CN113330044B - Powder and granule and use thereof - Google Patents

Powder and granule and use thereof Download PDF

Info

Publication number
CN113330044B
CN113330044B CN202080010125.6A CN202080010125A CN113330044B CN 113330044 B CN113330044 B CN 113330044B CN 202080010125 A CN202080010125 A CN 202080010125A CN 113330044 B CN113330044 B CN 113330044B
Authority
CN
China
Prior art keywords
resin
powder
fine particles
polymer
elastomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202080010125.6A
Other languages
Chinese (zh)
Other versions
CN113330044A (en
Inventor
舞鹤展祥
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaneka Corp
Original Assignee
Kaneka Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kaneka Corp filed Critical Kaneka Corp
Publication of CN113330044A publication Critical patent/CN113330044A/en
Application granted granted Critical
Publication of CN113330044B publication Critical patent/CN113330044B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a powder or granule comprising a polymer fine particle (A) having a grafting portion composed of a polymer having as a structural unit selected from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer and a (meth) acrylate monomer, and having a halogen element content of 500ppm or less.

Description

Powder and granule and use thereof
Technical Field
The present invention relates to a powder and granule and use thereof.
Background
In order to improve impact resistance of thermoplastic resins and thermosetting resins, a method of adding an elastomer, particularly crosslinked polymer fine particles, to a resin is widely used (patent documents 1 and 2).
Prior art literature
Patent literature
Patent document 1 Japanese patent laid-open publication No. 2001-278927 "
Patent document 2 Japanese laid-open patent publication No. 2010-001346 "
Disclosure of Invention
The present inventors have found that rust is generated when a resin composition containing the polymer fine particles is applied to a metal plate or the like. There are various causes of rust generation, and there is an urgent need for improvement in research on the causes and countermeasures thereof, because the causes affect the durability of metal plates and the like.
An embodiment of the present invention has been made in view of the above-described problems, and an object of the present invention is to provide a novel powder or granule which can suppress the occurrence of rust when applied to a metal plate or the like, and a technique for applying the same.
The present inventors have conducted intensive studies to solve the above problems, and as a result, they have found that halogen elements contained in polymer fine particles (powder particles) mixed in a resin composition are causative of rust generation, and have completed the present invention.
That is, an embodiment of the present invention includes the following configuration.
(1) A method for producing a powder or granule, comprising the steps of:
a step of adding a coagulant having a halogen element content of 500ppm or less to an aqueous latex containing polymer microparticles (A) and coagulating the aqueous latex; and
a step of mixing the polymer fine particles (A) with a resin (B) having a halogen element content of 500ppm or less;
the polymer particles (A) contain a rubber-containing graft copolymer having an elastomer and a graft unit graft-bonded to the elastomer,
the elastomer contains at least one selected from diene rubber, (meth) acrylate rubber and organosiloxane rubber,
the grafting portion includes a polymer containing, as a constituent unit, a constituent unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer and a (meth) acrylate monomer,
The resin (B) is a liquid, semi-solid or solid having a viscosity of 100 mPas to 1000000 mPas at 25 ℃,
when the total of the polymer fine particles (a) and the resin (B) is 100 wt%, the polymer fine particles (a) are 50 to 99 wt% and the resin (B) is 1 to 50 wt%.
(2) A powder comprising polymer particles (A) and a resin (B), wherein the polymer particles (A) comprise a rubber-containing graft copolymer having an elastomer and a graft unit grafted and bonded to the elastomer,
the elastomer contains at least one selected from diene rubber, (meth) acrylate rubber and organosiloxane rubber,
the grafting portion comprises a polymer containing, as a constituent unit, a structural unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer and a (meth) acrylate monomer,
the content of halogen element is below 500ppm,
the resin (B) is a liquid, semi-solid or solid having a viscosity of 100 mPas to 1000000 mPas at 25 ℃,
when the total of the polymer fine particles (a) and the resin (B) is 100 wt%, the polymer fine particles (a) are 50 to 99 wt% and the resin (B) is 1 to 50 wt%.
Effects of the invention
According to the powder or granular material according to an embodiment of the present invention, the powder or granular material can be added to a resin composition to suppress the occurrence of rust when applied to a metal plate or the like.
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 are possible within the scope of 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 the respective embodiments, new technical features can be formed. The academic literature and patent literature described in the present specification are all incorporated by reference in the present specification. Unless otherwise specified in the present specification, "a to B" representing a numerical range means "a or more (including a and being larger than a) and B or less (including B and being smaller than B)".
[ 1. Powder particle ]
The powder or granule according to an embodiment of the present invention is a powder or granule comprising a polymer fine particle (a) and a resin (B), wherein the polymer fine particle (a) comprises a rubber-containing graft copolymer having an elastomer and a graft unit bonded to the elastomer, the elastomer comprises at least one selected from a diene rubber, (meth) acrylate rubber and an organosiloxane rubber, the graft unit comprises a polymer containing a constituent unit derived from at least one monomer selected from an aromatic vinyl monomer, a vinyl cyano monomer and a (meth) acrylate monomer as a constituent unit, the resin (B) is a liquid, semi-solid or solid having a viscosity of 100mpa·s to 1000000mpa·s at 25 ℃, and the polymer fine particle (a) may be 50 to 99 wt% and the resin (B) may be 1 to 50 wt% when the total of the polymer fine particle (a) and the resin (B) is 100 wt%. Hereinafter, the powder or granule according to an embodiment of the present invention will be simply referred to as the present powder or granule. The powder particles are dispersed in a base resin (C) described later to form a resin composition.
In the present specification, the term "powder or granule" includes both powder and granule, and refers to an aggregate of powder, granule, and the like. In particular, the term "powder" means a volume average particle diameter of 0.01 to 0.1mm, and the term "pellet" means a volume average particle diameter of 0.1 to 10mm. Wherein the powder particles may contain 10mm or more as coarse particles. The "volume average particle diameter" in the range of less than 10 μm can be measured by using a Dynamic Light Scattering (DLS) particle size distribution measuring apparatus Nanotrac wave II-EX150 (manufactured by MicroTrack Bell Co., ltd.) and the "volume average particle diameter" in the range of 10 μm or more can be measured by using a laser diffraction particle size distribution measuring apparatus MicroTrack MT3000II (manufactured by MicroTrack Bell Co., ltd.).
The halogen element may be any element of group 17 of the periodic table such as fluorine, chlorine, bromine, iodine, astatine, and the content of chlorine or bromine is preferably a predetermined amount or less.
The halogen element content is preferably 500ppm or less, more preferably 400ppm or less, still more preferably 200ppm or less, particularly preferably 100ppm or less, and most preferably 50ppm or less. And, it is preferably 30ppm or less, more preferably 10ppm or less, further preferably 5ppm or less, particularly preferably 1ppm or less, and most preferably n.d. "n.d." means not detected, and may also be referred to as below the detection limit.
In addition, for the polymer fine particles (a), resin (B), monomer components of these materials, and other materials (e.g., antiblocking agent) used for polymerization, which will be described later, it is preferable to use a material having a small halogen element content in order to prevent the mixing of halogen elements. The preferred halogen element content of these raw materials is the same as the above numerical range.
The present inventors have found that halogen elements contained in powder particles mixed with a resin composition are responsible for rust generation. The powder particles have the above-described constitution, and therefore, even when the powder particles are mixed with a resin composition and applied to a metal plate or the like, the occurrence of rust can be suppressed.
In addition, in order to improve toughness of an epoxy glass substrate for an electronic substrate, a means of adding an elastomer is sometimes used. When the present powder or granule is used as an elastomer, excellent insulation reliability can be achieved when an electronic substrate is formed by mixing the powder or granule with a matrix resin by setting the content of halogen element, particularly chlorine, in the powder or granule to the above-described configuration. Specifically, ion migration is one of causes of insulation failure due to long-term use of an electronic substrate. When the amount of halogen element in the pellet is small, the generation of ion migration can be suppressed, and the generation of dendrite growth can be prevented. As a result, when the resin composition containing the powder or granule is formed into an electronic substrate, excellent insulation reliability can be achieved even when used for a long period of time.
(1-1. Polymer particles (A))
The polymer fine particles (A) have at least a grafting portion composed of a polymer containing, as a structural unit, a structural unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer and a (meth) acrylate monomer. The polymer particles (A) may also be referred to as graft copolymers.
(1-1-1. Grafting portion)
In the present specification, a polymer obtained by graft-polymerizing an arbitrary polymer is referred to as a graft portion. The graft portion is a polymer containing a structural unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer, and a (meth) acrylate monomer as a structural unit. The grafting portion has the above-described structure, and thus can serve various functions. The "various functions" mean, for example, (a) improving the compatibility of the polymer fine particles (a) with the thermosetting resin or the thermoplastic resin, (b) improving the dispersibility of the polymer fine particles (a) of the thermosetting resin or the thermoplastic resin as the matrix resin to be mixed, and (c) dispersing the polymer fine particles (a) in the form of primary particles in the resin composition or the cured product or molded article thereof.
Specific examples of the aromatic vinyl monomer include styrene, α -methylstyrene, p-methylstyrene, divinylbenzene, and the like.
Specific examples of the vinylcyano monomer include acrylonitrile and methacrylonitrile.
Specific examples of the (meth) acrylic acid ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, and hydroxybutyl (meth) acrylate. In the present specification, (meth) acrylate means acrylate and/or methacrylate.
The above-mentioned one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyano monomers and (meth) acrylate monomers may be used alone or in combination of two or more.
The total of the structural units derived from the aromatic vinyl monomer, the structural units derived from the vinyl cyano monomer, and the structural units derived from the (meth) acrylic acid ester monomer in the graft portion is preferably 10 to 95% by weight, more preferably 30 to 92% by weight, further 50 to 90% by weight, particularly preferably 60 to 87% by weight, and most preferably 70 to 85% by weight, based on 100% by weight of the total structural units.
In the grafting portion, a structural unit derived from a monomer having a reactive group is preferably contained as a structural unit. The reactive group-containing monomer is preferably selected from the group consisting of epoxy, oxetanyl, hydroxy, amino, imino, carboxylic acid, carboxylic anhydride, cyclic ester, cyclic amide, and benzo The monomer having one or more reactive groups selected from the group consisting of an epoxy group, a hydroxyl group and a carboxylic acid group is more preferable. According to the above constitution, the grafting portion of the polymer fine particles (a) can be chemically bonded to the thermosetting resin or the thermoplastic resin in the resin composition. Thus, the polymer fine particles (a) can be maintained in a well dispersed state in the resin composition, or in the cured product or molded article thereof without agglomerating the polymer fine particles (a).
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.
Specific examples of the monomer having a hydroxyl group include hydroxy linear alkyl (meth) acrylates (particularly hydroxy linear C1-6 alkyl (meth) acrylates) such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; caprolactone-modified hydroxy (meth) acrylates; hydroxy branched alkyl (meth) acrylates such as methyl alpha- (hydroxymethyl) acrylate and ethyl alpha- (hydroxymethyl) acrylate; hydroxyl group-containing (meth) acrylates such as mono (meth) acrylates of polyester diols (particularly saturated polyester diols) obtained from dicarboxylic acids (phthalic acid, etc.) and diols (propylene glycol, etc.), and the like.
Specific examples of the monomer having a carboxylic acid group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and dicarboxylic acids such as ethylmaleic acid, fumaric acid and itaconic acid. As the monomer having a carboxylic acid group, the above monocarboxylic acid may be preferably used.
The reactive group-containing monomer may be used alone or in combination of two or more.
The grafting unit preferably contains 0.5 to 90 wt%, more preferably 1 to 50 wt%, still more preferably 2 to 35 wt%, and particularly preferably 3 to 20 wt% of the structural unit derived from the reactive group-containing monomer in 100 wt% of the grafting unit. The graft portion provides a cured product or a molded article having sufficient impact resistance when the structural unit derived from the reactive group-containing monomer is contained in the graft portion in an amount of not less than 0.5% by weight, and the resin composition containing the obtained powder or granule provides a cured product or a molded article having sufficient impact resistance when the structural unit is contained in the graft portion in an amount of not more than 90% by weight, and has the advantage that the resin composition has good storage stability.
The structural unit derived from the reactive group-containing monomer is preferably contained in the graft portion, more preferably contained only in the graft portion.
The grafting unit may contain a structural unit derived from a polyfunctional monomer as a structural unit. In the case of containing a structural unit in which the grafting portion is derived from a polyfunctional monomer, there are advantages such as: the resin composition (a) can prevent swelling of the polymer fine particles (a), (b) has a tendency to improve the handleability of the resin composition due to a low viscosity of the resin composition, and (c) has an improved dispersibility of the polymer fine particles (a) of the thermosetting resin or the thermoplastic resin.
When the graft portion does not contain a structural unit derived from a polyfunctional monomer, the resin composition containing the obtained powder or granule can provide a cured product or molded article excellent in toughness and impact resistance, as compared with the case where the graft portion contains a structural unit derived from a polyfunctional monomer.
The polyfunctional monomer may be also referred to as a monomer having 2 or more reactive groups having radical polymerization property in the same molecule. The radical polymerizable reactive group is preferably a carbon-carbon double bond. Examples of the polyfunctional monomer include (meth) acrylates having an ethylenically unsaturated double bond such as allyl alkyl (meth) acrylates and allyloxyalkyl (meth) acrylates excluding butadiene. Examples of the monomer having 2 (meth) acrylic groups include ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, butane diol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexane dimethanol 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. Examples of the monomer having 3 (meth) acrylate groups include alkoxyl ester trimethylolpropane tri (meth) acrylate, glycerol propoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate. Examples of the alkoxyl ester trimethylolpropane tri (meth) acrylate include trimethylolpropane tri (meth) acrylate and trimethylolpropane triethoxy tri (meth) acrylate. Examples of the monomer having 4 (meth) acrylic groups include pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate. Further, dipentaerythritol penta (meth) acrylate and the like are exemplified as the monomer having 5 (meth) acrylic groups. Further, as the monomer having 6 (meth) acrylic groups, ditrimethylolpropane hexa (meth) acrylate and the like can be exemplified. Examples of the polyfunctional monomer include diallyl phthalate, triallyl isocyanurate, and divinylbenzene.
Among the above-mentioned polyfunctional monomers, preferable polyfunctional monomers for polymerization of the graft portion include allyl methacrylate, ethylene glycol di (meth) acrylate, butane diol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. These polyfunctional monomers may be used alone or in combination of two or more.
The graft portion 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 portion.
In the polymerization of the graft portion, only one kind of the above monomer may be used, or two or more kinds may be used in combination.
The grafting portion may contain, as a structural unit, a structural unit derived from another monomer in addition to the structural unit derived from the above-mentioned monomer.
The graft portion is preferably a polymer graft-bonded to an elastomer described later.
(glass transition temperature of grafting portion)
The glass transition temperature of the grafting portion is preferably 190 ℃ or less, more preferably 160 ℃ or less, more preferably 140 ℃ or less, more preferably 120 ℃ or less, more preferably 80 ℃ or less, more preferably 70 ℃ or less, more preferably 60 ℃ or less, more preferably 50 ℃ or less, more preferably 40 ℃ or less, more preferably 30 ℃ or less, more preferably 20 ℃ or less, more preferably 10 ℃ or less, more preferably 0 ℃ or less, more preferably-20 ℃ or less, more preferably-40 ℃ or less, more preferably-45 ℃ or less, more preferably-50 ℃ or less, more preferably-55 ℃ or less, more preferably-60 ℃ or less, more preferably-65 ℃ or less, more preferably-70 ℃ or less, more preferably-75 ℃ or less, more preferably-80 ℃ or less, more preferably-85 ℃ or less, more preferably-90 ℃ or less, more preferably-95 ℃ or less, more preferably-100 ℃ or less, more preferably-105 ℃ or less, more preferably-115 ℃.
The glass transition temperature of the grafting portion is preferably 0℃or higher, more preferably 30℃or higher, more preferably 50℃or higher, more preferably 70℃or higher, further preferably 90℃or higher, particularly preferably 110℃or lower.
The Tg of the graft portion may be determined according to 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 the production (polymerization) of the graft.
Tg of the graft portion can be obtained by performing viscoelasticity measurement using a flat plate composed of polymer microparticles. Specifically, tg can be determined as follows: (1) A graph of tan δ was obtained by measuring dynamic viscoelasticity of a flat plate composed of polymer microparticles using a dynamic viscoelasticity measuring device (for example, DVA-200, manufactured by IT measurement and control corporation) under stretching conditions; (2) For the obtained graph of tan δ, the peak temperature of tan δ was set as the glass transition temperature. Here, in the tan δ graph, when a plurality of peaks are obtained, the highest peak temperature is set as the glass transition temperature of the grafting portion.
(grafting ratio of grafting portion)
In one embodiment of the present invention, the polymer fine particles (a) are polymers having the same constitution as the graft portion, and may have polymers not graft-bonded to the above-mentioned elastomer. In the present specification, a polymer having the same constitution as the graft portion, and a polymer which is not graft-bonded to an elastomer is referred to as a non-graft polymer. The non-grafted polymer corresponds to a non-polymer (FP) described later. The above non-grafted polymer may be referred to as a polymer having no graft bond with respect to the above elastomer among polymers produced by polymerization of the graft portion.
In the present specification, the ratio of the graft portion, which is a polymer graft-bonded to the above-mentioned elastomer, among the polymers produced in the polymerization of the graft portion is referred to as a grafting ratio. The grafting ratio is also referred to as a value represented by (weight of grafted portion)/(weight of grafted portion) + (weight of non-grafted polymer) } ×100.
The grafting ratio of the grafting portion is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. When the grafting ratio is 80% or more, there is an advantage in that the viscosity of the resin composition becomes excessively high.
In the present specification, the method for calculating the grafting ratio is as follows. First, an aqueous latex containing the polymer fine particles (a) is obtained, and then, a powder of the polymer fine particles (a) is obtained from the aqueous latex. Specifically, the method for obtaining the powder of the polymer fine particles (a) from the aqueous latex includes (i) a method for coagulating the polymer fine particles (a) in the aqueous latex, (ii) a method for dehydrating the obtained condensate, and (iii) a method for further drying the condensate to obtain the powder of the polymer fine particles (a). Then, 2g of the powder of the polymer fine particles (A) was dissolved in 50mL of Methyl Ethyl Ketone (MEK). Thereafter, the resulting MEK lysate was separated into a MEK-soluble fraction (MEK-soluble fraction) and a MEK-insoluble fraction (MEK-insoluble fraction). Specifically, the obtained MEK solution was subjected to centrifugal separation at 30000rpm for 1 hour using a centrifugal separator (CP 60E manufactured by hitachi machine corporation), and the solution was separated into a MEK-soluble fraction and a MEK-insoluble fraction. Here, the centrifugal separation operation was performed in 3 groups in total. Next, 20ml of the concentrated MEK-soluble portion was mixed with 200ml of methanol, and an aqueous solution of calcium chloride obtained by dissolving 0.01g of calcium chloride in water was added thereto and stirred for 1 hour. Thereafter, the mixture was separated into a methanol-soluble fraction and a methanol-insoluble fraction, and the amount of the methanol-insoluble fraction was taken as the amount of non-polymer (FP).
The grafting ratio was calculated using the following formula.
Grafting ratio (%) =100- [ (FP amount)/{ (FP amount) + (MEK insoluble fraction) })/(weight of polymer of grafted 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 fine 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 input amount of the monomer constituting the polymer of the graft portion. In addition, in the calculation of the grafting ratio, the method of condensing the polymer fine particles (a) is not particularly limited, and a method using a solvent, a method using a condensing agent, a method of spraying an aqueous latex, and the like can be used.
(modification of grafting portion)
In one embodiment of the invention, the grafting portion may be constituted by one grafting portion having only structural units of the same composition. In one embodiment of the invention, the grafting portion may be composed of a plurality of grafting portions having structural units of different compositions.
In one embodiment of the present invention, a case where the grafting portion is constituted by a plurality of grafting portions will be described. In this case, each of the plural kinds of grafting portions is defined as a grafting portion 1 Grafting portion 2 … grafting portions n (n is an integer of 2 or more). The grafting portions may comprise grafting portions polymerized separately 1 Grafting portion 2 … and grafting portion n Is a complex of (a) and (b). The grafting portion may comprise a grafting portion 1 Grafting portion 2 … and grafting portion n A polymer obtained by multistage polymerization. The polymer obtained by multistage polymerizing a plurality of grafting portions is also called multistage polymerized grafting portion. The method for producing the multistage polymerized graft portion is described below.
In the case where the grafting portion is constituted of plural kinds of grafting portions, these plural kinds of grafting portions may not be all graft-bonded to the elastomer. At least a part of at least one kind of graft portion may be graft-bonded to the elastomer, and other kinds (other kinds) of graft portions may be graft-bonded to the graft portion graft-bonded to the elastomer. In addition, in the case where the graft portion is constituted of plural kinds of graft portions, it is a polymer having the same constitution as that of plural kinds of graft portions, and may have plural kinds of polymers (plural kinds of non-graft polymers) which do not undergo graft bonding with the elastomer.
Graft portion 1 Grafting portion 2 … and grafting portion n The multistage polymerization graft portion is described. In the multistage polymerization graft, the graft n Can cover the grafting part n－1 Or can coat the graft portion n－1 Is a whole of (a). Graft polymerization in the multistageIn the part, the grafting part n Part of (2) may also enter the grafting portion n－1 Is provided on the inner side of (a).
In the multistage polymeric graft, a plurality of grafts may have a layered structure. For example, in multistage polymeric grafts by grafts 1 Grafting portion 2 Grafting portion 3 In the case of the constitution, the grafting part 1 Is set as the innermost layer of the grafting part, at the grafting part 1 Is provided with a grafting part outside 2 Further in the graft portion 2 Outside of the layer, graft 3 The manner in which the layers of (a) are present as the outermost layers is also a manner of the present invention. Thus, a multistage polymerized graft having a layer structure of a plurality of grafts, respectively, may be referred to as a multilayer graft. That is, in one embodiment of the present invention, the grafting portion may comprise a mixture of multiple grafting portions, a multi-stage polymeric grafting portion, and/or a multi-layer grafting portion.
In the case where the elastomer and the graft portion are polymerized in this order in the production of the polymer fine particles (a), at least a part of the graft portion may coat at least a part of the elastomer in the obtained polymer fine particles (a). In other words, sequential polymerization of the elastomer and the graft portion may also be referred to as the elastomer and the graft portion being multistage polymerized. The polymer fine particles (a) obtained by multistage polymerization of the elastomer and the graft portion may also be referred to as multistage polymers.
In the case where the polymer fine particles (a) are multistage polymers, the grafting portion may cover at least a part of the elastomer, or may cover the whole of the elastomer. In the case where the polymer fine particles (a) are multistage polymers, a part of the graft portion may enter the inside of the elastomer.
In the case where the polymer fine particles (a) are multistage polymers, the elastomer and the graft portion may have a layer structure. For example, the mode in which the elastomer is the innermost layer (also referred to as a core layer) and the layer of the grafting portion is present as the outermost layer (also referred to as a shell layer) on the outer side of the elastomer is one mode of the present invention. The structure in which the elastomer is a core layer and the graft portion is a shell layer may be also referred to as a core-shell structure. Thus, the polymer particles (a) in which the elastomer and the graft portion have a layer structure (core-shell structure) may also be referred to as a multilayer polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer fine particles (a) may be a multistage polymer, and/or may also be a multilayer polymer or a core-shell polymer. The polymer fine particles (a) are not limited to the above-described structure, as long as the graft portion is graft-bonded to the elastomer.
At least a portion of the grafting portion preferably coats 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 fine particles (a).
(1-1-2. Elastomer)
The polymer fine particles (a) preferably further have an elastomer. That is, the polymer fine 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 with reference to the case where the polymer fine particles (a) are rubber-containing graft copolymers.
The elastomer preferably contains at least one selected from diene rubber, (meth) acrylate rubber and silicone rubber elastomers. The elastomer may also be referred to as rubber particles.
The case where the polymer fine particles (a) contain a diene rubber (case a) will be described. In the case of the case a, when the elastomer contains a diene rubber, the resin composition containing the obtained powder or granule can provide a cured product or molded article excellent in toughness and impact resistance.
The diene rubber is an elastomer containing a structural unit derived from a diene monomer as a structural unit. The diene monomer may be referred to as a conjugated diene monomer. In the case of the diene rubber, the diene rubber may contain 50 to 100% by weight of the structural unit derived from the diene monomer and 0 to 50% by weight of the structural unit derived from a vinyl monomer other than the diene monomer which is copolymerizable with the diene monomer, based on 100% by weight of the structural unit. In the case a, the diene rubber may contain a structural unit derived from a (meth) acrylic acid ester monomer as a structural unit in a smaller amount than a structural unit derived from a diene monomer.
Examples of the diene monomer include 1, 3-butadiene, isoprene, 2-chloro-1, 3-butadiene, and 2-methyl-1, 3-butadiene. These diene monomers may be used alone or in combination of two or more.
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, and dichlorostyrene; vinyl carboxylic acids such as acrylic acid and methacrylic acid; vinyl cyano groups such as acrylonitrile and methacrylonitrile; halogenated vinyl groups such as chlorinated vinyl groups, brominated vinyl groups, and chloroprene groups; vinyl acetate; olefins such as ethylene, propylene, butene, and isobutene; and polyfunctional monomers such as diallyl phthalate, triallyl isocyanurate and divinylbenzene. The vinyl monomers other than the diene monomers may be used alone or in combination of two or more. Among the vinyl monomers other than the diene monomers, styrene is particularly preferable. In the diene rubber of the case a, the structural unit derived from a vinyl monomer other than the diene monomer is an arbitrary component. In case a, the diene rubber may be composed of only structural units derived from a diene monomer.
In the case a, the diene rubber is preferably butadiene rubber (also referred to as polybutadiene rubber) composed 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. With the above configuration, the desired effect obtained by the polymer fine particles (a) containing the diene rubber can be further exhibited. Further, butadiene-styrene rubber is more preferable in that the transparency of the obtained cured product or molded article can be improved by adjusting the refractive index.
The case where the elastomer contains a (meth) acrylate rubber (case B) will be described. In case B, a wide range of polymer designs for the elastomer can be made by combining multiple 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 B, the (meth) acrylate rubber may contain 50 to 100% by weight of the structural unit derived from the (meth) acrylate monomer and 0 to 50% by weight of the structural unit derived from a vinyl monomer other than the (meth) acrylate monomer copolymerizable with the (meth) acrylate monomer, based on 100% by weight of the structural unit. In the case B, the (meth) acrylate rubber may contain a structural unit derived from a diene monomer as a structural unit in a smaller amount than a structural unit derived from a (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 alkyl (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) acrylate monomers may be used alone or in combination of two or more. Among these (meth) acrylic acid ester monomers, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferable, and butyl (meth) acrylate is more preferable.
Examples of the vinyl monomers other than the (meth) acrylic acid ester monomers (hereinafter also referred to as vinyl monomers other than the (meth) acrylic acid ester monomers) copolymerizable with the (meth) acrylic acid ester monomers include the monomers listed in the vinyl monomers a. The vinyl monomers other than the (meth) acrylic acid ester monomers may be used alone or in combination of two or more. Among vinyl monomers other than the (meth) acrylic acid ester monomers, styrene is particularly preferred. In the (meth) acrylate rubber of the case B, the structural unit derived from a vinyl monomer other than the (meth) acrylate monomer is an arbitrary component. In case B, the (meth) acrylate rubber may be composed of only structural units derived from the (meth) acrylate monomer.
The case where the elastomer contains a silicone rubber-based elastomer (case C) will be described. In case C, the resin composition containing the obtained powder or granule can provide a cured product or molded article having sufficient heat resistance and excellent impact resistance at low temperatures.
Examples of the silicone rubber-based elastomer include (a) a silicone-based polymer comprising an alkyl or aryl disubstituted silyloxy unit such as dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, dimethylsilyloxy-diphenylsilyloxy, and the like, and (b) a silicone-based polymer comprising an alkyl or aryl monosubstituted silyloxy unit such as organohydrogensilyloxy in which a part of the alkyl group of the side chain is substituted with a hydrogen atom. These polysiloxane-based polymers may be used alone or in combination of two or more. Among these polysiloxane polymers, (a) is preferably a polymer composed of dimethylsilyloxy units, methylphenyloxy units and/or dimethylsilyloxy-diphenylsilyloxy units because a cured product or molded article excellent in heat resistance of a resin composition containing the obtained powder or granule can be provided, and (b) is most preferably a polymer composed of dimethylsilyloxy units because it is easily available and economically advantageous.
In the case of C, the polymer fine particles (a) preferably contain 80 wt% or more, more preferably 90 wt% or more of the silicone rubber-based elastomer in 100 wt% of the elastomer contained in the polymer fine particles (a). According to the above constitution, the resin composition containing the obtained powder or granule can provide a cured product or molded article excellent in heat resistance.
The elastomer may further contain an elastomer other than diene rubber, (meth) acrylate rubber and silicone rubber elastomer. Examples of the elastomer other than the diene rubber, (meth) acrylate rubber and silicone rubber elastomer include natural rubber.
(crosslinked Structure of elastomer)
From the viewpoint of maintaining dispersion stability in the thermosetting resin or thermoplastic resin of the polymer fine particles (a), it is preferable to introduce a crosslinked structure into the elastomer. As a method for introducing a crosslinked structure into an elastomer, a method generally used can be used, and examples thereof include the following methods. Specifically, in the production of an elastomer, a method of mixing a crosslinkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound with a monomer capable of constituting an elastomer, and then polymerizing the mixture is exemplified. In this specification, a polymer such as a production elastomer is referred to as a polymer.
In addition, as a method for introducing a crosslinked structure into a silicone rubber-based elastomer, the following method can be mentioned: a method in which (a) a polyfunctional alkoxysilane compound is used together with other materials in the polymerization of the silicone rubber elastomer, (b) a method in which a reactive group such as a vinyl group reactive group or a mercapto group is introduced into the silicone rubber elastomer, and then a vinyl polymerizable monomer or an organic peroxide is added to react with the reactive group, or (c) a method in which a crosslinkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound is mixed together with other materials and then polymerized in the polymerization of the silicone rubber elastomer.
Examples of the polyfunctional monomer include the polyfunctional monomer exemplified in the item (1-1-1. Grafting portion) above.
Examples of the thiol-group-containing compound include alkyl-substituted thiol, allyl-substituted thiol, aryl-substituted thiol, hydroxy-substituted thiol, alkoxy-substituted thiol, amino-substituted thiol, silyl-substituted thiol, acid-substituted thiol, halogen-substituted thiol, and acyl-substituted thiol. 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, more preferably-120 ℃ or lower, particularly preferably-125 ℃ or lower. In this specification, the "glass transition temperature" may be referred to as "Tg". According to this constitution, a powder having a low Tg can be obtained. As a result, the resin composition containing the obtained powder particles can provide a cured product or molded article having excellent toughness. The Tg of an elastomer can be obtained by using a planar plate composed of an elastomer and performing viscoelasticity measurement. Specifically, tg can be determined as follows: (1) A graph of tan δ was obtained by performing dynamic viscoelasticity measurement under stretching conditions using a dynamic viscoelasticity measurement device (for example, DVA-200, manufactured by IT measurement and control co., ltd.) on a flat plate composed of polymer microparticles; (2) For the obtained graph of tan δ, the peak temperature of tan δ was set as the glass transition temperature. Here, in the graph 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, since the decrease in the elastic modulus (rigidity) of the obtained cured product or molded article can be suppressed, and 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 the elastomer may depend on the composition of the structural units contained in the elastomer, and the like. In other words, by varying the composition of the monomers used to make (polymerize) the elastomer, the Tg of the resulting elastomer can be adjusted.
Here, when a homopolymer in which only one monomer is polymerized is formed, a group of monomers providing a homopolymer having a Tg greater than 0 ℃ is set as the monomer group a. In addition, in forming a homopolymer obtained by polymerizing only one monomer, a group of monomers providing a homopolymer having a Tg of less than 0 ℃ is set as a monomer group b. An elastomer containing 50 to 100% by weight (more preferably 65 to 99% by weight) of a structural unit derived from at least one monomer selected from the monomer group a and 0 to 50% by weight (more preferably 1 to 35% by weight) of a structural unit derived from at least one monomer selected from the monomer group b is used as the elastomer X. In elastomer X, tg is greater than 0deg.C. In addition, when the elastomer includes the elastomer X, the resin composition including the obtained powder or granule can provide a cured product or molded article 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.
The monomer that can be contained in the monomer group a is not limited, 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; a cyclic oxyalkylated vinyl aromatic compound such as 4-methoxystyrene or 4-ethoxystyrene; cyclic halogenated vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; cyclic esters such as 4-ethoxystyrene substituted vinyl aromatic compounds; cyclic hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene; vinyl esters such as vinyl benzoate and vinyl cyclohexanoate; vinyl halides such as vinyl chloride; aromatic monomers such as naphthalene 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; a methacrylic monomer containing a methacrylic acid derivative such as methacrylonitrile; certain acrylates such as isobornyl acrylate and t-butyl acrylate; acrylic monomers including acrylic acid derivatives such as acrylonitrile, and the like. Examples of the monomer that can be contained in the monomer group a include monomers that form homopolymers such as acrylamide, isopropylacrylamide, N-vinylpyrrolidone, isobornyl methacrylate, dicyclopentyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1-adamantyl acrylate, and 1-adamantyl methacrylate, and that can provide homopolymers having a Tg of 120 ℃ or higher. These monomers a may be used alone or in combination of two or more.
Examples of the monomer b include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. These monomers b may be used alone or in combination of two or more. Among these monomers b, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
(volume average particle diameter of elastomer)
The volume average particle diameter of the elastomer is preferably 0.03 μm to 50.00. Mu.m, more preferably 0.05 μm to 10.00. Mu.m, still more preferably 0.08 μm to 2.00. Mu.m, still more preferably 0.10 μm to 1.00. Mu.m, still more preferably 0.10 μm to 0.80. Mu.m, particularly preferably 0.10 μm to 0.50. Mu.m. When the volume average particle diameter of the elastomer is (a) 0.03 μm or more, an elastomer having a desired volume average particle diameter can be stably obtained, and when it is (b) 50.00 μm or less, the heat resistance and impact resistance of the obtained cured product or molded article become good. The volume average particle diameter of the elastomer can be measured by using a dynamic light scattering particle diameter distribution measuring apparatus or the like using an aqueous latex 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 fine 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 whole polymer fine particles (a). When the proportion (a) of the elastomer is 40% by weight or more, the resin composition containing the obtained powder or granule can provide a cured product or molded article excellent in toughness and impact resistance, and when (b) is 97% by weight or less, the polymer fine particles (a) are not easily aggregated, and therefore the resin composition is not high in viscosity, and as a result, the resin composition containing the obtained powder or granule is excellent in handling.
(gel content of elastomer)
The elastomer may be swellable with respect to a suitable solvent, but is preferably substantially insoluble. The elastomer is preferably insoluble with respect to the thermosetting resin or thermoplastic resin 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, and particularly preferably 95% by weight or more. When the gel content of the elastomer is within the above range, the resin composition containing the obtained powder or granule can provide a cured product or molded article excellent in toughness.
The gel content calculation method in this specification is as follows. An aqueous emulsion containing the polymer fine particles (A) is first obtained, and then a powder of the polymer fine particles (A) is obtained from the aqueous emulsion. The method for obtaining the powder of the polymer fine particles (a) from the aqueous latex is not particularly limited, and examples thereof include (i) a method for obtaining the powder of the polymer fine particles (a) by agglomerating the polymer fine particles (a) in the aqueous latex, (ii) a method for dehydrating the obtained agglomerate, and (iii) a method for further drying the agglomerate. Next, 2.0g of the powder of the polymer fine particles (A) was dissolved in 50mL of Methyl Ethyl Ketone (MEK). Thereafter, the resulting MEK lysate was separated into a MEK-soluble fraction (MEK-soluble fraction) and a MEK-insoluble fraction (MEK-insoluble fraction). Specifically, the obtained MEK lysate was subjected to centrifugal separation at 30000rpm for 1 hour using a centrifugal separator (CP 60E manufactured by hitachi machine corporation), and the lysate was separated into a MEK-soluble fraction and a MEK-insoluble fraction. Here, the centrifugal separation operation was performed in 3 groups in total. The weights of the MEK-soluble fraction and MEK-insoluble fraction obtained were measured, and the gel content was calculated using the following formula.
Gel content (%) = (weight of methyl ethyl ketone insoluble portion)/{ (weight of methyl ethyl ketone insoluble portion) + (weight of methyl ethyl ketone soluble portion) } ×100.
(modification of elastomer)
In one embodiment of the present invention, the "elastomer" of the polymer fine particles (a) contains a structural unit derived from butadiene and a structural unit derived from one or more monomers copolymerizable with butadiene as structural units, and may be composed of only one elastomer having structural units of the same composition. In one embodiment of the present invention, the elastic body may be composed of a plurality of kinds of elastic bodies having different constituent structural units, respectively.
In one embodiment of the present invention, a case where the "elastomer" of the polymer fine particles (a) is composed of a plurality of elastomers will be described. In this case, a plurality of elastomersAre respectively set as elastic bodies 1 Elastic body 2 … and elastomer n . Here, n is an integer of 2 or more. The elastomer may comprise an elastomer to be polymerized separately 1 Elastic body 2 … and elastomer n The mixed mixture. The "elastomer" of the polymer particles (A) may comprise an elastomer 1 Elastic body 2 … and elastomer n And (3) a polymer obtained by polymerization in sequence. Thus, polymerizing a plurality of polymers (elastomers) in sequence, respectively, is referred to as multistage polymerization. The polymer obtained by multistage polymerization of a plurality of elastomers is also referred to as a multistage polymerized elastomer. The method for producing the multistage polymeric elastomer is described below.
Made of elastomer 1 Elastic body 2 …, elastomer n The multistage polymeric elastomer is described. In the multistage polymeric elastomer, the elastomer n Coated elastomer n－1 At least a portion of (a) or (b) may be coated with an elastomer n－1 Is a whole of (a). In the multistage polymeric elastomer, the elastomer n A part of (2) may also enter the elastomer n－1 Is provided on the inner side of (a).
In the multistage polymeric elastomer, the plurality of elastomers may have a layer structure. For example in multistage polymeric elastomers from elastomers 1 Elastic body 2 Elastomer 3 In the case of the constitution, the elastomer is 1 As the innermost layer, in an elastomer 1 Is provided with an elastomer outside 2 Further in an elastomer 2 Outside of the layer of (2), elastomer 3 The manner in which the layer of (a) is present as the outermost layer of the elastomer is one aspect of the present invention. Thus, a multi-stage polymeric elastomer in which a plurality of elastomers each have a layer structure may be referred to as a multi-layer elastomer. That is, in one embodiment of the present invention, the elastomer may comprise a mixture of multiple elastomers, a multi-stage polymeric elastomer, and/or a multi-layer elastomer.
(1-1-3. Surface crosslinked Polymer)
The polymer fine particles (a) preferably have a surface-crosslinked polymer in addition to the elastomer and the graft portion graft-bonded to the elastomer. According to the above constitution, (a) the blocking resistance agent can be improved in the production of the polymer fine particles (a), and (b) the polymer fine particles (a) of the thermosetting resin or the thermoplastic resin are more excellent in dispersibility. These reasons are not particularly limited, and can be estimated as follows: by coating at least a part of the elastomer with the surface-crosslinked polymer, the exposure of the elastomer portion of the polymer microparticles (a) is reduced, and as a result, the elastomers are less likely to adhere to each other, and the dispersibility of the polymer microparticles (a) is improved.
In the case where the polymer fine particles (a) have a surface cross-linked polymer, the following effects can be further obtained: (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 extent of the number of crosslinked structures of the elastomer as a whole.
The surface cross-linked polymer is composed of a polymer containing 30 to 100% by weight of structural units derived from a polyfunctional monomer and 0 to 70% by weight of structural units derived from another vinyl monomer as structural units, in total, 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, as polyfunctional monomers that can be preferably used in polymerization of the surface-crosslinked polymer, allyl methacrylate, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate (for example, 1, 3-butanediol dimethacrylate, etc.), butane diol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, and polyethylene glycol di (meth) acrylate can be cited. These polyfunctional monomers may be used alone or in combination of two or more.
The polymer fine 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 fine particles (a) may be a multistage polymer obtained by multistage polymerization of an elastomer, a surface cross-linked polymer and a graft portion in this order. In either of these embodiments, the surface cross-linked polymer may coat at least a portion of the elastomer.
Surface cross-linked polymers may also be considered as part of the elastomer. When the polymer fine 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 fine particles (a) contain a surface cross-linked polymer, the volume average particle diameter of the elastomer refers to the volume average particle diameter of the elastomer containing the surface cross-linked polymer.
The case (case D) where the polymer fine particles (a) are multistage polymers obtained by multistage polymerization of an elastomer, a surface cross-linked polymer and a graft portion in this order will be described. In case D, the surface cross-linked polymer may coat a part of the elastomer, or may coat the whole of the elastomer. In case D, a part of the surface cross-linked polymer may also enter the inside of the elastomer. In case D, the grafting portion may coat a part of the surface cross-linked polymer, or may coat the entirety of the surface cross-linked polymer. In case D, a part of the grafting portion may also enter the inside of the surface cross-linked polymer. In case D, the elastomer, the surface cross-linked polymer and the graft portion may have a layer structure. For example, the mode in which the elastomer is the innermost layer (core layer), the layer of the surface cross-linked polymer is present as the intermediate layer on the outer side of the elastomer, and the layer of the graft portion is present as the outermost layer (shell layer) on the outer side of the surface cross-linked polymer is one mode of the present invention.
(volume average particle diameter (Mv) of Polymer particles (A))
Since the volume average particle diameter (Mv) of the polymer fine particles (A) has a desired viscosity and a highly stable resin composition can be obtained, the volume average particle diameter (Mv) is preferably 0.03 μm to 50.00. Mu.m, more preferably 0.05 μm to 10.00. Mu.m, still more preferably 0.08 μm to 2.00. Mu.m, still more preferably 0.10 μm to 1.00. Mu.m, still more preferably 0.10 μm to 0.80. Mu.m, and particularly preferably 0.10 μm to 0.50. Mu.m. When the volume average particle diameter (Mv) of the polymer fine particles (a) is within the above range, there is also an advantage that the polymer fine particles (a) of the matrix resin have good dispersibility. In the present specification, the term "volume average particle diameter (Mv) of the polymer fine particles (a)" refers to the volume average particle diameter of the primary particles of the polymer fine particles (a), unless otherwise specified. The volume average particle diameter of the polymer fine particles (a) is measured using a dynamic light scattering type particle diameter distribution measuring apparatus or the like using an aqueous latex containing the polymer fine particles (a) as a sample. The volume average particle diameter of the polymer fine particles (A) is described in detail in the following examples. The volume average particle diameter of the polymer fine particles (a) can be measured by cutting the cured product of the resin composition, photographing the cut surface with an electron microscope or the like, and using the obtained photographed data (photographed image). The particle diameter of the elastomer and the particle diameter of the polymer fine particles of the graft portion may be the same.
The number distribution of the particle diameters of the polymer fine particles (a) in the thermosetting resin or the thermoplastic resin is preferably 0.5 to 1 times the half value width of the volume average particle diameter because a resin composition having a low viscosity and easy handling can be obtained.
(1-2. Process for producing Polymer particles (A))
The polymer fine particles (a) can be produced by polymerizing an arbitrary polymer, and then graft polymerizing a polymer constituting a graft portion with the polymer in the presence of the polymer. An example of a method for producing the polymer fine particles (a) will be described below, by way of example, in which the polymer fine particles (a) are produced by graft-polymerizing a polymer constituting a graft portion with respect to an elastomer in the presence of the elastomer after polymerizing the elastomer.
The polymer fine particles (A) can be produced by a known method, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, or the like. Specifically, the polymerization of the elastomer of the polymer fine particles (a), the polymerization of the grafting portion (graft polymerization), and the polymerization of the surface cross-linked polymer can be carried out by a known method such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. Among these, the aqueous latex of the polymer fine particles (a) which is easy to obtain, has a relatively easy composition design, is easy to be industrially produced, and can be preferably used in the production of the present resin composition is preferably emulsion polymerization as a production method of the polymer fine particles (a). Hereinafter, a method for producing the surface-crosslinked polymer, which is an optional structure of the elastomer and the graft portion contained in the polymer fine particles (a), will be described.
(method for producing elastomer)
The elastomer may contain at least one selected from the group consisting of 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.
Consider the case where the elastomer comprises a silicone rubber-based elastomer. 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 pair of elastic bodies is formed by a plurality of elastic bodies (such as elastic bodies 1 Elastic body 2 …, elastomer n ) The method for producing the elastomer in the case of the constitution will be described. In this case, the elastomer 1 Elastic body 2 …, elastomer n The polymerization can be performed by the above-described methods, respectively, and thereafter, by mixing, an elastomer having a plurality of elastomers can be produced. Alternatively, an elastomer 1 Elastic body 2 …, elastomer n The polymerization may be sequentially performed in multiple stages, or an elastomer having a plurality of elastomers may be produced.
The multistage polymerization of the elastomer is specifically described. For example (1) pair of elastomers 1 Polymerization is carried out to obtain the elastomer 1 The method comprises the steps of carrying out a first treatment on the surface of the (2) Next, in the elastomer 1 In the presence of (a) an elastomer 2 Polymerization is carried out to obtain 2-segment 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 In the presence of (C) an elastomer 3 Polymerization is carried out to obtain the 3-segment elastomer 1+2+3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The following is the same asAfter the sample is carried out, the elastic body 1+2+…+(n－1) In the presence of (C) n Polymerization is carried out to obtain the multistage polymerized 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 the polymer microparticle precursor comprising (a) an elastomer or (b) an elastomer and a surface cross-linked polymer is obtained as an aqueous latex, the polymerization of the graft portion is preferably carried out by an emulsion polymerization method. The graft portion can be produced, for example, according to the method described in WO 2005/028546.
The grafting portion being formed by a plurality of grafting portions (e.g. grafting portions 1 Grafting portion 2 Graft of … n ) The method for producing the grafting portion in the case of the constitution will be described. In this case, the grafting portion 1 Grafting portion 2 … grafting portions n Polymerization is performed by the above-described methods, and thereafter, a graft having a plurality of graft portions can be produced by mixing. Or a grafting portion 1 Grafting portion 2 Graft of … n The multistage polymerization may be sequentially performed, or a graft having a plurality of graft portions may be produced.
The multistage polymerization of the graft portion will be specifically described. For example, (1) grafting portions 1 Polymerization is carried out to obtain a graft portion 1 The method comprises the steps of carrying out a first treatment on the surface of the (2) Next, at the grafting portion 1 In the presence of (C) a grafting moiety 2 Polymerization is carried out to obtain 2-stage grafting part 1+2 The method comprises the steps of carrying out a first treatment on the surface of the (3) Next, at the grafting portion 1+2 In the presence of (C) a grafting moiety 3 Polymerization to obtain 3-stage grafting part 1+2+3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The following is carried out in the same manner, and then the grafting part 1+2+…+(n－1) Is opposite to the grafting part in the presence of (a) n Polymerization is carried out to obtain a multistage polymerized grafting part 1+2+…+n 。
When the graft portion is composed of a plurality of graft portions, the polymer fine particles (a) can be produced by polymerizing the graft portion having a plurality of graft portions, and then graft polymerizing the graft portions to the elastomer. In the presence of the elastomer, the polymer fine particles (a) may be produced by sequentially graft polymerizing a plurality of polymers comprising a plurality of graft portions with respect to the elastomer in a multistage manner.
(method for producing surface-crosslinked Polymer)
The surface cross-linked polymer may be formed by polymerizing monomers used for forming the surface cross-linked polymer by well-known free radical polymerization. In the case of obtaining an elastomer as an aqueous latex, the polymerization of the surface-crosslinked polymer is preferably performed by an emulsion polymerization method.
In the case of using the emulsion polymerization method as the method for producing the polymer fine particles (a), a known emulsifier (dispersant) can be used for producing the polymer fine particles (a).
In the case of using the emulsion polymerization method as the method for producing the polymer fine particles (a), a thermal decomposition type initiator can be used in the production of the polymer fine particles (a). Examples of the thermal decomposition initiator include known initiators such as 2,2' -azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and amine persulfate.
Redox initiators may also be used in the production of the polymer particles (A). The redox initiator is an initiator obtained by using a combination of (a) a peroxide such as an organic peroxide or an inorganic peroxide, (b) a reducing agent such as sodium formaldehyde sulfoxylate or glucose, if necessary, a transition metal salt such as iron (II) sulfate, if necessary, a chelating agent such as disodium ethylene diamine tetraacetate, if necessary, and a phosphorus-containing compound such as sodium pyrophosphate, if necessary. Examples of the organic peroxide include t-butylperoxy isopropyl carbonate, p-menthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl peroxide, di-t-butyl peroxide, and t-hexyl peroxide. Examples of the inorganic peroxide include hydrogen peroxide, potassium persulfate, and amine persulfate.
In the case of using the redox initiator, the polymerization can be carried out even at a low temperature at which the peroxide is not substantially thermally decomposed, and the polymerization temperature can be set in a wide range. Thus, redox type initiators are preferably used. Among redox initiators, organic peroxides such as cumene hydroperoxide, cumyl hydroperoxide, p-menthane hydroperoxide and t-butyl hydroperoxide are preferably used as redox initiators. In the case of using the amount of the above-mentioned initiator and redox initiator, the amount of the above-mentioned reducing agent, transition metal salt, chelating agent, etc. may be used in a known range.
For the purpose of introducing a crosslinked structure into the elastomer, graft portion or surface crosslinked polymer, in the case of using a polyfunctional monomer in the polymerization of the elastomer, graft portion or surface crosslinked polymer, a known chain transfer agent may be used in a known amount range. By using a chain transfer agent, the molecular weight and/or the degree of crosslinking of the resulting elastomer, graft or surface crosslinked polymer can be easily adjusted.
In the production of the polymer fine particles (A), a surfactant may be used in addition to the above components. The kind and the amount of the surfactant are in a known range.
In the production of the polymer fine particles (a), conditions such as polymerization temperature, pressure and deoxidation for polymerization can be applied in known ranges.
In the production of the polymer fine particles (a), since the halogen element may be held, the material used in the production of the polymer fine particles (a) is preferably a material having a halogen element content of a predetermined value or less. The halogen element content of the raw material is preferably 500ppm or less, more preferably 400ppm or less, still more preferably 300ppm or less, still more preferably 200ppm or less, particularly preferably 100ppm or less, and most preferably 50ppm or less. And, it is preferably 30ppm or less, more preferably 10ppm or less, further preferably 5ppm or less, particularly preferably 1ppm or less, and most preferably n.d.
(1-3. Resin (B))
The powder and granule preferably further comprises a resin (B). When the halogen element is contained in the present resin (B), the introduction of the halogen element occurs in the powder or granular material. Therefore, the halogen element content of the resin (B) may be 500ppm or less, preferably 400ppm or less, more preferably 300ppm or less, further 200ppm or less, particularly preferably 100ppm or less, and most preferably 50ppm or less. And, it is preferably 30ppm or less, more preferably 10ppm or less, further preferably 5ppm or less, particularly preferably 1ppm or less, and most preferably n.d.
The resin (B) may be the same as or different from the thermosetting resin or thermoplastic resin (C) as the matrix resin to be mixed, which will be described later. The thermosetting resin (B) and the resin (D) in the resin composition are preferably not separated from each other. The resin (D) is preferably a resin compatible with the thermosetting resin (B).
As an example, consider a case where the resin (B) is used in the method for producing the resin composition, and the resin (B) is the same kind of resin as the base resin (C). In this case, the matrix resin (C) and the resin (B) are not distinguished from each other in the resin composition containing the obtained powder or granular material. Thus, the resin composition containing the obtained powder particles has only the matrix resin (C) except the polymer fine particles (A) in appearance. Next, a case is considered in which the resin (B) is used in the method for producing the resin composition, and the resin (B) is a different type of resin from the base resin (C). In this case, the matrix resin (C) and the resin (B) can be identified in the resin composition containing the obtained powder or granular material. In this case, the resin composition containing the finally obtained powder or granule may contain the resin (B) as a resin other than the matrix resin (C) other than the polymer fine particles (a).
The resin (B) may be, for example, a thermosetting resin, a thermoplastic resin, or any combination of a thermosetting resin and a thermoplastic resin. When the powder or granule contains the resin (B), the resin (B) can have an effect of improving the dispersibility of the polymer fine particles (a) in the thermosetting resin or the thermoplastic resin.
Examples of the thermosetting resin (B) include various thermosetting resins described in the following items of the base resin (C). The thermosetting resin (B) may be used alone or in combination of two or more.
Examples of the thermoplastic resin (B) include various thermoplastic resins described in the following items of the matrix resin (C). Examples of the structural unit include a polymer containing a structural unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer and a (meth) acrylate monomer. In the resin (B), the thermoplastic resin may be used alone or in combination of two or more.
When the matrix resin (C) to be mixed is a thermosetting resin, the resin (B) is preferably the same type as the thermosetting resin of the matrix resin (C) because it does not affect various physical properties. That is, when the thermosetting resin of the base resin (C) is an epoxy resin, the resin (B) is also preferably an epoxy resin. When the resin (B) is a thermosetting resin different from the base resin (C), the resin (B) is preferably compatible with the thermosetting resin of the base resin (C).
(others)
In the present specification, the fat and oil and the fatty acid ester are also contained in the resin (B). Examples of oils and fats that can be preferably used as the resin (B) include epoxidized oils such as epoxidized soybean oil and epoxidized linseed oil. As the epoxidized soybean oil, commercially available products can be used, and examples thereof include ADEKAO-130P manufactured by ADEKA Co. Examples of fatty acid esters that can be preferably used as the resin (B) include epoxidized fatty acid esters such as epoxidized fatty acid butyl ester, epoxidized fatty acid 2-ethylhexyl ester, epoxidized fatty acid octyl ester and epoxidized fatty acid alkyl ester.
Epoxidized oils and epoxidized fatty acid esters may also be referred to as epoxy plasticizers. That is, in the present specification, the epoxy plasticizer may be contained in the resin (B). Examples of the epoxy plasticizer other than the epoxidized oil and the epoxidized fatty acid ester include epoxy-hexahydrophthalate di-epoxy stearyl and epoxy-hexahydrophthalate di-2-ethylhexyl ester.
The thermosetting resin, thermoplastic resin, mixture of thermosetting resin and thermoplastic resin, grease and fatty acid ester may be used by mixing with an antioxidant, respectively. In the present specification, the antioxidant is considered as a part of the resin (B) as long as it is used by being mixed with the above-mentioned respective substances. In the case where only an antioxidant is used, the antioxidant is not regarded as the resin (B). When only an antioxidant is used, the component does not contribute to crosslinking, and thus the physical properties of the finally obtained substance (for example, a cured product in the case where the base resin is a thermosetting resin) tend to be deteriorated when the base resin is mixed therewith. For example, the Tg of the final product may be lowered, or the impact resistance may be deteriorated. In the case of the radical curing system, curing inhibition tends to be inhibited, and when the total of the polymer fine particles (a) and the resin (B) is 100 wt%, the amount of the antioxidant is preferably 5 wt% or less, more preferably 3 wt% or less, and still more preferably 1.5 wt% or less. In the case where the elastomer of the polymer fine particles (a) contains a diene rubber, the amount of the antioxidant is preferably 0.5% by weight or more, more preferably 1% by weight or more, still more preferably 1.5% by weight or more, and still more preferably 2% by weight or more. With this configuration, oxidation of the elastic body can be prevented.
The antioxidant is not particularly limited. Examples of the antioxidant include (a) primary antioxidants such as phenol antioxidants, amine antioxidants, lactone antioxidants, and hydroxylamine antioxidants, and (b) secondary antioxidants such as sulfur antioxidants and phosphorus antioxidants.
Examples of the phenol-based antioxidant include hindered phenol-based antioxidants. Examples of the hindered phenol antioxidant include compounds having a hindered phenol structure or a lamellar hindered phenol structure in the molecule. As the phenol-based antioxidant, commercially available ones can be used, and examples thereof include Irganox 245, manufactured by BASF Japanese Co., ltd.
The amine-based antioxidant is not particularly limited, and conventionally known antioxidants can be widely used. Specific examples of the amine-based antioxidant include 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 6-ethoxy-1, 2-dihydro-2, 4-trimethylquinoline, and a reactant of diphenylamine and acetone.
The amine antioxidant further comprises an aromatic amine compound. Examples of the aromatic amine compound include naphthylamine-based antioxidants, diphenylamine-based antioxidants, and p-phenylenediamine-based antioxidants.
The lactone-based antioxidant, the hydroxylamine-based antioxidant, and the sulfur-based antioxidant are not limited, and conventionally known antioxidants can be widely used.
The phosphorus antioxidant is not particularly limited, and conventionally known antioxidants can be widely used. Phosphoric acid and phosphoric acid ester containing active hydrogen adversely affect the storage stability of the resin composition containing the obtained powder and particle and the heat resistance of the cured product or molded article provided with the resin composition. Thus, as the phosphorus antioxidant, alkyl phosphite, aryl phosphite, alkylaryl phosphite compounds and the like which do not contain phosphoric acid and a phosphoric acid ester in the molecule are preferable.
As the antioxidant, other known antioxidants can be used. As the antioxidant, various substances described in "antioxidant handbook" issued by the large-adult society (release of the first edition of 10/25/51 of sho) and "polymer additive handbook" issued by CMC publication (release of 1 st edition of 11/2010 of spring name, for example) can be used.
The resin (B) is preferably one or more selected from the group consisting of a thermosetting resin, a mixture of a thermosetting resin and an antioxidant, a thermoplastic resin, a mixture of a thermoplastic resin and a resin antioxidant, a fat, a mixture of a fat and an antioxidant, a fatty acid ester, a mixture of a fatty acid ester and an antioxidant, an epoxy curing agent, and a mixture of an epoxy curing agent and an antioxidant, more preferably one or more selected from the group consisting of an epoxy resin, an acrylic polymer, a mixture of an epoxy resin and an antioxidant, a mixture of an acrylic polymer and an antioxidant, and a mixture of an epoxy plasticizer and an antioxidant, still more preferably one or more selected from the group consisting of a mixture of an epoxy resin and an antioxidant, a mixture of an acrylic polymer and an antioxidant, and a mixture of an epoxy plasticizer and an antioxidant, and particularly preferably a mixture of an epoxy plasticizer and an antioxidant. According to this constitution, there are advantages that (a) the resin composition containing the obtained powder or granule can provide a cured product or molded article excellent in heat resistance, and (b) the dispersibility of the polymer fine particles (a) in the matrix resin can be improved.
(physical Properties of resin (B))
The resin (B) is not particularly limited as long as it is a liquid or a semi-solid or a solid having a viscosity of 100 mPas to 1000000 mPas at 25 ℃. The term "the resin (B) has a viscosity of 100 mPas to 1000000 mPas at 25 ℃ means that the resin (B) has a viscosity of 100 mPas to 1000000 mPas at 25 ℃.
When the resin (B) is a liquid, the viscosity of the resin (B) is preferably 750000mpa·s or less, more preferably 700000mpa·s or less, more preferably 500000mpa·s or less, more preferably 350000mpa·s or less, more preferably 300000mpa·s or less, more preferably 250000mpa·s or less, more preferably 100000mpa·s or less, more preferably 75000mpa·s or less, more preferably 50000mpa·s or less, more preferably 30000mpa·s or less, more preferably 25000mpa·s or less, more preferably 20000mpa·s or less, and particularly preferably 15000mpa·s or less at 25 ℃. According to the above constitution, the resin (B) has an advantage of excellent fluidity.
The viscosity of the resin (B) is more preferably 200mpa·s or more, more preferably 300mpa·s or more, more preferably 400mpa·s or more, more preferably 500mpa·s or more, still more preferably 750mpa·s or more, still more preferably 1000mpa·s or more, and particularly preferably 1500mpa·s or more at 25 ℃. According to this constitution, the resin (B) does not impregnate the polymer fine particles (A). This prevents the polymer fine particles (a) from fusing with each other based on the resin (B).
The viscosity of the resin (B) is more preferably 100 to 750000 mPas, more preferably 100 to 700000 mPas, more preferably 100 to 350000 mPas, more preferably 100 to 300000 mPas, more preferably 100 to 50000 mPas, more preferably 100 to 30000 mPas, and particularly preferably 100 to 15000 mPas at 25 ℃.
When the resin (B) is semi-solid, the resin (B) may be semi-liquid, or the resin (B) may have a viscosity of more than 1000000mpa·s. When the resin (B) is a semisolid or solid, the resin composition containing the obtained powder or granule has advantages of low tackiness and easy handling.
The viscosity of the resin (B) can be measured by a viscometer. The method for measuring the viscosity of the resin (B) is described in detail using the following examples.
The resin (B) is preferably a resin having an endothermic peak at 25 ℃ or lower in a thermogram of Differential Scanning Calorimetry (DSC), and more preferably a resin having an endothermic peak at 0 ℃ or lower.
The content of the resin (B) in the powder or granule is 50 to 99% by weight, and the content of the resin (B) is 1 to 50% by weight, based on 100% by weight of the total of the polymer fine particles (A) and the resin (B). The content of the resin (B) may be appropriately set in the range in which the above-mentioned numerical value and powder or granule can be obtained, depending on the type of the resin (B), the physical properties (solid, semisolid, liquid, viscosity, etc.) of the resin (B), and the like. The resin (B) is liquid at 25 ℃, and if the content of the resin (B) in the powder or granular material is large, the powder or granular material may not be obtained. When the resin (B) is liquid at 25 ℃ and the content of the resin (B) in the powder or granular material is large, the fluidity (smooth feeling) of the powder or granular material may be deteriorated.
The content of the resin (B) in the powder and granular material will be described in view of the excellent anti-blocking agent. When the total of the polymer fine particles (a) and the resin (B) is 100 wt%, the polymer fine particles (a) are 50 to 99 wt% and the resin (B) is 1 to 50 wt%. Since the blocking-resistant agent is excellent, it is more preferably 55 to 99% by weight of the polymer particles (A), 1 to 45% by weight of the resin (B), more preferably 60 to 99% by weight of the polymer particles (A), 1 to 40% by weight of the resin (B), more preferably 65 to 99% by weight of the polymer particles (A), 1 to 35% by weight of the resin (B), more preferably 70 to 99% by weight of the polymer particles (A), 1 to 30% by weight of the resin (B), more preferably 75 to 99% by weight of the polymer particles (A), 1 to 25% by weight of the resin (B), more preferably 80 to 99% by weight of the polymer particles (A), 1 to 20% by weight of the resin (B), more preferably 85 to 99% by weight of the polymer particles (A), 1 to 15% by weight of the resin (B), more preferably 90 to 99% by weight of the polymer particles (A), 1 to 10% by weight of the resin (B), particularly preferably 95 to 99% by weight of the polymer particles (A), and 1 to 5% by weight of the resin (B).
The content of the resin (B) in the powder or granular material will be described in terms of good dispersibility of the polymer fine particles (a) in the matrix resin. When the total of the polymer particles (a) and the resin (B) is 100 wt%, the polymer particles (a) are preferably 50 to 97 wt%, the resin (B) is 3 to 50 wt%, more preferably 50 to 95 wt%, the resin (B) is 5 to 50 wt%, more preferably 50 to 92 wt%, the resin (B) is 8 to 50 wt%, more preferably 50 to 90 wt%, the resin (B) is 10 to 50 wt%, more preferably 50 to 87 wt%, the resin (B) is 13 to 50 wt%, more preferably 50 to 85 wt%, the resin (B) is 15 to 50 wt%, more preferably 50 to 82 wt%, the resin (B) is 18 to 50 wt%, more preferably 50 to 80 wt%, the resin (B) is 20 to 50 wt%, and particularly preferably 60 to 80 wt%, and the resin (B) is 20 to 80 wt%.
In a Transmission Electron Microscope (TEM) image of the powder obtained by the method described later, from the viewpoint of preventing the polymer fine particles (a) from fusing with each other, chains having a long diameter of 1.5 times or more the average particle diameter of the polymer fine particles (a) are preferably five or less, more preferably three or less, still more preferably one or less, and most preferably zero or less.
The long diameter of the resin (B) in the TEM image means the maximum length (the length of the largest straight line among straight lines connecting 2 points on the outer circumference). The average particle diameter of the polymer particles (a) is an average value of diameters of circles (equivalent diameters of area circles) having the same projected area as the 30 polymer particles (a) extracted without difference in a TEM image, for example.
The volume average particle diameter (Mv) of the powder is preferably 30 μm to 500. Mu.m, more preferably 30 μm to 300. Mu.m, still more preferably 50 μm to 300. Mu.m, particularly preferably 100 μm to 300. Mu.m. According to this constitution, the powder particles are excellent in dispersibility in the matrix resin of the polymer fine particles (A). Further, according to this constitution, a resin composition which has a desired viscosity and is highly stable can be provided in which the polymer fine particles (a) are uniformly dispersed in the matrix resin. In the present specification, the volume average particle diameter of the powder is a value obtained by measurement using a laser diffraction type particle size distribution measuring apparatus (microtrackmt 3000 II) manufactured by microtrack Bell corporation.
Since the obtained powder or granule has an advantage of being less likely to contain fine powder which may possibly explode dust and coarse particles which deteriorate dispersibility, the number distribution of the volume average particle diameter of the powder or granule preferably has a half value width of 0.5 to 1 times the volume average particle diameter.
The powder particle preferably further contains an anti-blocking agent from the viewpoint of improving dispersibility into the anti-blocking agent and the matrix resin (C). The anti-blocking agent is not particularly limited as long as it has the effect of one embodiment of the present invention. Examples of the anti-blocking agent include an anti-blocking agent composed of inorganic fine particles such as silica, titanium oxide, alumina, zirconia, aluminum silicate, diatomaceous earth, zeolite, kaolin, talc, calcium carbonate, calcium phosphate, barium sulfate, magnesium hydrosilicate, etc.; an anti-blocking agent comprising organic microparticles; an anti-blocking agent for oils and fats, such as polyethylene wax, higher fatty acid amide, metal soap, and silicone oil. Among these, the anti-blocking agent is preferably composed of fine particles, more preferably composed of organic fine particles, and particularly preferably composed of organic fine particles of a polymer containing one or more monomer units selected from the group consisting of aromatic vinyl monomers, vinyl cyano monomers, and (meth) acrylate monomers. The antiblocking agent also preferably has a halogen element content within the above-mentioned numerical range.
The anti-blocking agent composed of fine particles is generally composed of fine particles dispersed in a liquid or is colloidal. The volume average particle diameter (Mv) of the fine particles in the anti-blocking agent is usually 10 μm or less, preferably 0.05 to 10. Mu.m. The content of the anti-blocking agent is preferably 0.01 to 5.0 wt%, more preferably 0.5 to 3.0 wt% based on the total weight of the powder.
The anti-blocking agent may be added appropriately in any step of the method for producing a powder or granule. For example, the anti-blocking agent and the additive may be added to the aqueous suspension of the polymer fine particles (a) before or after solidification, or may be added to the polymer fine particles (a) or the powder.
The powder has excellent anti-blocking agent. In the present specification, the blocking resistance of the powder or granular material can be evaluated based on the force required to disintegrate the bulk of the powder or granular material. The powder is preferably used to disintegrate the powder with a force of 30000Pa or less. Here, the block is a block obtained by placing a weight of 6.3kg on 30g of the powder or granule contained in a cylindrical container having a diameter of 50mm, and applying a load of 6.3kg to the powder or granule obtained by standing at 60 ℃ for 2 hours. The force (force required for disintegrating the bulk of the powder) is a value measured by a rheometer. The anti-blocking agent is also similar to the method for producing the powder or granular material described later.
[ 2 ] method for producing powder particles ]
(2-1. Process for producing powder particles)
The method for producing a powder or granular material according to an embodiment of the present invention includes the steps of: a step of adding a coagulant having a halogen element content of 500ppm or less to an aqueous latex containing polymer microparticles (A) and coagulating the aqueous latex; the polymer fine particles (a) include a rubber-containing graft copolymer having an elastomer containing at least one member selected from the group consisting of diene rubbers, (meth) acrylate rubbers and organosiloxane rubbers, and a graft unit formed by graft-bonding the elastomer, and the graft unit may include a polymer containing, as a structural unit, a structural unit derived from at least one member selected from the group consisting of aromatic vinyl monomers, vinyl cyano monomers and (meth) acrylate monomers. For example, the method for producing a powder or granule described in the above section [ 1 ] may be included. Hereinafter, the method for producing a powder or granular material according to an embodiment of the present invention may be simply referred to as the present production method. According to the present production method, a powder or granule with reduced halogen elements can be produced.
Examples of the method for producing the powder or granule containing the polymer fine particles (a) include (i) a method in which an aqueous emulsion is salted out and coagulated, and then dehydrated and dried, and (ii) a method in which the powder or granule is spray-dried from the aqueous emulsion. Conventionally, in the coagulation of an aqueous latex, a coagulant containing a halogen element (halogen-based coagulant) such as calcium chloride or magnesium chloride has been generally used. However, the present inventors have conducted intensive studies and found that when the above-mentioned halogen-based coagulant is used, the amount of halogen in the obtained powder or granular material increases. The present inventors have completed a method for producing a powder or granule by reducing the amount of halogen element by using a coagulant having a halogen element content of a predetermined value or less in the coagulation step.
The halogen element content in the coagulant is preferably 500ppm or less, more preferably 400ppm or less, still more preferably 300ppm or less, still more preferably 200ppm or less, particularly preferably 100ppm or less, and most preferably 50ppm or less. And, it is preferably 30ppm or less, more preferably 10ppm or less, further preferably 5ppm or less, particularly preferably 1ppm or less, and most preferably n.d.
The coagulant having a halogen element content of not more than a predetermined value is not particularly limited, but is preferably an alkali metal or alkaline earth metal acetate, citrate, formate, gluconate, lactate, oxalate, tartrate, phosphate, sulfate or the like. Particularly preferred are calcium acetate, magnesium acetate and aluminum acetate.
The concentration of the coagulant added in which the halogen element content is equal to or less than a predetermined value is preferably 0 to 10%. The method of adding the coagulant containing no halogen element is not particularly limited, and the same method as the known coagulation step can be preferably used.
(2-2. Mixing step of resin (B))
The production method further comprises a step of mixing the polymer fine particles (A) with the resin (B), wherein the resin (B) is a liquid, semi-solid or solid having a viscosity of 100 mPas to 1000000 mPas at 25 ℃, and when the total of the polymer fine particles (A) and the resin (B) is 100% by weight, the polymer fine particles (A) are preferably 50 to 99% by weight, and the resin (B) is preferably 1 to 50% by weight. The method of mixing the polymer fine particles (A) and the resin (B) can utilize various methods. Examples of the method of mixing the polymer fine particles (a) and the resin (B) include a method of directly adding the resin (B) in the polymerization step of the polymer fine particles (a), a method of adding the resin (B) in an aqueous emulsion state, a method of directly adding the resin (B) to the aqueous emulsion of the polymer fine particles (a), a method of adding the resin (B) in an aqueous emulsion state, a method of adding the resin (B) in a solution state, and the like, and a method of adding the resin (B) to the aqueous emulsion of the polymer fine particles (a) in an aqueous emulsion state is preferable. The mixing of the resin (B) with the polymer fine particles (a) may be performed before or after the addition of the coagulant, and the resin (B) may be mixed with the polymer fine particles (a) together with the coagulant.
That is, the present manufacturing method includes the steps of: a resin (B) adding step of adding a resin (B) to an aqueous latex containing the polymer fine particles (A); a coagulation step of preparing a coagulated body containing the polymer fine particles (a) and the resin (B) by using the aqueous latex obtained in the resin (B) addition step; and a recovery step of recovering the aggregate, wherein the resin (B) is a liquid, semi-solid or solid having a viscosity of 100 mPas to 1000000 mPas at 25 ℃, and the polymer particles (A) and the resin (B) are preferably obtained by a production method of a powder or granule having a total of 50 to 99% by weight of the polymer particles (A) and 1 to 50% by weight of the resin (B) based on 100% by weight. The present manufacturing method includes the following steps: a resin (B) polymerization step of polymerizing the resin (B) in an aqueous latex containing the polymer fine particles (A); a coagulation step of preparing a coagulated body containing the polymer fine particles (a) and the resin (B) by using the aqueous latex obtained; and a recovery step of recovering the aggregate, wherein the resin (B) is a liquid, semi-solid, or solid having a viscosity of 100 mPas to 1000000 mPas at 25 ℃, and the polymer particles (A) and the resin (B) are preferably obtained as other methods of producing a powder having a total of 50 to 99% by weight of the polymer particles (A) and 1 to 50% by weight of the resin (B) based on 100% by weight of the polymer particles (A). According to these production methods, a powder or granule having a low halogen element content can be produced efficiently.
The halogen element content in the resin (B) may be 500ppm or less, preferably 400ppm or less, more preferably 300ppm or less, further preferably 200ppm or less, particularly preferably 100ppm or less, and most preferably 50ppm or less. And, it is preferably 30ppm or less, more preferably 10ppm or less, further preferably 5ppm or less, particularly preferably 1ppm or less, and most preferably n.d.
(2-3. Cleaning step)
The present production method preferably further includes a cleaning step of cleaning the powder obtained by the production method. The content of halogen element can be reduced by performing the cleaning. The washing step is more preferably performed with water, and is also more preferably performed with ion-exchanged water or pure water.
The cleaning step may be a step of cleaning the powder or granular material, and the specific method is not particularly limited. Examples of the method include a method of mixing the powder and water with a stirrer, a method of kneading the powder and water with a kneader, and a method of mixing with a rotation/revolution mixer. As the kneader, various batch kneaders, continuous kneaders, extruders and the like can be used.
The washing time is not particularly limited, and examples thereof include 1 second to 60 minutes, preferably 1 second to 45 minutes, and more preferably 1 second to 30 minutes.
The number of times of washing is not particularly limited, and examples thereof include 1 to 10 times, preferably 1 to 6 times, and more preferably 1 to 4 times.
The amount of the washing water is not particularly limited, and for example, 10 to 1000 parts by weight, preferably 15 to 500 parts by weight, more preferably 20 to 200 parts by weight, based on 1 part by weight of the powder or granular material. In addition, in the case of washing by kneading using a kneader, washing water can be reduced, and more preferably.
The temperature of the washing water is not limited, and for example, normal temperature or heated warm water can be suitably used. The temperature of the warm water may be, for example, 10℃to 100℃and preferably 15℃to 90℃and more preferably 20℃to 85 ℃. The cleaning effect is in the middle of the cleaning effect. The warm water is higher, and thus heated washing water is preferably used.
The method for removing the washing water is not limited, and examples thereof include a method for removing the washing water, a method for filtering under reduced pressure, a method for separating oil from water, and a method for squeezing and dehydrating.
The aggregate and the powder containing the polymer fine particles (a) and the resin (B) are preferably handled (processed) by a production method in a temperature environment of less than the glass transition temperature of the grafting portion of the polymer fine particles (a). In other words, according to the production method, the shorter the time the agglomerate and powder containing the polymer fine particles (a) and the resin (B) are exposed to the temperature environment equal to or higher than the glass transition temperature of the graft portion of the polymer fine particles (a), the better. According to this constitution, the obtained powder particles are excellent in dispersibility into the matrix resin (C) of the polymer fine particles (A). As a result, the obtained powder or granule can provide a resin composition in which the polymer fine particles (A) are more uniformly dispersed in the matrix resin (C).
In the present production method, the exposure time (period) in the temperature environment of the glass transition temperature or higher of the grafting portion of the polymer fine particles (a) can be shortened by adjusting the following temperature, whereby the aggregate and the powder containing the polymer fine particles (a) and the resin (B) can be shortened: the temperature of the aqueous latex containing the polymer fine particles (a), the temperature of the aqueous latex containing the polymer fine particles (a) and the resin (B) (the aqueous latex before the coagulant is added), the temperature of the aqueous solution of the coagulant, the temperature of the aqueous latex containing the polymer fine particles (a), the resin (B) and the coagulant, the heating temperature of the heating step, the drying temperature of the drying step, the temperature of the washing water of the washing step, and the like.
The temperature of the graft portion of the polymer fine particle (A) which is less than the glass transition temperature varies depending on the composition of the graft portion, and can be appropriately set depending on the composition of the graft portion. The aggregate and the powder containing the polymer fine particles (a) and the resin (B) are preferably treated by the production method at less than 90 ℃, more preferably at less than 80 ℃, and even more preferably at less than 70 ℃. That is, the above temperatures are each preferably less than 90 ℃, more preferably less than 80 ℃, more preferably less than 70 ℃, more preferably less than 60 ℃, more preferably less than 50 ℃, and even more preferably less than 40 ℃.
In addition, for the details of other production methods, the column (1-2. Production method of polymer microparticles (A)) above can be appropriately referred to.
[ 3. Resin composition ]
The resin composition according to an embodiment of the present invention contains the powder and the matrix resin (C). Hereinafter, the resin composition according to an embodiment of the present invention may be simply referred to as the present resin composition.
(3-1. Matrix resin (C))
As the matrix resin, a thermosetting resin or a thermoplastic resin can be preferably used. The base resin (C) may have a halogen element, and thus the base resin (C) having a halogen element content of a predetermined value or less is preferably used. The halogen element content may be 500ppm or less, preferably 400ppm or less, more preferably 300ppm or less, further preferably 200ppm or less, particularly preferably 100ppm or less, and most preferably 50ppm or less. And, it is preferably 30ppm or less, more preferably 10ppm or less, further preferably 5ppm or less, preferably 1ppm or less, and most preferably n.d.
(3-1-1. Thermosetting resin)
The thermosetting resin is preferably at least one thermosetting resin selected from the group consisting of a resin containing a polymer obtained by polymerizing an ethylenically unsaturated monomer, an epoxy resin, a phenol resin, a polyol resin, and an amino-formaldehyde resin. 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 radical polymerizable monomers such as aromatic vinyl compounds, (meth) acrylic acid derivatives, cyanated vinyl compounds, maleimide compounds, dimethyl terephthalate, alkylene glycol, and the like. These thermosetting resins may be used alone or in combination of two or more.
(ethylenically unsaturated monomer)
The ethylenically unsaturated monomer is not particularly limited as long as it has at least one ethylenically unsaturated bond in the molecule.
Examples of the ethylenically unsaturated monomer include acrylic acid, α -alkylacrylic acid, β -alkylacrylic acid, 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 ethoxystyrene. These may be used singly or in combination of two or more.
(epoxy resin)
The epoxy resin is not particularly limited as long as it has at least one epoxy group in the molecule.
Specific examples of the epoxy resin include 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, water-added 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, epoxy resin of p-oxybenzoic acid glycidyl ether ester type, m-aminophenyl type epoxy resin, diaminodiphenylmethane type epoxy resin, epoxy resin having an unsaturated polymer such as urethane modified epoxy resin, various alicyclic epoxy resins, glycidyl ether of polyhydric alcohol, hydantoin type epoxy resin, petroleum resin, and the like, and amino group-containing glycidyl ether resin. Examples of the polyhydric alcohol include N, N-diglycidyl aniline, N-diglycidyl-orthotoluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin, and the like. Examples of the epoxy resin include an epoxy compound obtained by an addition reaction of the epoxy resin with bisphenol a (or F) or a polyhydroxy acid. The epoxy resin is not limited to these, and commonly used epoxy resins can be used. These epoxy resins may be used alone or in combination of two.
Among the above epoxy resins, those having at least 2 epoxy groups in one molecule are preferable in view of high reactivity and easiness of formation of a three-dimensional mesh in the obtained cured product during curing of the resin composition. Among the epoxy resins having at least 2 epoxy groups in one molecule, bisphenol-type epoxy resins are preferable as the main component, 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, catechol, resorcinol, hydroquinone, xylenol, p-tert-butylphenol, p-octylphenol, p-phenylphenol, bisphenol a, bisphenol F, and resorcinol. Particularly preferred phenols include phenol and cresol.
The aldehydes include, but are not particularly limited to, formaldehyde, acetaldehyde, butyraldehyde, acrolein, and the like, and mixtures thereof. As the aldehydes, the above-mentioned aldehydes may be used as a source of the aldehydes or as a solution of the aldehydes. 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) (hereinafter also referred to as the reaction molar ratio) in reacting the phenol with the aldehyde is not particularly limited. When an acid catalyst is used in the reaction, the 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 too low, and the molecular weight of the obtained phenolic resin is not reduced. On the other hand, when the reaction molar ratio is equal to or less than the upper limit, the molecular weight of the phenolic resin becomes too large and the softening point becomes too high, whereby sufficient fluidity is obtained upon heating. When the reaction molar ratio is not more than the upper limit, the control of the molecular weight is easy, and gelation of the ester or partial gelation due to the reaction conditions does not occur.
(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. Examples of the polyol resin include aliphatic alcohols, aromatic alcohols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols.
The aliphatic alcohol may be any of dihydric alcohol or trihydric or higher alcohol (triol, tetrahydric alcohol, etc.). Examples of the dihydric alcohol include alkylene glycols (particularly alkylene glycols having about 1 to 6 carbon atoms) such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-heptanediol, neopentyl glycol, and the like, and dehydration condensates (diethylene glycol, dipropylene glycol, tripropylene glycol, and the like) of 2 or more molecules (for example, about 2 to 6 molecules) of the alkylene glycols. Examples of the triol include glycerin, trimethylolpropane, trimethylolethane, and 1,2, 6-hexanetriol (in particular, triol having about 3 to 10 carbon atoms). Examples of the tetravalent alcohol include pentaerythritol and diglycerol. 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 an active hydrogen-containing initiator, one or more kinds of the above, and mixtures of these copolymers. Examples of the active hydrogen-containing initiator used for ring-opening polymerization of the polyether polyol include glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 3-butane diol, 1, 4-butane diol, 1, 6-hexane diol, neopentyl glycol, bisphenol a, and the like; triols such as trimethylolethane, trimethylolpropane, glycerol, etc.; 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 polyhydric alcohol such as (a) a polyhydric acid such as maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, dodecanedioic acid, isophthalic acid, azelaic acid, and the like, and/or an acid anhydride thereof, (b) ethylene glycol, propylene glycol, 1, 4-butane diol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 3-methyl-1, 5-pentanediol, and the like in the presence of an esterification catalyst at a temperature in the range of 150 to 270 ℃. Examples of the polyester polyol include (a) ring-opening polymers such as epsilon-caprolactone and valerolactone, 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 water additives thereof.
Examples of the acrylic polyol include (a) a hydroxyl group-containing monomer such as hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, and vinylphenol, (b) a copolymer with a general monomer such as n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, and a mixture of these copolymers.
Among these polyol resins, polyether polyols are preferred because the resin composition containing the obtained powder particles has low viscosity and excellent workability, and therefore a cured product having an excellent balance between hardness and toughness of the resin composition can be provided. Among these polyol resins, polyester polyol is preferable, and a cured product excellent in adhesion of the resin composition containing the obtained powder or granule can be provided.
(amino-formaldehyde resin)
The amino-formaldehyde resin is not particularly limited as long as it is a compound obtained by reacting an amino compound with an aldehyde in the presence of a basic catalyst. The amino compound includes 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 such as urea, thiourea, and ethylene urea. Examples of the amino compound include a substituted melamine compound in which an alkyl group, an alkenyl group and/or a phenyl group is substituted for the hydrogen of the amino group of melamine (as described in U.S. Pat. No. 5998573 (corresponding to Japanese unexamined patent publication: kokai) No. 9-143238), and a substituted melamine compound in which a hydroxyalkyl group, a hydroxyalkyloxyalkyl group and/or an aminoalkyl group is substituted for the hydrogen of the amino group of melamine (as described in U.S. Pat. No. 5322915 (corresponding to Japanese unexamined patent publication: no. 5-202157)), and the like. Among the above amino compounds, the polyfunctional amino compounds, that is, melamine, guanamine, acetoguanamine and benzoguanamine are preferable, and melamine is particularly preferable, because the amino compounds are industrially produced and inexpensive. The amino compound may be used alone or in combination of two or more. Further, in addition to these amino compounds, (a) phenols such as phenol, cresol, alkylphenol, resorcinol, hydroquinone and pyrogallol, and (b) anilines may be used.
Examples of the aldehydes include formaldehyde, para-formaldehyde, acetaldehyde, benzaldehyde, and furfural. The aldehydes are inexpensive and have good reactivity with the amino compounds mentioned above, and formaldehyde and para-formaldehyde are preferable. In the production of the amino-formaldehyde resin, the aldehyde is preferably used in an amount of 1.1 to 6.0 mol, particularly preferably 1.2 to 4.0 mol, per 1 mol of the amino compound per effective aldehyde group.
(aromatic polyester raw material)
Examples of the aromatic polyester raw material include radical polymerizable monomers such as aromatic vinyl compounds, (meth) acrylic acid derivatives, cyanated vinyl compounds, maleimide compounds, dimethyl phthalate, alkylene glycol, and the like. In the present specification, (meth) acrylic refers to acrylic acid and/or methacrylic acid.
(3-1-2. Thermoplastic resin)
Examples of the thermoplastic resin include acrylic polymers, vinyl copolymers, polycarbonates, polyamides, polyesters, polyphenylene ethers, polyurethanes, and polyvinyl acetates. These may be used singly or in combination of two or more.
The acrylic polymer contains a structural unit composed of an acrylic acid ester monomer as a main component. The acrylic acid ester monomer preferably has 1 to 20 carbon atoms in the ester moiety. Examples of the acrylic polymer include a homopolymer of (a) an acrylic monomer, and a copolymer of (b) an acrylic monomer with an unsaturated fatty acid, an acrylic amide monomer, a maleimide monomer, a vinyl acetate monomer, or a vinyl copolymer (hereinafter also referred to as an acrylic copolymer).
Examples of the acrylate monomer include Methyl Acrylate (MA), ethyl Acrylate (EA), 2-ethylhexyl acrylate (2 EHA), acrylic Acid (AA), methacrylic acid (MAA), 2-hydroxyethyl acrylate (2 HEA), 2-hydroxyethyl methacrylate (2 HEMA), butyl Acrylate (BA), methyl Methacrylate (MMA), ethyl Methacrylate (EMA), n-butyl acrylate (nmma), isobutyl methacrylate (iBMA), propyl acrylate, isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, octyl acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, tricyclodecyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, 2-methoxyethyl acrylate, dimethylaminoethyl acrylate, chloroethyl acrylate, trifluoroethyl acrylate, tetrahydrofurfuryl acrylate, and the like. These may be used singly or in combination of two or more.
In the acrylic copolymer, the ratio of (a) the structural unit (a)) derived from the acrylic acid ester monomer to (b) the structural unit (b)) derived from the unsaturated fatty acid, the acrylic acid amide monomer, the maleimide monomer, the vinyl acetate or the like or the vinyl copolymer is preferably 50 to 100% by weight, and the structural unit (b) is 0 to 50% by weight.
The acrylic polymer preferably contains 50 wt% or more, more preferably 60 wt% or more, still more preferably 70 wt% or more, particularly preferably 80 wt% or more, and most preferably 90 wt% or more of structural units derived from Butyl Acrylate (BA).
The vinyl copolymer is obtained by copolymerizing a mixture containing at least one vinyl monomer selected from the group consisting of aromatic vinyl monomers, cyanated vinyl monomers and unsaturated carboxylic acid alkyl ester monomers. The mixture of vinyl monomers may further contain another monomer copolymerizable with the above monomers (hereinafter also referred to as monomer C).
Examples of the aromatic vinyl monomer include styrene, α -methylstyrene, phosphomethylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, and vinyltoluene. These vinyl monomers may be used alone or in combination of two or more. Among these, aromatic vinyl monomers are preferred, and styrene is more preferred, from the viewpoint of easiness of increasing the refractive index.
The unsaturated carboxylic acid alkyl ester monomer is not particularly limited. For example, esters of an alcohol having 1 to 6 carbon atoms with acrylic acid or methacrylic acid are preferable. The ester of an alcohol having 1 to 6 carbon atoms with acrylic acid or methacrylic acid may have a substituent such as a hydroxyl group or a halogen group.
Examples of the ester of an alcohol having 1 to 6 carbon atoms with acrylic acid or methacrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5, 6-pentahydroxy hexyl (meth) acrylate, and 2,3,4, 5-tetrahydroxypentyl (meth) acrylate. These may be used alone or in combination of two or more.
Examples of the cyanated vinyl monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like. These may be used alone or in combination of two or more.
The monomer C is not particularly limited as long as the effects of the present invention are not impaired, as long as it is the above aromatic vinyl monomer, unsaturated carboxylic acid alkyl ester monomer, and vinyl monomer other than the cyanated vinyl monomer. Specific examples of the monomer C include unsaturated fatty acids, acrylic amide monomers, maleimide monomers, vinyl acetate, and acrylate monomers. These may be used singly or in combination of two or more.
The unsaturated fatty acid may be selected from itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic acid, methacrylic acid, and the like, for example.
The acrylic amide monomer may be selected from, for example, acrylic amide, methacrylic amide, and N-methacrylic amide.
Examples of the maleimide monomer include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide.
The method for producing the vinyl copolymer is not particularly limited, and examples thereof include emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization.
In the method for producing a vinyl copolymer, a polymerization initiator may be used as needed, and one or more selected from the group consisting of peroxides, nitrogen compounds, potassium persulfate, and the like may be appropriately selected as the polymerization initiator. The addition amount of the polymerization initiator is not particularly limited.
Examples of the peroxide include benzoyl peroxide, cumene hydroperoxide, cumyl hydroperoxide, dicumyl hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl isopropyl carbonate, di-t-butyl peroxide, t-butyl peroxyoctoate, 1-bis (t-butylperoxy) 3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane, and t-butyl peroxy-2-ethylhexanoate. Among them, cumene hydroperoxide, 1-bis (several butylperoxy) 3, 5-trimethylcyclohexane and 1, 1-bis (several butylperoxy) cyclohexane are particularly preferably used.
Examples of the nitrogen-based compound include azoisobutyronitrile, azo (2, 4-dimethylvaleronitrile), 2-phenylazo-2, 4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propylazoformamide, 1 '-azocyclohexane-1-carbonitrile, azo (4-methoxy-2, 4-dimethylvaleronitrile), dimethyl 2,2' -azoisobutyl ester, 1-dibutylazo-2-cyanobutane, and 2-dibutylazo-2-cyano-4-methoxy-4-methylpentane. Among them, 1' -azocyclohexane-1-carbonitrile is particularly preferred.
The amount of the polymerization initiator to be added is not particularly limited.
Specific examples of the vinyl-based copolymer include polyvinyl chloride, chlorinated polyvinyl chloride, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, α -methylstyrene-acrylonitrile copolymer, polymethyl methacrylate, and methyl methacrylate-styrene copolymer. These may be used singly or in combination of two or more.
Examples of the polyester include ethylene terephthalate and polybutylene terephthalate.
(3-1-3. Physical Properties of matrix resin (C))
The properties of the matrix resin (C) are not particularly limited. The matrix resin (C) preferably has a viscosity of 100 mPas to 1000000 mPas at 25 ℃. The viscosity of the matrix resin (C) is more preferably 50000 mPas or less, still more preferably 30000 mPas or less, particularly preferably 15000 mPas or less at 25 ℃. According to the above constitution, the matrix resin (C) has an advantage of excellent fluidity. The matrix resin (C) having a viscosity of 100 mPas to 1000000 mPas at 25℃may be referred to as a liquid.
If the fluidity of the matrix resin (C) becomes too large, in other words, the smaller the viscosity becomes, it is difficult to disperse the polymer fine particles (A) in the state of primary particles in the matrix resin (C). It has been very difficult to disperse the polymer fine particles (a) in the form of primary particles in the matrix resin (C) having a viscosity of 1000000mpa·s or less at 25 ℃. However, the resin composition according to an embodiment of the present invention has the following advantages: the polymer fine particles (A) having the above-described constitution are advantageously well dispersed in the matrix resin (C) having a viscosity of 1000000 mPas or less at 25 ℃.
The viscosity of the matrix resin (C) can prevent the polymer fine particles (a) from being fused with each other by providing the matrix resin (C) to the polymer fine particles (a), and 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 viscosity of the matrix resin (C) is more preferably 100 to 750000 mPas, more preferably 100 to 700000 mPas, more preferably 100 to 350000 mPas, more preferably 100 to 300000 mPas, more preferably 100 to 50000 mPas, more preferably 100 to 30000 mPas, and particularly preferably 100 to 15000 mPas at 25 ℃.
The matrix resin (C) may have a viscosity of more than 1000000 mPas. The matrix resin (C) may be semi-solid (semi-liquid) or solid. When the matrix resin (C) has a viscosity of more than 1000000 mPas, the resin composition containing the obtained powder or granule has the advantage of low tackiness and easy handling.
The matrix resin (C) 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 (C) has an advantage of excellent fluidity.
(3-2. Mixing ratio of powder and matrix resin (C), etc.)
The blending ratio of the powder and matrix resin (C) is usually preferably 0.5 to 50% by weight of the powder, more preferably 50 to 99.5% by weight of the matrix resin (C), still more preferably 1 to 35% by weight of the powder, 65 to 99% by weight of the matrix resin (C), particularly preferably 1.5 to 25% by weight of the powder, 75 to 98.5% by weight of the matrix resin (C), most preferably 2.5 to 20% by weight of the powder, and 80 to 97.5% by weight of the matrix resin (C), based on 100% by weight of the total of the powder and matrix resin (C).
When the total of the powder and matrix resin (C) is 100 wt%, the blending ratio of the powder and matrix resin (C) is usually preferably 0.5 to 50 wt%, the matrix resin (C) is 50 to 99.5 wt%, more preferably 1 to 50 wt%, the matrix resin (C) is 50 to 99 wt%, more preferably 1 to 45 wt%, the matrix resin (C) is 55 to 99 wt%, more preferably 1 to 40 wt%, the matrix resin (C) is 60 to 99 wt%, more preferably 1 to 35 wt%, the matrix resin (C) is 65 to 99 wt%, more preferably 1 to 30 wt%, the matrix resin (C) is 70 to 99 wt%, more preferably 1 to 25 wt%, the matrix resin (C) is 75 to 99 wt%, more preferably 1.5 to 25 wt%, the matrix resin (C) is 75 to 98.5 wt%, more preferably 1.5 to 20 wt%, the matrix resin (C) is 1 to 35 wt%, the matrix resin (C) is 60 to 99 wt%, more preferably 1 to 35 wt%, the matrix resin (C) is 65 to 99 wt%, more preferably 1 to 30 wt%, the matrix resin (C) is 70 to 99 wt%, and the matrix resin (C) is particularly preferably 2 to 80.5 to 80 wt%.
In the case where the matrix resin (C) is a thermosetting resin, the state of the matrix resin (C) is not particularly limited as long as it is flowable when mixed with the powder or granular material, and may be solid at room temperature, and is preferably liquid from the viewpoint of workability.
The temperature at which the powder or granule is mixed with the thermosetting matrix resin (C) is usually a temperature at which the thermosetting matrix resin (C) is flowable, but as long as the resin (B) is flowable at a temperature at which the thermosetting matrix resin (C) is flowable, it is easy to uniformly mix the resin (B) with the thermosetting matrix resin (C). Conversely, when the thermosetting matrix resin is in a liquid state and the epoxy resin added to the powder or granular material is in a solid state, it is difficult to uniformly mix the two. In the present specification, when the thermosetting matrix resin (C) is in a liquid state at 25 ℃, it can be interpreted as "the viscosity of the thermosetting matrix resin (C) at 25 ℃ is equal to or higher than the viscosity of the resin (B) at 25 ℃.
(3-3. Organic solvent)
The present resin composition preferably contains substantially no organic solvent. When the powder particles substantially do not contain an organic solvent, a resin composition substantially containing no organic solvent can be obtained. By "substantially free of organic solvent" is meant that the amount of organic solvent in the resin composition is 100ppm or less.
The amount of the organic solvent (also referred to as solvent-containing amount) contained in the present resin composition is preferably 100ppm or less, more preferably 50ppm or less, further preferably 25ppm or less, and particularly preferably 10ppm or less. The amount of the organic solvent contained in the present resin composition may also be referred to as the amount of the volatile component (excluding water) contained in the present resin composition. The amount of the organic solvent (volatile component) contained in the present resin composition can be determined as a reduced weight component by heating a predetermined amount of the resin composition with, for example, a hot air drying agent or the like, and measuring the weight of the resin composition before and after heating. The amount of the organic solvent (volatile component) contained in the present resin composition can be determined by gas chromatography. In the present resin composition and the production of the powder and granular material contained in the resin composition, the amount of the organic solvent contained in the obtained resin composition was regarded as 0ppm without using the organic solvent.
Examples of the organic solvent which is not substantially contained in the present resin composition include (a) esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, (b) ketones such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone, (c) alcohols such as ethanol, (isopropyl alcohol and butanol, (d) tetrahydrofuran, tetrahydropyran and dipyrrometheneAn alkane,Ethers such as diethyl ether, (e) aromatic hydrocarbons such as benzene, toluene and xylene, and (f) halogenated hydrocarbons such as methylene chloride and chloroform.
(3-4. Foreign matter grade)
The foreign matter grade of the present resin composition when evaluated by a fineness gauge is preferably 100 μm or less, more preferably 80 μm or less, further preferably 60 μm or less, further preferably 40 μm or less, further preferably 20 μm or less, and most preferably 0 μm. If the foreign matter level is within the above range, no foreign matter of the resin composition is present. The foreign matter level can be determined by the method described in example "(dispersibility of the polymer fine particles (a) in the resin composition)".
(3-5. Other optional Components)
The present resin composition may contain any other component than the above components as required. Examples of other optional components include colorants such as curing agents, pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, thermal stabilizers (gelation inhibitors), plasticizers, leveling agents, defoamers, silane coupling agents, antistatic agents, flame retardants, lubricants, adhesion reducers, low shrinkage agents, inorganic fillers, organic fillers, thermoplastic resins, drying agents, dispersants, and the like. Further, these arbitrary components may have halogen elements, and therefore, it is preferable to use arbitrary components having a halogen element content of a predetermined value or less. The halogen element content may be 500ppm or less, preferably 400ppm or less, more preferably 300ppm or less, further preferably 200ppm or less, particularly preferably 100ppm or less, and most preferably 50ppm or less. And, it is preferably 30ppm or less, more preferably 10ppm or less, further preferably 5ppm or less, particularly preferably 1ppm or less, and most preferably n.d.
The present resin composition may further contain a known thermosetting resin other than the base resin (C), or may further contain a known thermoplastic resin.
(3-6. Process for producing resin composition)
As a method for producing a resin composition according to an embodiment of the present invention, there is provided a method for producing a resin composition, which comprises a step of mixing a powder obtained by the method for producing a powder with a base resin (C) having a halogen element content of 500ppm or less. The respective components and specific steps are not particularly limited, and the above description is appropriately cited. According to the present production method, a resin composition having a small halogen element content can be produced.
The method for producing a resin composition may further include a step of cleaning the obtained resin composition. The resin composition is washed to produce a resin composition having a smaller halogen element content. In the present cleaning step, the "powder particles" in the column (2-3. Cleaning step) are replaced with "resin composition".
[ 4. Cured product ]
In the present resin composition described in item [ 3 ] the cured product of one embodiment of the present invention is a cured product of the base resin (C) which is a thermosetting resin. Hereinafter, the cured product according to an embodiment of the present invention will be referred to as the present cured product only.
The cured product has the above-described constitution, and is less likely to rust when applied to a metal plate or the like and cured. In addition, (a) has a beautiful surface, (b) has high rigidity and high elastic modulus, and (c) is excellent in toughness and adhesion.
[ 5. Metal-clad laminate ]
The metal-clad laminate according to one embodiment of the present invention may be one in which the resin composition described in item [ 3 ] is used, as long as the base resin (C) is a thermosetting resin. Hereinafter, the metal-clad laminate according to an embodiment of the present invention may be simply referred to as the present metal-clad laminate.
The metal-clad laminate has the above-described structure, and is less prone to rust. In addition, the alloy has the advantage of excellent toughness and impact resistance. In addition, as described above, dendrite growth caused by excessive ion utilization can be suppressed, and electrical insulation is excellent.
The use of the metal-clad laminate is not particularly limited, and examples thereof include printed circuits, printed wiring, printed circuit boards, printed circuit mountings, printed wiring boards, and printed boards.
[ 6 ] other uses ]
The powder or resin composition according to one embodiment of the present invention can be used for various applications, and these applications are not particularly limited. The powder particles or the resin composition can be used preferably for, for example, adhesives, coating materials, adhesives for reinforcing fibers, resin concretes, composite materials, molding materials for 3D printers, sealants, electronic boards, ink adhesives, adhesives for wood chips, adhesives for rubber chips, adhesives for foam sheets, adhesives for castings, binders for beds, and rock-consolidating materials for ceramics, polyurethane foams, and the like. Examples of the polyurethane foam include automobile sheets, automobile interior parts, sound absorbing materials, vibration absorbing materials, shock absorbers (impact absorbing materials), heat insulating materials, and bed material mats for construction sites.
The powder or resin composition is more preferably used as an adhesive, a coating material, a reinforcing fiber adhesive, a composite material, a molding material for a 3D printer, a sealant, or an electronic substrate in the above-mentioned applications.
(6-1. Adhesive)
The binder according to an embodiment of the present invention includes the powder or resin composition. The adhesive according to an embodiment of the present invention has the above-described configuration, and thus has excellent adhesion.
The adhesive according to an embodiment of the present invention is simply referred to as the present adhesive.
The adhesive is preferably used for various applications such as automobile interior materials, general woodworking, furniture, interior materials, wall materials, and food packaging.
The adhesive has excellent adhesion to various covers such as polyester (FRP) reinforced with cold rolled steel, aluminum, glass fiber, panel of cured product of thermosetting resin such as epoxy resin reinforced with carbon fiber, panel of thermoplastic resin sheet reinforced with carbon fiber, seat Molding Compound (SMC), acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl chloride (PVC), polycarbonate, polypropylene, TPO, wood and glass.
The adhesive is excellent in not only low temperature (-20 ℃ C.) to normal temperature, but also adhesion property and flexibility at high temperature (about 80 ℃ C.). The adhesive can thus be used more preferably as a structural adhesive.
The structural adhesive using the adhesive can be used as an adhesive for structural members in the fields of automobiles, vehicles (trunk lines, electric buses, etc.), civil engineering, construction, building materials, woodworking, electric and electronic products, spacecrafts, and the aerospace industry, for example. In particular, applications related to automobiles include adhesion of interior materials such as ceilings, doors, and sheets, adhesion of exterior materials such as automobile lighting fixtures such as lamps, and shopping malls, and the like.
The binder can be produced using the powder or resin composition. The method for producing the adhesive is not particularly limited, and a known method can be used.
(6-2. Coating materials)
The coating material according to an embodiment of the present invention includes the powder or resin composition. The coating material according to an embodiment of the present invention has the above-described configuration, and thus can provide a coating film excellent in load resistance and abrasion resistance.
The coating material according to an embodiment of the present invention is simply referred to as the present coating material.
The coating material contains, for example, an organic solvent in which the polymer fine particles (a) are dispersed in the form of primary particles and the powder. The coating material contains, for example, an organic solvent in which the polymer fine particles (a) are dispersed in the form of primary particles, and the resin composition. Conventionally, it has been very difficult to disperse the polymer fine particles (a) in the form of primary particles in an organic solvent. However, the present powder particles have an advantage of providing a coating material in which the polymer fine particles (a) are more uniformly dispersed in the organic solvent. The powder may be a powder for a coating material.
In the case of applying the present coating material to, for example, floors or hallways, a generally practiced application method can be applied. For example, after the primer is applied to the base of the base material, the coating material is uniformly applied using iron, a roller, a rake, a spray gun, or the like according to the working conditions. After the coating material is coated, curing is carried out, and the paving film with good performance is obtained. The coating film obtained by curing the present coating material can be a coating film excellent in load resistance and abrasion resistance.
The viscosity of the resin composition used for the coating material can be adjusted according to the method of application of the coating material. For example, in the case of using iron or a rake for the application of the present coating material, the viscosity of the resin composition used for the coating material can be generally adjusted to about 500 to 9000cps/25 ℃. In the case of using a roll or spray for the application of the present coating material, the viscosity of the resin composition used for the coating material can be generally adjusted to about 100 to 3000cps/25 ℃.
The substrate (in other words, the floor or corridor material) to which the coating material is applied is not particularly limited. Specific examples of the substrate include (a) inorganic substrates such as Concrete walls, concrete slabs, concrete blocks, CMU (Concrete Masonry Unit), mortar boards, ALC (automatic Light-weight Concrete) boards, gypsum boards (Dens Glass Gold: made by Georgia Pacific Co., ltd.), stone slabs, etc., (b) wood substrates (wood, plywood, OSB (Oriented Strand Board), etc.), asphalt, waterproof sheets of modified asphalt, waterproof sheets of ethylene-propylene-diene rubber (EPDM), waterproof sheets of TPO, organic substrates such as plastics, FRP, polyurethane foam heat insulators, etc., (c) metal substrates such as metal panels, etc.
The case where the present coating material is applied to a metal substrate or a porous substrate will be described. After the coating, the laminate obtained by curing the coating material is excellent in corrosion resistance to the substrate. In addition, after the above-mentioned coating, a coating film obtained by curing the coating material can impart excellent crack resistance and load resistance to the substrate. Thus, the method of applying the present coating material to a metal substrate or a porous substrate is not particularly preferable.
The coating method of the present coating material is not particularly limited, and may be carried out by a known coating method such as iron, rake, brush, roller, gas spraying, or spray coating.
The application of the coating material is not particularly limited, and examples thereof include automobiles, electrical machines, office machines, building materials, wood, floor boards, pavement, heavy duty, concrete, roof and roof water-proofing, roof and roof corrosion-proofing, underground water-proofing coating materials, automobile repair, tank coating, exterior coating, middle coating, interior coating, primer, electrocoating, high weather-resistant coating, and yellowing-free coating. In the case of being used for a coating material for floor coating, a coating material for coating, and the like, it can be used for factories, laboratories, warehouses, finishing houses, and the like.
The coating material can be produced using the powder or resin composition. The method for producing the present coating material is not particularly limited, and a known method can be used.
(6-2-1. Membrane)
The film according to an embodiment of the present invention includes the powder or resin composition. The film according to an embodiment of the present invention has the above-described configuration, and thus is excellent in load resistance and abrasion resistance.
The film according to an embodiment of the present invention is simply referred to as the present film.
The film is obtained by volatilizing an organic solvent, for example, from a dope containing the organic solvent and the powder. The film is obtained, for example, by volatilizing an organic solvent from a dope containing the organic solvent and the present resin composition. In these doping solutions, the polymer fine particles (a) are dispersed in the form of primary particles in an organic solvent. It has been very difficult to disperse the polymer fine particles (a) in the form of primary particles in an organic solvent. However, the present powder or granule provides a dope in which the polymer fine particles (a) are more uniformly dispersed in the organic solvent, thereby having an advantage that the polymer fine particles (a) can provide a film more uniformly dispersed. The powder may be a powder for a film.
The use of the film is not particularly limited, and the film may be used for an optical film such as a polarizer protective film, a decorative film, a conductive film, an electromagnetic wave absorbing sheet, an antireflection film, and the like.
The film can be produced using the powder or resin composition. The method for producing the present film is not particularly limited, and a known method can be used.
(6-3. Composite material)
The composite material according to an embodiment of the present invention includes the powder or resin composition as a binder for reinforcing fibers. The composite material according to an embodiment of the present invention has the above-described structure, and thus has advantages of excellent toughness and impact resistance.
The composite material according to an embodiment of the present invention is simply referred to as the present composite material.
The present composite material may comprise reinforcing fibers. The reinforcing fibers are not particularly limited, and examples thereof include glass fibers, long glass fibers, carbon fibers, natural fibers, metal fibers, thermoplastic resin fibers, boron fibers, aramid fibers, polyethylene fibers, sialon reinforcing fibers, and the like. Among these reinforcing fibers, glass fibers and carbon fibers are particularly preferable.
The method for producing the composite material (molding method) is not particularly limited, and examples thereof include autoclave molding, winding molding, hand lay-up molding, vacuum bag molding, resin injection molding (RTM), vacuum assisted resin injection molding (VARTM), drawing molding, injection molding, sheet winding molding, spraying, BMC (Bulk Molding Compound), SMC (Sheet MoldingCompound), and the like.
In particular, when carbon fibers are used as the reinforcing fibers, an autoclave molding method, a winding molding method, a hand lay-up molding method, a vacuum bag molding method, a resin injection molding (RTM) method, a vacuum assisted resin injection molding (VARTM) method, or the like using a prepreg is preferably used as the method for producing the present composite material.
The application of the composite material is not particularly limited, and examples thereof include aircraft, spacecraft, automobile, self-rotating vehicle, ship, weapon, windmill, sporting goods, container, building material, waterproof material, printed circuit board, and electric insulating material.
The composite material can be produced using the powder or resin composition. More details of the present composite material, such as the reinforcing fiber, the production method (molding method), the production conditions (molding conditions), the compounding agent, and the use thereof, include those described in U.S. patent publication No. 2006/0173128, U.S. patent publication No. 2012/024586, japanese patent application laid-open No. 2002-530445 (International publication No. WO 2000/029459), japanese patent application laid-open No. 55-157620 (U.S. patent publication No. 4251428), japanese patent application laid-open No. 2013-504007 (International publication No. WO 2011/028271), japanese patent application laid-open No. 2007-125889 (U.S. patent publication No. 2007/0098997), and Japanese patent application laid-open No. 2003-220661 (U.S. publication No. 2003/013685).
(shaping Material of 6-4.3D Printer)
The modeling material for a 3D printer according to an embodiment of the present invention includes the powder or resin composition. The modeling material for a 3D printer according to an embodiment of the present invention has the above-described configuration, and thus has advantages of excellent toughness and impact resistance.
The modeling material of the 3D printer according to an embodiment of the present invention is also simply referred to as the present modeling material.
The use of the molding material is not particularly limited, and examples thereof include test products, parts of aircraft, building parts, parts of medical equipment, and the like, which are aimed at the verification of design and functional verification before production of the product.
The molding material can be produced using the powder or the resin composition. The method for producing the molding material is not particularly limited, and a known method can be used.
(6-5. Sealant)
The sealant according to an embodiment of the present invention is formed using the powder or resin composition. The sealant according to an embodiment of the present invention has the above-described structure, and thus has advantages of excellent toughness and impact resistance.
The sealant according to an embodiment of the present invention is simply referred to as the present sealant.
The application of the present sealant is not particularly limited, and various electrical devices such as semiconductors, power devices, and the like are sealed.
The present sealant can be produced using the present powder or resin composition. The method for producing the present sealant is not particularly limited, and a known method can be used.
The present invention may include the following means.
(1) A process for producing a powder or granule, which comprises adding a coagulant having a halogen element content of 500ppm or less to an aqueous latex containing polymer fine particles (A) to coagulate the aqueous latex; and mixing the polymer fine particles (A) with a resin (B) having a halogen element content of 500ppm or less; the polymer fine particles (A) comprise a rubber-containing graft copolymer having an elastomer and a graft portion grafted and bonded to the elastomer, the elastomer comprises at least one selected from the group consisting of a diene rubber, (meth) acrylate rubber and an organosiloxane rubber, the graft portion comprises a polymer containing a structural unit derived from at least one monomer selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer and a (meth) acrylate monomer as a constituent unit, the resin (B) is a liquid, a semisolid or a solid having a viscosity of 100 mPas to 1000000 mPas at 25 ℃, and the polymer fine particles (A) are 50 to 99% by weight and the resin (B) is 1 to 50% by weight, based on 100% by weight of the total of the polymer fine particles (A) and the resin (B).
(2) The method for producing a powder or granular material according to (1), comprising the steps of: a resin (B) adding step of adding a resin (B) to an aqueous latex containing the polymer fine particles (A); a coagulation step of preparing a coagulated body containing the polymer fine particles (a) and the resin (B) by using the aqueous latex obtained in the resin (B) addition step; and a recovery step of recovering the aggregate, wherein the resin (B) has a viscosity of 100 mPas to 1000000 mPas at 25 ℃, and the polymer particles (A) are 50 to 99 wt% and the resin (B) is 1 to 50 wt% based on 100 wt% of the total of the polymer particles (A) and the resin (B).
(3) The method for producing a powder or granular material according to (1), comprising the steps of: a resin (B) polymerization step of polymerizing a resin (B) in an aqueous latex containing the polymer fine particles (A); a coagulation step of preparing a coagulated body containing the polymer fine particles (a) and the resin (B) by using the aqueous latex obtained; and a recovery step of recovering the aggregate, wherein the resin (B) is a liquid, semi-solid or solid having a viscosity of 100 mPas to 1,000,000 mPas at 25 ℃, and the polymer fine particles (A) are 50 to 99% by weight and the resin (B) is 1 to 50% by weight, based on 100% by weight of the total of the polymer fine particles (A) and the resin (B).
(4) A method for producing a powder or granular material according to any one of (1) to (3), wherein a force required for disintegrating the bulk of the powder or granular material is 30000Pa or less,
wherein the block is obtained by placing a weight of 6.3kg on 30g of the powder or granule contained in a cylindrical container having a diameter of 50mm, standing at 60 ℃ for 2 hours, and adding a load of 6.3kg to the powder or granule, and the force is a value measured by a rheometer.
(5) The method for producing a powder or granular material according to any one of (1) to (4), wherein the powder or granular material has a volume average particle diameter (Mv) of 30 μm to 500. Mu.m.
(6) The method for producing a powder or granular material according to any one of (1) to (5), wherein the halogen element is chlorine or bromine.
(7) A method for producing a resin composition comprising the step of mixing the powder or granule obtained by the method for producing a powder or granule according to any one of (1) to (6) with a matrix resin (C) having a halogen element content of 500ppm or less.
(8) A powder or granule comprising polymer particles (A) and a resin (B), wherein the polymer particles (A) comprise a rubber-containing graft copolymer having an elastomer and a graft unit bonded to the elastomer, the elastomer comprises at least one member selected from the group consisting of diene rubbers, (meth) acrylate rubbers and organosiloxane rubbers, the graft unit comprises a polymer comprising a structural unit derived from at least one member selected from the group consisting of aromatic vinyl monomers, vinyl cyano monomers and (meth) acrylate monomers as a constituent unit, the content of halogen elements is 500ppm or less, the resin (B) is a liquid, semi-solid or solid having a viscosity of 100 mPas to 1000000 mPas at 25 ℃, and the polymer particles (A) are 50 to 99 wt% and the resin (B) is 1 to 50 wt% when the total of the polymer particles (A) and the resin (B) is 100 wt%.
(9) A powder or granule according to (8), wherein the halogen element is chlorine or bromine.
(10) The powder or granule according to (8) or (9), wherein the force required for disintegrating the bulk of the powder or granule is 30000Pa or less,
here, the block is a block obtained by placing a weight of 6.3kg on 30g of the powder or granular material stored in a cylindrical container having a diameter of 50mm, standing at 60 ℃ for 2 hours, and adding a load of 6.3kg to the powder or granular material, and the force is a value measured by a rheometer.
(11) A powder or granular material according to any one of (8) to (10), wherein the powder or granular material has a volume average particle diameter (Mv) of 30 μm to 500. Mu.m.
(12) A resin composition comprising the powder or granule according to any one of (8) to (11) and a matrix resin (C).
(13) The resin composition according to (12), wherein the content of the halogen element in the matrix resin (C) is 500ppm or less.
(14) A cured product obtained by curing the resin composition according to (12) or (13), wherein the base resin (C) is a thermosetting resin.
(15) A metal-clad laminate obtained by using the resin composition according to (12) or (13), wherein the base resin (C) is a thermosetting resin.
Examples
Hereinafter, an embodiment of the present invention will be described in further detail with reference to examples and comparative examples, but the present invention is not limited thereto. An embodiment of the present invention may be appropriately modified within a range suitable for the gist described above or later, and both may be included in the scope of the technique of the present invention. In the following examples and comparative examples, "part" and "%" refer to parts by weight or% by weight.
< evaluation method >)
First, the method for evaluating the resin compositions produced in examples and comparative examples will be described below.
(measurement of volume average particle diameter)
The volume average particle diameter (Mv) of the elastomer or polymer fine particles (A) dispersed in the aqueous latex was measured using Nanotrac WaveII-EX150 (manufactured by MicroTrack Bell Co., ltd.). The aqueous latex was diluted with deionized water to obtain a sample for measurement. The refractive index of the elastomer or polymer fine particles (a) obtained in each production example was measured by adding water thereto, and the sample concentration was adjusted so that the measurement time was 120 seconds and the loading index was 1 to 10.
The volume average particle diameter (Mv) of the powder was measured using a laser diffraction type particle size distribution measuring apparatus microtrack mt3000II (manufactured by microtrack Bell corporation).
(differential scanning calorimeter (DSC) of resin (B))
The resin (B) contained in the aqueous emulsion was measured at a temperature rise rate of 10℃per minute by DSC7020 (manufactured by Hitachi High tech science, co., ltd.). As a result, the resin containing S-1 was-9.4℃and the resin containing S-2 was-16.9℃and the resin containing S-3 was-15.2 ℃.
(determination of viscosity of resin (B))
The viscosity of the resin (B) contained in the aqueous emulsion was measured by changing the Shear Rate (sliding speed) as required at a measurement temperature of 25℃using a digital viscometer DV-II+Pro type manufactured by BROOKFIELD, and using spindle CPE-52 according to the viscosity region. As a result, the content of the resin S-1 was 400 mPas, the content of the resin S-2 was 11000 mPas, and the content of the resin S-3 was 12000 mPas.
(dispersibility of Polymer particles (A) in resin composition)
The resin composition was placed on a grinder (fineness gauge), and polymer particles (a) on the fineness gauge were scraped off with a metal spatula, and the dispersion state was visually confirmed. The marks of 5 to 10 points in the 3mm wide tape were read as graining marks generated by the movement of the doctor blade. Further, the foreign matter level can be evaluated by the evaluation method of dispersibility.
< residual halogen content >)
The content of halogen (residual halogen amount) in the powder, coagulant and resin was measured using a fluorescent X-ray analytical device SPECTRO XEPOS (manufactured by SPECTRO Co.).
(anti-blocking agent of mixture (powder) of Polymer particles and resin (D))
Using the powder particles obtained in each production example, the following operations (1) to (3) were sequentially performed to prepare a block of powder particles: (1) The powder 30g is accommodated in a cylindrical container with a diameter of 50 mm; (2) Placing a weight of 6.3kg on the powder in the container, and adding 6.3kg of the powder at 60 ℃ for 2 hours; (3) removing the resulting block from the container. Next, the force required for disintegrating the obtained bulk of the powder was measured by a rheometer. Based on the obtained results, the antiblocking agent was evaluated according to the following criteria.
Qualified: the force required to disintegrate the bulk of the powder is 30000Pa or less.
Disqualification: the force required to disintegrate the mass of the powder exceeds 30000Pa.
< 1 formation of elastomer (core layer) >)
( Production example 1-1; preparation of polybutadiene rubber latex (R-1) )
200 parts by weight of deionized water, 0.03 part by weight of tripotassium phosphate, 0.002 part by weight of Ethylene Diamine Tetraacetic Acid (EDTA), 0.001 part by weight of ferrous sulfate 7 hydrated salt and 1.55 parts by weight of Sodium Dodecyl Benzene Sulfonate (SDBS) were charged into a pressure-resistant polymerizer. Next, nitrogen substitution is performed on the gas inside the pressure-resistant polymerizer while stirring the charged raw materials, so that oxygen is sufficiently removed from the inside of the pressure-resistant polymerizer. Thereafter, 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 ℃. Thereafter, 0.03 parts by weight of p-menthane hydroperoxide (PHP) was charged into the pressure-resistant polymerizer, and then 0.10 parts by weight of Sodium Formaldehyde Sulfoxylate (SFS) was charged into the pressure-resistant polymerizer, to start polymerization. The polymerization was terminated by devolatilizing at 15 hours from the start of the polymerization under reduced pressure to devolatilize the monomers remaining without being used for the polymerization. In the polymerization, PHP, EDTA and ferrous sulfate 7 hydrous salt are added in an arbitrary amount and in an arbitrary timing to the pressure-resistant polymerizer, respectively. By this polymerization, an aqueous latex (R-1) containing an elastomer (core layer) containing polybutadiene rubber as a main component was obtained. The volume average particle diameter of the elastomer (core layer) contained in the obtained aqueous latex was 90nm.
( Production examples 1 to 2; preparation of polybutadiene rubber latex (R-2) )
The polybutadiene rubber latex (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 7 hydrated salt were charged in a pressure-resistant polymerizer in a solid content of 7 parts by weight. 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. Thereafter, bd 93 parts by weight was charged into a pressure-resistant polymerizer, and the temperature in the pressure-resistant polymerizer was raised to 45 ℃. Thereafter, 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 start polymerization. The polymerization was terminated by devolatilizing at 30 hours from the start of the polymerization under reduced pressure to devolatilize the monomers remaining without being used for the polymerization. In the polymerization, PHP, EDTA and ferrous sulfate 7 hydrous salt are added to the pressure-resistant polymerizer in an arbitrary amount and in an arbitrary timing. By this polymerization, an aqueous latex (R-2) containing an elastomer (core layer) containing polybutadiene rubber as a main component was obtained. The volume average particle diameter of the elastomer (core layer) contained in the obtained aqueous latex was 195nm.
< 2. Preparation of Polymer particles (A) (formation of grafting sites (Shell layer))
( Production example 2-1; preparation of Polymer (core Shell Polymer) latex (L-1) with elastomer-graft portion )
215 parts by weight of the polybutadiene rubber latex (R-2) (comprising 70 parts by weight of an elastomer containing polybutadiene rubber as a main component) and 82 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 raw materials charged at 60℃were stirred while substituting nitrogen for the gas in the glass reactor. Next, 2.6 parts by weight of 1, 3-butanediol dimethacrylate and 0.07 parts by weight of t-Butylhydroperoxide (BHP) were charged into a glass reactor, and stirred for 10 minutes. Thereafter, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate 7 hydrated salt and 0.13 parts by weight of SFS were added to the glass reactor, and stirred for 30 minutes. Thereafter, 0.013 parts by weight of BHP was added to the glass reactor, and the mixture was stirred for further 30 minutes. Thereafter, a mixture of 28.5 parts by weight of Methyl Methacrylate (MMA), 1.5 parts by weight of Butyl Acrylate (BA) and 0.085 parts by weight of BHP was continuously added in a glass reactor for 120 minutes. Thereafter, 0.013 parts by weight of BHP was added to the glass reactor, and the mixture in the glass reactor was stirred for a further 1 hour to complete the polymerization. By the above procedure, an aqueous latex (L-1) containing the polymer fine particles (A) was obtained. The polymerization conversion rate of the monomer component is more than 99%. The volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 200nm.
< 3 > preparation of powder
Preparation example 3-1 preparation of powder (P-1)
An aqueous emulsion (S-1) (resin (B) content 50%) obtained by emulsifying the resin (B) was prepared by mixing 90 parts by weight of epoxidized soybean oil (ADK CIZER O-130P, manufactured by ADEKA Co., ltd.), 10 parts by weight of triethylene glycol bis [3- (-digital butyl-4-hydroxy-5-methylphenyl) propionate ] (Irganox 245, manufactured by BASF Japanese Co., ltd.) and SDBS as an emulsifier with a homogenizer. In addition, 4 parts by weight of calcium acetate was dissolved, and 600 parts by weight of ion-exchanged water adjusted to a temperature of 70℃was used. Next, 333 parts by weight of the aqueous emulsion (L-1) corresponding to 100 parts by weight of the polymer fine particles (a) and 22.2 parts by weight of the aqueous emulsion (S-1) (corresponding to 11.1 parts by weight of the resin (B)) were put into 600 parts by weight of the ion-exchanged water, to obtain a slurry containing coagulated matters of the polymer fine particles (a) and the resin (B). Next, the slurry was subjected to centrifugal dewatering to obtain wet powder as the coagulated material. Then, using the obtained wet powder, the operation of adding the wet powder to 500 parts by weight of ion-exchanged water and the operation of centrifugally dewatering the obtained mixture were repeated for a total of 2 cycles to obtain wet powder. Finally, the wet powder was dried in a dryer at 50℃for 48 hours to obtain a powder (P-1). In addition, the epoxidized soybean oil, triethylene glycol bis [3- (-n-butyl-4-hydroxy-5-methylphenyl) propionate ] and calcium acetate as the coagulant contained 500ppm or less of halogen as the resin (B). The obtained powder was evaluated for blocking resistance, and the result was acceptable. The volume average particle diameter of the obtained powder was measured, and as a result, the volume average particle diameter was 10mm or less.
Preparation example 3-2 preparation of powder (P-2)
An aqueous emulsion (S-2) (resin (B) content 50%) obtained by emulsifying the resin (B) was prepared by mixing 50 parts by weight of epoxidized soybean oil (ADK CIZER O-130P, manufactured by ADEKA Co., ltd.), 50 parts by weight of triethylene glycol bis [3- (-digital butyl-4-hydroxy-5-methylphenyl) propionate ] (Irganox 245, manufactured by BASF Japanese Co., ltd.) as water and the resin (B) together with SDBS as an emulsifier using a homogenizer. In addition, 4 parts by weight of calcium acetate was dissolved, and 600 parts by weight of ion-exchanged water adjusted to a temperature of 70℃was used. Next, 333 parts by weight of an aqueous emulsion (L-1) corresponding to 100 parts by weight of the polymer fine particles (a) and 22.2 parts by weight of the aqueous emulsion (S-2) (corresponding to 11.1 parts by weight of the resin (B)) were put into 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated material containing the polymer fine particles (a) and the resin (B). Next, the slurry was subjected to centrifugal dewatering to obtain wet powder as the coagulated material. Then, using the obtained wet powder, the operation of adding the wet powder to 500 parts by weight of ion-exchanged water and the operation of telecentrically dehydrating the obtained mixture were repeated for a total of 2 cycles to obtain the wet powder. Finally, the wet powder was dried in a dryer at 50℃for 48 hours to obtain a powder (P-2). The obtained powder was evaluated for blocking resistance, and the result was acceptable. The volume average particle diameter of the obtained powder was measured, and as a result, the volume average particle diameter was 10mm or less.
Preparation example 3-3 preparation of powder (P-3)
An aqueous emulsion (S-2) (resin (B) content 50%) obtained by emulsifying the resin (B) was prepared by mixing 50 parts by weight of epoxidized soybean oil (ADK CIZER O-130P, manufactured by ADEKA Co., ltd.) as water and the resin (B), 50 parts by weight of triethylene glycol bis [3- (-n-butyl-4-hydroxy-5-methylphenyl) propionate ] (Irganox 245, manufactured by BASF Japanese Co., ltd.) and SDBS as an emulsifier together using a homogenizer. In addition, 4 parts by weight of magnesium acetate was dissolved, and 600 parts by weight of ion-exchanged water adjusted to a temperature of 70 ℃. Next, 333 parts by weight of the aqueous emulsion (L-1) corresponding to 100 parts by weight of the polymer fine particles (a) and 22.2 parts by weight of the aqueous emulsion (S-2) (corresponding to 11.1 parts by weight of the resin (B)) were put into 600 parts by weight of the ion-exchanged water to obtain a slurry containing coagulated matters of the polymer fine particles (a) and the resin (B). Next, the slurry was subjected to centrifugal dewatering to obtain wet powder as the coagulated material. Then, using the obtained wet powder, the operation of adding the wet powder to 500 parts by weight of ion-exchanged water and the operation of centrifugally dewatering the obtained mixture were repeated for a total of 2 cycles to obtain wet powder. Finally, the wet powder was dried in a dryer at 50℃for 48 hours to obtain a powder (P-3). The magnesium acetate as the coagulant has a halogen content of 500ppm or less. The powder was evaluated for blocking resistance, and the result was acceptable. The volume average particle diameter of the obtained powder was measured, and as a result, the volume average particle diameter was 10mm or less.
Preparation examples 3 to 4, preparation of powder (P-4)
An aqueous emulsion (S-2) (resin (B) content 50%) in which the resin (B) was emulsified was prepared by mixing 50 parts by weight of epoxidized soybean oil (ADK CIZ ER O-130P, manufactured by ADEKA Co., ltd.), 50 parts by weight of triethylene glycol bis [3- (-n-butyl-4-hydroxy-5-methylphenyl) propionate ] (Irganox 245, manufactured by BASF Japanese Co., ltd.) as water and the resin (B) together with SDBS as an emulsifier using a homogenizer. In addition, 4 parts by weight of calcium chloride was dissolved, and 600 parts by weight of ion-exchanged water adjusted to a temperature of 70℃was used. Next, 333 parts by weight of the aqueous emulsion (L-1) corresponding to 100 parts by weight of the polymer fine particles (a) and 22.2 parts by weight of the aqueous emulsion (S-2) (corresponding to 11.1 parts by weight of the resin (B)) were put into 600 parts by weight of the ion-exchanged water to obtain a slurry containing coagulated matters of the polymer fine particles (a) and the resin (B). Next, the slurry was subjected to centrifugal dewatering to obtain wet powder as the coagulated material. Then, using the obtained wet powder, the operation of adding the wet powder to 500 parts by weight of ion-exchanged water and the operation of centrifugally dewatering the obtained mixture were repeated for a total of 2 cycles to obtain wet powder. Finally, the wet powder was dried in a dryer at 50℃for 48 hours to obtain a powder (P-4).
Preparation examples 3 to 5, preparation of powder (P-5)
An aqueous emulsion (S-3) (resin (B) content 50%) in which the resin (B) was emulsified was prepared by mixing 90 parts by weight of bisphenol A type epoxy (manufactured by Mitsubishi chemical corporation, JER 828) as water and the resin (B), 10 parts by weight of triethylene glycol bis [3- (-n-butyl-4-hydroxy-5-methylphenyl) propionate ] (Irganox 245, manufactured by BASF Japanese Co., ltd.) and SDBS as an emulsifier together using a homogenizer. In addition, 4 parts by weight of calcium chloride was dissolved, and 600 parts by weight of ion-exchanged water adjusted to a temperature of 70℃was used. Next, 333 parts by weight of the aqueous emulsion (L-1) corresponding to 100 parts by weight of the polymer fine particles (a) and 22.2 parts by weight of the aqueous emulsion (S-3) (corresponding to 11.1 parts by weight of the resin (B)) were put into 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated material containing the polymer fine particles (a) and the resin (B). Next, the slurry was subjected to centrifugal dewatering to obtain wet powder as the coagulated material. Then, using the obtained wet powder, the operation of adding the wet powder to 500 parts by weight of ion-exchanged water and the operation of centrifugally dewatering the obtained mixture were repeated for a total of 2 cycles to obtain wet powder. Finally, the wet powder was dried in a dryer at 50℃for 48 hours to obtain a powder (P-5).
Preparation examples 3 to 6, preparation of powder (P-6)
An aqueous emulsion (S-2) (resin (B) content 50%) was prepared by mixing 50 parts by weight of epoxidized soybean oil (ADK CIZER O-130P, manufactured by ADEKA Co., ltd.), triethylene glycol bis [3- (-digital butyl-4-hydroxy-5-methylphenyl) propionate ] (Irganox 245, manufactured by BASF Japanese Co., ltd.) as water and resin (B), 50 parts by weight, and SDBS as an emulsifier together using a homogenizer. In addition, 4 parts by weight of magnesium bromide was dissolved, and 600 parts by weight of ion-exchanged water adjusted to a temperature of 70℃was used. Next, 333 parts by weight of the aqueous emulsion (L-1) corresponding to 100 parts by weight of the polymer fine particles (a) and 22.2 parts by weight of the aqueous emulsion (S-2) (corresponding to 11.1 parts by weight of the resin (B)) were put into 600 parts by weight of the ion-exchanged water to obtain a slurry containing coagulated matters of the polymer fine particles (a) and the resin (B). Next, the slurry was subjected to centrifugal dewatering to obtain wet powder as the coagulated material. Then, using the obtained wet powder, the operation of adding the wet powder to 500 parts by weight of ion-exchanged water and the operation of centrifugally dewatering the obtained mixture were repeated for a total of 2 cycles to obtain wet powder. Finally, the wet powder was dried in a dryer at 50℃for 48 hours to obtain a powder (P-6).
Preparation examples 3 to 7, preparation of powder (P-7)
333 parts by weight of an aqueous latex (L-1) corresponding to 100 parts by weight of the polymer fine particles (A) and 42 parts by weight (25 parts by weight of a resin (B)) of tetrabromobisphenol A type epoxy (EPICLON 153-60M, manufactured by DIC Co., ltd.) were put into 600 parts by weight of ion-exchanged water in which 4 parts by weight of the above magnesium bromide was dissolved and the temperature was adjusted to 70℃to obtain a slurry containing a coagulated product of the polymer fine particles (A) and the resin (B). Next, the slurry was subjected to centrifugal dewatering to obtain wet powder as the coagulated material. Then, using the obtained wet powder, the operation of putting the wet powder into 500 parts by weight of ion-exchanged water and the operation of centrifugally dewatering the obtained mixture were repeated for 2 cycles to obtain wet powder. Finally, the wet powder was dried in a dryer at 50℃for 48 hours to obtain a powder (P-7).
Preparation examples 3 to 8, preparation of powder (P-8)
An aqueous emulsion (S-5) (resin (B) content 50%) obtained by emulsifying the resin (B) was prepared by mixing 33 parts by weight of epoxidized soybean oil (ADK CIZER O-130P, manufactured by ADEKA Co., ltd.), 67 parts by weight of triethylene glycol bis [3- (-digital butyl-4-hydroxy-5-methylphenyl) propionate ] (Irganox 245, manufactured by BASF Japanese Co., ltd.) and SDBS as an emulsifier together using a homogenizer. In addition, 4 parts by weight of calcium acetate was dissolved, and 600 parts by weight of ion-exchanged water adjusted to a temperature of 70℃was used. Next, 333 parts by weight of an aqueous emulsion (L-1) corresponding to 100 parts by weight of the polymer fine particles (a), and 22.2 parts by weight of the aqueous emulsion (S-5) (corresponding to 11.1 parts by weight of the resin (B)) were put into 600 parts by weight of the ion-exchanged water to obtain a slurry containing a coagulated material containing the polymer fine particles (a) and the resin (B). Next, the slurry was subjected to centrifugal dewatering to obtain wet powder as the coagulated material. Then, using the obtained wet powder, the operation of adding the wet powder to 500 parts by weight of ion-exchanged water and the operation of centrifugally dewatering the obtained mixture were repeated for a total of 2 cycles to obtain wet powder. Finally, the wet powder was dried in a dryer at 50℃for 48 hours to obtain a powder (P-8). In addition, the epoxidized soybean oil, triethylene glycol bis [3- (-n-butyl-4-hydroxy-5-methylphenyl) propionate ] and calcium acetate as the coagulant contained 500ppm or less of halogen as the resin (B). The obtained powder was evaluated for blocking resistance, and the result was acceptable. The volume average particle diameter of the obtained powder was measured, and as a result, the volume average particle diameter was 10mm or less.
The halogen content of the powder particles (P-1) to (P-8) was evaluated.
Further, based on the formulation shown in Table 2, as a base resin (C), CELLOXIDE 2021P (alicyclic epoxy resin, manufactured by Daicel Co., ltd.) and powder particles (P-1) to (P-8) were each calculated, and mixed at 2000rpm for 30 minutes by using a rotation/revolution mixer to obtain resin compositions (examples 1 to 4 and comparative examples 1 to 4). In any of the resin compositions, the dispersibility of the powder particles was 0. Mu.m. In addition, SPCC steel plate was immersed in the above resin composition placed in a glass bottle, and whether or not rust was generated was confirmed under a humidified condition of 60 ℃. The results are shown in Table 2. No rust formation was observed in examples 1 to 4. On the other hand, rust generation was observed in comparative examples 1 to 4. The halogen content of CELLOXIDE 2021P as the base resin (C) is 500ppm or less.
Industrial applicability
According to an embodiment of the present invention, in the case of being used for a metal plate or the like, the generation of rust can be suppressed. Therefore, an embodiment of the present invention can be preferably used for an electronic substrate or the like.

Claims (21)

1. A method for producing a powder or granule, comprising the steps of:
a step of mixing the polymer fine particles (A) with a resin (B) having a halogen element content of 500ppm or less in an aqueous emulsion state; and
A step of adding a coagulant having a halogen element content of 500ppm or less to the aqueous latex containing the polymer fine particles (A) to coagulate the aqueous latex;
the polymer microparticles (A) comprise a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer,
the elastomer contains at least one selected from diene rubber, (methyl) acrylic rubber and organic siloxane rubber,
the grafting portion includes a polymer containing a constituent unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer, and a (meth) acrylate monomer,
the resin (B) is a liquid, semi-solid or solid having a viscosity of 100mPa, or s to 1000000mPa, or a seed s at 25 ℃,
when the total of the polymer fine particles (A) and the resin (B) is 100 wt%, the polymer fine particles (A) are 55 to 99 wt%, the resin (B) is 1 to 45 wt%,
the resin (B) is at least one thermosetting resin selected from the group consisting of epoxy resins, phenolic resins, polyol resins, amino-formaldehyde resins, and resins containing a polymer obtained by polymerizing an aromatic polyester raw material.
2. A method for producing a powder or granule, comprising the steps of:
a step of mixing the polymer fine particles (A) with a resin (B) having a halogen element content of 500ppm or less in an aqueous emulsion state; and
a step of adding a coagulant having a halogen element content of 500ppm or less to the aqueous latex containing the polymer fine particles (A) to coagulate the aqueous latex;
the polymer microparticles (A) comprise a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer,
the elastomer contains at least one selected from diene rubber, (methyl) acrylic rubber and organic siloxane rubber,
the grafting portion includes a polymer containing a constituent unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer, and a (meth) acrylate monomer,
the resin (B) is a liquid, semi-solid or solid having a viscosity of 100mPa, or s to 1000000mPa, or a seed s at 25 ℃,
when the total of the polymer fine particles (A) and the resin (B) is 100 wt%, the polymer fine particles (A) are 55 to 99 wt%, the resin (B) is 1 to 45 wt%,
The thermogram of the differential scanning calorimetry DSC of the resin (B) has an endothermic peak at 25 ℃ or lower,
the resin (B) is a thermosetting resin.
3. A method for producing a powder or granule, comprising the steps of:
a step of mixing the polymer fine particles (A) with a resin (B) having a halogen element content of 500ppm or less in an aqueous emulsion state; and
a step of adding a coagulant having a halogen element content of 500ppm or less to the aqueous latex containing the polymer fine particles (A) to coagulate the aqueous latex;
the polymer microparticles (A) comprise a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer,
the elastomer contains at least one selected from diene rubber, (methyl) acrylic rubber and organic siloxane rubber,
the grafting portion includes a polymer containing a constituent unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer, and a (meth) acrylate monomer,
the resin (B) is a liquid, semi-solid or solid having a viscosity of 100mPa, or s to 1000000mPa, or a seed s at 25 ℃,
When the total of the polymer fine particles (A) and the resin (B) is 100 wt%, the polymer fine particles (A) are 80 to 97 wt%, the resin (B) is 3 to 20 wt%,
the resin (B) is a thermosetting resin.
4. A method for producing a powder or granular material according to claim 1 or 2, comprising the steps of:
a resin (B) addition step of adding a resin (B) to an aqueous latex containing the polymer fine particles (A);
a coagulation step of preparing a coagulated body containing the polymer fine particles (a) and the resin (B) by using the aqueous latex obtained in the resin (B) addition step; and
and a recovery step of recovering the aggregate.
5. A method for producing a powder or granular material according to claim 1 or 2, comprising the steps of:
a resin (B) polymerization step of polymerizing the resin (B) in an aqueous latex containing the polymer fine particles (A);
a coagulation step of preparing a coagulated body containing the polymer fine particles (a) and the resin (B) using the aqueous latex obtained; and
and a recovery step of recovering the aggregate.
6. A method for producing a powder or granular material according to claim 3, comprising the steps of:
a resin (B) addition step of adding a resin (B) to an aqueous latex containing the polymer fine particles (A);
a coagulation step of preparing a coagulated body containing the polymer fine particles (a) and the resin (B) by using the aqueous latex obtained in the resin (B) addition step; and
and a recovery step of recovering the aggregate.
7. A method for producing a powder or granular material according to claim 3, comprising the steps of:
a resin (B) polymerization step of polymerizing the resin (B) in an aqueous latex containing the polymer fine particles (A);
a coagulation step of preparing a coagulated body containing the polymer fine particles (a) and the resin (B) using the aqueous latex obtained; and
and a recovery step of recovering the aggregate.
8. A method for producing a powder or granular material according to any one of claims 1 to 3, wherein,
the force required for disintegrating the block of the powder or granule is 30000Pa or less,
wherein the block is obtained by placing a weight of 6.3kg on 30g of the powder or granule contained in a cylindrical container having a diameter of 50mm, standing at 60 ℃ for 2 hours, and applying a load of 6.3kg to the powder or granule,
The force is a value measured using a rheometer.
9. A method for producing a powder or granular material according to any one of claims 1 to 3, wherein,
the volume average particle diameter of the powder is 30-500 mu m.
10. A method for producing a powder or granular material according to any one of claims 1 to 3, wherein,
the halogen element is chlorine or bromine.
11. A method for producing a resin composition comprising the step of mixing the powder or granule obtained by the method for producing a powder or granule according to any one of claims 1 to 10 with a matrix resin (C) having a halogen element content of 500ppm or less.
12. A powder comprising polymer particles (A) and a resin (B), wherein the polymer particles (A) comprise a rubber-containing graft copolymer having an elastomer and a graft unit grafted and bonded to the elastomer,
the elastomer contains at least one selected from diene rubber, (methyl) acrylic rubber and organic siloxane rubber,
the grafting portion comprises a polymer containing a constituent unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer and a (meth) acrylate monomer,
The content of halogen element is below 500ppm,
the resin (B) is a liquid, semi-solid or solid having a viscosity of 100mPa, or s to 1000000mPa, or a seed s at 25 ℃,
when the total of the polymer fine particles (A) and the resin (B) is 100 wt%, the polymer fine particles (A) are 55 to 99 wt%, the resin (B) is 1 to 45 wt%,
the resin (B) is at least one thermosetting resin selected from the group consisting of epoxy resins, phenolic resins, polyol resins, amino-formaldehyde resins, and resins containing a polymer obtained by polymerizing an aromatic polyester raw material.
13. A powder comprising polymer particles (A) and a resin (B), wherein the polymer particles (A) comprise a rubber-containing graft copolymer having an elastomer and a graft unit grafted and bonded to the elastomer,
the elastomer contains at least one selected from diene rubber, (methyl) acrylic rubber and organic siloxane rubber,
the grafting portion comprises a polymer containing a constituent unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer and a (meth) acrylate monomer,
The content of halogen element is below 500ppm,
the resin (B) is a liquid, semi-solid or solid having a viscosity of 100mPa, or s to 1000000mPa, or a seed s at 25 ℃,
when the total of the polymer fine particles (A) and the resin (B) is 100 wt%, the polymer fine particles (A) are 55 to 99 wt%, the resin (B) is 1 to 45 wt%,
the thermogram of the differential scanning calorimetry DSC of the resin (B) has an endothermic peak at 25 ℃ or lower,
the resin (B) is a thermosetting resin.
14. A powder comprising polymer particles (A) and a resin (B), wherein the polymer particles (A) comprise a rubber-containing graft copolymer having an elastomer and a graft unit grafted and bonded to the elastomer,
the elastomer contains at least one selected from diene rubber, (methyl) acrylic rubber and organic siloxane rubber,
the grafting portion comprises a polymer containing a constituent unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyano monomer and a (meth) acrylate monomer,
the content of halogen element is below 500ppm,
The resin (B) is a liquid, semi-solid or solid having a viscosity of 100mPa, or s to 1000000mPa, or a seed s at 25 ℃,
when the total of the polymer fine particles (A) and the resin (B) is 100 wt%, the polymer fine particles (A) are 80 to 97 wt%, the resin (B) is 3 to 20 wt%,
the resin (B) is a thermosetting resin.
15. A powder or granule according to any one of claims 12 to 14, wherein the halogen element is chlorine or bromine.
16. A powder or granular material according to any one of claims 12 to 14, wherein the force required to disintegrate the bulk of the powder or granular material is 30000Pa or less,
wherein the block is obtained by placing a weight of 6.3kg on 30g of the powder or granule contained in a cylindrical container having a diameter of 50mm, standing at 60 ℃ for 2 hours, and applying a load of 6.3kg to the powder or granule,
the force is a value measured using a rheometer.
17. A powder or granule according to any one of claims 12 to 14, wherein,
the volume average particle diameter of the powder is 30-500 mu m.
18. A resin composition comprising the powder or granule according to any one of claims 12 to 17 and a matrix resin (C).
19. The resin composition according to claim 18, wherein the content of the halogen element of the base resin (C) is 500ppm or less.
20. A cured product obtained by curing the resin composition according to claim 18 or 19, wherein the base resin (C) is a thermosetting resin.
21. A metal-clad laminate obtained by using the resin composition according to claim 18 or 19, wherein the base resin (C) is a thermosetting resin.
CN202080010125.6A 2019-03-28 2020-03-30 Powder and granule and use thereof Active CN113330044B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2019063422 2019-03-28
JP2019-063422 2019-03-28
JP2019-177483 2019-09-27
JP2019177483 2019-09-27
PCT/JP2020/014660 WO2020196922A1 (en) 2019-03-28 2020-03-30 Particulate matter and use of same

Publications (2)

Publication Number Publication Date
CN113330044A CN113330044A (en) 2021-08-31
CN113330044B true CN113330044B (en) 2024-04-16

Family

ID=72611587

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080010125.6A Active CN113330044B (en) 2019-03-28 2020-03-30 Powder and granule and use thereof

Country Status (3)

Country Link
JP (1) JP7461931B2 (en)
CN (1) CN113330044B (en)
WO (1) WO2020196922A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022186248A1 (en) * 2021-03-05 2022-09-09 株式会社カネカ Resin composition, method for producing polymer fine particles, and method for producing resin composition

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05163359A (en) * 1991-12-13 1993-06-29 Mitsubishi Rayon Co Ltd Production of powdery polymer
JP2005112907A (en) * 2003-10-03 2005-04-28 Mitsubishi Rayon Co Ltd Graft copolymer, impact resistance modifier and thermoplastic resin composition
CN102307918A (en) * 2009-02-05 2012-01-04 三菱丽阳株式会社 Powdery vinyl polymer, curable resin composition, and cured object
CN102459374A (en) * 2009-06-09 2012-05-16 株式会社钟化 Vinyl ester resin composition that contains polymer fine particles, process for production of same, and cured products of same
CN104918969A (en) * 2012-12-17 2015-09-16 株式会社可乐丽 Rubber-containing graft polymer powder, and laminated-glass interlayer and solar-cell sealing material including same
CN107250260A (en) * 2014-12-24 2017-10-13 阿肯马法国公司 Composition, Its Preparation Method And Use comprising multistage polymerization thing
CN110325588A (en) * 2017-02-27 2019-10-11 株式会社可乐丽 Resin combination containing polymer particle

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102203170B (en) 2008-08-29 2014-02-19 三菱丽阳株式会社 Silicone-polymer-containing vinyl polymer powder and manufacturing method thereof, resin composition, and compact
JP6769547B2 (en) 2017-05-17 2020-10-14 三菱ケミカル株式会社 Polyorganosiloxane-containing rubber graft polymer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05163359A (en) * 1991-12-13 1993-06-29 Mitsubishi Rayon Co Ltd Production of powdery polymer
JP2005112907A (en) * 2003-10-03 2005-04-28 Mitsubishi Rayon Co Ltd Graft copolymer, impact resistance modifier and thermoplastic resin composition
CN102307918A (en) * 2009-02-05 2012-01-04 三菱丽阳株式会社 Powdery vinyl polymer, curable resin composition, and cured object
CN102459374A (en) * 2009-06-09 2012-05-16 株式会社钟化 Vinyl ester resin composition that contains polymer fine particles, process for production of same, and cured products of same
CN104918969A (en) * 2012-12-17 2015-09-16 株式会社可乐丽 Rubber-containing graft polymer powder, and laminated-glass interlayer and solar-cell sealing material including same
CN107250260A (en) * 2014-12-24 2017-10-13 阿肯马法国公司 Composition, Its Preparation Method And Use comprising multistage polymerization thing
CN110325588A (en) * 2017-02-27 2019-10-11 株式会社可乐丽 Resin combination containing polymer particle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
耿孝全等.《双螺杆挤出机及其应用》.中国轻工业出版社,2003,352-353. *

Also Published As

Publication number Publication date
WO2020196922A1 (en) 2020-10-01
JPWO2020196922A1 (en) 2020-10-01
CN113330044A (en) 2021-08-31
JP7461931B2 (en) 2024-04-04

Similar Documents

Publication Publication Date Title
CN113227249B (en) Resin composition and use thereof
CN113330044B (en) Powder and granule and use thereof
US20240026092A1 (en) Method for producing purified polymer fine particles and method for producing resin composition
JP7502314B2 (en) Granular material and method for producing same
JP7451498B2 (en) Method for producing resin composition and resin composition
JP7249845B2 (en) Method for producing powder and granular material
US20220010037A1 (en) Method for producing resin composition, and resin composition
CN113677720A (en) Powder and granular material and use thereof
JP7377793B2 (en) Powder with improved dispersibility in thermosetting matrix resin
WO2020196923A1 (en) Particulate manufacturing method, and particulate
JP7356883B2 (en) Method for producing particle-containing composition and system for producing particle-containing composition
CN114364765B (en) Adhesive and method for producing adhesive
CN116783226A (en) Resin composition
US20230331982A1 (en) Resin composition
WO2022071406A1 (en) Latex and resin composition, and methods for producing same
JP2022135756A (en) Method for producing resin composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant