there is no limitation on the type of resin. The wax adheres to the outer surface of the solid body. In general, the thickness of the attached wax is smaller than the size of the solid body.
Solid particle B (1) is comprised from the solid main body as a resin particle main body, the wax adhering to a solid main body, and the microparticles | fine-particles adhering to a solid main body. The solid body of the solid particles B is not limited as long as it is made of a resin, but is preferably a thermoplastic resin because of the adhesion of fine particles.

The wax adheres to the outer surface of the solid body. In general, the thickness of the attached wax is smaller than the size of the solid body. Fine particles are also attached to the outer surface of the solid body.
The true specific gravity of the solid particles A is 2.0 or less, preferably 1.5 or less, more preferably 1.4 or less, particularly preferably 1.35 or less, and most preferably 1.3 or less. When the true specific gravity is larger than 2.0, when blended in the adhesive composition, the specific gravity of the adhesive composition increases, leading to an increase in cost.

The true specific gravity of the solid particles B is 2.0 or less, preferably 1.8 or less, more preferably 1.5 or less, particularly preferably 1.45 or less, and most preferably 1.4 or less. When the true specific gravity is larger than 2.0, when blended in the adhesive composition, the specific gravity of the adhesive composition increases, leading to an increase in cost.
The average particle size (volume average particle size) of the solid particles A and B is not particularly limited because it can be freely designed according to the application, but is usually 0.1 to 1000 μm, preferably 0.3 to It is 500 μm, more preferably 0.5 to 300 μm, particularly preferably 0.8 to 200 μm.

The water content of the solid particles A and B is usually 5% by weight or less, preferably 4% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less. When the amount of water exceeds 5% by weight, there is a possibility of affecting the curing of the adhesive component shown below.
The solid main body constituting the solid particles A and B is made up of particles that are packed. In the solid particles B, since the fine particles are attached to the outer surface of the outer shell, the hardness is sufficient and the true specific gravity is also increased.

The average particle size of the solid body is not particularly limited, but is preferably 0.1 to 1000 μm, more preferably 0.3 to 500 μm, particularly preferably 0.5 to 300 μm, and most preferably 0.8 to 200 μm.
The true specific gravity of the solid body is not particularly limited, but is 2.0 or less, preferably 1.8 or less, more preferably 1.5 or less, particularly preferably 1.45 or less, and most preferably 1. 4 or less. When the true specific gravity is larger than 2.0, the specific gravity of the adhesive composition is increased, leading to an increase in cost.

The wax constituting the solid particles A and B has been described in detail above, but the weight ratio between the wax and the solid body (wax / solid body, hereinafter sometimes referred to as wax weight ratio) is particularly limited. However, it is preferably 0.0015 to 3.5, more preferably 0.010 to 2.0, and particularly preferably 0.025 to 1.0. When the wax weight ratio is larger than 3.5, solid particles may aggregate and the uniform dispersibility in the adhesive composition may be reduced. On the other hand, when the wax weight ratio is smaller than 0.0015, the elongation of the cured product of the adhesive composition may be low.
The fine particles constituting the solid particles B have been described in detail above, but the ratio between the average particle diameter of the fine particles and the average particle diameter of the solid main body (average particle diameter of the fine particles / average particle diameter of the solid main body) is From the viewpoint of adhesion to the surface of the solid main body, it is preferably 1.0 or less, more preferably 0.8 or less, and particularly preferably 0.6 or less.

  The weight ratio between the fine particles and the solid body (fine particles / solid body, hereinafter may be referred to as the fine particle weight ratio) is not particularly limited, but is preferably 0.65 to 9.5, more preferably 1.0. To 7.5, particularly preferably 1.5 to 5.5. When the fine particle weight ratio is larger than 9.5, the ratio of the solid particles B is low, and the elongation of the cured product of the adhesive composition may be low. On the other hand, when the weight ratio of the fine particles is smaller than 0.65, the surface coating of the fine particles becomes insufficient and the production stability may be lacking.

[Method for producing solid particles A and B]
The manufacturing method of the solid particles A is a manufacturing method including a wax adhering step in which the solid main body and the wax are heated and mixed. The production method of the solid particles B is a production method in which fine particles are further mixed in the wax adhering step of the production method of the solid particles A.
The wax attaching step is a step of mixing solid particles and wax.

The weight ratio of the solid main body, the wax and the fine particles used in the wax adhesion step is as described above.
The wax used in this wax adhesion step is as described above. The description of the apparatus in this wax adhesion step is the same as the description of the apparatus described in the expansion step of the method for producing hollow particles A, and this description can be applied as it is.

The process temperature of the wax adhering step is preferably a temperature that is at least the melting point of the wax and at least 5 ° C. lower than the glass transition temperature of the solid body, and that is at least 10 ° C. It is more preferable that When the melting point of the wax is higher than the temperature lower by 5 ° C. than the glass transition point of the solid main body, a part of the solid particle main body aggregates due to local overheating, and in the adhesive composition The dispersibility of the resin particles may decrease.
The process temperature of the wax adhesion process is preferably 20 to 200 ° C., more preferably 30 to 190 ° C., and further preferably 40 to 180 ° C., although it depends on the solid body and the type of wax.

  In the solid particles B, fine particles are further mixed. When the fine particles are organic, the softening temperature is preferably 5 ° C. or more, more preferably 10 ° C. or more, higher than the process temperature of the wax adhesion step. When the softening temperature of the fine particles is lower than the temperature 5 ° C. higher than the process temperature of the wax adhering step, some of the fine particles aggregate due to partial overheating and the uniform dispersibility in the adhesive composition decreases. In addition, there is a possibility that the wax is covered with the softened fine particles and buried in the solid body instead of the outer surface of the solid body.

[Adhesive composition]
The modifier for adhesive composition of the present invention can be applied to an adhesive composition. As an example, the adhesive composition of the present invention is a composition including an adhesive component and the above-described modifier for an adhesive composition.
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 Toray Dow Corning), 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 adhesive component and the adhesive composition modifier (adhesive composition modifier / adhesive component) blended in the adhesive composition is not particularly limited, but is preferably 0.0005. ˜0.30, more preferably 0.001 to 0.20, and particularly preferably 0.01 to 0.1. When the modifier / adhesive component (weight ratio) for the adhesive composition is less than 0.0005, the amount of the modifier for the adhesive composition added is too small and the elongation of the cured product of the adhesive composition. There is a possibility that the effect of improvement will fade. On the other hand, when the modifier / adhesive component (weight ratio) for the adhesive composition 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 elongation of the cured product obtained from the adhesive composition of the present invention is large, and the cured product is not easily destroyed when deformed by receiving external force or the like.

Examples will be specifically described below. The present invention is not limited to these examples.
About what was obtained by the Example and the comparative example, preparation of a test body, the measurement of various physical properties, and performance evaluation were performed in the way shown below.

[Average particle size]
As a measuring device, a laser diffraction particle size distribution measuring device (HEROS & RODOS, manufactured by SYMPATEC) was used to measure hollow particles, solid particles, and fine particles by a wet measurement method, and the volume average diameter D50 value was defined as the average particle size.

[Thermal expansion start temperature of thermally expandable microspheres]
The thermal expansion start temperature of the thermally expandable microspheres was measured using DMA (DMA Q800 type, manufactured by TA instruments) as a measuring device. Thermally expandable microspheres (0.5 mg) were placed in an aluminum cup having a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, and an aluminum lid (5.6 mm, thickness of 0.2 mm) was formed on the thermally expandable microsphere layer. A sample was prepared by placing 1 mm). The sample height was measured in a state where a force of 0.01 N was applied to the sample with a pressurizer from above. In a state where a pressure of 0.01 N is applied, heating is performed from 20 ° C. to 300 ° C. at a rate of temperature increase of 10 ° C./min, and the displacement of the pressurizer in the vertical direction is measured. The displacement start temperature in the positive direction was defined as the expansion start temperature.

[Measurement of true specific gravity of resin particles]
Weigh the weight a of the 100 ml volumetric flask and then add the sample to a 1-volume volumetric flask and weigh the weight b. To this, isopropyl alcohol is accurately added up to the 100 ml mark and the total weight c is measured. Separately, the empty weight x of the volumetric flask is weighed, and isopropyl alcohol is accurately added up to the marked line to measure the total weight y. These values are applied to the following formula (1) to calculate the specific gravity.
True specific gravity = (b−a) × (y−x) / {100 (y−x) − (c−b)} (1)
With this measurement method, the true specific gravity of the resin particles was measured.
[Measurement of moisture content of resin particles]
The measurement was performed using a Karl Fischer moisture meter (MKA-510N type, manufactured by Kyoto Electronics Industry Co., Ltd.) as a measuring device.

[Preparation of specimen using adhesive composition]
The adhesive composition is adjusted to a width of 10 mm, a length of 60 mm, and a thickness of 3 mm, and this is cured for 3 days under conditions of 23 ° C. and 50% RH, and further for 3 days under conditions of 50 ° C. and 50% RH. Then, the cured product of the adhesive composition was cured to prepare a test body.

[Tensile test of cured product of adhesive composition]
The tensile test of the cured product of the adhesive composition was carried out in a room at 23 ° C. under a tensile speed of 50 mm / min and a load cell of 100 kg with a Tensilon tester (UTM-III-100, manufactured by TOYO BALDMIN). The elongation under load was measured.

(Measurement of true specific gravity of cured product of adhesive composition)
As a measuring apparatus, an upper plate electronic analysis balance (manufactured by Shimadzu Corporation, AX200) was used, and the true specific gravity of the cured product of the adhesive composition was measured.

[Example 1]
(Production of hollow particles B 1)
30 parts by weight of thermally expandable microspheres (Matsumoto Yushi Seiyaku Co., Ltd., Matsumoto Microsphere F-60D, expansion start temperature: about 120 ° C., hereinafter sometimes referred to as F-60D), 69 parts by weight of calcium carbonate powder (Bihoku Powder Chemical Co., Ltd., Whiten SB red, average particle size 2.5 μm) and 1 part by weight of powdered polyethylene wax (Asahi Kasei Chemical Co., Ltd., Sunfine LH311, melting point 128 ° C.) are mixed and separable. It was added to the flask and heated to 150 ° C. over 5 minutes with stirring. Thereafter, the obtained heated mixture was cooled and classified with a 60-mesh sieve to obtain hollow particles a. The production conditions and physical properties of the hollow particles a are shown in Table 1.

[Examples 2 to 4]
Hollow particles b to d were obtained in the same manner as in Example 1 except that the amount of raw material to be blended was changed as shown in Table 1 in Example 1. The production conditions and physical properties of the hollow particles b to d are also shown in Table 1.

Example 5
(Production of hollow particles B 2)
98 parts by weight of thermally expandable microspheres (Matsumoto Yushi Seiyaku Co., Ltd., Matsumoto Microsphere F-60D), 2 parts by weight of paraffin wax (Nippon Seiki Co., Ltd., Paraffin Lux 155, melting point of about 68 ° C.) are separable. The mixture was added to the flask, heated to 80 ° C. with stirring for 5 minutes, then cooled and passed through a 100 mesh sieve to obtain coated particles whose surface was coated with paraffin wax. Next, 30 parts by weight of the coated particles and 70 parts by weight of calcium carbonate (manufactured by Bihoku Flour Industry Co., Ltd., Whiten SB red, average particle size 2.5 μm) are mixed and added to the separable flask. Heated to 150 ° C. over minutes. Thereafter, the obtained heated mixture was cooled and classified with a 60-mesh sieve to obtain hollow particles e whose surfaces were coated with paraffin wax. The production conditions and physical properties of the hollow particles e are shown in Table 1.

Example 6
(Production of solid particles A)
98 parts by weight of plastic beads (manufactured by Matsumoto Yushi Seiyaku, Matsumoto Microsphere M-503B, glass transition point: 125 to 135 ° C., hereinafter sometimes referred to as M-503B) and 2 parts by weight of paraffin wax (Nippon Seiki) Was added to a separable flask and heated to 80 ° C. over 5 minutes with stirring. Thereafter, the obtained heated mixture was cooled and classified with a 100 mesh sieve to obtain solid particles f. The production conditions and physical properties of the solid particles f are shown in Table 1.

Example 7
(Production of hollow particles A)
A mixture of 98 parts by weight of thermally expandable microspheres (Matsumoto Yushi Seiyaku Co., Ltd., Matsumoto Microsphere F-60D) and 2 parts by weight of powdered polyethylene wax (Asahi Kasei Chemical Co., Ltd., Sunfine LH311, melting point 128 ° C.) The mixture was heated while being stirred with a Digger mixer, and cooled down as soon as it reached 150 ° C. Thereafter, the particles were classified with a 60 mesh sieve to obtain hollow particles g whose surfaces were coated with paraffin wax. The production conditions and physical properties of the hollow particles g are shown in Table 1.
In any of the above Examples 1 to 7, after classification with a sieve, there was almost no residue on the sieve. Therefore, the obtained hollow particles a to e, solid particles f, and hollow particles g are all configured in proportions according to the blending amount of each raw material, and the weight ratio of wax and the fine particles in the entire resin particles The weight ratios were as shown in Table 1, respectively.

[Comparative Example 1]
A commercially available hollow particle (MFL-60CA, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), which is composed of a hollow main body and calcium carbonate powder attached to the hollow main body and has no wax attached thereto, was prepared as a hollow particle h. Table 1 shows the physical properties and the like of the hollow particles h.

[Comparative Example 2]
Commercially available solid particles (made by Matsumoto Yushi Seiyaku Co., Ltd., Matsumoto Microsphere M-503B), which is composed of a solid body and has no wax attached thereto, were prepared as solid particles i. The physical properties of the solid particles i are shown in Table 1.
In Tables 1 to 4 below, the hollow particles a to e, the hollow particles g, the hollow particles h, the solid particles f, and the solid particles i are denoted as particles a to i for simplicity.

  In the following examples and comparative examples, the hollow particles and solid particles obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were used as the modifier for the adhesive composition.

[Example S1]
87 parts by weight of a base component of a two-component modified silicone adhesive component and 8.7 parts by weight of a curing agent component (SEICA Flex MC-2C, manufactured by Nippon Seika Co., Ltd.), 4.3 parts by weight of a color toner, 1.75 parts by weight of hollow particles a as a modifier for the adhesive composition and 2 parts by weight of hydrocarbon (IP-2835, manufactured by Idemitsu Kosan Co., Ltd.) were added and premixed, and then a conditioning mixer (Sinky Using an AR-360), an adhesive composition was obtained by stirring and defoaming at 500 rpm for rotation and 2000 rpm for revolution for 150 seconds. The obtained adhesive composition was cured under the above conditions, and physical properties such as elongation at the maximum load were measured. The results are shown in Table 2.
[Examples S2 to S7 and Comparative Examples S1 to S2]
In Example S1, an adhesive composition was obtained in the same manner as in Example S1 except that the type and amount of the modifier for the adhesive composition were changed as shown in Table 2, and these were obtained under the conditions described above. And the physical properties such as elongation at the maximum load were measured. The results are shown in Table 2.

[Example S8]
100 parts by weight of a one-component type modified silicone adhesive composition (manufactured by Cemedine, POS seal), 1.2 parts by weight of hollow particles e as a modifier for the adhesive composition, and 2 parts by weight of carbonized After adding hydrogen (Idemitsu Kosan Co., Ltd., IP-2835) and premixing, using a conditioning mixer (Sinky Corp., AR-360), stirring and defoaming at 500 rpm, revolution 2000 rpm, 150 seconds, An adhesive composition was obtained. The obtained adhesive composition was cured under the above conditions, and physical properties such as elongation at the maximum load were measured. The results are shown in Table 3.
[Comparative Example S3]
In Example S8, an adhesive composition was obtained in the same manner as in Example S8 except that the amount and type of the hollow particles as the modifier for the adhesive composition were changed to 1.5 parts by weight of the hollow particles h. . The obtained adhesive composition was cured under the above conditions, and physical properties such as elongation at the maximum load were measured. The results are shown in Table 3.

[Example U1]
80 parts by weight of a two-component polyurethane adhesive component curing agent component and 20 parts by weight of a base material component (Bond UP Seal Gray, manufactured by Konishi Co., Ltd.), 3.8 parts by weight of an adhesive composition modifier The hollow particles a and 2 parts by weight of hydrocarbon (Idemitsu Kosan Co., Ltd., IP-2835) were added and premixed, and then the rotation speed was 500 rpm using a conditioning mixer (Sinky Corp., AR-360). The mixture was stirred and degassed at 2000 rpm for 150 seconds to obtain an adhesive composition. The obtained adhesive composition was cured under the above conditions, and physical properties such as elongation at the maximum load were measured. The results are shown in Table 4.
[Examples U2-U6 and Comparative Examples U1-U2]
In Example U1, adhesive compositions were obtained in the same manner as in Example U1, except that the types and amounts of the adhesive composition modifiers were changed as shown in Table 4. The obtained adhesive composition was cured under the above conditions, and physical properties such as elongation at the maximum load were measured. The results are shown in Table 4.

In order to compare Examples S1 to S5 and S7 with Comparative Example S1, Table 2 shows the elongation of Examples S1 to S5 and S7, assuming that the elongation of Comparative Example S1 not using the hollow particles of the present invention is 100%. Compared. Moreover, in order to compare Comparative Example S2 and Example S6, the elongation of Comparative Example S2 that does not use the solid particles of the present invention was set to 100%, and the elongation of Example S6 was compared. As a result, when hollow particles were used, the elongations of Examples S1 to S5 and S7 were 108 to 140%, which was higher than the elongation of Comparative Example S1. Even when solid particles were used, the elongation of Example S6 was 113%, which was higher than the elongation of Comparative Example S2.
Similarly to Table 2, Example S8 was compared with Comparative Example S3 in Table 3. The elongation of Example S8 was 135%, which was higher than the elongation of Comparative Example S3.
Similarly to Table 2, also in Table 4, Examples U1 to U4 and U6 using hollow particles were compared with Comparative Example U1, and Example U5 using solid particles and Comparative Example U2 were compared. When hollow particles were used, the elongations of Examples U1 to U4 and U6 were 104 to 128%, which was higher than that of Comparative Example U1. Even when solid particles were used, the elongation of Example U5 was 115%, which was higher than that of Comparative Example U2.

  These results show that the elongation is improved when the resin particles to which the wax adheres are blended into the adhesive composition. Therefore, it was confirmed that the resin particles are useful as a modifier for the adhesive composition.

1 Resin particles as a modifier for an adhesive composition, a hollow body (hollow particle B) composed of a hollow body and wax and fine particles attached to the hollow body
2 outer shell 3 hollow 4 microparticles (adsorbed state)
5 Fine particles (indented and fixed state)

Claims (13)

  A modifier for an adhesive composition comprising a resin particle body and resin particles composed of wax adhered to the resin particle body.   The modifier for adhesive composition according to claim 1, wherein the weight ratio of the wax is 0.1 to 30% by weight of the entire resin particles.   The modifier for adhesive composition according to claim 1 or 2, wherein the resin particles are resin particles to which fine particles further adhere.   The modifier for adhesive composition of Claim 3 whose weight ratio of the said microparticles | fine-particles is 40 to 90 weight% of the whole resin particle.   The modifier for adhesive composition in any one of Claims 1-4 whose said resin particle main body is a hollow main body.   The modifier for adhesive composition in any one of Claims 1-4 whose said resin particle main body is a solid main body.   The adhesive composition containing an adhesive component and the modifier for adhesive compositions in any one of Claims 1-6.   The adhesive component is a one-component polyurethane adhesive component, a two-component polyurethane adhesive component, a one-component modified silicone adhesive component, a two-component modified silicone adhesive component, a one-component polysulfide adhesive component, and a two-component type. The adhesive composition according to claim 7, which is at least one selected from the group consisting of a polysulfide adhesive component and an acrylic adhesive component. A wax mixing step of mixing thermally expandable microspheres and wax;
An expansion step of heating the wax mixture obtained in the wax mixing step to a temperature equal to or higher than the expansion start temperature of the thermally expandable microspheres.
A method for producing resin particles.   The method for producing resin particles according to claim 9, wherein the wax mixing step is a step of further mixing fine particles. A wax adhesion step of mixing thermally expandable microspheres and wax and heating to a temperature below the expansion start temperature of said thermally expandable microspheres to obtain wax-attached thermally expandable microspheres;
A fine particle mixing step of mixing the wax-adhering thermally expandable microspheres and fine particles;
An expansion step of heating the fine particle mixture obtained in the fine particle mixing step to a temperature equal to or higher than the expansion start temperature of the thermally expandable microspheres.
A method for producing resin particles.   The method for producing resin particles according to any one of claims 9 to 11, wherein the thermally expandable microspheres are microspheres composed essentially of an outer shell made of a thermoplastic resin and a foaming agent included therein.   The manufacturing method of the resin particle in any one of Claims 9-12 whose said resin particle is a modifier for adhesive compositions.

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