CN116783226A

CN116783226A - Resin composition

Info

Publication number: CN116783226A
Application number: CN202180086063.1A
Authority: CN
Inventors: 舞鹤展祥; 冈本敏彦
Original assignee: Kaneka Corp
Current assignee: Kaneka Corp
Priority date: 2020-12-25
Filing date: 2021-12-23
Publication date: 2023-09-19

Abstract

The invention aims to provide a resin composition with excellent operability. The resin composition according to one embodiment of the present invention comprises polymer particles (A) and a matrix resin (B), wherein the polymer particles (A) have a graft portion, and the glass transition temperature of the graft portion is from-25 ℃ to 18 ℃.

Description

Resin composition

Technical Field

The present invention relates to a resin composition.

Background

Thermosetting resins have various excellent properties such as high heat resistance and mechanical strength, and thus are used in various fields. Among thermosetting resins, epoxy resins are used in a wide variety of applications, for example, as matrix resins for electronic circuit sealants, coatings, adhesives, and fiber reinforcements. Epoxy resins are excellent in heat resistance, chemical resistance, insulation properties, etc., but have a problem of insufficient impact resistance, which is a characteristic of thermosetting resins. In order to improve the impact resistance of thermosetting resins, a method of adding an elastomer to a thermosetting resin is widely used.

Examples of the elastomer include polymer particles (for example, crosslinked polymer particles). It is easy to simply mix the polymer particles with a thermosetting resin (e.g., an epoxy resin). Examples of the mixing method include a method of preparing a powder of polymer particles having a particle size of 1 μm or more by aggregating a plurality of polymer particles having a particle size of less than 1 μm, and mechanically mixing the powder with a thermosetting resin. The powder of polymer particles obtained by aggregating a plurality of polymer particles in this way is referred to as secondary particles, and polymer particles having a particle diameter of less than 1 μm before the powder is referred to as primary particles. By the above mixing method, the secondary particles of the polymer particles can be dispersed in the thermosetting resin. However, it is very difficult to disperse primary particles of polymer particles having a particle diameter of less than 1 μm in thermosetting resins on an industrial level.

Patent document 1 describes an epoxy resin composition comprising a core-shell polymer, wherein the shell layer comprises a structural unit containing an alkoxy group or an aryloxy group.

In addition, various types of polymer particles having a core-shell structure have been developed (for example, patent documents 2 to 7).

Prior art literature

Patent literature

Patent document 1: international publication No. WO2015/053289

Patent document 2: japanese patent application laid-open No. 2015-182248

Patent document 3: japanese patent application laid-open No. H8-183836

Patent document 4: japanese patent laid-open No. 2008-29153

Patent document 5: japanese patent application laid-open No. 2020-512426

Patent document 6: international publication No. WO2017-145953

Patent document 7: japanese patent laid-open No. 2018-177826

Disclosure of Invention

Problems to be solved by the invention

However, from the viewpoint of operability, the above-described prior art still has room for further improvement.

In view of the above problems, an object of the present invention is to provide a resin composition having excellent handleability.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, they have completed the present invention.

That is, the resin composition according to one embodiment of the present invention comprises polymer particles (a) and a matrix resin (B), wherein the polymer particles (a) have a graft portion, and the graft portion is a polymer satisfying the following (i) to (iii), (i) (i-a) contains no structural unit containing an aromatic group, or (i-B) contains more than 0% by weight and 10% by weight or less of a structural unit containing an aromatic group in 100% by weight of the graft portion; (ii) Comprising at least one of structural units derived from an alkyl methacrylate and structural units derived from an alkyl acrylate; (iii) The composition does not contain an alkoxy group-containing structural unit, an aryloxy group-containing structural unit, an oxetanyl group-containing structural unit, a hydroxyl group-containing structural unit, an amino group-containing structural unit, an imide group-containing structural unit, a carboxylic acid anhydride group-containing structural unit, a cyclic ester group-containing structural unit, a cyclic amide group-containing structural unit, a benzo group-containing structural unit Structural units of oxazinyl groups and structural units containing cyanate groups, and the glass transition temperature of the grafting portion is from-25 ℃ to 18 ℃.

The resin composition according to another embodiment of the present invention comprises a polymer particle (a) and a matrix resin (B), wherein the polymer particle (a) has a graft unit, and the graft unit is a polymer satisfying the following (i) to (ii) in 100 wt% of the graft unit, (i) (i-a) contains no structural unit containing an aromatic group, or (i-B) contains more than 0 wt% and 10 wt% or less of a structural unit containing an aromatic group; (ii) (ii-a) comprises at least one of a structural unit derived from an alkyl methacrylate and a structural unit derived from an alkyl acrylate, and (ii-B) the total content of the structural unit derived from the alkyl methacrylate and the structural unit derived from the alkyl acrylate is 50% by weight or more, the glass transition temperature of the grafting portion is-25 ℃ or more and 18 ℃ or less, and when the total of the polymer particles (a) and the matrix resin (B) is 100% by weight, the polymer particles (a) are 20% by weight or more and 50% by weight or less, and the matrix resin (B) is 50% by weight or more and 80% by weight or less.

ADVANTAGEOUS EFFECTS OF INVENTION

According to one embodiment of the present invention, a resin composition excellent in handleability can be provided.

Detailed Description

An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope shown in the claims. Further, embodiments or examples obtained by appropriately combining the technical means disclosed in the different embodiments or examples are also included in the technical scope of the present invention. Further, by combining the technical means disclosed in each embodiment, new technical features can be formed. The entire contents of the academic literature and patent literature described in the present specification are incorporated into the present specification by reference. In the present specification, "a to B" representing a numerical range means "a or more (including a and more than a) and B or less (including B and less than B)", unless otherwise specified.

[ 1 ] technical idea of one embodiment of the present invention

As described above, there is a technique of adding polymer particles to a thermosetting resin in order to improve the impact resistance of the thermosetting resin. Here, a resin composition containing polymer particles in a matrix resin at a high concentration is sometimes required. For example, a resin composition containing polymer particles at a high concentration may be further mixed with other matrix resins to obtain a resin composition having a low concentration of polymer particles. In this case, a resin composition containing polymer particles at a high concentration is used as a so-called "masterbatch". In order to improve the modifying effect of the matrix resin based on the polymer particles, a resin composition containing the polymer particles in a high concentration in the matrix resin is sometimes required.

However, when the concentration of the polymer particles in the resin composition is high, the viscosity of the resin composition increases, and the operability of the resin composition is poor. An object of one embodiment of the present invention is to provide a resin composition having excellent handleability, i.e., low viscosity, even when the resin composition contains polymer particles at a high concentration.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be achieved by using polymer particles having a graft portion with a low glass transition temperature, and have completed the present invention.

In addition, an inorganic filler may be further blended in the resin composition in addition to the polymer particles. In this case, the functional groups contained in the polymer particles react with the inorganic filler to increase the viscosity of the resin composition, and the handleability of the resin composition may be poor.

An additional object of one embodiment of the present invention is to provide a resin composition having excellent handleability, i.e., low viscosity, even when the resin composition contains polymer particles and an inorganic filler.

As a result of intensive studies, the present inventors have newly found that the above-mentioned additional problems can be achieved by using polymer particles having a graft portion that does not contain a functional group capable of interacting with an inorganic filler.

[ 2. Resin composition ]

The resin composition according to one embodiment of the present invention is a resin composition comprising polymer particles (a) and a matrix resin (B). The polymer particles (A) have a graft portion.

The grafting part is a polymer satisfying the following (I) or (II),

(I) (i) (i-a) contains no structural unit containing an aromatic group, or

(i-b) 100 wt% of the grafting unit contains more than 0 wt% and 10 wt% or less of a structural unit containing an aromatic group;

(ii) Comprising at least one of structural units derived from an alkyl methacrylate and structural units derived from an alkyl acrylate;

(iii) The composition does not contain an alkoxy group-containing structural unit, an aryloxy group-containing structural unit, an oxetanyl group-containing structural unit, a hydroxyl group-containing structural unit, an amino group-containing structural unit, an imide group-containing structural unit, a carboxylic acid anhydride group-containing structural unit, a cyclic ester group-containing structural unit, a cyclic amide group-containing structural unit, a benzo group-containing structural unitStructural units of oxazinyl groups, structural units containing cyanate groups,

(II) in the above-mentioned 100% by weight of the graft portion,

(i) (i-a) does not contain a structural unit containing an aromatic group, or

(i-b) containing more than 0% by weight and 10% by weight or less of structural units containing aromatic groups;

(ii) (ii-a) comprising at least one of structural units derived from an alkyl methacrylate and structural units derived from an alkyl acrylate

(ii-b) the total content of the structural units derived from the alkyl methacrylate and the structural units derived from the alkyl acrylate is 50% by weight or more.

The glass transition temperature of the grafting part is-25 ℃ to 18 ℃. When the total of the polymer particles (a) and the matrix resin (B) is 100 wt%, the polymer particles (a) are preferably 20 wt% to 50 wt%, and the matrix resin (B) is preferably 50 wt% to 80 wt%.

In the present specification, hereinafter, the "resin composition according to one embodiment of the present invention" may be simply referred to as "present resin composition".

The present resin composition has the advantage of excellent handleability due to the above-described structure. In the present specification, "excellent handleability of the resin composition" means that the viscosity of the resin composition is low, for example, 20000 mpa·s or less at 50 ℃. That is, the present resin composition has an advantage of low viscosity (for example, the viscosity of the resin composition is 20000 mpa·s or less at 50 ℃) by the above-described constitution.

With the above-described structure, the present resin composition has an advantage of excellent handleability even when the resin composition further contains an inorganic filler. That is, the present resin composition has an advantage that even when the resin composition further contains an inorganic filler, the viscosity is low (for example, the viscosity of the resin composition containing an inorganic filler is 280000mpa·s or less at 25 ℃).

(2-1. Polymer particles (A))

The polymer particles (a) are microparticles obtained by polymerization. The polymer particles (A) have a graft portion. The polymer particles (a) may have any grafting portions, and other structures are not particularly limited. The polymer particles (A) may also be referred to as graft copolymers.

(grafting portion)

In this specification, a polymer graft-bonded to an arbitrary polymer is referred to as a graft portion.

The graft is preferably a polymer which does not contain the following structural units: structural units comprising alkoxy groups, structural units comprising aryloxy groups, structural units comprising oxetanyl groups, structural units comprising hydroxy groups, structural units comprising amino groups, structural units comprising imide groups, structural units comprising carboxylic acid groups, structural units comprising carboxylic anhydride groups, structural units comprising cyclic ester groups, structural units comprising cyclic amide groups, structural units comprising benzo groups Structural units of oxazinyl groups, and structural units containing cyanate groups. The structural units described above may interact with the inorganic filler material. Therefore, the graft portion does not contain the above-mentioned structural unit, and even when the obtained resin composition further contains an inorganic filler, the resin composition has an advantage of excellent handleability.

The graft portion is a polymer containing (a) no structural unit containing an aromatic group or (b) more than 0% by weight and 10% by weight or less of structural unit containing an aromatic group in 100% by weight of the graft portion. The resin composition has the advantage of excellent handleability (i.e., low viscosity) by having such a constitution. From the viewpoint of further excellent handleability of the obtained resin composition, the grafting portion more preferably does not contain a structural unit containing an aromatic group (the content of the structural unit containing an aromatic group is 0% by weight in 100% by weight of the grafting portion).

The grafting portion includes at least one of structural units derived from an alkyl methacrylate and structural units derived from an alkyl acrylate. This structure has an advantage that the glass transition temperature (Tg) of the grafting portion can be reduced. In view of the easiness of obtaining a graft portion in which (a) the glass transition temperature (Tg) of the graft portion is further reduced to have a desired range, it is preferable that (a) the graft portion contains at least one of a structural unit derived from an alkyl methacrylate and a structural unit derived from an alkyl acrylate, and (b) the total content of the structural unit derived from an alkyl methacrylate and the structural unit derived from an alkyl acrylate in 100 wt% of the graft portion is 50 wt% or more, more preferably 55 wt% or more, still more preferably 60 wt% or more, still more preferably 65 wt% or more, still more preferably 70 wt% or more, still more preferably 75 wt% or more, still more preferably 78 wt% or more, still more preferably 80 wt% or particularly preferably 83 wt% or more. The upper limit of the total content of the structural units derived from the alkyl methacrylate and the structural units derived from the alkyl acrylate in 100% by weight of the grafting portion is not particularly limited, and may be, for example, 100% by weight. In one embodiment of the present invention, from the viewpoint of easily obtaining a grafted part in which (a) the interaction with an inorganic filler is not easy and (b) the glass transition temperature (Tg) of the grafted part is further reduced to have a Tg in a desired range, it is preferable that at least one of the structural unit derived from an alkyl methacrylate and the structural unit derived from an alkyl acrylate is 50% by weight or more, more preferably 55% by weight or more, still more preferably 60% by weight or more, still more preferably 65% by weight or more, still more preferably 70% by weight or more, still more preferably 75% by weight or more, still more preferably 78% by weight or more, still more preferably 80% by weight or more, and particularly preferably 83% by weight or more, of the grafted part is 100% by weight or more. The upper limit of the content of at least one of the structural unit derived from the alkyl methacrylate and the structural unit derived from the alkyl acrylate in 100% by weight of the grafting portion is not particularly limited, and may be, for example, 100% by weight.

In the present specification, the alkyl (meth) acrylate means at least one of alkyl methacrylate and alkyl acrylate. The number of carbon atoms of the alkyl group of the alkyl (meth) acrylate, which is the source of the structural unit of the graft portion, is preferably 1 to 4 from the viewpoint of easiness in lowering the glass transition temperature of the graft portion. The graft portion is preferably a copolymer of monomer components containing an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms. From the viewpoint of the handleability of the resin composition, the monomer component preferably contains 55 wt% or more, more preferably 65 wt% or more, still more preferably 75 wt% or more, still more preferably 78 wt% or more, and particularly preferably 83 wt% or more of the alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms. In addition, from the viewpoint that the polymer particles (a) can be dispersed in the form of primary particles in the resin composition or the cured product thereof, the monomer component preferably contains 95 wt% or less, more preferably 90 wt% or less of the alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms. The term "handleability" of the resin composition means "handleability" of the resin composition. Accordingly, the expression "from the viewpoint of the handleability of the resin composition" means "from the viewpoint of the excellent handleability of the resin composition".

In other words, the grafting portion preferably contains a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms. In the graft portion, from the viewpoint of the handleability of the resin composition, the structural unit containing an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms is preferably 55 wt% or more, more preferably 65 wt% or more, still more preferably 75 wt% or more, still more preferably 78 wt% or more, and particularly preferably 83 wt% or more, in 100 wt% of the graft portion. In addition, from the viewpoint that the polymer particles (a) can be dispersed in the resin composition or a cured product thereof in the form of primary particles, the graft portion is preferably 95% by weight or less, more preferably 90% by weight or less, of a structural unit containing an alkyl (meth) acrylate ester having an alkyl group having 1 to 4 carbon atoms, in 100% by weight of the graft portion.

The monomer component preferably contains an alkyl (meth) acrylate having an alkyl group having 1 carbon atom. From the viewpoint of the handling property of the resin composition, the monomer component preferably contains 10 to 100 wt%, more preferably 11 to 95 wt%, still more preferably 12 to 92 wt%, still more preferably 13 to 55 wt%, and particularly preferably 14 to 50 wt% of the alkyl (meth) acrylate having an alkyl group having 1 carbon atom number. The monomer component preferably contains an alkyl (meth) acrylate having an alkyl group having 2 carbon atoms. From the viewpoint of the handleability of the resin composition, the monomer component preferably contains 10 to 100% by weight, more preferably 11 to 95% by weight, of an alkyl (meth) acrylate having an alkyl group having 2 carbon atoms. The monomer component preferably contains an alkyl (meth) acrylate having an alkyl group having 3 carbon atoms. From the viewpoint of the handleability of the resin composition, the monomer component preferably contains 10 to 100% by weight, more preferably 11 to 95% by weight, of an alkyl (meth) acrylate having an alkyl group having 3 carbon atoms. The monomer component preferably contains an alkyl (meth) acrylate having an alkyl group having 4 carbon atoms. From the viewpoint of the handling property of the resin composition, the monomer component preferably contains 0 to 80 wt%, more preferably 1 to 78 wt%, still more preferably 2 to 76 wt%, still more preferably 20 to 74 wt%, and particularly preferably 35 to 72 wt% of the alkyl (meth) acrylate having an alkyl group having 4 carbon atoms.

In other words, the grafting portion preferably contains a structural unit derived from an alkyl (meth) acrylate having an alkyl group of 1 carbon atoms. From the viewpoint of excellent handleability of the resin composition, the graft portion preferably contains 10 to 100 wt%, more preferably 11 to 95 wt%, still more preferably 12 to 92 wt%, still more preferably 13 to 55 wt%, and particularly preferably 14 to 50 wt% of the structural unit derived from the alkyl (meth) acrylate having an alkyl group having 1 carbon atom in 100 wt% of the graft portion. The grafting unit preferably contains a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 2 carbon atoms. In the graft portion, from the viewpoint of excellent handleability of the resin composition, the structural unit containing an alkyl (meth) acrylate having an alkyl group having 2 carbon atoms is preferably 10 to 100 wt%, more preferably 11 to 95 wt% in 100 wt% of the graft portion. The grafting unit preferably contains a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 3 carbon atoms. In the graft portion, from the viewpoint of excellent handleability of the resin composition, the structural unit containing an alkyl (meth) acrylate having an alkyl group having 3 carbon atoms is preferably 10 to 100 wt%, more preferably 11 to 95 wt% in 100 wt% of the graft portion. The grafting unit preferably contains a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 4 carbon atoms. From the viewpoint of excellent handleability of the resin composition, the grafted portion preferably contains, in 100 wt%, from 0 to 80 wt%, more preferably from 1 to 78 wt%, still more preferably from 2 to 76 wt%, still more preferably from 20 to 74 wt%, and particularly preferably from 35 to 72 wt% of a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 4 carbon atoms.

The grafting portion has the above-described configuration, and thus can serve various functions. The "various actions" mean, for example, (a) improving the compatibility of the polymer particles (a) with the matrix resin (B), (B) improving the dispersibility of the polymer particles (a) in the matrix resin to be mixed, and (c) enabling the polymer particles (a) to be dispersed in the form of primary particles in the resin composition or the cured product thereof.

In the present specification, "alkyl methacrylate" refers to an alkyl methacrylate that does not contain a functional group having reactivity (for example, an alkoxy group, a hydroxyl group, or the like). Specific examples of the alkyl methacrylate include: methyl Methacrylate (MMA), ethyl Methacrylate (EMA), butyl Methacrylate (BMA), 2-ethylhexyl methacrylate (EHMA), and the like.

In the present specification, "alkyl acrylate" refers to an alkyl acrylate that does not contain a functional group having reactivity (for example, an alkoxy group, a hydroxyl group, or the like). Specific examples of the alkyl acrylate include: methyl Acrylate (MA), ethyl Acrylate (EA), n-Butyl Acrylate (BA), 2-ethylhexyl acrylate (EHA), and the like.

The grafting portion may be a polymer containing only either a structural unit derived from an alkyl methacrylate or a structural unit derived from an alkyl acrylate, or may be a polymer containing both.

The grafting portion preferably contains a structural unit having an epoxy group as a structural unit. According to the above constitution, the graft portion of the polymer particle (a) can be chemically bonded to the matrix resin (B) in the resin composition. Thus, the polymer particles (a) can be maintained in a good dispersion state in the resin composition or the cured product thereof without agglomerating the polymer particles (a).

In order to obtain a graft portion including a structural unit having an epoxy group, a monomer having an epoxy group may be used in the production (polymerization) of the graft portion. Specific examples of the monomer having an epoxy group include: glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and allyl glycidyl ether. In the present specification, (meth) acrylate means acrylate and/or methacrylate.

The monomer having an epoxy group may be used alone or in combination of 1 or more than 2.

The grafting unit preferably contains more than 0 wt% and 50 wt% or less of the structural unit having an epoxy group, more preferably contains 1 wt% or more and 40 wt% or less, still more preferably contains 3 wt% or more and 30 wt% or less, particularly preferably contains 3 wt% or more and 20 wt% or less, and most preferably contains 3 wt% or more and 16 wt% or less, in 100 wt% of the grafting unit. In the case where the structural unit (a) of the monomer having an epoxy group is contained in the graft portion in 100 wt%, the resulting resin composition can provide a cured product having sufficient impact resistance, and (b) in the case where it is contained in 50 wt% or less, the resulting resin composition can provide a cured product having sufficient impact resistance, and has an advantage that the storage stability of the resin composition becomes good.

The epoxy groups are capable of reacting (interacting) with an inorganic filler material (e.g., silica, etc.). Therefore, from the viewpoint of operability of the resin composition further comprising the inorganic filler, it is preferable that the amount of the structural unit having an epoxy group contained in the graft portion is small.

The structural unit derived from the monomer having an epoxy group is preferably contained in the graft portion, more preferably contained only in the graft portion.

The grafting portion may contain a structural unit derived from a polyfunctional monomer as a structural unit. In the case where the grafting portion contains a structural unit derived from a polyfunctional monomer, (a) swelling of the polymer particles (a) can be prevented in the resin composition; (b) Since the viscosity of the resin composition is lowered, the workability of the resin composition tends to become good; and (c) the dispersibility of the polymer particles (a) in the matrix resin (B) is improved; and the like.

When the graft portion does not contain a structural unit derived from a polyfunctional monomer, the obtained resin composition can provide a cured product having more excellent toughness and impact resistance than when the graft portion contains a structural unit derived from a polyfunctional monomer.

The polyfunctional monomer may be a monomer having 2 or more radical polymerizable reactive groups in the same molecule. The radical polymerizable reactive group is preferably a carbon-carbon double bond. Examples of the polyfunctional monomer include (meth) acrylic esters having an ethylenically unsaturated double bond, such as allyl alkyl (meth) acrylate and allyloxyalkyl (meth) acrylate, and the like, excluding butadiene. As the monomer having 2 (meth) acrylic groups, there may be mentioned: ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexylene glycol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. Examples of the polyethylene glycol di (meth) acrylates include: triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (600) di (meth) acrylate, and the like. In addition, as the monomer having 3 (meth) acrylic groups, there can be exemplified: alkoxylated trimethylolpropane tri (meth) acrylate, glycerol propoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and the like. As the alkoxylated trimethylolpropane tri (meth) acrylate, there may be mentioned: trimethylolpropane tri (meth) acrylate, trimethylolpropane triethoxy tri (meth) acrylate, and the like. Further, as the monomer having 4 (meth) acrylic groups, there may be exemplified: pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like. Further, as the monomer having 5 (meth) acrylic groups, dipentaerythritol penta (meth) acrylate and the like can be exemplified. Further, as the monomer having 6 (meth) acrylic groups, ditrimethylolpropane hexa (meth) acrylate and the like can be exemplified. In addition, as the polyfunctional monomer, there may be mentioned: diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and the like.

Among the above-mentioned polyfunctional monomers, the polyfunctional monomers that can be preferably used for polymerization of the graft portion include: allyl methacrylate, diallyl phthalate, triallyl isocyanurate, divinylbenzene, and the like. These polyfunctional monomers may be used alone or in combination of 1 or more than 2.

The graft unit preferably contains 1 to 20% by weight, more preferably 5 to 15% by weight of the structural unit derived from the polyfunctional monomer in 100% by weight of the graft unit.

In the polymerization of the graft portion, only 1 kind of the above monomer may be used, or 2 or more kinds may be used in combination. In addition, as the structural unit, the grafting portion may contain a structural unit derived from another monomer in addition to the structural unit derived from the above-described monomer.

The graft portion is preferably a polymer graft-bonded to an elastomer described later.

(glass transition temperature of grafting portion)

From the viewpoint of preventing the polymer particles (A) in the resin composition from fusing to each other, the glass transition temperature (hereinafter, sometimes simply referred to as "Tg") of the graft portion is-25℃or higher, preferably-23℃or higher, more preferably-21℃or higher, more preferably-19℃or higher, more preferably-17℃or higher, still more preferably-15℃or higher, particularly preferably-13℃or higher.

From the viewpoint of obtaining a resin composition having a low viscosity (i.e., a resin composition excellent in handleability), the Tg of the grafted portion is 18℃or less, preferably 16℃or less, 14℃or less, more preferably 12℃or less, more preferably 10℃or less, more preferably 8℃or less, more preferably 6℃or less, more preferably 4℃or less, more preferably 2℃or less, more preferably 0℃or less, more preferably-2℃or less, more preferably-4℃or less, more preferably-5℃or less, more preferably-7℃or less, more preferably-9℃or less, and particularly preferably-11℃or less.

The Tg of the graft portion can be determined by the composition of the structural unit contained in the graft portion, and the like. In other words, the Tg of the resulting graft can be adjusted by changing the composition of the monomer used in producing (polymerizing) the graft.

When the graft portion is a copolymer of 2 or more monomers and the monomers used for the production (polymerization) of the graft portion are known, the glass transition temperature Tg of the graft portion can be calculated by the FOX formula (formula 1) shown below.

1/Tg＝w ₁ /Tg ₁ +w ₂ /Tg ₂ +···+w _n /Tg _n (mathematics 1)

Here, tg ₁ 、Tg ₂ 、···、Tg _n Tg (K), w of homopolymers of components 1, 2, & gtand n, respectively, constituting the graft portion (i.e., monomers used in the production of the graft portion) ₁ 、w ₂ 、···、w _n The weight fractions of the components (i.e., monomers used in the production of the graft) 1, 2, & gtand n, respectively, constituting the graft. As the Tg of the homopolymer, for example, polymer Handbook Fourth Edition (J.Brandup et al, jphn Wiley)&Sons, inc), and the like. In the case of the novel polymer, the peak temperature of loss tangent (tan. Delta.) in the viscoelastometry (shear method, measurement frequency: 1 Hz) can be used as Tg.

In the case where the monomer used for producing (polymerizing) the graft portion is unknown, tg of the graft portion can also be obtained by performing viscoelasticity measurement using a planar plate formed of the polymer particles (a). Specifically, tg can be determined as follows: (1) For a flat sheet formed of the polymer particles (A), dynamic viscoelasticity measurement was performed under stretching conditions using a dynamic viscoelasticity measuring apparatus (for example, manufactured by IT measurement control Co., ltd., DVA-200) to obtain a curve of tan delta; (2) Regarding the curve of tan delta obtained, the peak temperature of tan delta was taken as the glass transition temperature. Here, in the curve of tan δ, when a plurality of peaks are obtained, the highest peak temperature is taken as the glass transition temperature of the grafting portion.

Here, a monomer that provides a homopolymer having Tg of 0 ℃ or lower is used as the monomer a. As monomer a, there may be mentioned: ethyl acrylate, butyl acrylate (trade name: butyl acrylate), 2-ethylhexyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, and the like. These monomers a may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among these monomers a, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are particularly preferred.

The graft part preferably contains 20 wt% or more, more preferably 30 wt% or more, and still more preferably 40 wt% or more of the structural unit derived from the monomer a in 100 wt% of the graft part. The grafting unit preferably contains 95 wt% or less, more preferably 90 wt% or less, and still more preferably 80 wt% or less of the structural unit derived from a monomer having a glass transition temperature of 0 ℃ or less in 100 wt% of the grafting unit. When the graft portion contains 20 wt% or more of the structural unit derived from the monomer a in 100 wt% of the graft portion, a resin composition having a lower viscosity can be obtained.

(grafting ratio of grafting portion)

In one embodiment of the present invention, the polymer particles (a) may be provided with a polymer having the same structure as the graft portion and not graft-bonded to any polymer (for example, an elastomer described later). In this specification, the "polymer having the same constitution as the graft portion and not graft-bonded to any polymer" is referred to as a non-graft polymer. The non-grafted polymer is also a polymer that forms part of the polymer particles (a) of one embodiment of the invention. The non-grafted polymer may be referred to as a polymer which is not graft-bonded to any polymer among polymers produced in polymerization of a grafting portion (production process).

In the present specification, the ratio of the polymer which is not graft-bonded to any polymer among the polymers produced in the polymerization of the graft portion, that is, the graft portion, is referred to as a graft ratio. The grafting ratio is also referred to as a value expressed as (weight of grafted portion)/(weight of grafted portion) + (weight of non-grafted polymer) } ×100.

In addition, in the preparation step of the graft portion, soluble components are present in addition to the graft portion and the non-graft polymer. The soluble component refers to the unpolymerized monomer, initiator and other side raw materials.

Examples of the method for determining whether the polymer particles (A) are non-grafted polymers or soluble components include a method for determining whether the polymer particles (A) are soluble or insoluble in a solvent. Examples thereof include: a method in which (i) the case of being insoluble in MEK is determined as polymer particles (A), (ii) the case of being soluble in MEK and insoluble in methanol is determined as a non-grafted polymer, and (iii) the case of being soluble in MEK and soluble in methanol is determined as a soluble component.

The grafting ratio of the grafting portion is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. When the grafting ratio is 70% or more, there is an advantage that the viscosity of the resin composition does not become excessively high.

In the present specification, the method for calculating the grafting ratio is as follows. First, an aqueous suspension containing the polymer particles (a) is obtained, and then, a powder of the polymer particles (a) is obtained from the aqueous suspension. The method for obtaining the powder of the polymer particles (a) from the aqueous suspension includes the following methods: (i) coagulating the polymer particles (A) in the aqueous suspension, (ii) dehydrating the obtained condensate, and (iii) further drying the condensate, thereby obtaining a powder of the polymer particles (A). Next, 2g of the powder of the polymer particles (a) was dissolved in 50mL of methyl ethyl ketone (hereinafter also referred to as MEK). Then, the resulting MEK lysate was separated into a MEK-soluble component (MEK-soluble component) and a MEK-insoluble component (MEK-insoluble component). Specifically, the following (1) to (3) are performed: (1) Using a centrifuge (CP 60E, manufactured by hitachi corporation) at a rotation speed of 30000rpm for 1 hour, the obtained MEK solution was subjected to centrifugal separation, and the solution was separated into a MEK soluble component and a MEK insoluble component; (2) Mixing the obtained MEK-soluble component with MEK, and using the above-mentioned centrifuge, subjecting the obtained MEK mixture to centrifugation at 30000rpm for 1 hour, and separating the MEK mixture into a MEK-soluble component and a MEK-insoluble component; (3) The operation of (2) above was repeated 1 time (i.e., the centrifugal separation operation was performed 3 times in total). Through the above procedure, a concentrated MEK-soluble fraction was obtained. Next, 20ml of the concentrated MEK-soluble component was mixed with 200ml of methanol. An aqueous calcium chloride solution obtained by dissolving 0.01g of calcium chloride in water was added to the obtained mixture, and the obtained mixture was stirred for 1 hour. The resulting mixture is then separated into a methanol soluble fraction and a methanol insoluble fraction. The weight of the methanol insoluble component is the weight of the non-grafted polymer.

The grafting ratio was calculated by the following formula.

Grafting ratio (%) =100- [ (weight of methanol-insoluble component)/(weight of methanol-insoluble component) + (weight of MEK-insoluble component) } ]/(weight of polymer of grafting portion) ×10000.

The weight of the polymer other than the graft portion is the amount of the monomer constituting the polymer other than the graft portion. The polymer other than the graft portion is, for example, an elastomer. In the case where the polymer particles (a) contain a surface cross-linked polymer described later, the polymer other than the graft portion contains both an elastomer and a surface cross-linked polymer. The weight of the polymer of the graft portion is the total weight of the monomer components (the monomer mixture for forming the graft portion) used for the preparation of the polymer of the graft portion. In addition, in the calculation of the grafting ratio, the method of coagulating the polymer particles (a) is not particularly limited, and a method using a solvent, a method using a coagulant, a method of spraying an aqueous suspension, and the like can be used.

(modification of grafting portion)

In one embodiment of the present invention, the grafting portion may be composed of only 1 grafting portion having the same constituent structural unit. In one embodiment of the present invention, the grafting portion may be formed of various grafting portions having structural units having different compositions.

In one embodiment of the present invention, a case where the grafting portion is formed of a plurality of grafting portions will be described. In this case, plural kinds of grafting portions are respectively defined as grafting portions ₁ Grafting portion ₂ (ii) grafting unit _n (n is an integer of 2 or more). The grafting portions may comprise grafting portions each polymerized separately ₁ Grafting portion ₂ (ii) and grafting unit _n Is a complex of (a) and (b). The grafting portion may comprise a grafting portion ₁ Grafting portion ₂ (ii) and grafting unit _n And 1 polymer obtained by polymerization in sequence. This polymerization of the plurality of polymerization units (graft units) in sequence is also called multi-stage polymerization. The polymer obtained by polymerizing a plurality of kinds of graft portions in multiple steps is also called a multi-step polymerized graft portion. The method for producing the multi-stage polymerized graft portion will be described in detail later.

In the case where the grafting portions are formed of plural kinds of grafting portions, not all of these plural kinds of grafting portions are graft-bonded to the elastomer. Other graft(s) may be graft-bonded to the graft(s) bonded to the elastomer graft as long as at least a portion of at least 1 graft is graft-bonded to the elastomer. In the case where the graft portion is formed of a plurality of graft portions, a plurality of polymers (a plurality of non-graft polymers) having the same constitution as the plurality of graft portions and not graft-bonded to the elastomer may be provided.

For the grafting part ₁ Grafting portion ₂ (ii) and grafting unit _n The multi-stage polymeric grafts formed are illustrated. In the multi-step polymeric graft, the graft _n Can cover the grafting part _n-1 At least a part of (2) or can coat the graft part _n-1 Is a whole of (a). In the multi-step polymerized graft portion, the graft portion may be _n A part of (C) also enters the grafting part _n-1 Is provided on the inner side of (a).

In the multi-step polymeric grafting portion, a plurality of grafting portions may each form a layer structure. For example, in a multi-stage polymerization graft, the graft is formed from ₁ Grafting portion ₂ Grafting part ₃ In the case of formation, the graft portion ₁ Forming the innermost layer in the grafting portion, at the grafting portion ₁ Is formed with a grafting part on the outer side ₂ Further on the grafting part ₂ Forms a grafting part on the outer side of the layer of (C) ₃ The mode of the layer as the outermost layer is also one mode of the present invention. Such that the plurality of grafts respectively form a layer structureAlso referred to as multi-layer grafts. That is, in one embodiment of the present invention, the grafting portion may comprise (a) a complex of multiple grafting portions, (b) a multi-step polymeric grafting portion, and/or (c) a multi-layer grafting portion.

In the case where an arbitrary polymer (for example, an elastomer described later) and a graft portion are sequentially polymerized in the production of the polymer particles (a), at least a part of the graft portion can coat at least a part of the arbitrary polymer in the obtained polymer particles (a). In other words, sequential polymerization of any polymer and graft may also be referred to as multi-stage polymerization of any polymer and graft. The polymer particles (a) obtained by polymerizing an arbitrary polymer with a graft portion in multiple steps are also called a multi-step polymer.

In the case where the polymer particles (a) are multi-step polymers, the graft portion can coat at least a part of any polymer (for example, an elastomer described later), or can coat the whole of any polymer. In the case where the polymer particles (a) are multi-step polymers, a part of the graft portion may enter the inside of any polymer. Preferably, at least a portion of the grafting portion encapsulates at least a portion of the elastomer. In other words, at least a part of the grafting portion is preferably present at the outermost side of the polymer particles (a).

In the case where the polymer particles (a) are multi-step polymers, any of the polymers (for example, an elastomer described later) and the graft portion may form a layer structure. For example, a mode in which an elastomer forms an innermost layer (also referred to as a core layer) and a layer in which a graft portion is formed on the outer side of the elastomer as an outermost layer (also referred to as a shell layer) is also one mode of the present invention. A structure having an elastomer as a core layer and a graft portion as a shell layer is also called a core-shell structure. The polymer particles (a) in which the elastomer and the graft portion form a layer structure (core-shell structure) are also called a multilayer polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer particles (a) may be multi-step polymers, and/or may be multi-layer polymers or core-shell polymers. The polymer particles (a) are not limited to the above-described structure as long as they have a graft portion.

(elastomer)

The polymer particles (a) preferably further have an elastomer. The grafting portion is preferably a polymer graft-bonded to the elastomer. That is, the polymer particles (a) are preferably rubber-containing graft copolymers having an elastomer and a graft portion graft-bonded to the elastomer. Hereinafter, an embodiment of the present invention will be described by taking a case where the polymer particles (A) are rubber-containing graft copolymers as an example.

The elastomer preferably contains 1 or more kinds selected from diene rubbers, (meth) acrylate rubbers and organosiloxane rubbers. The elastomer may contain natural rubber in addition to the rubber described above. The elastomer may also be referred to as an elastic portion or rubber particles.

The case (1)) in which the elastomer contains a diene rubber will be described. In case (1), the obtained resin composition can provide a cured product excellent in toughness and impact resistance. The cured product excellent in toughness and/or impact resistance is also referred to as a cured product excellent in durability.

The diene rubber is an elastomer containing a structural unit derived from a diene monomer as a structural unit. The diene monomer may be also referred to as a conjugated diene monomer. In the case (1), the diene rubber may contain 50 to 100% by weight of a structural unit derived from a diene monomer and 0 to 50% by weight of a structural unit derived from a vinyl monomer other than a diene monomer copolymerizable with the diene monomer in 100% by weight of the structural unit. In the case (1), the diene rubber may contain a structural unit derived from a (meth) acrylic acid ester monomer as a structural unit in an amount smaller than that of the structural unit derived from a diene monomer.

Examples of the diene monomer include: 1, 3-butadiene, isoprene (2-methyl-1, 3-butadiene), 2-chloro-1, 3-butadiene, and the like. Only 1 kind of these diene monomers may be used, or 2 or more kinds may be used in combination.

Examples of the vinyl monomer other than the diene monomer copolymerizable with the diene monomer (hereinafter, also referred to as a vinyl monomer a) include: vinyl aromatic hydrocarbons such as styrene, α -methylstyrene, monochlorostyrene, dichlorostyrene, etc.; vinyl carboxylic acids such as acrylic acid and methacrylic acid; vinyl cyanides such as acrylonitrile and methacrylonitrile; halogenated vinyl groups such as vinyl chloride, vinyl bromide and chloroprene; vinyl acetate; olefins such as ethylene, propylene, butene, and isobutene; and polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and divinylbenzene. The vinyl monomer a may be used alone or in combination of 1 or more than 2. Of the vinyl monomers a, styrene is particularly preferred. In the diene rubber of the case (1), the structural unit derived from the vinyl monomer a is an arbitrary component. In the case (1), the diene rubber may be constituted only by structural units derived from a diene monomer.

In the case (1), the diene rubber is preferably butadiene rubber (also referred to as polybutadiene rubber) formed of a structural unit derived from 1, 3-butadiene or butadiene-styrene rubber (also referred to as polystyrene-butadiene) which is a copolymer of 1, 3-butadiene and styrene, and more preferably butadiene rubber. According to the above configuration, the desired effect of the polymer particles (a) containing the diene rubber can be further exhibited. In addition, butadiene-styrene rubber is more preferable from the viewpoint of improving the transparency of the cured product obtained by adjustment of the refractive index.

The case where the elastomer contains a (meth) acrylate rubber (case (2)) will be described. In case (2), a wide range of polymers of the elastomer can be designed by a combination of a plurality of monomers.

The (meth) acrylate rubber is an elastomer containing a structural unit derived from a (meth) acrylate monomer as a structural unit. In the case (2), the (meth) acrylate rubber may contain, in 100% by weight of the structural units, 50 to 100% by weight of the structural units derived from the (meth) acrylate monomer and 0 to 50% by weight of the structural units derived from a vinyl monomer other than the (meth) acrylate monomer copolymerizable with the (meth) acrylate monomer. In the case (2), the (meth) acrylate rubber may contain a structural unit derived from a diene monomer as a structural unit in an amount smaller than that of the structural unit derived from the (meth) acrylate monomer.

Examples of the (meth) acrylic acid ester monomer include: alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate; aromatic ring-containing (meth) acrylates such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; glycidyl (meth) acrylates such as glycidyl (meth) acrylate and glycidyl alkyl (meth) acrylate; alkoxyalkyl (meth) acrylates; allyl (meth) acrylates such as allyl (meth) acrylate and allyl alkyl (meth) acrylate; and polyfunctional (meth) acrylates such as monoethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. These (meth) acrylic acid ester monomers may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among these (meth) acrylic acid ester monomers, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.

In the case (2), the (meth) acrylic rubber is preferably 1 or more selected from the group consisting of ethyl (meth) acrylate rubber, butyl (meth) acrylate rubber and 2-ethylhexyl (meth) acrylate rubber, and more preferably butyl (meth) acrylate rubber. The ethyl (meth) acrylate rubber is a rubber formed of a structural unit derived from ethyl (meth) acrylate, the butyl (meth) acrylate rubber is a rubber formed of a structural unit derived from butyl (meth) acrylate, and the 2-ethylhexyl (meth) acrylate rubber is a rubber formed of a structural unit derived from 2-ethylhexyl (meth) acrylate. According to this constitution, the glass transition temperature (Tg) of the elastomer is lowered, and thus the polymer particles (a) and the resin composition having a low Tg can be obtained. As a result, (a) the obtained resin composition can provide a cured product having excellent toughness, and (b) the viscosity of the resin composition can be further reduced.

Examples of the vinyl monomer other than the (meth) acrylic acid ester monomer (hereinafter also referred to as vinyl monomer B) copolymerizable with the (meth) acrylic acid ester monomer include the monomers listed in the vinyl monomer a. The vinyl monomer B may be used alone or in combination of 1 or more than 2. Of the vinyl monomers B, styrene is particularly preferred. In the (meth) acrylate rubber in the case (2), the structural unit derived from the vinyl monomer B is an arbitrary component. In the case (2), the (meth) acrylate rubber may be composed of only structural units derived from the (meth) acrylate monomer.

The case where the elastomer contains an organosiloxane rubber (case (3)) will be described. In case (3), the obtained resin composition can provide a cured product having sufficient heat resistance and excellent impact resistance at low temperatures.

Examples of the organosiloxane rubber include: (a) An organosiloxane polymer comprising an alkyl or aryl-disubstituted siloxy unit such as dimethylsiloxy, diethylsiloxy, methylphenylsiloxy, diphenylsiloxy, or dimethylsiloxy-diphenylsiloxy, and an organosiloxane polymer comprising an alkyl or aryl-monosubstituted siloxy unit such as organohydrogensiloxy wherein a part of the alkyl group in the side chain is substituted with a hydrogen atom. These organosiloxane polymers may be used alone or in combination of 1 or more than 2.

In the present specification, a polymer composed of dimethylsiloxy units is referred to as dimethylsiloxy rubber, a polymer composed of methylphenylsiloxy units is referred to as methylphenylsiloxy rubber, and a polymer composed of dimethylsiloxy units and diphenylsiloxy units is referred to as dimethylsiloxy-diphenylsiloxy rubber. In the case (3), the organosiloxane rubber (a) is preferably 1 or more selected from the group consisting of dimethylsiloxy rubber, methylphenylsiloxy rubber and dimethylsiloxy-diphenylsiloxy rubber, from the viewpoint that the resin composition containing the obtained powder or granule can provide a cured product or molded product excellent in heat resistance, and the dimethylsiloxy rubber (b) is more preferably from the viewpoint of easy availability and economical efficiency.

In the case (3), the polymer particles (a) preferably contain 80 wt% or more, more preferably 90 wt% or more of the organosiloxane rubber in 100 wt% of the elastomer contained in the polymer particles (a). According to the above configuration, the obtained resin composition can provide a cured product excellent in heat resistance.

The elastomer may further contain an elastomer other than diene rubber, (meth) acrylate rubber and organosiloxane rubber. Examples of the elastomer other than the diene rubber, (meth) acrylate rubber and organosiloxane rubber include natural rubber.

In one embodiment of the present invention, the elastomer is preferably 1 or more selected from butadiene rubber, butadiene-styrene rubber, butadiene- (meth) acrylate rubber, ethyl (meth) acrylate rubber, butyl (meth) acrylate rubber, 2-ethylhexyl (meth) acrylate rubber, dimethylsiloxy rubber, methylphenylsiloxy rubber, and dimethylsiloxy-diphenylsiloxy rubber, more preferably 1 or more selected from butadiene rubber, butadiene-styrene rubber, butyl (meth) acrylate rubber, and dimethylsiloxy rubber, still more preferably at least 1 of butadiene rubber and butadiene-styrene rubber, and particularly preferably butadiene rubber. With this configuration, there is an advantage that the viscosity of the obtained resin composition can be further reduced.

(crosslinked Structure of elastomer)

From the viewpoint of maintaining the dispersion stability of the polymer particles (a) in the matrix resin (B), the elastomer is preferably incorporated with a crosslinked structure. As a method for introducing a crosslinked structure into an elastomer, a generally used method can be used, and for example, the following method can be used. Specifically, in the production of an elastomer, a method is exemplified in which a polyfunctional monomer and/or a crosslinkable monomer such as a mercapto compound is mixed with a monomer capable of constituting an elastomer, followed by polymerization. In this specification, the production of a polymer such as an elastomer is also referred to as polymerization into a polymer.

In addition, as a method for introducing a crosslinked structure into an organosiloxane rubber, the following method can be mentioned: (1) A method of using a combination of a polyfunctional alkoxysilane compound and other materials in polymerizing an organosiloxane-based rubber; (2) A method in which a reactive group (e.g., (i) a mercapto group and (ii) a reactive vinyl group, etc.) is introduced into an organosiloxane rubber, and then (a) an organic peroxide or (b) a polymerizable vinyl monomer, etc. are added to the resultant reaction product to perform a radical reaction; or (3) a method in which a crosslinkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound is mixed with another material and polymerized when polymerized into an organosiloxane rubber; etc.

The polyfunctional monomer may be exemplified by the one (graft) of the above.

Examples of the thiol-group-containing compound include: alkyl-substituted thiols, allyl-substituted thiols, aryl-substituted thiols, hydroxy-substituted thiols, alkoxy-substituted thiols, cyano-substituted thiols, amino-substituted thiols, silyl-substituted thiols, acid-substituted thiols, halo-substituted thiols, acyl-substituted thiols, and the like. The alkyl-substituted thiol is preferably an alkyl-substituted thiol having 1 to 20 carbon atoms, more preferably an alkyl-substituted thiol having 1 to 10 carbon atoms. As aryl-substituted thiols, phenyl-substituted thiols are preferred. The alkoxy-substituted thiol is preferably an alkoxy-substituted thiol having 1 to 20 carbon atoms, more preferably an alkoxy-substituted thiol having 1 to 10 carbon atoms. The acid-group-substituted thiol is preferably an alkyl-substituted thiol having 1 to 10 carbon atoms and having a carboxyl group, or an aryl-substituted thiol having 1 to 12 carbon atoms and having a carboxyl group.

(glass transition temperature of elastomer)

The glass transition temperature of the elastomer is preferably 80 ℃ or lower, more preferably 70 ℃ or lower, more preferably 60 ℃ or lower, more preferably 50 ℃ or lower, more preferably 40 ℃ or lower, more preferably 30 ℃ or lower, more preferably 20 ℃ or lower, more preferably 10 ℃ or lower, more preferably 0 ℃ or lower, more preferably-20 ℃ or lower, more preferably-40 ℃ or lower, more preferably-45 ℃ or lower, more preferably-50 ℃ or lower, more preferably-55 ℃ or lower, more preferably-60 ℃ or lower, more preferably-65 ℃ or lower, more preferably-70 ℃ or lower, more preferably-75 ℃ or lower, more preferably-80 ℃ or lower, more preferably-85 ℃ or lower, more preferably-90 ℃ or lower, more preferably-95 ℃ or lower, more preferably-100 ℃ or lower, more preferably-105 ℃ or lower, more preferably-110 ℃ or lower, more preferably-115 ℃ or lower, and particularly preferably-120 or lower. In this specification, the "glass transition temperature" is sometimes referred to as "Tg". According to this constitution, the polymer particles (A) having a low Tg and the resin composition having a low Tg can be obtained. As a result, the obtained resin composition can provide a cured product having excellent toughness. In addition, according to this configuration, the viscosity of the obtained resin composition can be further reduced.

When the elastomer is a copolymer of 2 or more monomers and the monomers used for the production (polymerization) of the elastomer are known, the glass transition temperature Tg of the elastomer can be determined by the above-mentioned FOX formula (formula 1) ₁ 、Tg ₂ 、···、Tg _n W ₁ 、w ₂ 、···、w _n Calculated by replacing the Tg of the component constituting the elastomer (i.e., the monomer used in the production of the graft portion) and the weight ratio of the component constituting the elastomer (i.e., the monomer used in the production of the graft portion), respectively.

In the case where the monomer used for producing (polymerizing) the elastomer is unknown, the Tg of the elastomer can also be obtained by performing viscoelasticity measurement using a planar plate formed of the polymer particles (a). Specifically, tg can be determined as follows: (1) For a flat sheet formed of the polymer particles (A), dynamic viscoelasticity measurement was performed under stretching conditions using a dynamic viscoelasticity measuring apparatus (for example, manufactured by IT measurement control Co., ltd., DVA-200) to obtain a curve of tan delta; (2) Regarding the curve of tan delta obtained, the peak temperature of tan delta was taken as the glass transition temperature. Here, in the curve of tan δ, when a plurality of peaks are obtained, the lowest peak temperature is taken as the glass transition temperature of the elastomer.

On the other hand, from the viewpoint that the decrease in the elastic modulus (rigidity) of the obtained cured product can be suppressed, that is, a cured product having a sufficient elastic modulus (rigidity) can be obtained, the Tg of the elastomer is preferably greater than 0 ℃, more preferably 20 ℃ or higher, still more preferably 50 ℃ or higher, particularly preferably 80 ℃ or higher, and most preferably 120 ℃ or higher.

The Tg of an elastomer can be determined by the composition of the structural units contained in the elastomer, and the like. In other words, the Tg of the resulting elastomer can be adjusted by varying the composition of the monomers used in the manufacture (polymerization) of the elastomer.

Here, monomers which provide homopolymers having a Tg of greater than 0deg.C are used as monomers b. The monomer b is not limited to the following monomers, and examples thereof include: unsubstituted vinyl aromatic compounds such as styrene and 2-vinyl naphthalene; vinyl-substituted aromatic compounds such as α -methylstyrene; cycloalkyl vinyl aromatic compounds such as 3-methylstyrene, 4-methylstyrene, 2, 4-dimethylstyrene, 2, 5-dimethylstyrene, 3, 5-dimethylstyrene, and 2,4, 6-trimethylstyrene; ring-alkoxylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; cyclic halogenated vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; cyclic esters such as 4-acetoxystyrene, etc., substituted vinyl aromatic compounds; 4-hydroxystyrene and other ring-hydroxylated vinyl aromatic compounds; vinyl esters such as vinyl benzoate and vinyl cyclohexanoate; vinyl halides such as vinyl chloride; aromatic monomers such as acenaphthene and indene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and isopropyl methacrylate; aromatic methacrylates such as phenyl methacrylate; methacrylates such as isobornyl methacrylate and trimethylsilyl methacrylate; methacrylic acid monomers including methacrylic acid derivatives such as methacrylonitrile; certain acrylic esters such as isobornyl acrylate and t-butyl acrylate; acrylic acid monomers including acrylic acid derivatives such as acrylonitrile; etc. Examples of the monomer that can be contained in the monomer group a include: acrylic amide, isopropyl acrylic amide, N-vinylpyrrolidone, isobornyl methacrylate, dicyclopentanyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, and the like can provide a monomer which can form a homopolymer having a Tg of 120℃or higher when formed into a homopolymer. These monomers b may be used alone or in combination of 1 or more than 2.

As the elastomer G, an elastomer containing 0 to 50 (more preferably 1 to 35% by weight) structural units derived from at least 1 monomer selected from the above monomers a and 50 to 100 (more preferably 65 to 99% by weight) structural units derived from at least 1 monomer selected from the monomers b is used. The Tg of the elastomer G is greater than 0 ℃. In addition, in the case where the elastomer includes the elastomer G, the obtained resin composition can provide a cured product having sufficient rigidity.

When the Tg of the elastomer is greater than 0 ℃, it is preferable to introduce a crosslinked structure into the elastomer. The method for introducing the crosslinked structure includes the above-mentioned methods.

(volume average particle diameter of elastomer)

The volume average particle diameter of the elastomer is not particularly limited, but is preferably 0.03 μm to 50.00 μm, more preferably 0.05 μm to 10.00 μm, still more preferably 0.08 μm to 2.00 μm, still more preferably 0.10 μm to 1.00 μm, still more preferably 0.10 μm to 0.80 μm, still more preferably 0.10 μm to 0.50 μm, still more preferably 0.15 μm to 0.30 μm, still more preferably 0.15 μm to less than 0.30 μm, still more preferably 0.16 μm to 0.28 μm, still more preferably 0.17 μm to 0.27 μm, and particularly preferably 0.18 μm to 0.25 μm. When the volume average particle diameter (a) of the elastomer is 0.03 μm or more, an elastomer having a desired volume average particle diameter can be stably obtained, and when (b) is 50.00 μm or less, the heat resistance and impact resistance of the obtained cured product or molded article are improved. When the volume average particle diameter (a) of the elastomer is 0.15 μm or more, the viscosity of the resin composition is reduced, and when (b) is 0.30 μm or less, the resin composition has an advantage of excellent handleability, and when the polymerization time of the elastomer is not short, the productivity is improved. The volume average particle diameter of the elastomer may be measured using a dynamic light scattering particle diameter distribution measuring apparatus or the like using an aqueous suspension containing the elastomer as a sample. The method for measuring the volume average particle diameter of the elastomer is described in detail in the following examples.

(elastomer ratio)

The proportion of the elastomer in the polymer particles (a) is preferably 40 to 97% by weight, more preferably 60 to 95% by weight, still more preferably 70 to 93% by weight, based on 100% by weight of the total polymer particles (a). When the proportion (a) of the elastomer is 40% by weight or more, the obtained resin composition can provide a cured product excellent in toughness and impact resistance, and when (b) is 97% by weight or less, the polymer particles (a) are less likely to agglomerate, and therefore the resin composition does not have a high viscosity, and as a result, the obtained resin composition is excellent in handleability.

(gel content of elastomer)

The elastomer is preferably one that is capable of swelling but is substantially insoluble in a suitable solvent. The elastomer is preferably incompatible with the matrix resin (B) used.

The gel content of the elastomer is preferably 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, particularly preferably 95% by weight or more. When the gel content of the elastomer is within the above range, the obtained resin composition can provide a cured product excellent in toughness.

In the present specification, the gel content is calculated as follows. First, an aqueous suspension containing the polymer particles (a) is obtained, and then, a powder of the polymer particles (a) is obtained from the aqueous suspension. The method for obtaining the powder of the polymer particles (a) from the aqueous suspension is not particularly limited, and examples thereof include (i) a method for agglomerating the polymer particles (a) in the aqueous suspension, (ii) a method for dehydrating the obtained agglomerate, and (iii) a method for further drying the agglomerate to obtain the powder of the polymer particles (a). Next, 2.0g of the powder of the polymer particles (A) was dissolved in 50mL of Methyl Ethyl Ketone (MEK). Then, the resulting MEK lysate was separated into a MEK-soluble component (MEK-soluble component) and a MEK-insoluble component (MEK-insoluble component). Specifically, the obtained MEK solution was subjected to centrifugal separation using a centrifugal separator (CP 60E, manufactured by hitachi corporation) at a rotation speed of 30000rpm for 1 hour, and the solution was separated into a MEK soluble component and a MEK insoluble component. Here, the centrifugation operation was performed in 3 groups in total. The weights of the MEK-soluble component and MEK-insoluble component obtained were measured, and the gel content was calculated by the following formula.

Gel content (%) = (weight of methyl ethyl ketone insoluble component)/{ (weight of methyl ethyl ketone insoluble component) + (weight of methyl ethyl ketone soluble component) } ×100

(modification of elastomer)

In one embodiment of the present invention, the "elastomer" of the polymer particles (a) may be composed of only 1 kind of elastomer having the same composition of the structural unit. In this case, the "elastomer" of the polymer particles (a) is 1 selected from diene rubber, (meth) acrylate rubber and organosiloxane rubber.

In one embodiment of the present invention, the "elastomer" of the polymer particle (a) may contain a plurality of elastomers each having a different composition of the structural unit. In this case, the "elastomer" of the polymer particles (a) may be 2 or more kinds selected from diene rubber, (meth) acrylate rubber and organosiloxane rubber. In this case, the "elastomer" of the polymer particles (a) may be 1 kind selected from diene rubber, (meth) acrylate rubber and organosiloxane rubber. In other words, the "elastomer" of the polymer particles (a) may be a plurality of diene rubbers, (meth) acrylate rubbers or organosiloxane rubbers each having a different composition of the structural unit.

In one embodiment of the present invention, a case where the "elastomer" of the polymer particle (a) includes plural kinds of elastomers each having a different composition of the structural unit will be described. In this case, the plurality of elastomers are respectively referred to as elastomers ₁ Elastic body ₂ (ii) and (iii) an elastomer _n . Here, n is an integer of 2 or more. The "elastomer" of the polymer particles (A) may comprise an elastomer polymerized separately ₁ Elastic body ₂ (ii) and (iii) an elastomer _n Is a complex of (a) and (b). The "elastomer" of the polymer particles (A) may comprise an elastomer ₁ Elastic body ₂ (ii) and (iii) an elastomer _n And 1 elastomer obtained by polymerization in turn. Such sequential polymerization of a plurality of elastomers (polymers) is also referred to as multi-stage polymerization. 1 elastomer obtained by polymerizing a plurality of elastomers in multiple steps is also called a multi-step polymerized elastomer. The method for producing the multi-step polymeric elastomer will be described in detail later.

For inclusion of an elastomer ₁ Elastic body ₂ (ii) and (iii) an elastomer _n Is illustrated for the multi-stage polymeric elastomer. In the multi-step polymeric elastomer, the elastomer _n Can cover the elastomer _n-1 Or can be coated with an elastomer _n-1 Is a whole of (a). In the multi-step polymeric elastomer, the elastomer _n A part of (a) sometimes enters the elastomer _n-1 Is provided on the inner side of (a).

In a multi-step polymeric elastomer, a plurality of elastomers may each form a layer structure. For example, in multi-stage polymeric elastomers comprising an elastomer ₁ Elastic body ₂ And elastomer ₃ In the case of (a) an elastomer ₁ Forming the innermost layer in the elastomer ₁ Is formed into an elastomer on the outer side of (a) ₂ Further in an elastomer ₂ Is formed into an elastomer on the outside of the layer of (a) ₃ The manner in which the layer of (a) serves as the outermost layer of the elastomer is also one aspect of the present invention. Such multi-step polymeric elastomers in which a plurality of elastomers form a layer structure, respectively, are also referred to as multi-layer elastomers. That is, in one embodiment of the present invention, "polymer particles (A)"The elastomer "may comprise (a) a composite of multiple elastomers, (b) a multi-step polymeric elastomer, and/or (c) a multi-layer elastomer.

From the viewpoint of the handling property of the resin composition, the weight ratio of the elastomer/graft portion of the polymer particles (A) is preferably 65/35 to 92/8, more preferably 68/32 to 91/9, and still more preferably 70/30 to 90/10.

(surface-crosslinked Polymer)

The rubber-containing graft copolymer preferably has a surface-crosslinked polymer in addition to the elastomer and the graft portion graft-bonded to the elastomer. In other words, the polymer particles (a) preferably further have a surface cross-linked polymer in addition to the elastomer and the graft portion graft-bonded to the elastomer. Hereinafter, an embodiment of the present invention will be described by taking a case where the polymer particles (a) (for example, rubber-containing graft copolymer) further have a surface cross-linked polymer as an example. In this case, (a) the blocking resistance can be improved in the production of the polymer particles (a), and (B) the dispersibility of the polymer particles (a) in the matrix resin (B) is more excellent. The cause of this is not particularly limited, and can be presumed as follows: the surface-crosslinked polymer coats at least a part of the elastomer, so that the elastomer portion of the polymer particles (a) is less exposed, and as a result, the elastomer is less likely to be adsorbed by each other, and thus the dispersibility of the polymer particles (a) is improved.

In the case where the polymer particles (a) have a surface-crosslinked polymer, the following effects can be further exhibited: (a) an effect of reducing the viscosity of the present resin composition, (b) an effect of improving the crosslinking density of the elastomer, and (c) an effect of improving the grafting efficiency of the grafting portion. The crosslinking density of the elastomer refers to the degree of the number of crosslinked structures in the whole elastomer.

The surface cross-linked polymer contains a polymer containing 30 to 100% by weight of a structural unit derived from a polyfunctional monomer and 0 to 70% by weight of a structural unit derived from another vinyl monomer as structural units, and they add up to 100% by weight.

The polyfunctional monomer that can be used for polymerization of the surface-crosslinked polymer includes the same monomers as those described above. Among these polyfunctional monomers, polyfunctional monomers that can be preferably used for polymerization of the surface-crosslinked polymer include: allyl methacrylate, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate (e.g., 1, 3-butanediol dimethacrylate, etc.), butanediol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. These polyfunctional monomers may be used alone or in combination of 1 or more than 2.

The polymer particles (a) may contain a surface-crosslinked polymer polymerized independently of the polymerization of the rubber-containing graft copolymer, or may contain a surface-crosslinked polymer polymerized together with the rubber-containing graft copolymer. The polymer particles (a) may be a multi-stage polymer obtained by sequentially polymerizing an elastomer, a surface-crosslinked polymer, and a graft portion in a multi-stage manner. In any of these ways, the surface cross-linked polymer is capable of coating at least a portion of the elastomer.

Surface cross-linked polymers may also be considered as part of the elastomer. In other words, the surface cross-linked polymer may also be considered as part of the rubber-containing graft copolymer, and may also be referred to as a surface cross-linked polymer portion. When the polymer particles (a) contain a surface cross-linked polymer, the grafting unit (a) may be graft-bonded to an elastomer other than the surface cross-linked polymer, (b) may be graft-bonded to the surface cross-linked polymer, and (c) may be graft-bonded to both the elastomer other than the surface cross-linked polymer and the surface cross-linked polymer. In the case where the polymer particles (a) contain a surface-crosslinked polymer, the volume average particle diameter of the elastomer mentioned above means the volume average particle diameter of the elastomer containing the surface-crosslinked polymer.

The case (4)) will be described where the polymer particles (a) are a multi-stage polymer obtained by sequentially polymerizing an elastomer, a surface-crosslinked polymer, and a graft portion in a multi-stage manner. In the case (4), the surface-crosslinked polymer may coat a part of the elastomer or may coat the whole of the elastomer. In the case (4), a part of the surface cross-linked polymer sometimes enters the inside of the elastomer. In the case (4), the grafting portion may coat a part of the surface cross-linked polymer or may coat the whole of the surface cross-linked polymer. In the case (4), a part of the graft portion sometimes enters the inside of the surface cross-linked polymer. In the case (4), the elastomer, the surface-crosslinked polymer and the graft portion may have a layer structure. For example, the mode of using an elastomer as the innermost layer (core layer), a layer having a surface cross-linked polymer on the outer side of the elastomer as the intermediate layer, and a layer having a graft portion on the outer side of the surface cross-linked polymer as the outermost layer (shell layer) is also one mode of the present invention.

(volume average particle diameter (Mv) of Polymer particles (A))

The volume average particle diameter of the polymer particles (a) is not particularly limited, but is preferably 0.03 μm to 50.00 μm, more preferably 0.05 μm to 10.00 μm, still more preferably 0.08 μm to 2.00 μm, still more preferably 0.10 μm to 1.00 μm, still more preferably 0.10 μm to 0.80 μm, still more preferably 0.10 μm to 0.50 μm, still more preferably 0.15 μm to 0.30 μm, still more preferably 0.15 μm to less than 0.30 μm, still more preferably 0.16 μm to 0.28 μm, yet more preferably 0.17 μm to 0.27 μm, and particularly preferably 0.18 μm to 0.25 μm, from the viewpoint of industrial productivity and handling properties of the resin composition, i.e., from the viewpoint of being able to obtain a resin composition having a low viscosity. The volume average particle diameter (a) of the polymer particles (A) is 0.15 μm or more, whereby the viscosity of the resin composition is reduced, and the resin composition is excellent in handleability, and the polymerization time of the polymer particles (A) is reduced by 0.30 μm or less, whereby the productivity is improved. The volume average particle diameter of the polymer particles is a volume average particle diameter (Mv) obtained by measuring a latex of the polymer particles using Microtrac UPA150 (manufactured by daily nectar corporation).

The polymer particles (a) are preferably dispersed in the resin composition in the form of primary particles. In the present specification, "polymer particles (a) are dispersed in the state of primary particles" means that polymer particles (a) are dispersed substantially independently of each other (without contact), and the dispersion state thereof can be confirmed, for example, by: a part of the resin composition is dissolved in a solvent such as methyl ethyl ketone, and the particle diameter is measured by a particle diameter measuring device or the like based on laser light scattering.

The value of the volume average particle diameter (Mv)/number average particle diameter (Mn) obtained by the particle diameter measurement is not particularly limited, but is preferably 3.0 or less, more preferably 2.5 or less, further preferably 2.0 or less, and particularly preferably 1.5 or less. It is considered that when the volume average particle diameter (Mv)/number average particle diameter (Mn) is 3.0 or less, the polymer particles (a) can be well dispersed, and the physical properties such as impact resistance and adhesiveness of the obtained cured product are good.

The volume average particle diameter (Mv)/number average particle diameter (Mn) can be determined by measuring using Microtrac UPA (manufactured by daily nectar corporation) and dividing Mv by Mn.

The number distribution of the volume average particle diameter of the polymer particles (a) in the matrix resin (B) is preferably a half-value width of 0.5 to 1 times the volume average particle diameter, from the viewpoint that a resin composition having low viscosity and easy handling can be obtained.

(2-2. Process for producing Polymer particles (A))

The polymer particles (a) can be produced by polymerizing an arbitrary polymer, and then graft-polymerizing the polymer in the presence of the polymer to form a polymer of a graft portion. Hereinafter, an example of a method for producing the polymer particles (a) will be described by taking as an example a case where the polymer particles (a) are produced by graft polymerizing the elastomer to the polymer constituting the graft portion in the presence of the elastomer after the polymerization to the elastomer.

The polymer particles (a) can be produced by a known method, for example, an emulsion polymerization method, a suspension polymerization method, a microsuspension polymerization method, or the like. Specifically, the polymerization of the elastomer, the polymerization of the grafting portion (graft polymerization) and the polymerization of the surface cross-linked polymer in the polymer particles (a) can be carried out by a known method, for example, an emulsion polymerization method, a suspension polymerization method, a microsuspension polymerization method, or the like. Among them, the method for producing the polymer particles (a) is particularly preferably an emulsion polymerization method. According to the emulsion polymerization method, the method has the following advantages: (a) the composition of the polymer particles (A) is easy to design; (b) the polymer particles (A) are easy to industrially produce; and (c) a latex comprising polymer particles (A) which can be preferably used for the production of the present resin composition is easily obtained. Hereinafter, a method for producing the elastomer, the graft portion, and the surface cross-linked polymer which may be contained in the polymer particles (a) and which is an arbitrary structure will be described.

(method for producing elastomer)

It is conceivable that the elastomer contains at least 1 or more selected from diene rubbers and (meth) acrylate rubbers. In this case, the elastomer can be produced by, for example, emulsion polymerization, suspension polymerization, or microsuspension polymerization, and the method described in, for example, WO2005/028546 can be used as the production method.

The case where the elastomer contains an organosiloxane-based rubber can be considered. In this case, the elastomer can be produced by, for example, emulsion polymerization, suspension polymerization, or microsuspension polymerization, and the method described in, for example, WO2006/070664 can be used as the production method.

The "elastomer" for the polymer particles (A) includes a plurality of elastomers (e.g., elastomers ₁ Elastic body ₂ (ii) elastomer _n ) The case of (2) will be described. In this case, the elastomer ₁ Elastic body ₂ (ii) elastomer _n The composite formed of a plurality of elastomers can be produced by polymerizing by the above-described methods, respectively, and then mixing and compounding. Alternatively, an elastomer ₁ Elastic body ₂ (ii) elastomer _n The polymerization may be sequentially performed in multiple steps, respectively, to produce 1 elastomer formed from a plurality of elastomers.

The multi-stage polymerization of the elastomer is specifically described. For example, a multi-step polymer elastomer can be obtained by sequentially performing the following steps (1) to (4): (1) Polymeric elastomer ₁ To obtain an elastomer ₁ The method comprises the steps of carrying out a first treatment on the surface of the (2) Next, in the elastomer ₁ Polymeric elastomer in the presence of (C) ₂ To obtain a 2-step elastomer ₁₊₂ The method comprises the steps of carrying out a first treatment on the surface of the (3) Next, in the elastomer ₁₊₂ Polymeric elastomer in the presence of (C) ₃ To obtain the 3-step elastomer ₁₊₂₊₃ The method comprises the steps of carrying out a first treatment on the surface of the (4) After the same procedure, the elastomer is obtained ₁₊₂₊ Polymerizing an elastomer in the presence of + (n-1) _n To give a multi-stage polymeric elastomer ¹ + ² +···+n。

(method for producing graft portion)

The graft portion can be formed, for example, by polymerizing a monomer used for forming the graft portion by a known radical polymerization. In the case where (a) the elastomer or (b) the polymer particle precursor comprising the elastomer and the surface cross-linked polymer is obtained as an aqueous suspension, the polymerization of the graft portion is preferably carried out by an emulsion polymerization method. The graft portion can be produced, for example, by the method described in WO 2005/028546.

For grafting portions comprising a plurality of grafting portions (e.g. grafting portions ₁ Grafting portion ₂ (ii) grafting unit _n ) The method for producing the graft portion in the case of (a) will be described. In this case, the grafting portion ₁ Grafting portion ₂ (ii) grafting unit _n The graft (composite) formed of a plurality of graft types can be produced by polymerizing by the above-described methods, respectively, and then mixing and compounding. Alternatively, the grafting portion ₁ Grafting portion ₂ (ii) grafting unit _n The polymerization may be sequentially performed in multiple steps to produce 1 graft formed from a plurality of grafts.

The multistage polymerization of the graft portion is specifically described. For example, the multi-stage polymerized graft portion can be obtained by sequentially performing the following steps (1) to (4): (1) Polymeric grafting portion ₁ To obtain a grafting part ₁ The method comprises the steps of carrying out a first treatment on the surface of the (2) Grafting at the grafting part ₁ Polymerized graft in the presence of (C) ₂ To obtain a 2-step grafting part ₁₊₂ The method comprises the steps of carrying out a first treatment on the surface of the (3) Grafting at the grafting part ₁₊₂ Polymerized graft in the presence of (C) ₃ To obtain a 3-step grafting part ₁₊₂₊₃ The method comprises the steps of carrying out a first treatment on the surface of the (4) After the same procedure, the grafting portions were followed _{1+2+···+(n-1)} Polymerized graft in the presence of (C) _n To obtain a multi-step polymerized graft _1+2+···+n 。

When the graft portion includes a plurality of graft portions, the polymer particles (a) can be produced by graft-polymerizing the graft portions to the elastomer after polymerizing the graft portions having the plurality of graft portions. The polymer particles (A) may be produced by graft polymerizing a plurality of polymers constituting the graft portion to an elastomer in the presence of the elastomer in a plurality of steps in sequence.

(method for producing surface-crosslinked Polymer)

The surface cross-linked polymer can be formed by polymerizing monomers used for forming the surface cross-linked polymer by a known radical polymerization. In the case of obtaining the elastomer in the form of an aqueous suspension, the polymerization of the surface-crosslinked polymer is preferably carried out by emulsion polymerization.

In the case of using the emulsion polymerization method as the method for producing the polymer particles (a), a known emulsifier (dispersant) can be used for producing the polymer particles (a).

Examples of the emulsifier include: anionic emulsifiers, nonionic emulsifiers, polyvinyl alcohol, alkyl-substituted celluloses, polyvinylpyrrolidone, polyacrylic acid derivatives, and the like. As the anionic emulsifier, there may be mentioned: sulfur-based emulsifiers, phosphorus-based emulsifiers, sarcosine-based emulsifiers, carboxylic acid-based emulsifiers, and the like. Examples of the sulfur-based emulsifier include sodium dodecylbenzenesulfonate (abbreviated as "SDBS"). Examples of the phosphorus-based emulsifier include sodium polyoxyethylene lauryl ether phosphate.

In the case of using the emulsion polymerization method as the method for producing the polymer particles (a), a thermal decomposition type initiator can be used for producing the polymer particles (a). Examples of the thermal decomposition initiator include: (a) Known initiators such as 2,2' -azobisisobutyronitrile and (b) peroxides such as organic peroxides and inorganic peroxides. The organic peroxides include: tert-butyl peroxyisopropyl carbonate, terpene hydroperoxide, cumene hydroperoxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-hexyl peroxide and the like. The inorganic peroxides include: hydrogen peroxide, potassium persulfate, ammonium persulfate, and the like.

Redox initiators may also be used in the production of the polymer particles (A). The redox initiator is an initiator in which (a) a peroxide such as an organic peroxide or an inorganic peroxide and (b) a transition metal salt such as iron (II) sulfate, a reducing agent such as sodium formaldehyde sulfoxylate or glucose are used in combination. Chelating agents such as disodium ethylenediamine tetraacetate may be used in combination as needed, and phosphorus-containing compounds such as sodium pyrophosphate may be used in combination as needed.

When the redox initiator is used, polymerization can be carried out at a low temperature at which the peroxide is not substantially thermally decomposed, and the polymerization temperature can be set in a wide range. Therefore, redox type initiators are preferably used. Among redox initiators, preferred are those using an organic peroxide as a peroxide, such as cumene hydroperoxide, diisopropylbenzene peroxide, terpene hydroperoxide, and t-butyl hydroperoxide. The amount of the initiator and the amount of the reducing agent, the transition metal salt, the chelating agent, and the like when the redox initiator is used may be in a known range.

In the case of using a polyfunctional monomer in the polymerization of the elastomer, the graft portion or the surface cross-linked polymer for the purpose of introducing a cross-linked structure into the elastomer, the graft portion or the surface cross-linked polymer, a known chain transfer agent may be used in a known amount range. The molecular weight and/or the degree of crosslinking of the resulting elastomer, graft or surface crosslinked polymer can be readily adjusted by using chain transfer agents.

In the production of the polymer particles (a), a surfactant may be further used in addition to the above-described components. The type and amount of the surfactant are within a known range.

In the production of the polymer particles (a), conditions such as polymerization temperature, pressure, and deoxidation during polymerization can be applied to conditions in a known numerical range.

By the above-described method for producing polymer particles (a), a latex can be obtained. That is, the description of (2-2) the method for producing the polymer particles (A) can be cited as the description of the method for producing the latex.

(2-3. Matrix resin (B))

As the matrix resin (B), a thermosetting resin can be preferably used. The thermosetting resin preferably comprises at least 1 thermosetting resin selected from the group consisting of: resins comprising polymers obtained by polymerizing ethylenically unsaturated monomers, epoxy resins, phenolic resins, polyol resins and amino-formaldehyde resins (melamine resins). The thermosetting resin may be a resin containing a polymer obtained by polymerizing an aromatic polyester raw material. Examples of the aromatic polyester raw material include: free radical polymerizable monomers such as aromatic vinyl compounds, (meth) acrylic acid derivatives, vinyl cyanide compounds, and maleimide compounds, dimethyl terephthalate, and alkylene glycols. These thermosetting resins may be used in an amount of 1 or 2 or more.

(ethylenically unsaturated monomer)

The ethylenically unsaturated monomer is not particularly limited as long as it is a monomer having at least 1 ethylenically unsaturated bond in the molecule.

Examples of the ethylenically unsaturated monomer include: acrylic acid, alpha-alkyl acrylate, beta-alkyl acrylic acid, beta-alkyl acrylate, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, vinyl acetate, vinyl esters, unsaturated esters, polyunsaturated carboxylic acids, polyunsaturated esters, maleic acid esters, maleic anhydride, and acetoxystyrene. These monomers may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(epoxy resin)

The epoxy resin is not particularly limited as long as it is an epoxy resin having at least 1 epoxy bond in a molecule.

Specific examples of the epoxy resin include, for example: bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, novolac type epoxy resin, glycidyl ether type epoxy resin of bisphenol a propylene oxide adduct, hydrogenated bisphenol a (or F) type epoxy resin, fluorinated epoxy resin, rubber modified epoxy resin containing polybutadiene or NBR, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol a, glycidyl ether-p-hydroxybenzoate type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin having urethane bond, epoxy of various alicyclic epoxy resins, glycidyl ether of polyhydric alcohol, hydantoin type epoxy resin, unsaturated polymer such as petroleum resin, amino group containing glycidyl ether resin, and the like. The above-mentioned polyols may be exemplified by: n, N-diglycidyl aniline, N-diglycidyl o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin, and the like. The epoxy resin may be an epoxy compound obtained by an addition reaction of bisphenol a (or F) or a polybasic acid or the like with the epoxy resin. The epoxy resin is not limited thereto, and commonly used epoxy resins can be used. The epoxy resin may be used in an amount of 1 or 2 or more.

Among the above epoxy resins, epoxy resins having at least 2 epoxy groups in one molecule are preferable from the viewpoints of high reactivity in curing the resin composition and easiness of forming a 3-dimensional mesh of the resulting cured product. Among the epoxy resins having at least 2 epoxy groups in one molecule, epoxy resins containing bisphenol type epoxy resins as a main component are preferable from the viewpoints of economy and ease of obtaining.

(phenolic resin)

The phenolic resin is not particularly limited as long as it is a compound obtained by reacting phenols with aldehydes. The phenols are not particularly limited, and examples thereof include: phenols such as phenol, o-cresol, m-cresol, p-cresol, xylenol, p-tert-butylphenol, p-octylphenol, p-phenylphenol, bisphenol A, bisphenol F, and resorcinol. Particularly preferred phenols include phenol and cresol.

The aldehydes are not particularly limited, and examples thereof include: formaldehyde, acetaldehyde, butyraldehyde, acrolein, and the like, and mixtures thereof. As the aldehydes, substances which are sources of the aldehydes described above, or solutions of these aldehydes may be used. Formaldehyde is preferred as the aldehyde from the viewpoint of easy handling when reacting phenols with aldehydes.

The molar ratio (F/P) of the phenol (P) to the aldehyde (F) in reacting the phenol with the aldehyde (hereinafter also referred to as reaction molar ratio) is not particularly limited. When an acid catalyst is used in the reaction, the above reaction molar ratio (F/P) is preferably 0.4 to 1.0, more preferably 0.5 to 0.8. When a base catalyst is used in the reaction, the above reaction molar ratio (F/P) is preferably 0.4 to 4.0, more preferably 0.8 to 2.5. When the reaction molar ratio is not less than the lower limit, the yield is not excessively low, and there is no risk of the molecular weight of the obtained phenolic resin decreasing. On the other hand, when the reaction molar ratio is not more than the upper limit, the molecular weight of the phenolic resin does not become excessively large and the softening point does not become excessively high, so that sufficient fluidity can be obtained upon heating. When the reaction molar ratio is equal to or less than the upper limit, control of the molecular weight becomes easy, and there is no risk of gelation due to the reaction conditions or occurrence of a partially gelled product.

(polyol resin)

The polyol resin is a compound having 2 or more active hydrogens at the terminal, and is a polyol having a molecular weight of about 50 to 20000 and having 2 or more functions. As the polyol resin, there may be mentioned: aliphatic alcohols, aromatic alcohols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, and the like.

The aliphatic alcohol may be any of dihydric alcohol or trihydric or higher alcohol (triol, tetrahydric alcohol, etc.). As the diol, there may be mentioned: ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol and other alkylene glycols (particularly alkylene glycols having about 1 to 6 carbon atoms), and dehydration condensates of alkylene glycols of 2 or more molecules (for example, about 2 to 6 molecules) (diethylene glycol, dipropylene glycol, tripropylene glycol and the like), and the like. As the triol, there may be mentioned: glycerol, trimethylolpropane, trimethylolethane, 1,2, 6-hexanetriol, etc. (in particular, triols having about 3 to 10 carbon atoms). The tetrahydric alcohol includes pentaerythritol, diglycerol, and the like. Further, saccharides such as monosaccharides, oligosaccharides, and polysaccharides can be mentioned.

Examples of the aromatic alcohol include: bisphenols such as bisphenol a and bisphenol F; biphenyls such as dihydroxybiphenyl; polyhydric phenols such as hydroquinone and phenol formaldehyde condensate; naphthalene diol, and the like.

Examples of the polyether polyol include: random copolymers or block copolymers obtained by ring-opening polymerization of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. in the presence of 1 or 2 or more active hydrogen-containing initiators, mixtures of these copolymers, etc. Examples of the active hydrogen-containing initiator used for ring-opening polymerization of the polyether polyol include: diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, and bisphenol A; triols such as trimethylolethane, trimethylolpropane, and glycerin; saccharides such as monosaccharides, oligosaccharides, and polysaccharides; sorbitol; amines such as ammonia, ethylenediamine, urea, monomethyl diethanolamine, monoethyl diethanolamine; etc.

Examples of the polyester polyol include a polymer obtained by polycondensing (a) a polybasic acid such as maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, dodecanedioic acid, isophthalic acid, azelaic acid and/or an acid anhydride thereof, and (b) a polyhydric alcohol such as ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 3-methyl-1, 5-pentanediol in the presence of an esterification catalyst at a temperature in the range of 150 to 270 ℃. Further, there may be mentioned (a) ring-opening polymers such as epsilon-caprolactone and valerolactone as polyester polyols, and (b) active hydrogen compounds having 2 or more active hydrogens such as polycarbonate diol and castor oil.

Examples of the polyolefin type polyol include polybutadiene polyol, polyisoprene polyol, and hydrogenated products thereof.

Examples of the acrylic polyol include copolymers of hydroxyl group-containing monomers such as (a) hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate and vinylphenol and general-purpose monomers such as (b) n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, and mixtures of these copolymers.

Among these polyol resins, polyether polyols are preferable from the viewpoints that the obtained resin composition has low viscosity and excellent handleability, and that the resin composition can provide a cured product having an excellent balance between hardness and toughness. Among these polyol resins, polyester polyol is preferable in view of providing a cured product excellent in adhesion of the obtained resin composition.

(amino-formaldehyde resin)

The amino-formaldehyde resin is not particularly limited as long as it is a compound obtained by reacting an amino compound and an aldehyde in the presence of a basic catalyst. The amino compounds mentioned above may be exemplified by: melamine; 6-substituted guanamines such as guanamine, acetoguanamine and benzoguanamine; amine-substituted triazine compounds such as CTU guanamine (3, 9-bis [2- (3, 5-diamino-2, 4, 6-triazenophenyl) ethyl ] -2,4,8, 10-tetraoxaspiro [5,5] undecane) and CMTU guanamine (3, 9-bis [ (3, 5-diamino-2, 4, 6-triazenophenyl) methyl ] -2,4,8, 10-tetraoxaspiro [5,5] undecane); urea, thiourea, ethylene urea and the like. Further, as the amino compound, a substituted melamine compound obtained by substituting the hydrogen of the amino group of melamine with an alkyl group, an alkenyl group and/or a phenyl group (described in U.S. Pat. No. 5,998,573 (corresponding to Japanese unexamined patent publication: JP-A No. 9-143238)), a substituted melamine compound obtained by substituting the hydrogen of the amino group of melamine with a hydroxyalkyl group, a hydroxyalkoxyalkyl group and/or an aminoalkyl group (described in U.S. Pat. No. 5,322,915 (corresponding to Japanese unexamined patent publication: JP-A No. 5-202157)), or the like can be used. Among the above amino compounds, melamine, guanamine, acetoguanamine, and benzoguanamine are preferable as polyfunctional amino compounds, and melamine is particularly preferable from the viewpoint of industrial production and low cost. The amino compound may be used in an amount of 1 or 2 or more. In addition to these amino compounds, (a) phenols such as phenol, cresol, alkylphenol, resorcinol, hydroquinone, and pyrogallol, and (b) aniline may be added.

The aldehydes include: formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, furfural, and the like. The aldehyde is preferably formaldehyde or paraformaldehyde from the viewpoints of low cost and good reactivity with the amino compounds listed previously. In the production of the amino-formaldehyde resin, it is preferable to use 1.1 to 6.0 mol of an aldehyde per unit effective aldehyde group, and it is particularly preferable to use 1.2 to 4.0 mol of an aldehyde per 1 mol of the amino compound.

As the matrix resin (B), an epoxy resin is particularly preferable.

(physical Properties of matrix resin (B))

The properties of the matrix resin (B) are not particularly limited. The matrix resin (B) preferably has a viscosity of 100 mPas to 1000000 mPas at 25 ℃. More preferably, the viscosity of the matrix resin (B) is 50000 mPas or less, still more preferably 30,000 mPas or less, particularly preferably 15,000 mPas or less at 25 ℃. According to the above constitution, the matrix resin (B) has an advantage of excellent fluidity. The matrix resin (B) having a viscosity of 100 mPas to 1000000 mPas at 25℃can be considered as a liquid.

The greater the flowability of the matrix resin (B), in other words, the smaller the viscosity, the more difficult it is to disperse the polymer particles (a) in the matrix resin (B) in the state of primary particles. It has been very difficult to disperse the polymer particles (A) in the form of primary particles in the matrix resin (B) having a viscosity of 1000000 mPas or less at 25 ℃. However, the resin composition according to one embodiment of the present invention has the following advantages: the polymer particles (A) having the above-described constitution are well dispersed in the matrix resin (B) having a viscosity of 1000000 mPas or less at 25 ℃.

In addition, from the viewpoint of preventing the matrix resin (B) from entering the polymer particles (a) and causing the polymer particles (a) to melt and adhere to each other, the viscosity of the matrix resin (B) is more preferably 100mpa·s or more, still more preferably 500mpa·s or more, still more preferably 1000mpa·s or more, and particularly preferably 1500mpa·s or more at 25 ℃.

The matrix resin (B) may have a viscosity of more than 1000000 mPa-s. The matrix resin (B) may be semi-solid (semi-liquid) or solid. In the case where the matrix resin (B) has a viscosity of more than 1000000 mPas, the resulting resin composition has the advantages of less tackiness and easy handling.

The matrix resin (B) preferably has an endothermic peak at 25 ℃ or lower, more preferably has an endothermic peak at 0 ℃ or lower in a thermogram of Differential Scanning Calorimetry (DSC). According to the above constitution, the matrix resin (B) has an advantage of excellent fluidity.

(2-4. Blending ratio of Polymer particles (A) to matrix resin (B), etc.)

When the total of the polymer particles (a) and the matrix resin (B) is 100 wt%, the blending ratio of the polymer particles (a) to the matrix resin (B) is preferably 20 wt% or more and 80 wt% or less. When the total of the polymer particles (a) and the matrix resin (B) is 100 wt%, the resin composition containing 20 wt% or more of the polymer particles (a) may be referred to as a masterbatch. When the total of the polymer particles (a) and the matrix resin (B) is 100 wt%, the total of the polymer particles (a) is preferably 20 wt% or more and 50 wt% or less, the total of the matrix resin (B) is preferably 50 wt% or more and 80 wt% or less, the total of the polymer particles (a) is preferably 30 wt% or more and 50 wt% or less, the total of the polymer particles (B) is preferably 50 wt% or more and 70 wt% or less, the total of the polymer particles (a) is preferably 35 wt% or more and 50 wt% or less, the total of the polymer particles (B) is preferably 50 wt% or more and 65 wt% or less, the total of the polymer particles (a) is preferably 40 wt% or more and 50 wt% or less, the total of the polymer particles (B) is preferably 50 wt% or more and 60 wt% or less, the total of the polymer particles (a) is preferably 40 wt% or more and 60 wt% or less. When the blending ratio of the polymer particles (a) and the matrix resin (B) is the above-described constitution, there is an advantage that the degree of blending freedom is improved. The present resin composition can achieve a low viscosity even when the polymer particles (a) are contained in a high concentration. In addition, when a resin composition containing a small amount of polymer particles (a) is further produced using a masterbatch, the total amount of polymer particles (a) and matrix resin (B) is preferably 1 to 20 wt% and preferably 80 to 99 wt% of the polymer particles (a), more preferably 1 to 16 wt% of the polymer particles (a), more preferably 84 to 99 wt% of the matrix resin (B), even more preferably 1 to 12 wt% of the polymer particles (a), and even more preferably 88 to 99 wt% of the matrix resin (B) based on 100 wt% of the resin composition.

(2-5. Other optional ingredients)

The present resin composition may contain any other component than the above components as required. As other optional components, there may be mentioned: inorganic filler, organic filler, anti-blocking agent, curing agent, pigment, dye and other coloring agent, extender pigment, ultraviolet absorber, antioxidant, thermal stabilizer (gelation inhibitor), plasticizer, leveling agent, defoamer, silane coupling agent, antistatic agent, flame retardant, lubricant, viscosity reducer, low shrinkage agent, desiccant, dispersant and the like.

The other optional components may be added appropriately in any step of the method for producing the present resin composition. For example, other optional components may be added to the aqueous suspension of the polymer particles (A) before or after solidification, or may be added to the present resin composition.

(inorganic filler)

As described above, the present resin composition may contain an inorganic filler. The present resin composition does not have a functional group that reacts with the inorganic filler, and therefore, even when the inorganic filler is contained, it is possible to achieve a reduction in viscosity. As the inorganic filler, there may be mentioned: silicic acid, silicate, dolomite, reinforcing filler, calcium oxide, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide, aluminum hydroxide, aluminum micropowder, zinc oxide, active zinc white, etc. When the present resin composition contains an inorganic filler, the resin composition has the advantage of excellent economy, and the cured product obtained from the resin composition has the advantage of excellent strength and flame retardancy.

Examples of the silicic acid include wet silica and dry silica.

The dry silica is also referred to as fumed silica. Examples of the dry silica include hydrophilic fumed silica having no surface treatment and hydrophobic fumed silica produced by chemically treating the silanol moiety of hydrophilic fumed silica with silane and/or siloxane. The dry silica is preferably hydrophilic fumed silica (a) from the viewpoint of excellent handleability, and the hydrophobic fumed silica (B) from the viewpoint of excellent dispersibility in the matrix resin (B) and excellent storage stability of the obtained resin composition.

The method for producing the dry silica includes: (a) The Aerosil method for producing silicon halide by decomposition, and (b) the arc method for producing silicic acid by heating and reducing silica sand and oxidizing it with air are not particularly limited. The method for producing dry silica is preferably Aerosil method from the viewpoint of availability.

As the surface treatment agent for hydrophobic fumed silica, there can be mentioned: silane coupling agents, octamethyltetracyclosiloxane, polydimethylsiloxane, and the like. The silane coupling agent may be exemplified by: dimethyldichlorosilane, (meth) acrylic silane, hexamethyldisilazane, octylsilane, hexadecylsilane, aminosilane, methacrylic silane, and the like. From the viewpoint of excellent dispersion stability in the matrix resin (B) and storage stability of the obtained resin composition, hydrophobic fumed silica surface-treated with polydimethylsiloxane is preferred.

When the present resin composition contains dry silica as an inorganic filler, the shear rate dependence of the viscosity of the resin composition increases.

As the silicate, there may be mentioned: aluminum silicate, magnesium silicate, calcium silicate, wollastonite, talc, etc.

As the calcium carbonate, there may be mentioned: heavy calcium carbonate, colloidal calcium carbonate, and the like.

Colloidal calcium carbonate is usually produced by reacting carbon dioxide gas with lime milk obtained by adding water to quicklime. Colloidal calcium carbonate is a homogeneous particulate calcium carbonate, sometimes also referred to as "precipitated calcium carbonate", "colloidal calcium carbonate", or "synthetic calcium carbonate".

From the viewpoint of economy, the inorganic filler preferably contains calcium carbonate.

The inorganic filler is preferably surface-treated with a surface treating agent. The dispersibility of the inorganic filler in the resin composition is improved by the surface treatment, and as a result, various physical properties of the obtained cured product are improved.

Examples of the surface treatment agent for the inorganic filler include: fatty acids such as saturated fatty acids and unsaturated fatty acids, resin acids, and silane coupling agents.

The content of the inorganic filler in 100 wt% of the resin composition is preferably 0.1 wt% to 60.0 wt%, more preferably 0.5 wt% to 55.0 wt%, and still more preferably 1.0 wt% to 50.0 wt%. When the content of the inorganic filler in 100% by weight of the resin composition is 0.1% by weight or more, the resin composition can provide a cured product excellent in adhesion. When the content of the inorganic filler in 100% by weight of the resin composition is 60.0% by weight or less, the decrease in elongation properties due to the inorganic filler becomes insignificant, and the resin composition can provide a cured product excellent in elongation properties. The content of the inorganic filler in 100 wt% of the resin composition may be 0.1 wt% to 15.0 wt%, may be 0.5 wt% to 10.0 wt%, or may be 1.0 wt% to 5.0 wt%.

The inorganic filler may be used alone or in combination of at least 2 kinds.

(calcium oxide)

As described above, the present resin composition may contain calcium oxide as an inorganic filler. When the present resin composition contains calcium oxide as an inorganic filler, the calcium oxide reacts with moisture in the resin composition to remove the moisture from the resin composition, and thus problems in various physical properties due to the presence of moisture can be solved. Calcium oxide functions as, for example, a bubble preventing agent for removing moisture, and can suppress a decrease in the adhesive strength of the resulting cured product.

The calcium oxide may be surface-treated by a surface treatment agent. The dispersibility of calcium oxide in the resin composition is improved by the surface treatment. As a result, when the surface-treated calcium oxide is used, physical properties such as adhesive strength of the obtained cured product are improved as compared with the case of using calcium oxide not subjected to surface treatment. The surface-treated calcium oxide can significantly improve the T-peel adhesion and impact-resistant peel adhesion of the cured product. The surface treatment agent capable of realizing the surface treatment of calcium oxide is not particularly limited, and is preferably a fatty acid.

When the present resin composition contains calcium oxide as an inorganic filler, the content of calcium oxide in the resin composition is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, still more preferably 0.5 to 3 parts by weight, and particularly preferably 1 to 2 parts by weight, relative to 100 parts by weight of the matrix resin (B). When the content of calcium oxide is 0.1 part by weight or more based on 100 parts by weight of the matrix resin (B) (a), the effect of removing moisture is sufficient, and when the content of calcium oxide is 10 parts by weight or less, there is no risk of lowering the strength of the resulting cured product.

The calcium oxide may be used alone or in combination of 1 or more than 2.

The resin composition may use a dehydrating agent other than calcium oxide. Examples of the dehydrating agent other than calcium oxide include various compounds described in the paragraph [0155] of the specification of WO 2014-196607.

(aluminum hydroxide)

As described above, the present resin composition may contain aluminum hydroxide as an inorganic filler. Aluminum hydroxide is prepared from Al (OH) ₃ Or Al ₂ O ₃ ·3H ₂ The white powder crystal represented by the chemical formula of O is generally produced by the bayer process using bauxite as a raw material. Aluminum hydroxide exists in products having various average particle diameters by classification.

When the present resin composition contains aluminum hydroxide as the inorganic filler, the content of aluminum hydroxide in the resin composition is preferably 55% by weight or more and 85% by weight or less relative to 100% by weight of the resin composition. The cured product obtained by adding aluminum hydroxide has the advantage of excellent heat conductivity and flame retardance.

(2-6. Physical Properties of the resin composition)

The resin composition has a low viscosity and thus has an advantage of excellent handleability. In one embodiment of the present invention, when the viscosity of the resin composition at 50 ℃ is 20000mpa·s or less in the case where the resin composition does not contain an inorganic filler, the viscosity of the resin composition (not containing an inorganic filler) is low, and the workability is judged to be excellent. In the present specification, "viscosity of the resin composition at X" means "viscosity of the resin composition at X". When the present resin composition does not contain an inorganic filler, the viscosity of the resin composition at 50 ℃ is preferably 20900mpa·s or less, more preferably 20500mpa·s or less, more preferably 20000mpa·s or less, more preferably 18000mpa·s or less, more preferably 15000mpa·s or less, more preferably 14000mpa·s or less, more preferably 13000mpa·s or less, more preferably 12000mpa·s or less, and particularly preferably 11000mpa·s or less. With this configuration, the resin composition also has an advantage of excellent fluidity.

The resin composition has an advantage of excellent handleability even when it further contains an inorganic filler. In one embodiment of the present invention, when the viscosity of the resin composition at 25 ℃ is 280000mpa·s or less when the resin composition further contains an inorganic filler, the viscosity of the resin composition (containing the inorganic filler) is low, and the resin composition is determined to be excellent in handleability. When the present resin composition further contains an inorganic filler, the viscosity of the resin composition at 25 ℃ is preferably 280000mpa·s or less, more preferably 250000mpa·s or less, more preferably 230000mpa·s or less, more preferably 200000mpa·s or less, more preferably 170000mpa·s or less, more preferably 150000mpa·s or less, more preferably 140000mpa·s or less, more preferably 130000mpa·s or less, more preferably 120000mpa·s or less, and particularly preferably 110000mpa·s or less. With this configuration, the resin composition also has an advantage of excellent fluidity.

The resin composition has an advantage of excellent handleability even when the concentration of the polymer particles (a) in the resin composition is high (for example, 20 wt% or more). Here, the case (5)) will be described in which the content of the polymer particles (a) in the resin composition is 20 wt% or more based on 100 wt% of the total of the polymer particles (a) and the matrix resin (B), and the resin composition does not contain an inorganic filler. In the case (5), when the viscosity of the resin composition at 50℃is 20000 mPas or less, the viscosity of the resin composition (excluding the inorganic filler) is low, and the handling property is judged to be excellent. In the case (5), the viscosity of the resin composition at 50℃is preferably 20900 mPas or less, more preferably 20500 mPas or less, more preferably 20000 mPas or less, more preferably 18000 mPas or less, more preferably 15000 mPas or less, more preferably 14000 mPas or less, more preferably 13000 mPas or less, more preferably 12000 mPas or less, and particularly preferably 11000 mPas or less. With this configuration, the resin composition also has an advantage of excellent fluidity.

The resin composition has an advantage of excellent handleability even when the concentration of the polymer particles (a) in the resin composition is higher (for example, 40 wt% or more). Here, the case where the content of the polymer particles (a) in the resin composition is 40 wt% or more based on 100 wt% of the total of the polymer particles (a) and the matrix resin (B), and the resin composition does not contain an inorganic filler (case (6)) will be described. In the case (6), when the viscosity of the resin composition at 50℃is 20000 mPas or less, the viscosity of the resin composition (excluding the inorganic filler) is low, and the handling property is judged to be excellent. In the case (6), the viscosity of the resin composition at 50℃is preferably 20900 mPas or less, more preferably 20500 mPas or less, more preferably 20000 mPas or less, more preferably 18000 mPas or less, more preferably 15000 mPas or less, more preferably 14000 mPas or less, more preferably 13000 mPas or less, more preferably 12000 mPas or less, and particularly preferably 11000 mPas or less. With this configuration, the resin composition also has an advantage of excellent fluidity.

(2-7. Process for producing resin composition)

As described above, the present resin composition is preferably a composition in which the polymer particles (a) are dispersed in the matrix resin (B) in the form of primary particles. As a method for obtaining a composition in which such polymer particles (a) are dispersed in the matrix resin (B) in the form of primary particles (i.e., a method for producing the present resin composition), various methods can be utilized. Examples of the method for producing the present resin composition include: (i) A method in which polymer particles (A) obtained in the form of an aqueous latex are brought into contact with a matrix resin (B) and then unnecessary components such as water are removed; (i) A method in which polymer particles (A) obtained in a water-based latex state are temporarily extracted into an organic solvent, and then an organic solvent solution of the obtained polymer particles (A) is mixed with a matrix resin (B) to remove the organic solvent; etc. As a method for producing the present resin composition, a method described in International publication No. 2005/028546 is preferably used. The specific manufacturing method sequentially comprises the following steps: (i) Step 1, mixing an aqueous latex containing polymer particles (a) (specifically, a reaction mixture obtained by emulsion polymerization to produce polymer particles (a)) with an organic solvent having a solubility of 5 to 40 wt% with respect to water at 20 ℃, and then adding an excessive amount of water to the obtained mixture to mix the mixture, thereby agglomerating the polymer particles (a); (ii) Step 2, separating and recovering the aggregated polymer particles (a) from the mixture (liquid phase), and then mixing the recovered polymer particles (a) with an organic solvent again to obtain an organic solvent solution of the polymer particles (a); and (iii) step 3, further mixing the obtained organic solvent solution with a matrix resin (B), and then distilling off the organic solvent. The present resin composition is preferably prepared by a production method including the above-mentioned step 1, step 2 and step 3.

In order to facilitate the above step 3, the matrix resin (B) is preferably liquid at 23 ℃. The term "the matrix resin (B) is in a liquid state at 23 ℃ means that the softening point of the matrix resin (B) is 23 ℃ or less, and that the matrix resin (B) exhibits fluidity at 23 ℃.

[ 3. Cured product ]

The cured product according to one embodiment of the present invention is obtained by curing the resin composition described in item [ 2 ] above. In the present specification, the "cured product according to one embodiment of the present invention" may be simply referred to as "present cured product".

The present cured product has the above-described structure, and therefore, even when it is applied to a metal plate or the like and then cured, it is less likely to rust. In addition, (a) has a beautiful surface, (b) has high rigidity and high elastic modulus, and (c) has excellent toughness and adhesion.

[ 4. Other uses ]

The present resin composition described above can be used for various applications, and these applications are not particularly limited. The resin composition and the like can be preferably used for applications such as adhesives, coating materials, adhesives for reinforcing fibers, composite materials, molding materials for 3D printers, sealants, electronic boards, ink adhesives, wood sheet adhesives, adhesives for rubber sheets, adhesives for foam sheets, adhesives for castings, matrix consolidation materials for flooring materials and ceramics, polyurethane foams, and the like, respectively. Examples of the adhesive include a one-component adhesive and a two-component adhesive. In the case of using the present resin composition as an adhesive, an epoxy curing agent may be used. As the epoxy curing agent, various epoxy curing agents can be used. Examples of the epoxy curing agent include aromatic amines. As the polyurethane foam, there may be mentioned: car seats, car interior parts, sound absorbing materials, vibration absorbing materials, shock absorbers (impact absorbing materials), heat insulating materials, floor material cushioning pads for engineering, and the like.

In the above-mentioned applications, the present resin composition is more preferably used as an adhesive, a coating material, a binder for reinforcing fibers, a composite material, a molding material for 3D printers, a sealant, and an electronic substrate.

One embodiment of the present invention may have the following configuration.

[ X1 ] A resin composition comprising polymer particles (A) and a matrix resin (B),

the polymer particles (A) have a graft portion,

the graft portion is a polymer satisfying the following (i) to (iii),

(i) (i-a) does not contain a structural unit containing an aromatic group, or

(iii) The composition does not contain an alkoxy group-containing structural unit, an aryloxy group-containing structural unit, an oxetanyl group-containing structural unit, a hydroxyl group-containing structural unit, an amino group-containing structural unit, an imide group-containing structural unit, a carboxylic acid anhydride group-containing structural unit, a cyclic ester group-containing structural unit, a cyclic amide group-containing structural unit, a benzo group-containing structural unit Structural units of oxazinyl groups, structural units containing cyanate groups,

the glass transition temperature of the grafting part is-25 ℃ to 18 ℃.

[ X2 ] the resin composition according to [ X1 ], wherein,

when the total of the polymer particles (a) and the matrix resin (B) is 100 wt%, the polymer particles (a) are 20 wt% or more and 50 wt% or less, and the matrix resin (B) is 50 wt% or more and 80 wt% or less.

[ X3 ] A resin composition comprising polymer particles (A) and a matrix resin (B),

the polymer particles (A) have a graft portion,

the graft part is a polymer satisfying the following (i) to (ii) in 100% by weight of the graft part,

(i) (i-a) does not contain a structural unit containing an aromatic group, or

(ii) Comprises 50% by weight or more of at least one structural unit derived from an alkyl methacrylate,

the glass transition temperature of the grafting part is more than-25 ℃ and less than 18 ℃,

The resin composition according to any one of [ X1 ] to [ X3 ], wherein,

the grafting portion does not contain a structural unit containing an aromatic group.

The resin composition according to any one of [ X1 ] to [ X4 ], wherein,

the volume average particle diameter of the polymer particles (A) is 0.15 μm or more and 0.30 μm or less.

The resin composition according to any one of [ X1 ] to [ X5 ], wherein,

in the 100 wt% of the grafting portion, the grafting portion includes more than 0 wt% and 50 wt% or less of a structural unit having an epoxy group.

The resin composition according to any one of [ X1 ] to [ X6 ], wherein,

in the 100 wt% of the grafting portion, the grafting portion includes 20 wt% or more of a structural unit derived from a monomer providing a homopolymer having a glass transition temperature of 0 ℃ or lower.

The resin composition according to any one of [ X1 ] to [ X7 ], wherein the viscosity at 50℃is 20000 mPas or less.

The resin composition according to any one of [ X1 ] to [ X8 ], wherein,

when the total of the polymer particles (A) and the matrix resin (B) is 100 wt%, the polymer particles (A) are 40 wt% to 50 wt%,

The viscosity of the resin composition at 50 ℃ is 20000 mPas or less.

The resin composition according to any one of [ X1 ] to [ X9 ], which further comprises an inorganic filler.

The resin composition according to any one of [ X1 ] to [ X10 ], wherein,

the matrix resin (B) is an epoxy resin.

One embodiment of the present invention may have the following configuration.

[ Y1 ] a resin composition comprising polymer particles (A) and a matrix resin (B),

the polymer particles (A) have a graft portion,

the graft portion is a polymer satisfying the following (i) to (iii),

(i) (i-a) does not contain a structural unit containing an aromatic group, or

(iii) Structural monomers not containing alkoxy groupsA member, a structural unit containing an aryloxy group, a structural unit containing an oxetanyl group, a structural unit containing a hydroxyl group, a structural unit containing an amino group, a structural unit containing an imide group, a structural unit containing a carboxylic acid anhydride group, a structural unit containing a cyclic ester group, a structural unit containing a cyclic amide group, a structural unit containing a benzo group Structural units of oxazinyl groups, structural units containing cyanate groups,

the glass transition temperature of the grafting part is-25 ℃ to 18 ℃.

[ Y2 ] the resin composition according to [ Y1 ], wherein,

[ Y3 ] a resin composition comprising polymer particles (A) and a matrix resin (B),

the polymer particles (A) have a graft portion,

(i) (i-a) does not contain a structural unit containing an aromatic group, or

(ii) (ii-a) comprises at least one of structural units derived from an alkyl methacrylate and structural units derived from an alkyl acrylate; and is also provided with

(ii-b) the total content of the structural units derived from the alkyl methacrylate and the structural units derived from the alkyl acrylate is 50% by weight or more,

The resin composition according to any one of [ Y1 ] to [ Y3 ], wherein,

The resin composition according to any one of [ Y1 ] to [ Y4 ], wherein,

The resin composition according to any one of [ Y1 ] to [ Y5 ], wherein,

The resin composition according to any one of [ Y1 ] to [ Y6 ], wherein,

The resin composition according to any one of [ Y1 ] to [ Y7 ], wherein the viscosity at 50℃is 20000 mPas or less.

The resin composition according to any one of [ Y1 ] to [ Y8 ], wherein,

the viscosity of the resin composition at 50 ℃ is 20000 mPas or less.

The resin composition according to any one of [ Y1 ] to [ Y9 ], which further comprises an inorganic filler.

The resin composition according to any one of [ Y1 ] to [ Y10 ], wherein the matrix resin (B) is an epoxy resin.

Examples

Hereinafter, an embodiment of the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited thereto. An embodiment of the present invention can be implemented with appropriate modifications within a range that can be adapted to the gist described above or below, and these are included in the technical scope of the present invention.

[ evaluation method ]

The method for evaluating the resin compositions produced in examples and comparative examples will be described below.

< determination of volume average particle size >)

(a) The volume average particle diameter (Mv) of the elastomer dispersed in the aqueous suspension and (b) the polymer particles (A) dispersed in the latex was measured using Nanotrac WaveII-EX150 (manufactured by microtricEL Co.). The aqueous suspension or latex was diluted with deionized water and used as a test sample. The refractive index of the water and the elastomer or polymer particles (a) obtained in each production example was measured by adjusting the sample concentration so that the measurement time was 120 seconds and the load index (loading index) was 1 to 20.

< measurement of viscosity >

The liquid epoxy resin (JER 828, mitsubishi chemical corporation) as the matrix resin (B) used in the examples and comparative examples below, or the viscosity of the obtained resin composition was measured. The device used was a digital viscometer model DV-II+Pro manufactured by BROOKFIELD Co. Further, the viscosity was measured by using rotor CPE-52 according to the viscosity region and changing the Shear Rate as required at a measurement temperature of 25℃or 50 ℃. As a result, the viscosity of the liquid epoxy resin as the matrix resin (B) was 12000 mPas.

< Tg of grafting portion >)

Tg of the graft portion the Tg value of the homopolymer of the monomer described below was calculated according to the above equation 1.

1. Polymerization of elastomer

Production example 1-1; preparation of an aqueous suspension (R-1) comprising an elastomer based on polybutadiene rubber

200 parts by weight of deionized water, 0.03 part by weight of tripotassium phosphate, 0.002 part by weight of disodium ethylenediamine tetraacetate (EDTA), 0.001 part by weight of ferrous sulfate heptahydrate, and 1.55 parts by weight of Sodium Dodecylbenzenesulfonate (SDBS) as an emulsifier were charged into the pressure-resistant polymerizer. Next, the gas inside the pressure-resistant polymerizer was replaced with nitrogen while stirring the charged raw materials, whereby oxygen was sufficiently removed from the pressure-resistant polymerizer. Then, 100 parts by weight of butadiene (Bd) was charged into a pressure-resistant polymerizer, and the temperature in the pressure-resistant polymerizer was raised to 45 ℃. Then, 0.03 parts by weight of terpene hydroperoxide (PHP) was charged into a pressure-resistant polymerizer, and then 0.10 parts by weight of Sodium Formaldehyde Sulfoxylate (SFS) was charged into the pressure-resistant polymerizer to initiate polymerization. At 15 hours from the initiation of polymerization, the residual monomer not used for polymerization was devolatilized under reduced pressure to terminate the polymerization. During polymerization, PHP, EDTA and ferrous sulfate heptahydrate were added to the pressure-resistant polymerizer in arbitrary amounts and at arbitrary timing. By this polymerization, an aqueous suspension (R-1) containing an elastomer containing polybutadiene rubber as a main component was obtained. The volume average particle diameter of the elastomer contained in the resulting aqueous suspension (R-1) was 90nm.

Production examples 1 to 2; preparation of an aqueous suspension (R-2) comprising an elastomer based on polybutadiene rubber

7 parts by weight of the aqueous suspension (R-1) obtained above, 200 parts by weight of deionized water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts by weight of EDTA, and 0.001 parts by weight of ferrous sulfate heptahydrate were charged into a pressure-resistant polymerizer as a solid content. Next, the gas inside the pressure-resistant polymerizer was replaced with nitrogen while stirring the charged raw materials, whereby oxygen was sufficiently removed from the pressure-resistant polymerizer. Then, bd 93 parts by weight was charged into a pressure-resistant polymerizer, and the temperature in the pressure-resistant polymerizer was raised to 45 ℃. Then, 0.02 parts by weight of PHP was charged into a pressure-resistant polymerizer, and then 0.10 parts by weight of SFS was charged into the pressure-resistant polymerizer to initiate polymerization. At 30 hours from the initiation of polymerization, the residual monomer not used for polymerization was devolatilized under reduced pressure to terminate the polymerization. In the polymerization, PHP, EDTA, ferrous sulfate heptahydrate and SDBS were added to the pressure-resistant polymerizer in arbitrary amounts and at arbitrary timing. By this polymerization, an aqueous suspension (R-2) containing an elastomer containing polybutadiene rubber as a main component was obtained. The volume average particle diameter of the elastomer contained in the resulting aqueous suspension (R-2) was 195nm.

Production examples 1 to 3; preparation of an aqueous suspension (R-3) comprising an elastomer based on polybutadiene rubber

200 parts by weight of deionized water, 0.03 part by weight of tripotassium phosphate, 0.002 part by weight of disodium ethylenediamine tetraacetate (EDTA), 0.001 part by weight of ferrous sulfate heptahydrate, and 0.15 part by weight of Sodium Dodecylbenzenesulfonate (SDBS) as an emulsifier were charged into the pressure-resistant polymerizer. Next, the gas inside the pressure-resistant polymerizer was replaced with nitrogen while stirring the charged raw materials, whereby oxygen was sufficiently removed from the pressure-resistant polymerizer. Then, 100 parts by weight of butadiene (Bd) was charged into a pressure-resistant polymerizer, and the temperature in the pressure-resistant polymerizer was raised to 45 ℃. Then, 0.03 parts by weight of terpene hydroperoxide (PHP) was charged into a pressure-resistant polymerizer, and then 0.10 parts by weight of Sodium Formaldehyde Sulfoxylate (SFS) was charged into the pressure-resistant polymerizer to initiate polymerization. At 15 hours from the initiation of polymerization, the residual monomer not used for polymerization was devolatilized under reduced pressure to terminate the polymerization. In the polymerization, PHP, EDTA and ferrous sulfate heptahydrate were added to the pressure-resistant polymerizer in arbitrary amounts and at arbitrary timing. By this polymerization, an aqueous suspension (R-3) containing an elastomer containing polybutadiene rubber as a main component was obtained. The volume average particle diameter of the elastomer contained in the resulting aqueous suspension (R-3) was 120nm.

2. Preparation of Polymer particles (A) (polymerization of grafting portion)

Production example 2-1; preparation of latex (L-1) comprising Polymer particles (A)

250 parts by weight of the aqueous suspension (R-2) (containing 87 parts by weight of an elastomer containing polybutadiene rubber as a main component) and 50 parts by weight of deionized water were charged into a glass reactor. Here, the glass reactor includes a thermometer, a stirrer, a reflux cooler, a nitrogen inlet, and a device for adding a monomer. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60 ℃. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate and 0.20 parts by weight of SFS were charged into a glass reactor, and stirred for 10 minutes. Then, a mixture of 6.0 parts by weight of a monomer for forming a graft portion (hereinafter also referred to as a graft monomer) (n-Butyl Acrylate (BA), 5.2 parts by weight of Methyl Acrylate (MA), and 1.8 parts by weight of Glycidyl Methacrylate (GMA)) and 0.035 parts by weight of t-Butyl Hydroperoxide (BHP) was continuously added to the glass reactor over 80 minutes. Then, 0.013 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was further stirred for 1 hour to complete polymerization. By the above operation, a latex (L-1) comprising the polymer particles (A) and an emulsifier was obtained. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-1) was 200nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-1) was 30% by weight relative to 100% by weight of the latex (L-1). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion.

Production example 2-2; preparation of latex (L-2) comprising Polymer particles (A)

A latex (L-2) was obtained in the same manner as in production example 2-1, except that 9.2 parts by weight of Ethyl Acrylate (EA), 2.0 parts by weight of n-Butyl Acrylate (BA), and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as a grafting monomer in production example 2-1. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-2) was 200nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-2) was 30% by weight relative to 100% by weight of the latex (L-2). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion.

Production examples 2 to 3; preparation of latex (L-3) comprising Polymer particles (A)

A latex (L-3) was obtained in the same manner as in production example 2-1, except that 11.2 parts by weight of Ethyl Acrylate (EA) and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as the grafting monomer in production example 2-1. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-3) was 200nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-3) was 30% by weight relative to 100% by weight of the latex (L-3). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion.

Preparation examples 2 to 4; preparation of latex (L-4) comprising Polymer particles (A)

A latex (L-4) was obtained in the same manner as in production example 2-1, except that 4.0 parts by weight of n-Butyl Acrylate (BA), 7.2 parts by weight of Methyl Acrylate (MA), and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as the grafting monomer in production example 2-1. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-4) was 200nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-4) was 30% by weight relative to 100% by weight of the latex (L-4). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion.

Preparation examples 2 to 5; preparation of latex (L-5) comprising Polymer particles (A)

A latex (L-5) was obtained in the same manner as in production example 2-1, except that 11.2 parts by weight of Methyl Acrylate (MA) and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as the grafting monomer in production example 2-1. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-5) was 200nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-5) was 30% by weight relative to 100% by weight of the latex (L-5). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion.

Preparation examples 2 to 6; preparation of latex (L-6) comprising Polymer particles (A)

A latex (L-6) was obtained in the same manner as in production example 2-1, except that 6.2 parts by weight of Methyl Methacrylate (MMA), 5.0 parts by weight of n-Butyl Acrylate (BA), and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as the grafting monomer in production example 2-1. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-6) was 200nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-6) was 30% by weight relative to 100% by weight of the latex (L-6). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion.

Preparation examples 2 to 7; preparation of latex (L-7) comprising Polymer particles (A)

A latex (L-7) was obtained in the same manner as in production example 2-1, except that 6.0 parts by weight of n-Butyl Acrylate (BA), 4.0 parts by weight of Methyl Acrylate (MA), and 3.0 parts by weight of Glycidyl Methacrylate (GMA) were used as the grafting monomer in production example 2-1. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-7) was 200nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-7) was 30% by weight relative to 100% by weight of the latex (L-7). The graft portion of the polymer particle (a) contained 23 wt% of the structural unit having an epoxy group in 100 wt% of the graft portion.

Preparation examples 2 to 8; preparation of latex (L-8) comprising Polymer particles (A)

A latex (L-8) was obtained in the same manner as in production examples 2 to 6, except that (R-3) was used as an elastomer containing polybutadiene rubber as a main component in production examples 2 to 6. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-8) was 130nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-8) was 30% by weight relative to 100% by weight of the latex (L-8). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion.

Preparation examples 2 to 9; preparation of latex (L-9) comprising Polymer particles (A)

A latex (L-9) was obtained in the same manner as in production examples 2 to 8, except that 2.2 parts by weight of Methyl Methacrylate (MMA), 5.0 parts by weight of n-Butyl Acrylate (BA), 4.0 parts by weight of styrene (St) and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as the grafting monomer in production examples 2 to 8. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-9) was 130nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-9) was 30% by weight relative to 100% by weight of the latex (L-9). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion. The graft portion of the polymer particle (A) contains a structural unit containing an aromatic group derived from St.

Preparation examples 2 to 10; preparation of latex (L-10) comprising Polymer particles (A)

A latex (L-10) was obtained in the same manner as in production example 2-1, except that 10.2 parts by weight of Methyl Methacrylate (MMA), 1.0 part by weight of n-Butyl Acrylate (BA), and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as the grafting monomer in production example 2-1. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-10) was 200nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-10) was 30% by weight relative to 100% by weight of the latex (L-10). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion.

Preparation examples 2 to 11; preparation of latex (L-11) comprising Polymer particles (A)

A latex (L-11) was obtained in the same manner as in production example 2-1, except that 9.2 parts by weight of Methyl Methacrylate (MMA), 2.0 parts by weight of 4-hydroxybutyl acrylate (4 HBA) and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as a grafting monomer in production example 2-1. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-11) was 200nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-11) was 30% by weight relative to 100% by weight of the latex (L-11). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion. The graft portion of the polymer particle (a) contains a structural unit containing a hydroxyl group derived from 4 HBA.

Preparation examples 2 to 12; preparation of latex (L-12) comprising Polymer particles (A)

A latex (L-12) was obtained in the same manner as in production example 2-1, except that 11.2 parts by weight of 2-methoxyethyl methacrylate (MEMA) and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as a grafting monomer in production example 2-1. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-12) was 200nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-12) was 30% by weight relative to 100% by weight of the latex (L-12). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion. The graft portion of the polymer particle (a) contains a structural unit containing an alkoxy group derived from MEMA.

Preparation examples 2 to 13; preparation of latex (L-13) comprising Polymer particles (A)

A latex (L-13) was obtained in the same manner as in production examples 2 to 8, except that 10.2 parts by weight of Methyl Methacrylate (MMA), 1.0 part by weight of n-Butyl Acrylate (BA), and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as the grafting monomer in production examples 2 to 8. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-13) was 130nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-13) was 30% by weight relative to 100% by weight of the latex (L-13). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion.

Preparation examples 2 to 14; preparation of latex (L-14) comprising Polymer particles (A)

A latex (L-14) was obtained in the same manner as in production examples 2 to 8, except that 2.2 parts by weight of Methyl Methacrylate (MMA), 9.0 parts by weight of n-Butyl Acrylate (BA), and 1.8 parts by weight of Glycidyl Methacrylate (GMA) were used as the grafting monomer in production examples 2 to 8. The polymerization conversion of the monomer component is 96% by weight or more. The volume average particle diameter of the polymer particles (A) contained in the obtained latex (L-14) was 130nm. The concentration of the solid content (concentration of the polymer particles (A)) in the obtained latex (L-14) was 30% by weight relative to 100% by weight of the latex (L-14). The graft portion of the polymer particle (a) contained 14% by weight of the structural unit having an epoxy group in 100% by weight of the graft portion.

In all the above polymer particles (A), the elastomer/graft weight ratio of the polymer particles (A) was 87/13.

Example 1

After the temperature in the mixing tank of the 1L mixing tank was set to 30 ℃, 126 parts by weight of Methyl Ethyl Ketone (MEK) was charged into the mixing tank. Then, 143 parts by weight of latex (L-1) of polymer particles (A) was charged into the mixing tank while stirring MEK in the mixing tank. After the charged materials were uniformly mixed, 200 parts by weight (total 452 parts by weight) of water was charged into the mixing tank at a feed rate of 80 parts by weight/min while stirring. After the end of the water supply, the stirring was stopped rapidly, and as a result, a slurry containing a floatable aggregate was obtained.

Next, the aggregate remained in the mixing tank, and 350 parts by weight of the liquid phase was discharged from a discharge port in the lower part of the mixing tank. To the obtained aggregate (doped polymer particles (a)) was added MEK 150 parts by weight and mixed, to obtain an organic solvent solution in which polymer particles (a) were dispersed. To 277 parts by weight of the organic solvent solution (containing 42.9 parts by weight of polymer particles (a)) was charged 64 parts by weight of a liquid epoxy resin (JER 828, mitsubishi chemical Co., ltd.) as a matrix resin (B), and the resultant mixture was mixed, and MEK was distilled off under reduced pressure to obtain a resin composition (a-1). When the total of the polymer particles (a) and the matrix resin (B) is 100 wt%, the resin composition (a-1) contains 40 wt% of the polymer particles (a) and 60 wt% of the matrix resin (B).

Further, 25g of the resin composition (A-1), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (manufactured by Dragon chemical corporation, CMC-12S) as an inorganic filler were mixed using a rotation and revolution mixer to obtain a silica mixture (resin composition). The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Example 2

A resin composition (A-2) was obtained in the same manner as in example 1, except that the latex (L-2) was used as the latex of the polymer particles (A). When the total of the polymer particles (a) and the matrix resin (B) is 100 wt%, the resin composition (a-2) contains 40 wt% of the polymer particles (a) and 60 wt% of the matrix resin (B).

Further, 25g of the resin composition (A-2), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (manufactured by Dragon chemical corporation, CMC-12S) as an inorganic filler were mixed using a rotation and revolution mixer to obtain a silica mixture (resin composition). The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Example 3

A resin composition (A-3) was obtained in the same manner as in example 1, except that the latex (L-3) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-3) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-3), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (manufactured by Dragon chemical corporation, CMC-12S) as an inorganic filler were mixed using a rotation and revolution mixer to obtain a silica mixture (resin composition). The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Example 4

A resin composition (A-4) was obtained in the same manner as in example 1, except that the latex (L-4) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-4) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-4), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (manufactured by Dragon chemical corporation, CMC-12S) as an inorganic filler were mixed using a rotation and revolution mixer to obtain a silica mixture (resin composition). The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Example 5

A resin composition (A-5) was obtained in the same manner as in example 1, except that latex (L-5) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-5) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-5), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (manufactured by Dragon chemical corporation, CMC-12S) as an inorganic filler were mixed using a rotation and revolution mixer to obtain a silica mixture (resin composition). The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Example 6

A resin composition (A-6) was obtained in the same manner as in example 1, except that the latex (L-6) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-6) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-6), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (manufactured by Dragon chemical corporation, CMC-12S) as an inorganic filler were mixed using a rotation and revolution mixer to obtain a silica mixture (resin composition). The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Example 7

A resin composition (A-7) was obtained in the same manner as in example 1, except that the latex (L-7) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-7) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-7), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (manufactured by Dragon chemical corporation, CMC-12S) as an inorganic filler were mixed using a rotation and revolution mixer to obtain a silica mixture (resin composition). The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Example 8

A resin composition (A-8) was obtained in the same manner as in example 1, except that latex (L-8) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-8) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-8), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (manufactured by Dragon chemical corporation, CMC-12S) as an inorganic filler were mixed using a rotation and revolution mixer to obtain a silica mixture (resin composition). The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Comparative example 1

A resin composition (A-9) was obtained in the same manner as in example 1, except that latex (L-9) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-9) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-9), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (manufactured by Dragon chemical corporation, CMC-12S) as an inorganic filler were mixed using a rotation/revolution mixer to obtain a silica mixture. The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Comparative example 2

A resin composition (A-10) was obtained in the same manner as in example 1, except that latex (L-10) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-10) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-10), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (CMC-12S, manufactured by Dragon chemical corporation) as an inorganic filler were mixed using a rotation/revolution mixer to obtain a silica mixture. The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Comparative example 3

A resin composition (A-11) was obtained in the same manner as in example 1, except that latex (L-11) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-11) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-11), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (CMC-12S, manufactured by Dragon chemical corporation) as an inorganic filler were mixed using a rotation/revolution mixer to obtain a silica mixture. The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Comparative example 4

A resin composition (A-12) was obtained in the same manner as in example 1, except that latex (L-12) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-12) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-12), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (CMC-12S, manufactured by Dragon chemical corporation) as an inorganic filler were mixed using a rotation/revolution mixer to obtain a silica mixture. The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Comparative example 5

A resin composition (A-13) was obtained in the same manner as in example 1, except that latex (L-13) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-13) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B).

Further, 25g of the resin composition (A-13), 85g of the liquid epoxy resin (Mitsubishi chemical corporation, JER 828) and 100g of silica (CMC-12S, manufactured by Dragon chemical corporation) as an inorganic filler were mixed using a rotation/revolution mixer to obtain a silica mixture. The weight ratio of the polymer particles (A) of the silica mixture to the matrix resin (B) to the inorganic filler is 10:100:100. The results are shown in table 1 below.

Comparative example 6

A resin composition (A-14) was obtained in the same manner as in example 1, except that latex (L-14) was used as the latex of the polymer particles (A). When the total of the polymer particles (A) and the matrix resin (B) is 100% by weight, the resin composition (A-14) contains 40% by weight of the polymer particles (A) and 60% by weight of the matrix resin (B). However, the resulting resin composition (A-14) gelled during degassing, and thus the viscosity at 50℃could not be measured.

The resin compositions (A-1) to (A-8) of examples 1 to 8 have a viscosity of 20000 mPas or less at 50 ℃. The resin compositions (A-1) to (A-8) of examples 1 to 8 had a viscosity of 230000 mPas or less at 25℃when the inorganic filler was added. In particular, the resin compositions (A-1) to (A-6) and (A-8) of examples 1 to 6 and 8 have a viscosity of 140000 mPas or less at 25℃when the inorganic filler is added.

Industrial applicability

The resin composition according to one embodiment of the present invention can be preferably used for adhesives, coating materials, binders for reinforcing fibers, composite materials, molding materials for 3D printers, sealants, electronic boards, ink binders, wood sheet binders, binders for rubber sheets, binders for foaming sheets, binders for castings, matrix consolidation materials for flooring materials and ceramics, polyurethane foams, and the like.

Claims

1. A resin composition comprising polymer particles (A) and a matrix resin (B),

the polymer particles (A) have a graft portion,

the graft portion is a polymer satisfying the following (i) to (iii),

(i) (i-a) does not contain a structural unit containing an aromatic group, or

(i-b) containing more than 0% by weight and 10% by weight or less of a structural unit containing an aromatic group in 100% by weight of the grafting portion;

the glass transition temperature of the grafting part is more than-25 ℃ and less than 18 ℃.

2. The resin composition according to claim 1, wherein,

3. A resin composition comprising polymer particles (A) and a matrix resin (B),

the polymer particles (A) have a graft portion,

(i) (i-a) does not contain a structural unit containing an aromatic group, or

4. The resin composition according to any one of claim 1 to 3, wherein,

the grafting portion does not contain a structural unit comprising an aromatic group.

5. The resin composition according to any one of claim 1 to 4, wherein,

6. The resin composition according to any one of claims 1 to 5, wherein,

in 100 wt% of the grafting portion, the grafting portion includes more than 0 wt% and 50 wt% or less of structural units having an epoxy group.

7. The resin composition according to any one of claims 1 to 6, wherein,

of the 100 wt% of the graft portion, the graft portion contains 20 wt% or more of a structural unit derived from a monomer providing a homopolymer having a glass transition temperature of 0 ℃ or lower.

8. The resin composition according to any one of claims 1 to 7, which has a viscosity of 20000 mPa-s or less at 50 ℃.

9. The resin composition according to any one of claims 1 to 8, wherein,

when the total of the polymer particles (A) and the matrix resin (B) is 100 wt%, the polymer particles (A) are 40 wt% or more and 50 wt% or less,

The viscosity of the resin composition is 20000 mPas or less at 50 ℃.

10. The resin composition according to any one of claims 1 to 9, further comprising an inorganic filler material.

11. The resin composition according to any one of claims 1 to 10, wherein,

the matrix resin (B) is an epoxy resin.