JP2011241258A - Polymer particle assembly - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer particle assembly imparting excellent handleability and thermal shock resistance to a matrix resin.SOLUTION: The polymer particle assembly obtained by assembling polymer particles (A) has an average particle diameter of 2-1,000 times as long as the volume average particle diameter of the polymer particles constituting the assembly. It is discovered that the liquid resin does not exhibit stringing properties when polymer assembly is present in the liquid resin, and the thermal shock resistance of a cured product is improved when the polymer assembly is present in the cured product, and the invention is completed.

Description

The present invention relates to a polymer particle aggregate that imparts excellent handling properties and thermal shock resistance to a matrix resin.

  Recent progress in polymer composite materials is remarkable, and by adding fillers to matrix resins to make composite materials, for example, the impact resistance of curable resins can be improved. It is possible to give such characteristics (for example, Patent Document 1).

  In addition, in polymer composite materials, it is well known that not only the chemical structure of the polymer used as the matrix resin but also the dispersion state of the added filler greatly affects the properties of the composite material. What dispersion state is preferable depends on the characteristics required of the composite material. In some cases, it is better that the filler is uniformly dispersed (for example, prior art document 1). In some cases, it is preferable (for example, prior art document 2).

  In a situation where it is particularly preferable that the filler forms an aggregate, the characteristics of the composite material can be controlled by controlling the secondary particle diameter of the filler. For example, when silica is used as a filler, a method of controlling the secondary particle size by crushing or applying strong shear to silica having a large secondary particle size is used. In the conventional method for finely dividing the structure, it is difficult to accurately control the size of the aggregate.

  On the other hand, when a filler is added to the matrix resin, if many fillers are added in an attempt to improve the properties of the composite material, for example, an adhesive composition causes stringing of the composition, and handling derived therefrom The deterioration of the property has been a problem (Patent Document 2).

JP 62-50361 A JP 2009-120826 A

Matsushita Electric Works Technical Report, Vol. 53, No. 3, p. 77 Journal of Japan Rubber Association, Vol.82, No.9, page 394

  The present invention has been made in view of the above situation. For example, when dispersed as a filler in a liquid resin, stringing does not occur, and when dispersed in a curable resin, the cold-heat shock resistance of the cured product is improved. An object of the present invention is to provide a polymer particle aggregate.

  As a result of intensive studies to solve the above problems, the present inventors have found that when the polymer aggregate obtained by aggregating the polymer particles is present in the liquid resin, for example, the liquid resin It has been found that the cold-heat shock resistance of the cured product is improved when it does not exhibit stringiness or is present in a curable resin, and has completed the present invention. That is, the present invention has the following configuration.

  1) A polymer particle aggregate in which the average particle diameter of the polymer particle aggregate is 2 to 1000 times the volume average particle diameter of the polymer particles (A) constituting the aggregate.

  2) The polymer particle aggregate according to 1), which is obtained by mixing the polymer particles (A) and the aggregation assistant (B).

3) The polymer particle aggregate according to 1) or 2), wherein the polymer particle (A) is a polymer particle having a hydroxy group on its surface. 4) The aggregation aid (B) is silanol. The polymer particle aggregate according to 2) or 3), which is a silicon compound having at least one functional group selected from a group, a siloxane group and an alkoxy group in one molecule.

  5) The polymer particle aggregate according to 2) or 3), wherein the aggregation assistant (B) is an acid or base catalyst.

  6) The polymer particle aggregate according to any one of 1) to 5), wherein the polymer particles (A) are silicone-based particles.

  7) The silicone-based particles are particles (A-2) obtained by synthesizing core particles and then adding alkoxysilane (C) in the presence of the core particles and condensing them. The polymer particle aggregate described in 1.

  8) The silicone-based particles are particles (A-3) obtained by further adding alkoxysilane (D) and condensing in the presence of the particles (A-2) 7) The polymer particle aggregate described in 1.

  9) The polymer particle aggregate according to 7) or 8), wherein the core particle is obtained by polymerizing a silicon compound containing at least one kind of cyclic siloxane.

  10) The polymer particle aggregate according to 8) or 9), wherein the alkoxysilane (D) contains at least one monofunctional alkoxysilane.

  11) The silicone particles (A-2) are particles obtained by polymerizing 1 to 50% by weight of alkoxysilane as the component (C) with respect to 50 to 99% by weight of the core particles. The polymer aggregate according to any one of 7) to 10).

  12) The silicone particles (A-3) polymerize 1 to 40% by weight of the alkoxysilane as the component (C) with respect to 40 to 98% by weight of the core particles, and further add 1 to the alkoxysilane as the component (D). The polymer particle aggregate according to any one of 8) to 10), which is a particle obtained by polymerization of -30%.

  13) A liquid resin composition in which the polymer particle aggregate according to any one of 1) to 12) is dispersed.

  14) The liquid resin composition according to 13), wherein the liquid resin is a photocurable liquid resin.

  15) The liquid resin composition according to 13), wherein the liquid resin is a thermosetting liquid resin.

  16) The liquid resin composition according to any one of 13) to 15), wherein the liquid resin is a curable silicone resin.

  17) The liquid resin composition according to 16), wherein the curable silicone resin contains an organopolysiloxane (E) having at least two alkenyl groups.

  18) The liquid resin composition according to 16) or 17), wherein the curable silicone resin contains an organohydrogenpolysiloxane (F) having at least two hydrosilyl groups.

19) The component (E) is represented by the general formula (1)
SiO _4/2 (1)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (2) and (3).
R ^a1 R ^a2 ₂ SiO _1/2 (2)
R ^a2 ₃ SiO _1/2 (3)
(Wherein R ^a1 is an alkenyl group, and R ^a2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
At least two alkenyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by the formula (II) and having at least two terminals of the main structure blocked with the general formula (2). The liquid resin composition as described in 17) or 18), which is an organopolysiloxane.

20) The component (F) is represented by the general formula (1)
SiO _4/2 (1)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (4) and (5).
R ^b1 R ^b2 ₂ SiO _1/2 (4)
R ^b2 ₃ SiO _1/2 (5)
(Wherein R ^b1 is a hydrogen atom, and R ^b2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And having at least 2 hydrosilyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by formula (1) and having at least two terminals of the main structure blocked with the general formula (4) The liquid resin composition as described in 18) or 19), which is an organohydrogenpolysiloxane.

  21) A cured product obtained by curing the liquid resin composition according to any one of 13) to 20).

  According to the present invention, for example, when dispersed in a liquid resin, a polymer particle aggregate capable of improving various properties of the liquid resin composition without exhibiting stringiness can be obtained.

Hereinafter, the present invention will be described in detail.

<(A) Polymer particles>
The polymer particles in the present invention indicate particles mainly composed of a polymer. The weight average molecular weight is preferably 1000 or more, more preferably 10,000 or more, further preferably 100,000 or more from the viewpoint of maintaining the shape of the particles. When the weight average molecular weight is less than 1000, the shape of the particles may not be maintained. The measurement of a weight average molecular weight can be performed using GPC (the Tosoh make, HLC-8220GPC), for example.

  The polymer particle polymerization method in the present invention is not particularly limited, and examples thereof include emulsion polymerization and suspension polymerization. The particle diameter of the polymer particles in the present invention is not particularly limited, but from the viewpoint of efficiently forming a polymer particle aggregate, the volume average particle diameter is preferably 0.005 μm to 3.0 μm, 0.01 μm to 2 μm is more preferable, and 0.05 μm to 0.5 μm is more preferable. When the volume average particle diameter of the polymer particles is less than 0.005 μm, the assembly of the polymer particles may not be efficient.

  The volume average particle diameter of the polymer particles can be measured using, for example, a nanotrack particle size analyzer UPA150 (manufactured by Nikkiso Co., Ltd.). The average particle size of the polymer particle aggregate is determined by observing the matrix resin in which the polymer particle aggregate is present with a transmission electron microscope and measuring the size of the polymer particle aggregate present in the field of view. Can do.

  As long as the characteristics of the present invention are not hindered, (A) the polymer particles can be surface-treated. By performing the surface treatment, the component (A) can be promoted to form an aggregate. As the surface treating agent used at this time, for example, a silylating agent can be used. Examples of the silylating agent used here generally include alkylsilanes such as trimethylchlorosilane, dimethyldichlorosilane, and hexamethyl (di) silazane. These silylating agents can be used alone or in combination of two or more.

  In addition, during the surface treatment, polymer particles are introduced by introducing functional groups having binding ability with the matrix resin component, such as alkenyl group, alkynyl group, epoxy group, amino group, carboxyl group, etc. to the surface of the component (A). The size of the aggregate can be controlled. The surface-treated component (A) is preferable when the (A) component forms an aggregate in the liquid matrix resin component. As a silylating agent for introducing a functional group having a binding ability with the matrix liquid resin component to the polymer surface, alkenyl silanes such as chlorodimethylvinyl silane, dichloromethyl vinyl silane, dichlorodivinyl silane, and trichlorovinyl silane are generally used. Can be mentioned. These silylating agents can be used alone or in combination of two or more.

  For the polymer particles in the present invention, for example, silicone-based particles (component (A-1)) are used from the viewpoint of heat resistance of the composition when the polymer particle aggregate of the present invention is present in a liquid resin. It is desirable. The silicone-based particle (A-1) is not particularly limited as long as it has at least one siloxane group in the particle, and the shape thereof is not particularly limited, but the volume average particle diameter is 0.005 μm. -3.0 μm is preferable, 0.01 μm-2.0 μm is more preferable, and 0.05 μm-0.5 μm is particularly preferable. When the volume average particle size is small, the viscosity of the composition containing the silicone particles (A-1) may increase, and when the volume average particle size is large, the transparency of the cured product may deteriorate. is there.

  In order to control the aggregate size and shape of the component (A-1), it is possible to introduce an organic group on the surface or inside of the silicone-based particles. Means such as inclusion using the. Examples of the organic group to be introduced include vinyl group, acrylic group, carboxyl group, ester group, ether group, thiol group, mercapto group, cyano group, and aryl group.

  The component (A-1) is preferably the component (A-2) obtained by adding alkoxysilane (C) in the presence of core particles. The core particle in this case is not particularly limited as long as it does not interfere with the alkoxysilane condensation reaction described below, and various organic polymer particles and inorganic polymer particles can be used. Specific examples include polyethylene particles, polystyrene particles, butyl acrylate rubber particles, butadiene rubber particles, butadiene-styrene particles, butadiene-acrylonitrile rubber particles, butyl acrylate-styrene copolymer particles and styrene-acrylonitrile copolymer particles. Specific examples of the inorganic polymer particles include silicone-based particles, calcium carbonate particles, carbon black particles, carbon nanotube particles, and titanium oxide particles. From the viewpoint of heat resistance of the polymer aggregate, inorganic polymers It is preferable to use particles, and further It is more preferable to use a silicone-based particles in terms of easy control of the diameter.

  Silicone particles preferable as the core particles are preferably particles obtained by polymerization of organosiloxane, and the organosiloxane may be any of linear, branched and cyclic structures, but it is easily available and has low cost. From the viewpoint, it is preferable to use an organosiloxane having a cyclic structure.

  Specific examples of the organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and trimethyltriphenylcyclotrisiloxane. In addition to cyclic compounds such as these, linear or branched organosiloxanes can be mentioned. These organosiloxanes can be used alone or in combination of two or more. Examples of the substituted or unsubstituted monovalent hydrocarbon group possessed by the organosiloxane include a methyl group, an ethyl group, a propyl group, a phenyl group, and a substituted hydrocarbon group obtained by substituting them with a cyano group. it can.

  The method for producing the core particles is not particularly limited, but can be obtained by ordinary emulsion polymerization, dispersion polymerization, solution polymerization, and the like, and the particle size distribution can be controlled. In view of convenience and the like, it is preferable to obtain by emulsion polymerization. For the core particles, it is preferable to use seed polymerization in view of the advantage that particles having a smaller particle diameter can be obtained and the particle diameter in the latex state can be narrowed. The seed polymer used for seed polymerization is not particularly limited, but rubber components such as butyl acrylate rubber, butadiene rubber, butadiene-styrene and butadiene-acrylonitrile rubber, butyl acrylate-styrene copolymer, styrene-acrylonitrile copolymer, etc. A polymer can be used.

  When silicone-based particles are used as core particles, the core particles can be produced by an ordinary emulsion polymerization method performed under acidic or basic conditions. However, reaction under acidic conditions is more effective under basic conditions. This is advantageous because the condensation reaction of alkoxysilane proceeds faster than the above. For example, various raw materials containing the aforementioned organosiloxane are made into an emulsion using an emulsifier and water together with a homomixer, a colloid mill, a homogenizer, etc., and then the pH of the system is adjusted to 5 or less, preferably 4 or less with an acid component, Polymerize by heating. As the acid component used in this case, it is preferable that the emulsion polymerization can proceed stably and also has an emulsifying ability itself, and examples thereof include alkylbenzenesulfonic acid, alkylsulfuric acid, alkylsulfosuccinic acid and the like. .

  In the polymerization of the silicone-based core particles, after adding all of the raw materials at once, the pH may be adjusted to an arbitrary value after stirring for a certain period of time. Alternatively, a part of the raw materials may be charged to adjust the pH to an arbitrary value. The remaining ingredients may be added sequentially to the adjusted emulsion. In the case of sequential addition, it may be added as it is or mixed with water and an emulsifier to form an emulsified liquid, but since the polymerization rate can be increased, a method of adding in an emulsified state is used. It is preferable. The reaction temperature and time are preferably from 0 to 100 ° C, more preferably from 50 to 95 ° C, because of easy reaction control. The reaction time is preferably 1 to 100 hours, more preferably 3 to 50 hours.

  When polymerization is performed under acidic conditions, the Si—O—Si bond forming the skeleton of the silicone-based core particles is usually in an equilibrium state between cleavage and bond formation. This equilibrium changes depending on the temperature, and the higher the temperature, the easier the formation of high molecular weight core particles. Therefore, in order to obtain high molecular weight core particles, it is preferable to perform aging by polymerizing by heating and then cooling to a polymerization temperature or lower. Specifically, the polymerization is carried out at 50 ° C. or higher, and the heating is stopped when the polymerization conversion rate reaches 75 to 90%, more preferably 82 to 89%, and the temperature is lower than the polymerization temperature, for example, 10 to 50 ° C., preferably Can be cooled to 20 to 45 ° C. and aged for about 5 to 100 hours. In addition, the polymerization conversion rate said here means the conversion rate to the core particle of the organosiloxane of the low volatile content in a raw material.

  Moreover, there is no restriction | limiting in particular about the quantity of the water used for emulsion polymerization, What is necessary is just an amount required in order to carry out emulsification dispersion | distribution of various raw materials, if it dares illustrate, it will be 1-20 times weight with respect to the total amount of a normal raw material. Should be used.

  As the emulsifier used for the emulsion polymerization, any known emulsifier can be used without particular limitation as long as it does not lose the emulsifying ability in the pH range where the reaction is carried out. Examples of such emulsifiers include, for example, alkylbenzene sulfonic acid, sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium alkyl sulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfonate, and the like. Moreover, there is no limitation in particular in the usage-amount of this emulsifier, What is necessary is just to adjust suitably according to the particle diameter of the target core particle.

  In synthesizing the core particles used in the present invention, what is called a crosslinking agent or a graft crossing agent can be used if necessary.

  As the crosslinking agent that can be used for the synthesis of the core particle of the present invention, when the core particle is a silicone-based particle, for example, a functional group that can participate in a condensation reaction such as trimethoxymethylsilane, phenyltrimethoxysilane, or ethyltriethoxysilane. A so-called trifunctional crosslinking agent containing three groups, tetraethoxysilane, 1,3-bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [2- (dimethoxymethylsilyl) ethyl] benzene, 1 , 3-bis [1- (dimethoxymethylsilyl) ethyl] benzene, 1,4-bis [1- (dimethoxymethylsilyl) ethyl] benzene, 1- [1- (dimethoxymethylsilyl) ethyl] -3- [2 -(Dimethoxymethylsilyl) ethyl] benzene, 1- [1- (dimethoxymethylsilyl) ethyl] -4- [ - so-called four-functional crosslinking agent 4 containing a functional group capable of participating in condensation reactions such as dimethoxymethylsilyl] ethyl] benzene, and further can be mentioned partial condensate obtained by condensation of alkoxy groups of these crosslinking agents.

  These crosslinking agents can be used alone or in combination of two or more as required. The amount of the crosslinking agent used is preferably 0.1 to 10% by weight of the core particles. When the use of a crosslinking agent is large, the flexibility of the core particles is impaired, so when the polymer aggregate is blended into the matrix, the impact resistance may be reduced. For example, when the matrix is an organopolysiloxane resin In some cases, the cold-heat shock resistance of the cured resin at a low temperature may decrease. Moreover, the elasticity of a core particle can be arbitrarily adjusted by adjusting the usage-amount of a crosslinking agent by changing a crosslinking degree. The core particles are preferably a polymer having a glass transition temperature (Tg) of 0 ° C. or lower.

  The grafting agent that can be used in the present invention is, for example, p-vinylphenylmethyldimethoxysilane, p-vinylphenylethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxy when the core particles are silicone-based particles. Silane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane, mercaptopropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc. can give.

  The polymer particles constituting the polymer aggregate of the present invention preferably have a core / shell structure from the viewpoint of controlling the morphology of the polymer aggregate and improving the characteristics of the matrix.

  When the polymer particles are silicone-based particles, polymer particles (A-2) obtained by polymerizing an alkoxysilane (C) component in the presence of the silicone-based core particles can be exemplified as a preferable particle form. The alkoxysilane used as the component (C) preferably does not use the monofunctional alkoxysilane that is the component (a) represented by the following general formula (6) from the viewpoint of maintaining the shape of the polymer particle aggregate. The structure is not particularly limited as long as it is an alkoxysilane other than the monofunctional alkoxysilane that is the component (a), but if it is intentionally exemplified, it is the component (b) 2 represented by the following general formula (7). Functional alkoxysilane, trifunctional alkoxysilane which is component (c) represented by general formula (4), tetrafunctional alkoxysilane represented by general formula (5), and partial condensates thereof (alkoxy groups) And the like. These alkoxysilanes can be used alone or in combination of two or more.

  (A) Component: General formula (6)

(In General Formula (6), R ¹² represents an alkyl group, and R ¹³ , R ¹⁴ , and R ¹⁵ represent the same or different monovalent organic groups.)
(B) Component: General formula (7)

(Wherein R ²² and R ²³ represent the same or different monovalent alkyl groups, and R ²⁴ and R ²⁵ represent the same or different monovalent organic groups) and / or Or a partial condensate thereof.

  (C) Component: General formula (8)

(Wherein R ³² , R ³³ and R ³⁴ represent the same or different monovalent alkyl groups and R ³⁵ represents a monovalent organic group) and / or Partial condensate.

  (D) Component: General formula (9)

(Wherein R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ represent the same or different monovalent alkyl groups), and / or a partial condensate thereof.

  Examples of the alkoxy group mentioned in the general formulas (7) to (9) include methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, hexyloxy and the like. These are alkoxy groups having 1 to 6 carbon atoms. Examples of the organic group include hydrocarbon groups such as alkyl groups, alkenyl groups, allyl groups, and aralkyl groups.

  The component (A-2) is obtained by adding 1 to 40% by weight of the component (C) (100% by weight of the core particle and the component (C) in total) with respect to 40 to 98% by weight of the core particles and polymerizing the components. It is more preferable that the component (C) is added in an amount of 2 to 37% by weight with respect to 35 to 96% by weight of the core particles, and polymerization is more preferable. When there are few core particles, the softness | flexibility of particle | grains will be impaired, Therefore For example, the thermal shock resistance of the hardened | cured material which hardened | cured the curable composition containing a polymer particle aggregate may be impaired. Further, when the amount of the component (C) is small, the shape of the core particles cannot be maintained, and the physical properties may be lowered, for example, the strength of the cured product obtained by curing the curable composition containing the polymer particle aggregate may be reduced. .

  Further, the component (A-1) is more preferably a component (A-3) obtained by adding and polymerizing an alkoxysilane (D) after the polymerization of the component (C). Alkoxysilane (D) can reduce, for example, many silanol groups present on the surface of the core particles. This avoids various problems derived from silanol groups on the particle surface, for example, when the polymer particle aggregate is contained in a liquid resin, the compatibility and affinity between the polymer particle aggregate and the matrix decrease. it can. For example, when the polymer particle aggregate of the present invention is contained in silicone rubber or silicone resin, the problem that the viscosity of the composition becomes too high and the viscosity gradually increases as the composition changes over time can do.

  The polymer particles (A-3) obtained by polymerizing by adding the alkoxysilane (D) component have few silanol groups on the surface of the particles. For example, when they are contained in the curable silicone composition, the polymer particles (A-3) are subjected to a thermal test. Moreover, it is excellent in that the generation of cracks in the sealing layer due to moisture absorption of the cured product is reduced.

  As the alkoxysilane of the component (D), the monofunctional alkoxysilane which is the component (a) represented by the following general formula (6) and a partial condensate thereof (partial condensate obtained by condensing an alkoxy group) are essential. It is preferable to use as a component. These can be used alone or in combination of two or more.

  (A) Component: General formula (6)

(In General Formula (6), R ¹² represents an alkyl group, and R ¹³ , R ¹⁴ , and R ¹⁵ represent the same or different monovalent organic groups.)
Examples of the alkoxy group mentioned in the general formula (6) include methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy, hexyloxy and the like. 1 to 6 alkoxy groups.

  Examples of the organic group include hydrocarbon groups such as alkyl groups, alkenyl groups, allyl groups, and aralkyl groups.

  Furthermore, the component (D) is preferably selected from at least one of the component (b), the component (c) and the component (d). By combining the component (a) and at least one of the component (b), the component (c), and the component (d), the reaction efficiency of the component (a) can be increased.

  Here, if a component containing an alkenyl group is used in any of (a) to (d), the alkenyl group can be introduced onto the particle surface. The introduction of an alkenyl group into the component (A-3) is performed by, for example, an organopolysiloxane (E) component having at least two alkenyl groups that are cured by a hydrosilylation reaction and an organohydrogenpolysiloxane having at least two hydrosilyl groups (F When the polymer particle aggregate is present in the curable silicone resin comprising the component, the thermal shock resistance of the cured product obtained by curing the curable silicone composition can be improved.

  The component (A-3) is polymerized by adding 1 to 40% by weight of the alkoxysilane as the component (C) with respect to 40 to 98% by weight of the core particles, and 1 to 1% of the alkoxysilane as the component (D). It is preferably obtained by adding 30% by weight (however, 100% by weight of the core particles, the component (C) and the component (D) in total) is added. Furthermore, 2 to 37% by weight of alkoxysilane as component (C) is added and polymerized with respect to 35 to 96% by weight of core particles, and 2 to 28% by weight of alkoxysilane as component (D) is added and polymerized. It is more preferable to be obtained. In addition, when the component (D) is within the above range, the silanol groups on the surface of the core particles are sufficiently reduced, and good physical properties are obtained with respect to the strength and the like of the cured product obtained by curing the curable composition containing the polymer aggregate. It is done.

  The component (A-2) and the component (A-3) preferably have a core-shell structure. The core-shell structure in the present invention is a polymer structure obtained by adding a monomer component different from the core component in the presence of the core particles. From the viewpoint of maintaining the shape of the polymer assembly, the shell component A structure in which a shell structure is formed on the outer side of the core particle while absorbing the core particles is preferable, and a structure in which an inclined structure from the core part to the shell part is further formed is more preferable. Further, the core particle and the shell component may each have a multilayer structure.

  There is no particular limitation on the method for separating the particles from the silicone particle latex (A-1) obtained by emulsion polymerization. For example, a metal salt such as calcium chloride, magnesium chloride or magnesium sulfate is added to the latex. Examples of the method include adding the latex to coagulate, separate, wash, dehydrate, and dry the latex. A spray drying method can also be used.

  As a method for separating particles from latex, it is possible to uniformly disperse the component (A-1) in the matrix resin, and further to obtain a transparent cured product, the master batch method is used. preferable.

  Masterbatch methods include water-soluble or partially soluble organic solvents such as alcohols (methanol, ethanol, 2-propanol, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), acetic acid. By adding esters (ethyl acetate, butyl acetate, methyl acetate), etc., the particles can be slowly aggregated, and then the aggregate can be recovered by centrifugal sedimentation or filtration. An example is a method of redispersing in a suitable solvent, mixing with a matrix resin, and distilling off the solvent.

<Polymer particle assembly>
The polymer particle aggregate in the present invention is an aggregate formed by aggregating two or more polymer particles (A). Moreover, the aggregate | assembly in this invention shows that the polymer particle (A) was couple | bonded chemically or physically, As a coupling | bonding mode, a covalent bond and intermolecular force are mentioned, for example. The aggregate of polymer particles is formed during the polymerization of the polymer particles (A), after the polymerization of the polymer particles (A), or when the polymer particles (A) are mixed with the matrix resin or after mixing. .

  For example, the aggregation aid (B) is added to the dispersion liquid in which the polymer particles (A) are dispersed in an organic solvent, or after the polymer particles (A) are mixed with the liquid resin, the aggregation aid ( By adding B), a polymer particle aggregate can be formed.

  Further, the number of the polymer particles (A) constituting the polymer particle aggregate in the present invention is not particularly limited, but is preferably 10 or more, more preferably from the viewpoint of maintaining the shape of the polymer particle aggregate. Is 100 or more, more preferably 1000 or more. When the number of the polymer particles is less than 10, for example, the stringiness when the polymer particle aggregate is mixed with the liquid resin may not be suppressed.

  The average secondary particle diameter of the polymer particle aggregate is preferably within the range of 0.3 μm to 20 μm from the viewpoint of the stringiness of the blend when the aggregate is dispersed in the liquid resin. , More preferably in the range of 1.0 μm to 15 μm, and still more preferably in the range of 3 μm to 10 μm. When it is less than 0.3 μm, the blend may exhibit stringiness.

  Regarding the ratio of the average secondary particle diameter of the polymer particle aggregate to the volume average particle diameter of the polymer particles (A) forming the aggregate, handling of the blend when the aggregate is dispersed in a liquid resin From the viewpoint of properties, the volume average particle diameter of the polymer particles (A) is preferably 2 to 1000 times, more preferably 2 to 500 times, and even more preferably 2 to 100 times. When the said ratio exceeds 1000 times, the viscosity of a formulation may become high and handling property may worsen.

  Measurement of the average secondary particle diameter of the polymer particle aggregate and the number of polymer particles (A) constituting the polymer particle aggregate are, for example, TEM observation of a cured product obtained by dispersing the aggregate in a curable resin. Can be done.

<(B) Aggregation aid>
The aggregation aid (B) in the present invention refers to a compound having a function of promoting the polymer particles (A) to form a polymer aggregate. As an aspect of the promotion of aggregate formation here, for example, the component (B) is physically or chemically combined with the component (A) in the formation process of the polymer particle aggregate to form the polymer particle aggregate. Although it is mentioned that it is taken in etc., it is not necessarily limited to these aspects.

  The weight ratio of the component (B) to the component (A) is not particularly limited, but is preferably 20 parts by weight or less with respect to 100 parts by weight of the polymer particles from the viewpoint of efficiently performing aggregation. The amount is more preferably at most 5 parts by weight, even more preferably at most 5 parts by weight. When the component (B) exceeding 30 parts by weight is used, the assembly of the component (A) may be hindered and an aggregate may not be obtained.

  Examples of the coagulation aid (B) in this case include metal salts such as calcium chloride, magnesium sulfate and magnesium chloride, and 3-glycidoxypropyltrimethoxy as an organosilicon compound having an epoxy functional group and a silicon atom-bonded alkoxy group. Examples include silane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Further, as an organosilicon compound having a methacryl group or an acryl group and a silicon atom-bonded alkoxy group, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxy Examples include, but are not limited to, propyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

  Further, as a preferred example of the coagulation aid in the present invention, for example, when the component (A) has a reactive group on the surface, it is selected from silanol groups, siloxane groups and alkoxy groups from the viewpoint of promoting the formation of polymer particle aggregates. The silicon compound which has at least 1 type of functional group in 1 molecule is mentioned, and an acid or a base catalyst is raised from a viewpoint of raising the reaction rate of aggregate formation. These aggregating aids may be used alone or in combination of two types, but from the viewpoint of more efficiently forming a polymer particle aggregate, from the above-mentioned silanol group, siloxane group and alkoxy group. It is preferable to use together a silicon compound having at least one selected functional group in one molecule and an acid or base catalyst.

  The silicon compound having at least one functional group selected from the silanol group, siloxane group and alkoxy group in the present invention, which is preferable as the flocculant (B), is a compound having the functional group and containing a silicon atom. The organic silicon compound is preferably used from the viewpoint of the formation efficiency of the aggregate when the polymer particles are formed in an organic solvent, for example, hexamethylcyclotrisiloxane (D3), In addition to cyclic compounds such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and trimethyltriphenylcyclotrisiloxane, methyltrimethoxysilane, methyltriethoxysilane , Methyltripropoxy Run, methylbutoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, butyltri Examples include straight-chain compounds such as methoxysilane, butyltriethoxysilane, butyltripropoxysilane, and butyltributoxysilane, and branched organosiloxanes. These organosiloxanes can be used alone or in combination of two or more. Examples of the substituted or unsubstituted monovalent hydrocarbon group possessed by the organosiloxane include a methyl group, an ethyl group, a propyl group, a phenyl group, and a substituted hydrocarbon group obtained by substituting them with a cyano group. it can.

  The acid or base catalyst in the present invention is not particularly limited as long as the catalyst has an effect of promoting aggregation of the polymer particles (A), and various organic or inorganic acid / base catalysts can be used. Specific examples of the organic acid catalyst include formic acid, acetic acid, citric acid, oxalic acid, maleic acid, malic acid, and the like. Specific examples of the inorganic acid catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like. Examples of the catalyst include trimethylamine, triethylamine, diisopropyldiethylamine, ammonium nitrate, and ammonia. Examples of the inorganic base catalyst include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydride, and the like. From the viewpoint of controlling the particle size, an organic acid catalyst is preferably used, and formic acid or acetic acid is more preferably used.

<Method for producing polymer particle assembly>
The method for producing the polymer particle aggregate in the present invention is not particularly limited. However, for example, the aggregation aid (B) is added to the dispersion in which the polymer particles (A) are dispersed in an organic solvent. And a method of stirring. Examples of the organic solvent used in this case include toluene, xylene, ethyl acetate, hexane, acetone, methyl ethyl ketone, 1,4-dioxane, and dimethyl sulfoxide. However, side reactions such as decomposition reaction of the solvent itself by the catalyst are suppressed. From this viewpoint, it is preferable to use toluene, xylene, or hexane.

  Further, the solid content concentration of the component (A) in the polymer particle dispersion is preferably 3% by weight or more, more preferably 5% by weight or more, from the viewpoint of efficiently performing assembly. More preferably, it is the above.

  The amount of component (B) is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and more preferably 5 parts by weight or less with respect to 100 parts by weight of the dispersion of component (A). More preferably. When there are too many (B) components, it may return and an assembly formation may be prevented.

<Liquid resin composition>
The liquid resin composition in the present invention is not particularly limited as long as it is a composition obtained by dispersing polymer particle aggregates in a liquid resin. The liquid resin used in the present invention is not particularly limited, and a curable resin such as a photocurable resin or a thermosetting resin, or a resin that flows at room temperature or a resin that does not flow can be used. It is preferable to use a curable resin from the viewpoint of heat resistance and light resistance, and it is more preferable to use a curable silicone resin.

  In addition, the chemical structure of the liquid resin in the present invention is not particularly limited. However, if exemplified, an epoxy resin, a phenol resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, an acrylic resin, a urethane resin, A urea resin, a silicone resin, etc. are mentioned.

  The polymer particle aggregate forming the polymer particle aggregate contained in the liquid resin composition in the present invention is liquid from the viewpoint of the thermal shock resistance of a cured product obtained by curing the liquid resin composition. The amount is preferably 1 to 80 parts by weight, more preferably 5 to 50 parts by weight, and still more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the resin. In the range of 1 to 80 parts by weight, the thermal shock resistance of the cured product can be improved.

  By containing the polymer aggregate of the present invention, it is possible to obtain a liquid resin composition having excellent handling properties that does not exhibit stringiness in the liquid resin composition, and further curing the liquid resin composition. In the product, a cured product having excellent thermal shock resistance can be obtained.

<Photocurable liquid resin>
The photocurable liquid resin in the present invention is not particularly limited as long as it is a liquid resin that cures when irradiated with light, and examples thereof include an epoxy resin, a silicone resin, and an acrylic resin. Moreover, a photoinitiator may be added depending on the case, and it may be used independently and may be used in combination of 2 or more types. The content of the photopolymerization initiator is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, with respect to 100 parts by weight of the liquid resin. When the content of the photopolymerization initiator exceeds 20 parts by weight, the handling property of the liquid resin composition may be deteriorated, and when it is less than 0.5 parts by weight, the curing reaction proceeds sufficiently. May not.

<Thermosetting liquid resin>
The thermosetting resin in the present invention is not particularly limited as long as it is a liquid resin that is cured by heating. For example, epoxy resin, silicone resin, acrylic resin, phenol resin, unsaturated polyester resin, polyimide resin, melamine resin, urea resin Is mentioned.

  The method of curing the liquid resin composition used in the present invention is not particularly limited, but the reaction can be performed by simply mixing the components, or the reaction can be performed by heating. From the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained, a method of heating and reacting is preferable.

  Although various reaction temperatures can be set, a temperature range of 25 ° C to 300 ° C is preferable, 30 ° C to 280 ° C is more preferable, and 35 ° C to 260 ° C is more preferable. When the reaction temperature is lower than 25 ° C, the reaction time for sufficient reaction tends to be long, and when the reaction temperature is higher than 300 ° C, the product tends to be thermally deteriorated.

  The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than carrying out the reaction at a constant temperature, the reaction is preferably carried out while raising the temperature in a multistage manner or continuously in that a uniform cured product without distortion can be easily obtained. The pressure during the reaction can be variously set as required, and the reaction can be carried out at normal pressure, high pressure or reduced pressure.

<Curable silicone resin>
The curable silicone resin in the present invention is not particularly limited as long as it is a silicone resin that is cured by light or heat, but is preferably an addition-type silicone resin from the viewpoint of curing speed. The structure of the addition type silicone is not particularly limited, but from the viewpoint of operability and availability, organopolysiloxane (E) having at least two alkenyl groups in one molecule or at least two hydrosilyl groups in one molecule An organohydrogenpolysiloxane (F) is preferred.

  The component (E) in the present invention is an organohydrogenpolysiloxane having at least two hydrosilyl groups in one molecule, which will be described later as the component (F), and is cured by a hydrosilylation reaction to form a silicone matrix. is there. Therefore, any organopolysiloxane containing two or more alkenyl groups in one molecule is not particularly limited, and widely known ones can be used. The structure may be any of linear, branched, cyclic and three-dimensional cross-linked structures.

  Examples of the linear (E) component include polysiloxanes whose ends are blocked with dimethylvinylsilyl groups, and copolymers of dimethylsiloxane units with methylvinylsiloxane units and terminal trimethylsiloxy units.

  Examples of the cyclic (E) component include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1 3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, and the like.

In addition, examples of the component (E) having a three-dimensional crosslinked structure are not particularly limited, but the general formula (10)
SiO _4/2 (10)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (11) and (12).
R ^a1 R ^a2 ₂ SiO _1/2 (11)
R ^a2 ₃ SiO _1/2 (12)
(Wherein R ^a1 is an alkenyl group, and R ^a2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And a structure in which at least two ends of the main structure are blocked by the general formula (11) are exemplified.
Since the cured product obtained from the organopolysiloxane composition containing the assembly of the component (A) represented by the general formula (10), the general formula (11), and the general formula (12) has a high crosslinking density, This is preferable because a cured product having high hardness and high strength can be obtained.

  The alkenyl group is preferably a vinyl group, an allyl group, a butenyl group, or a hexenyl group, and more preferably a vinyl group from the viewpoints of availability, heat resistance, and light resistance. Examples of substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and tolyl groups. The same or different aryl groups or the same or different selected from chloromethyl group, trifluoropropyl group, cyanoethyl group, etc. in which part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. Of these, preferred are unsubstituted or substituted monovalent hydrocarbon groups having preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

  Furthermore, the component (E) is preferably liquid at room temperature because it is easy to handle. The viscosity at room temperature is preferably 1000 Pa · s or less, more preferably 100 Pa · s or less. .

  The component (F) in the present invention is cured by the hydrosilylation reaction with the component (E) to form a silicone matrix. For this reason, there is no particular limitation as long as it is an organohydrogenpolysiloxane containing two or more hydrosilyl groups in one molecule, and widely known ones can be used. The structure may be any of linear, branched, cyclic and three-dimensional cross-linked structures.

  Examples of the linear component (F) include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups, and copolymers of dimethylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units. sell.

  Examples of the cyclic (F) component include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydro Examples include Gen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane.

Further, examples of the component (F) having a three-dimensional crosslinked structure are not particularly limited, but the general formula (10)
SiO _4/2 (10)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (13) and (14).
R ^b1 R ^b2 ₂ SiO _1/2 (13)
R ^b2 ₃ SiO _1/2 (14)
(Wherein R ^b1 is a hydrogen atom, and R ^b2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And those having a structure in which at least two terminals of the main structure are blocked by the general formula (13) are exemplified.

  The cured product obtained from the organopolysiloxane composition blended with the component (D) represented by the general formula (10), the general formula (13), and the general formula (14) has a high crosslink density, and thus has high hardness. This is preferable because a high-strength cured product can be obtained.

  Examples of substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and tolyl groups. The same or different aryl groups or the same or different selected from chloromethyl group, trifluoropropyl group, cyanoethyl group, etc. in which part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. Of these, preferred are unsubstituted or substituted monovalent hydrocarbon groups having preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Among these, a methyl group is more preferable from the viewpoint of heat resistance and light resistance.

  The addition amount of the organohydrogenpolysiloxane (F) is such that the hydrosilyl group of the component (F) is 30 to 500 mol%, preferably 40 to 200 mol% with respect to the alkenyl group of the component (E). It is desirable that

  Furthermore, the component (F) is preferably liquid at room temperature because of easy handling, and the viscosity at room temperature is preferably 1000 Pa · s or less, more preferably 100 Pa · s or less. .

<Adhesive agent>
In the present invention, an adhesion-imparting agent can be added to the liquid resin as necessary.

  As the adhesion-imparting agent in the present invention, a silane coupling agent, a boron-based coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, or the like can be preferably used.

  Examples of the silane coupling agent include at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group in the molecule, and a silicon atom-bonded alkoxy group. A silane coupling agent having a group is preferred. About the said functional group, an epoxy group, a methacryl group, and an acryl group are especially preferable in a molecule | numerator from the point of sclerosis | hardenability and adhesiveness especially.

  Specifically, as the organosilicon compound having an epoxy functional group and a silicon atom-bonded alkoxy group, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxy) And cyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

  Examples of the organosilicon compound having a methacryl group or an acryl group and a silicon atom-bonded alkoxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acrylonitrile. Examples include, but are not limited to, loxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

  Examples of boron coupling agents include trimethyl borate, triethyl borate, tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, triborate triborate. Examples include, but are not limited to, normal butyl, tri-sec-butyl borate, tri-tert-butyl borate, triisopropyl borate, trinormal propyl borate, triallyl borate, and boron methoxyethoxide.

  Examples of titanium coupling agents include tetra (n-butoxy) titanium, tetra (i-propoxy) titanium, tetra (stearoxy) titanium, di-i-propoxy-bis (acetylacetonate) titanium, i-propoxy ( 2-ethylhexanediolate) titanium, di-i-propoxy-diethylacetoacetate titanium, hydroxy-bis (lactate) titanium, i-propyltriisostearoyl titanate, i-propyl-tris (dioctylpyrophosphate) titanate, tetra- i-propyl) -bis (dioctyl phosphite) titanate, tetraoctyl-bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene Taneto, i- propyl trioctanoyl titanate, but i- propyl dimethacrylate -i- stearoyl titanate is exemplified, but not limited thereto.

  Examples of the aluminum coupling agent include, but are not limited to, aluminum butoxide, aluminum isopropoxide, aluminum acetylacetonate, aluminum ethylacetoacetonate, and acetoalkoxyaluminum diisopropylate.

  The adhesiveness imparting agent in the present invention may be used alone or in combination of two or more. The addition amount is preferably 0.05 to 30% by weight of the total weight of the component (A) and the component (B). Also, depending on the type or addition amount of the adhesion-imparting agent, for example, when a curable liquid resin is used for the matrix resin, there is a possibility that it may become a cause of inhibition of curing, so care must be taken.

A curing catalyst can be used as needed for the curable silicone resin in the present invention. As examples of the curing catalyst, for example, a platinum-based catalyst, a palladium-based catalyst, or a rhodium-based catalyst can be added as a hydrosilylation catalyst. Known platinum-based catalysts can be used. Specifically, platinum element alone, platinum compounds, platinum complexes, chloroplatinic acid, chloroplatinic acid alcohol compounds, aldehyde compounds, ether compounds, various olefins and vinyl Examples include complexes with siloxane. The addition amount of the platinum-based catalyst is preferably in the range of 10 ⁻¹ to 10 ⁻¹⁰ mol as a platinum atom with respect to 1 mol of the alkenyl group in the curable silicone resin, and is in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. It is more preferable to use it. If the platinum catalyst is too much, light having a short wavelength is absorbed, and thus the light resistance of the obtained cured product may be lowered. If it is too little, the matrix may not be cured.

  A curing retarder can be used for the purpose of improving the storage stability of the curable silicone resin used in the present invention or adjusting the reactivity of the hydrosilylation reaction during the curing process. Known curing retarders can be used, and specific examples include compounds containing aliphatic unsaturated bonds, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides. . These may be used alone or in combination of two or more.

  Examples of the compound containing an aliphatic unsaturated bond include 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 3 -Methyl-1-hexyn-3-ol, 3-ethyl-1-pentyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, en-in Examples thereof include compounds, maleic esters such as maleic anhydride and dimethyl maleate.

  Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N-dibutyl-1,3 -Propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ', N'-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, 2,2'-bipyridine, etc. Is mentioned.

  Examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

The addition amount of the curing retardant is not particularly limited, but it is preferably used in the range of 10 ⁻¹ to 10 ⁴ mol, preferably in the range of 1 to 10 ³ mol, relative to 1 mol of the hydrosilylation catalyst. More preferred. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

  In the organopolysiloxane composition used in the present invention, fillers such as pulverized quartz, calcium carbonate, and carbon may be added as a bulking agent as needed within a range not impeding the effects of the present invention.

<Other additives>
In the liquid resin composition used in the present invention, various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, or a dispersion for a filler, as long as the effects of the present invention are not hindered. An agent or the like can be optionally added.

  Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like.

In addition, in order to make the liquid resin composition described in the present invention flame retardant and fire resistant, known additives such as titanium dioxide, manganese carbonate, Fe ₂ O ₃ , ferrite, mica, glass fiber, and glass flake are added. May be. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

  In the liquid resin composition used in the present invention, the above components are mixed uniformly using a kneader such as a two-roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and heat-treated as necessary. It can be obtained by applying.

  The polymer aggregate in the present invention can be used as a liquid resin composition by being dispersed in various liquid resins. The use thereof is as a base polymer for adhesives, a high damping rubber, a sealing material for optical devices such as LEDs. However, the present invention is not limited to these examples.

  The present invention will be described in more detail based on the following examples, but the present invention is not limited only to these examples.

(Threading test)
Scrape the obtained liquid resin composition with a stainless steel spatula and visually observe the liquid resin composition flowing down from the spatula. Thus, the stringiness of the liquid resin composition was judged.

(Creation of cured product for evaluation)
Enomoto Co., Ltd. LED package (product name: TOP LED 1-IN-1), 0.4mm x 0.4mm x 0.2mm single crystal silicon chip, Henkel Japan Co., Ltd. epoxy adhesive (product name) : LOCTITE 348), and fixed in an oven at 150 ° C. for 30 minutes. A liquid resin composition in which polymer particle aggregates for forming a sealing layer are dispersed is injected into this, and the sample is thermally cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours. It was created.

(Evaluation of thermal shock resistance of cured products)
After the cured product for evaluation prepared as described above was subjected to 100 cycles of a high temperature holding at 100 ° C. for 5 minutes and a low temperature holding at −40 ° C. for 5 minutes using a thermal shock tester (TSA-71H-W manufactured by Espec). The sample was observed. After the test, if there was no change visually, it was rated as “C”, and if it cracked or peeled off or colored with the package, it was marked “X”.

(Synthesis Example 1)
After mixing 400 parts by weight of pure water and 12 parts by weight of sodium dodecylbenzenesulfonate (solid content) in a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer The temperature was raised to 50 ° C. in a nitrogen atmosphere. Thereafter, 10 parts by weight of butyl acrylate (BA), 3 parts by weight of t-dodecyl mercaptan and 0.01 part by weight of paramentane hydroperoxide (solid content) were added. After 30 minutes, 0.18 part of sodium formaldehyde sulfoxylate (SFS), 0.019 part by weight of ethylenediaminetetraacetic acid (EDTA) and 0.019 part by weight of ferrous sulfate were added and stirred for 1 hour. A mixed solution of 90 parts by weight of BA, 27 parts by weight of t-dodecyl mercaptan and 0.18 parts by weight of paramentane hydroperoxide (solid content) was continuously added over 3 hours. Further, post-polymerization was performed for 1 hour to obtain a latex containing a seed polymer (volume average particle size 0.020 μm).

  Next, in a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port, and a thermometer, 2.0 parts by weight (solid content) of the above seed polymer (10 wt% aqueous solution dodecylbenzene) After charging 1.5 parts by weight of sulfonic acid (solid content) and 300 parts by weight of pure water (including the carry-in from the latex containing the seed polymer), the mixture was stirred for 10 minutes and then the system was heated to 80 ° C. under a nitrogen atmosphere. The temperature was raised to. Separately, a mixture of 150 parts by weight of pure water, 0.5 parts by weight of 5% by weight aqueous sodium dodecylbenzenesulfonate (solid content), 97 parts by weight of octamethylcyclotetrasiloxane, and 3 parts by weight of trimethoxymethylsilane was homogenized. After forcedly emulsifying with a mixer at 8000 rpm for 5 minutes, this mixed solution was continuously added over 3.5 hours. Further, after 2.5 hours of post-polymerization, cooled to 25 ° C. and allowed to stand for 20 hours to complete the polymerization, and latex containing silicone-based particles (volume average particle size 0.110 μm) as component (A-1) Got.

(Synthesis Example 2)
In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer, 90 parts by weight (solid content) of silicone-based particles as component (A-1) obtained in Synthesis Example 1 , And 0.45 parts by weight (solid content) of 10% by weight aqueous solution of dodecylbenzenesulfonic acid were added, and the temperature was raised to 40 ° C. in a nitrogen atmosphere.

Separately, 40 parts by weight of pure water, 0.1 part by weight (solid content) of 15% by weight aqueous solution of sodium dodecylbenzenesulfonate, 7.30 parts by weight of dimethoxydimethylsilane ((CH ₃ ) ₂ SiO _2/2 Equivalent to 4.5 parts by weight in terms of a complete condensate of the structural unit represented by the following formula: ethyl silicate condensate (manufactured by Tama Chemical Industry Co., Ltd., trade name: ethyl silicate 40, SiO ₂ content: 39.0 to 42) 0.0 wt%) 11.16 parts by weight (corresponding to 4.5 parts by weight in terms of the complete condensate of the structural unit represented by SiO ₂ ) was forcibly emulsified with a homomixer at 5000 rpm for 5 minutes. Later, it was added dropwise over 20 minutes. (A-2) component was formed by stirring this solution for 5 hours, keeping at 40 degreeC.

Next, in this solution, 27 parts by weight of pure water and 0.03 part by weight (solid content) of sodium dodecylbenzenesulfonate in a 15% by weight aqueous solution and 6.42 parts by weight of methoxytrimethylsilane ((CH ₃ ) ₃ SiO _{1 / 2} equivalent to 5.0 parts by weight in terms of the complete condensate of the structural unit represented by ₂ ), 1.40 parts by weight of ethoxydimethylvinylsilane (Vi (CH ₃ ) ₂ SiO _1/2 Equivalent to 1.0 part by weight in terms of a complete condensate), 0.81 part by weight of dimethoxydimethylsilane (corresponding to a complete condensate of a structural unit represented by (CH ₃ ) ₂ SiO _2/2 ). Equivalent to 5 parts by weight), ethyl silicate condensate (manufactured by Tama Chemical Industry Co., Ltd., trade name: ethyl silicate 40, SiO ₂ content: 39.0 to 42.0% by weight) 1.24 parts by weight (expressed as SiO ₂ 0 in terms of the complete condensate of the structural unit The mixture was forcibly emulsified with a homomixer at 5000 rpm for 5 minutes and added dropwise over 10 minutes.

  (A-3) component was formed by stirring this solution for 4.5 hours, keeping at 40 degreeC. This system was cooled to 25 ° C. and allowed to stand for 20 hours to complete the polymerization, and a latex containing silicone particles (volume average particle size 0.112 μm) as component (A) was obtained.

Example 1
Mixed solvent 200 comprising methyl ethyl ketone / methanol = 5/5 (vol / vol) with respect to 35 parts by weight of resin solid content of the latex (resin solid content concentration 16% by weight) containing component (A) obtained in Synthesis Example 2 After adding parts by weight to agglomerate the particles, the mixture was centrifuged at 2000 rpm for 5 minutes using a centrifuge. The obtained precipitate was dispersed in 200 parts by weight of a mixed solvent of methyl ethyl ketone / methanol = 2/8 (vol / vol) and washed, and then the solvent was distilled off by centrifugation at 2000 rpm for 5 minutes using a centrifuge. Repeated 3 times. Thereafter, 315 parts by weight of toluene was added to 35 parts by weight of the obtained precipitate to obtain a toluene dispersion of component (A) prepared to 10 wt%.

With respect to 100 parts by weight of the obtained component (A) toluene dispersion, ethyl silicate condensate (manufactured by Tama Chemical Industry Co., Ltd., trade name: ethyl silicate 40, SiO ₂ content: 39.0 to 42.0% by weight) 10 parts by weight and 1 part by weight of formic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added, stirred for 30 minutes at room temperature, and then allowed to stand overnight at room temperature to obtain a toluene dispersion of polymer particle aggregates.

  A vinyl group-containing polysiloxane having a three-dimensional structure as component (E) (made by Clariant, trade name MQV-7, vinyl group content based on 30 parts by weight of the solid content of the polymer particle aggregate thus obtained. 3.5 mol / kg), 36.2 parts by weight, (F) component hydrosilyl group-containing polysiloxane having a three-dimensional structure (manufactured by Clariant, trade name MQH-5, hydrosilyl group content 2.3 mol / kg) and a hydrosilyl group-containing polysiloxane having a three-dimensional structure which is also the component (F) (manufactured by Clariant, trade name MQH-8, hydrosilyl group content 7.5 mol / kg). 5.9 parts by weight were blended, and the mixture was concentrated by a rotary evaporator to distill off toluene.

  Thereafter, 5.0 parts by weight of 3-glycidoxypropyltrimethoxysilane, 1.0 part by weight of trimethyl borate, 0.0011 part by weight of 1% xylene solution of 1-ethynyl-1-cyclohexanol, N, N, N ′ , N'-tetramethylethylenediamine in 1% xylene solution (0.0010 parts by weight) and platinum vinylsiloxane complex in xylene solution (containing 3% by weight as platinum) (0.0062 parts by weight) were added to a planetary stirring deaerator. Then, stirring and defoaming were performed to obtain a liquid composition.

  The obtained liquid composition was used as it was for the yarn drawing test, and a cured product for evaluation was prepared according to the above-described procedure for the thermal shock test.

(Example 2)
Mixed solvent 200 comprising methyl ethyl ketone / methanol = 5/5 (vol / vol) with respect to 35 parts by weight of resin solid content of the latex (resin solid content concentration 16% by weight) containing component (A) obtained in Synthesis Example 2 After adding parts by weight to agglomerate the particles, the mixture was centrifuged at 2000 rpm for 5 minutes using a centrifuge. The obtained precipitate was dispersed in 200 parts by weight of a mixed solvent of methyl ethyl ketone / methanol = 2/8 (vol / vol) and washed, and then the solvent was distilled off by centrifugation at 2000 rpm for 5 minutes using a centrifuge. Repeated 3 times. Thereafter, 315 parts by weight of toluene was added to 35 parts by weight of the obtained precipitate to obtain a toluene dispersion of component (A) prepared to 10 wt%.

With respect to 100 parts by weight of the obtained component (A) toluene dispersion, ethyl silicate condensate (manufactured by Tama Chemical Industry Co., Ltd., trade name: ethyl silicate 40, SiO ₂ content: 39.0 to 42.0% by weight) 10 parts by weight and 1 part by weight of formic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added, stirred for 30 minutes at room temperature, and then allowed to stand overnight at room temperature to obtain a toluene dispersion of polymer particle aggregates. 100 parts by weight of a thermosetting epoxy resin (“Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.) and a curing catalyst for thermosetting epoxy (“ 30 parts by weight of EpiCure 113 (Oilized Shell Epoxy) was blended, and the mixture was concentrated by a rotary evaporator to distill off toluene.

Stirring and defoaming were performed with a planetary stirring and defoaming machine to obtain a liquid resin composition.
The obtained liquid composition was used as it was for the yarn drawing test, and a cured product for evaluation was prepared according to the above-described procedure for the thermal shock test.

(Comparative Example 1)
Mixed solvent 200 comprising methyl ethyl ketone / methanol = 5/5 (vol / vol) with respect to 35 parts by weight of resin solid content of the latex (resin solid content concentration 16% by weight) containing component (A) obtained in Synthesis Example 2 After adding parts by weight to agglomerate the particles, the mixture was centrifuged at 2000 rpm for 5 minutes using a centrifuge. The obtained precipitate was dispersed in 200 parts by weight of a mixed solvent of methyl ethyl ketone / methanol = 2/8 (vol / vol) and washed, and then the solvent was distilled off by centrifugation at 2000 rpm for 5 minutes using a centrifuge. Repeated 3 times. Thereafter, 315 parts by weight of toluene was added to 35 parts by weight of the obtained precipitate to obtain a toluene dispersion of component (A) prepared to 10 wt%.

  With respect to 30 parts by weight of the resin solid content of the component (A) thus obtained, a vinyl group-containing polysiloxane having a three-dimensional structure as the component (E) (manufactured by Clariant, trade name MQV-7, vinyl group content) 3.5 mol / kg), 36.2 parts by weight, (F) component hydrosilyl group-containing polysiloxane having a three-dimensional structure (manufactured by Clariant, trade name MQH-5, hydrosilyl group content 2.3 mol / kg) and a hydrosilyl group-containing polysiloxane having a three-dimensional structure which is also the component (F) (manufactured by Clariant, trade name MQH-8, hydrosilyl group content 7.5 mol / kg). 5.9 parts by weight were blended, and the mixture was concentrated by a rotary evaporator to distill off ethyl acetate.

  Thereafter, 5.0 parts by weight of 3-glycidoxypropyltrimethoxysilane, 1.0 part by weight of trimethyl borate, 0.0011 part by weight of 1% xylene solution of 1-ethynyl-1-cyclohexanol, N, N, N ′ , N'-tetramethylethylenediamine in 1% xylene solution (0.0010 parts by weight) and platinum vinylsiloxane complex in xylene solution (containing 3% by weight as platinum) (0.0062 parts by weight) were added to a planetary stirring deaerator. Then, stirring and defoaming were performed to obtain a liquid resin composition.

  The obtained liquid composition was used as it was for the yarn drawing test, and a cured product for evaluation was prepared according to the above-described procedure for the thermal shock test.

(Comparative Example 2)
Mixed solvent 200 comprising methyl ethyl ketone / methanol = 5/5 (vol / vol) with respect to 35 parts by weight of resin solid content of the latex (resin solid content concentration 16% by weight) containing component (A) obtained in Synthesis Example 2 After adding parts by weight to agglomerate the particles, the mixture was centrifuged at 2000 rpm for 5 minutes using a centrifuge. The obtained precipitate was dispersed in 200 parts by weight of a mixed solvent of methyl ethyl ketone / methanol = 2/8 (vol / vol) and washed, and then the solvent was distilled off by centrifugation at 2000 rpm for 5 minutes using a centrifuge. Repeated 3 times. Thereafter, 315 parts by weight of toluene was added to 35 parts by weight of the obtained precipitate to obtain a toluene dispersion of component (A) prepared to 10 wt%.

  100 parts by weight of a thermosetting epoxy resin (“Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.) and a curing catalyst for thermosetting epoxy (“ EpiCure 113 (Oilized Shell Epoxy) EpiCure 113 was blended in 30 parts by weight, and the mixture was concentrated with a rotary evaporator to distill off toluene.

  The obtained liquid composition was used as it was for the yarn drawing test, and a cured product for evaluation was prepared according to the above-described procedure for the thermal shock test.

  Various test results are shown in Table 1.

  As shown in Table 1, Examples 1 and 2 are excellent in thermal shock resistance, and at the same time, the liquid composition does not exhibit stringing and is excellent in handling properties. On the other hand, although Comparative Example 1 has thermal shock resistance, the liquid composition exhibits stringiness and handling properties are inferior. Further, in Comparative Example 2, it is understood that the cured product has low thermal shock resistance, and the liquid composition also exhibits stringiness and handling properties are inferior. From the above, the polymer particle aggregate in the present invention is improved in the handling property of the liquid resin composition containing the aggregate because the particles form an aggregate, and the cured product has a thermal shock resistance. It turns out that it is excellent in.

Claims (21)

A polymer particle aggregate in which the average particle diameter of the polymer particle aggregate is 2 to 1000 times the volume average particle diameter of the polymer particles (A) constituting the aggregate. 2. The polymer particle aggregate according to claim 1, wherein the polymer particle aggregate is obtained by mixing the polymer particles (A) and the aggregation aid (B). 3. The polymer particle aggregate according to claim 1 or 2, wherein the polymer particle (A) is a polymer particle having a hydroxy group on a surface thereof. The polymer particle according to claim 2 or 3, wherein the aggregation assistant (B) is a silicon compound having in a molecule thereof at least one functional group selected from a silanol group, a siloxane group and an alkoxy group. Aggregation. The polymer particle aggregate according to claim 2 or 3, wherein the aggregation assistant (B) is an acid or base catalyst. The polymer particle aggregate according to any one of claims 1 to 5, wherein the polymer particles (A) are silicone-based particles. The silicone particle is a particle (A-2) obtained by synthesizing a core particle, adding alkoxysilane (C) in the presence of the core particle, and condensing it. The polymer particle aggregate as described. 8. The silicone particle according to claim 7, wherein the silicone particle is a particle (A-3) obtained by further adding and condensing an alkoxysilane (D) in the presence of the particle (A-2). The polymer particle aggregate as described. The polymer particle aggregate according to claim 7 or 8, wherein the core particles are obtained by polymerizing a silicon compound containing at least one kind of cyclic siloxane. 10. The polymer particle aggregate according to claim 8 or 9, wherein the alkoxysilane (D) contains at least one monofunctional alkoxysilane. The silicone particles (A-2) are particles obtained by polymerizing 1 to 50% by weight of alkoxysilane as the component (C) with respect to 50 to 99% by weight of the core particles. The polymer aggregate according to any one of 7 to 10. The silicone particles (A-3) polymerize 1 to 40% by weight of alkoxysilane as the component (C) with respect to 40 to 98% by weight of the core particles, and further 1 to 30% of alkoxysilane as the component (D). The polymer particle aggregate according to any one of claims 8 to 10, wherein the polymer particle aggregate is obtained by% polymerization. A liquid resin composition in which the polymer particle aggregate according to any one of claims 1 to 12 is dispersed. The liquid resin composition according to claim 13, wherein the liquid resin is a photocurable liquid resin. The liquid resin composition according to claim 13, wherein the liquid resin is a thermosetting liquid resin. The liquid resin composition according to claim 13, wherein the liquid resin is a curable silicone resin. The liquid resin composition according to claim 16, wherein the curable silicone resin contains an organopolysiloxane (E) having at least two alkenyl groups. The liquid resin composition according to claim 16 or 17, wherein the curable silicone resin contains an organohydrogenpolysiloxane (F) having at least two hydrosilyl groups. The component (E) is represented by the general formula (1)
SiO _4/2 (1)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (2) and (3).
R ^a1 R ^a2 ₂ SiO _1/2 (2)
R ^a2 ₃ SiO _1/2 (3)
(Wherein R ^a1 is an alkenyl group, and R ^a2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
At least two alkenyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by the formula (II) and having at least two terminals of the main structure blocked with the general formula (2). The liquid resin composition according to claim 17 or 18, wherein the liquid resin composition is an organopolysiloxane. The component (F) is represented by the general formula (1)
SiO _4/2 (1)
The main structure is a three-dimensional network structure composed of tetrafunctional structural units represented by general formulas (4) and (5).
R ^b1 R ^b2 ₂ SiO _1/2 (4)
R ^b2 ₃ SiO _1/2 (5)
(Wherein R ^b1 is a hydrogen atom, and R ^b2 is a substituted or unsubstituted monovalent hydrocarbon group other than an alkenyl group, which may be the same or different.)
And having at least 2 hydrosilyl groups in one molecule having a structure blocked with a monofunctional structural unit represented by formula (1) and having at least two terminals of the main structure blocked with the general formula (4) The liquid resin composition according to claim 18, wherein the liquid composition is an organohydrogenpolysiloxane. Hardened | cured material which hardened the liquid resin composition as described in any one of Claims 13-20.