JP7217258B2 - resin composition - Google Patents

Description

The present invention relates to liquid polymer compositions comprising a resin component, a curing agent and a particulate system.

Specifically, the present invention relates to liquid polymer compositions, particularly liquid resin compositions comprising a curing agent and a particulate system that can be used as infusion resins.

More specifically, the present invention also relates to processes for preparing liquid resin compositions comprising monomers, curing agents and multi-stage polymers.

Various impact modifiers reduce the polymer resin composition's inherent brittleness, i.e. embrittlement, notch sensitivity and crack propagation that occurs at ambient temperatures, but also especially at temperatures below freezing. It is widely used to improve impact strength with the aim of compensating for Thus, an impact modified polymer is a polymeric material that has its impact resistance and toughness increased by incorporating phase micro domains of a rubbery material.

This is usually done due to the introduction of microscopic rubber particles into the polymer matrix that can absorb or dissipate the energy of impact. One possibility is to introduce the rubber particles in the form of core-shell particles. These core-shell particles, very generally having a rubber core and a polymer shell, have the appropriate particle size of the rubber core for effective reinforcement and grafting to have adhesion and compatibility with the thermoplastic matrix. It has the advantage of a transparent shell.

Impact modification performance is a function of particle size, particularly the particle size of the rubber portion of the particles, and the amount thereof. An optimum average particle size exists to have maximum impact strength for a given amount of added impact modifier particles.

These primary impact modifier particles are usually added to the polymeric material in the form of powder particles. These powder particles are agglomerated primary impact modifier particles. During the period of blending the polymer resin composition with such powder particles, the primary impact modifier particles are distributed in the polymer resin, but the distribution is not sufficiently uniform resulting in a decrease in viscosity. Undesirable growth results.

The particle size of the impact modifier particles is in the nanometer range, while the range of the agglomerated powder particles is in the micrometer range. The latter is much easier to handle.

For many polymers, thermoplastic or thermoset, it is very difficult or near impossible to accurately disperse these multi-stage polymers in the form of core-shell particles as agglomerated dry powders. An ideal homogeneous dispersion of core-shell particles is one in which no agglomerates are observed after dispersion in the matrix.

WO2014/013028 discloses an impregnation process for fibrous substrates, a liquid (meth)acrylic syrup for the impregnation process, a polymerization method thereof and the resulting structured product . The syrup comprises (meth)acrylic monomers, (meth)acrylic polymers, and optionally impact modifiers in the form of fine particles.

WO 2014/135815 describes a viscous polymer mainly containing a methacrylic or acrylic component and an impact modifier additive for enhancing the impact strength of the thermoplastic material obtained after syrup polymerization. A liquid (meth)acrylic syrup is disclosed. Impact modifier additives are based on elastomeric domains consisting of flexible polymeric blocks. Multistage polymers, especially in the form of core/shell particles, are not disclosed.

WO 2014/135816 mainly contains a methacrylic or acrylic component and an organic or inorganic filler intended to reduce the proportion of residual monomers after (meth)acrylic syrup polymerization. A viscous liquid (meth)acrylic syrup is disclosed. Organic fillers are selected from crosslinked PMMA beads. Multistage polymers, especially in the form of core/shell particles, are not disclosed.

EP 0985692 discloses improved MBS impact modifiers. This MBS impact modifier is a multi-stage polymer in the form of core/shell polymer and its preparation process is by emulsion polymerization.

WO2014062531 discloses a polymer comprising b) a thermosetting epoxy-terminated oxazolidinone ring-containing polymer modified by core-shell rubber particles, wherein at least 50% of said core-shell rubber particles are I) aqueous conducting emulsion polymerization of monomers in a dispersing medium to form thermoplastic core-shell rubber particles; II) coagulating said thermoplastic core-shell rubber particles to form a slurry; and III) dewatering said slurry. to form dehydrated particles; and IV) drying said dehydrated particles to form dry particles.

None of these prior art documents disclose a liquid polymer composition as claimed in the present application, or a process for obtaining it.

It is an object of the present invention to provide liquid polymer compositions containing multi-stage polymers and/or to provide improvements or advantages as a whole.

A further object of the present invention is also to obtain a liquid curable polymer resin composition comprising a multi-stage polymer with a uniform dispersion of said multi-stage polymer that can be used in polymerization.

Another object of the present invention is to avoid or significantly reduce multi-stage polymer agglomeration in curable liquid polymer resin compositions, specifically, but not exclusively, liquid epoxy resin compositions. It is to let

Yet another object is to have a process for preparing a liquid polymer composition comprising an epoxy component, a curing agent and a multi-stage polymer with a uniform dispersion of said multi-stage polymer.

A still further object is the use of a composition comprising the monomer, (meth)acrylic polymer, for impact modification of polymers.

According to the present invention there is provided a composition, composite material or composite part, process and use as defined in any one of the appended claims.

According to one embodiment of the present invention, a resin system comprising at least one resin component, a curing agent system comprising at least one component in the form of an amine-based curing agent, and a particle system comprising multi-stage polymer particles and having a viscosity of 100 mPa.s at a temperature of 110°C. s, preferably less than 90 mPa.s. s, more preferably 80 mPa.s. is less than s.

The viscosity is preferably 1 mPa.s at a temperature of 110°C. s to 100 mPa.s. s range, 5 mPa.s. s to 90 mPa.s. s, or 15 mPa.s. s~80 mPa.s. s, and/or combinations of the foregoing ranges.

In a further embodiment, the resin system comprises an epoxy resin component with a functionality of at least two, preferably an epoxy resin component with a functionality of at least four. In another embodiment, the amine-based curing agent is an aromatic amine, including alkylene-bridged aromatic amines.

Preferably, the amine curing agent is methylenebisaniline, preferably 4,4-methylenebisaniline.

In a preferred embodiment, the amine curing agent is selected from alkylalkanoanilines, preferably methylene-bis(diethylaniline) (MDEA), 4,4-methylenebis(isopropyl-6-methylaniline) (MMIPA), methylene-bis -(chlorodiethylaniline) (MCDEA) or bismethylethylaniline-bis(chlorodiethylaniline) (MMEACDEA). More preferably, the amine curing agent is a mixture of methylene-bis(diethylaniline) (MDEA) and 4,4-methylenebis(isopropyl-6-methylaniline) (MMIPA) with a ratio of MDEA to MMIPA of 2:1. is.

In a further embodiment, the curing agent system contains additional components in the form of alkylbenzene diamines. Preferably, the additional component comprises an alkylthioalkylbenzenediamine, preferably a dialkylthioalkylbenzenediamine. The curing agent system may comprise 10 wt% to 50 wt% dialkylthioalkylbenzenediamine, preferably 20 wt% to 40 wt% dialkylthioalkylbenzenediamine.

A dialkylthioalkylbenzenediamine can be of the formula:

wherein Y is an alkyl group containing 1 to 4 carbon atoms, X is hydrogen or an alkyl group containing 1 to 4 carbon atoms, and R and R' are alkyl or an alkylthio group, preferably an alkyl or alkylthio group containing 1 to 4 carbon atoms.

In a further embodiment, the dialkylthioalkylbenzenediamine is a mixture composed of the formula:

Preferably, both the dialkylthioalkylbenzene and the amine component are liquids at room temperature.

式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ１’、Ｒ２’、Ｒ３’およびＲ４’は独立して、水素、Ｃ１～Ｃ６アルコキシ、好ましくはＣ１～Ｃ４アルコキシ（ただし、前記アルコキシ基は直鎖状または分岐型であり得る）（例えば、メトキシ、エトキシおよびイソプロポキシ）、Ｃ１～Ｃ６アルキル、好ましくはＣ１～Ｃ４アルキル（ただし、前記アルキル基は直鎖状または分岐型であり得るし、任意選択で置換され得る）（例えば、メチル、エチル、イソプロピルおよびトリフルオロメチル）、ハロゲンから選択され、かつ、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ１’、Ｒ２’、Ｒ３’およびＲ４’の少なくとも１つがＣ１～Ｃ６アルキル基である。 In one embodiment, the methylenebisaniline compound is liquid at 20° C. and has the formula:

wherein R1, R2, R3, R4, R1', R2', R3' and R4' are independently hydrogen, C1-C6 alkoxy, preferably C1-C4 alkoxy, provided that said alkoxy groups are linear or branched) (e.g. methoxy, ethoxy and isopropoxy), C1-C6 alkyl, preferably C1-C4 alkyl, provided said alkyl groups may be linear or branched and optionally (e.g., methyl, ethyl, isopropyl and trifluoromethyl), halogen, and at least one of R1, R2, R3, R4, R1', R2', R3' and R4' is C1- It is a C6 alkyl group.

In another embodiment of the invention, the resin system may comprise a first resin component (a) comprising a glycidyl ether epoxy resin, a second resin component (b) comprising a naphthalene-based epoxy resin component, and an amine Curing agents include amino-phenylfluorene curing agents (c). Preferably, epoxy resin component a) and epoxy resin component b) contain at most 33 wt% of the second resin component, based on the total weight of components (a) and (b).

In one embodiment of the present invention, epoxy resin component a) and epoxy resin component b) are between 5 wt% and 33 wt% of the second resin component, preferably between 7 wt% and 32.5 wt% of the second resin component. %, more preferably from 12 wt% to 32 wt% of the second resin component, even more preferably from 19 wt% to 32 wt% of the second resin component, most preferably from 20 wt% to 33 wt% of the second resin component. no, but up to 33 wt% and/or combinations of the aforementioned ranges.

This composition has the significant advantage of providing a desired high wet Tg of at least 130°C in combination with a variety of excellent mechanical properties, including high toughness and compressive strength after impact (CAI) strength. while also providing a suitably long processing window (processing window/process width) to enable the manufacture of large composite parts.

In one embodiment, the resin composition has a wet Tg of at least 130°C, preferably at least 140°C, and more preferably at least 150°C when cured at 190°C for 120 minutes. Dry Tg and wet Tg are measured by dynamic mechanical analysis (DMA) according to ASTM D7028. A wet test was performed on the samples after two weeks of immersion in water at a temperature of 70°C.

In a further embodiment of the invention, one or more of the mechanical properties of the neat cured resin composition are as follows:
Critical strain in the range of 500 J/m2 to 1000 J/m2, preferably in the range of 700 J/m2 to 1000 J/m2, and/or combinations of the foregoing ranges, when measured according to ASTM D5045-99 (2007) e1 energy release rate GIc;
・When measured according to ASTM D5045-99 (2007) e1, the range of 1.0 to 2.5 MPa 0.5, preferably the range of 1.4 to 2.0 MPa 0.5 or 1.6 to 2.0 MPa critical stress intensity factors KIc in the range of 0.5, and/or combinations of the foregoing ranges;
- when measured according to ASTM D790, in the range of 3.0 to 3.8, preferably in the range of 3.2 to 3.6 or in the range of 3.0 to 3.8 or in the range of 3.3 to 3.5 , and/or elastic modulus G in any combination of the foregoing ranges;
- Tg onset (dry) is in the range 130°C to 220°C or in the range 150°C to 200°C, preferably in the range 170°C to 190°C, and/or combinations of the foregoing ranges;
- Tg onset (wet) in the range 100°C to 180°C or in the range 120°C to 170°C, preferably in the range 130°C to 160°C or in the range 125°C to 145°C, and/or combinations of the foregoing ranges Range.

The second resin component may comprise at least one of bisphenol-A (BPA) diglycidyl ether and/or bisphenol-F (BPF) diglycidyl ether and derivatives thereof.

In one embodiment, the second resin component is present in an amount of 10 wt% or greater, preferably 15 wt% or greater, and more preferably 20 wt% or greater.

The non-naphthalene component of the composition is in an amount in the range of 10 wt% to 90 wt%, preferably in an amount in the range of 20 wt% to 45 wt%, more preferably 65 wt% to 80 wt%, based on the total weight of the composition. It may be present in amounts in ranges and/or in amounts in combinations of the foregoing ranges.

式中、それぞれのＲ^０は独立して、水素、ならびにエポキシド基含有化合物の重合において不活性である基で、好ましくはハロゲン、１個～６個の炭素原子を有する直鎖状アルキル基および分岐型アルキル基、フェニル、ニトロ、アセチルならびにトリメチルシリルから選択される基から選択される；
それぞれのＲは独立して、水素、ならびに１個～６個の炭素原子を有する直鎖状アルキル基および分岐型アルキル基から選択される；かつ
それぞれのＲ^１は独立して、Ｒ、水素、フェニルおよびハロゲンから選択される。 In one embodiment, the curing agent has the following structural formula:

wherein each R ⁰ is independently hydrogen and a group that is inert in the polymerization of the epoxide group-containing compound, preferably halogen, linear alkyl groups having 1 to 6 carbon atoms and branched type alkyl groups, phenyl, nitro, acetyl and trimethylsilyl;
each R is independently selected from hydrogen, and linear and branched alkyl groups having 1 to 6 carbon atoms; and each R ¹ is independently R, hydrogen, selected from phenyl and halogen;

The curing agent system may include one or more of the following curing agent components: bis(secondary aminophenyl)fluorene, or bis(secondary aminophenyl)fluorene and (primary aminophenyl) (primary A mixture of secondary aminoenyl)fluorenes. Preferably, the curing agent comprises one or more of the following curing agents: 9,9-bis(4-aminophenyl)fluorene, 4-methyl-9,9-bis(4-aminophenyl)fluorene, 4- Chloro-9,9-bis(4-aminophenyl)fluorene, 2-ethyl-9,9-bis(4-aminophenyl)fluorene, 2-iodo-9,9-bis(4-aminophenyl)fluorene, 3 -bromo-9,9-bis(4-aminophenyl)fluorene, 9-(4-methylaminophenyl)-9-(4-ethylaminophenyl)fluorene, 1-chloro-9,9-bis(4-amino phenyl)fluorene, 2-methyl-9,9-bis(4-aminophenyl)fluorene, 2,6-dimethyl-9,9-bis(4-aminophenyl)fluorene, 1,5-dimethyl-9,9- Bis(4-aminophenyl)fluorene, 2-fluoro-9,9-bis(4-aminophenyl)fluorene, 1,2,3,4,5,6,7,8-octafluoro-9,9-bis (4-aminophenyl)fluorene, 2,7-dinitro-9,9-bis(4-aminophenyl)fluorene, 2-chloro-4-methyl-9,9-bis(4-aminophenyl)fluorene, 2, 7-dichloro-9,9-bis(4-aminophenyl)fluorene, 2-acetyl-9,9-bis(4-aminophenyl)fluorene, 2-methyl-9,9-bis(4-methylaminophenyl) Fluorene, 2-chloro-9,9-bis(4-ethylaminophenyl)fluorene, or 2-t-butyl-9,9-bis(4-methylaminophenyl)fluorene, 9,9-bis(4-methyl aminophenyl)fluorene, 9-(4-methylaminophenyl)-9-(4-aminophenyl)fluorene, 9,9-bis(4-ethylaminophenyl)fluorene, 9-(4-ethylaminophenyl)-9 -(4-aminophenyl)fluorene, 9,9-bis(4-propylaminophenyl)fluorene, 9,9-bis(4-isopropylaminophenyl)fluorene, 9,9-bis(4-butylaminophenyl)fluorene , 9,9-bis(3-methyl-4-methylaminophenyl)fluorene, 9,9-bis(3-chloro-4-methylaminophenyl)fluorene, 9-(4-methylaminophenyl)-9-( 4-ethylaminophenyl)fluorene, 4-methyl-9,9-bis(4-methylaminophenyl)fluorene fluorene, or 4-chloro-9,9-bis(4-methylaminophenyl)fluorene.

In one embodiment, the curing agent component comprises a sterically hindered bis(primary aminophenyl)fluorene. In preferred embodiments, the curing agent is 9,9-bis(3-methyl-4-aminophenyl)fluorene, 9,9-bis(3-ethyl-4-aminophenyl)fluorene, 9,9-bis(3 -phenyl-4-aminophenyl)fluorene, 9,9-bis(3,5-dimethyl-4-methylaminophenyl)fluorene, 9,9-bis(3,5-dimethyl-4-aminophenyl)fluorene, 9 -(3,5-dimethyl-4-methylaminophenyl)-9-(3,5-dimethyl-4-aminophenyl)fluorene, 9-(3,5-diethyl-4-aminophenyl)-9-(3 -methyl-4-aminophenyl)fluorene, 1,5-dimethyl-9,9-bis(3,5-dimethyl-4-methylaminophenyl)fluorene, 9,9-bis(3,5-diisopropyl-4- aminophenyl)fluorene, 9,9-bis(3-chloro-4-aminophenyl)fluorene, 9,9-bis(3,5-dichloro-4-aminophenyl)fluorene, 9,9-bis(3,5 -diethyl-4-methylaminophenyl)fluorene, or 9,9-bis(3,5-diethyl-4-aminophenyl)fluorene, and/or combinations of any of the foregoing curatives.

In another embodiment, the hardener component comprises a halogen-substituted amino-phenylfluorene hardener.

In one embodiment of the invention, the particle system comprises multi-stage polymer particles.

In another embodiment, the particle system consists of multistage polymer particles.

In a further embodiment of the invention, the polymer particles comprise at least one layer (A) comprising a polymer (A1) with a glass transition temperature below 0°C and a polymer (B1) with a glass transition temperature above 30°C. It has a multi-layered structure formed by a multi-stage polymer containing another layer (B).

In another embodiment, polymer (B1) has a glass transition temperature of at least 30° C. and forms the outer layer of the polymer particles.

In a preferred embodiment, the polymer particles comprise at least one stage (A) comprising a polymer (A1) with a glass transition temperature below 0°C and at least one stage (A) comprising a polymer (B1) with a glass transition temperature above 30°C. It has a multilayer structure comprising stage (B) and at least one stage (P1) comprising a (meth)acrylic polymer (P1) having a glass transition temperature between 30°C and 150°C.

(Meth)acrylic polymer (P1) may not be grafted to either polymer (A1) or polymer (B1). Alternatively, the (meth)acrylic polymer (P1) may be grafted to one or both of polymer (A1) and polymer (B1).

In a further embodiment, polymer (B1) has a glass transition temperature of at least 30° C. and forms an intermediate layer of polymer particles.

In another embodiment, step (A) is the first step and step (B) comprising polymer (B1) is grafted onto step (A) comprising polymer (A1) or another intermediate layer, However, in this case the first stage is defined as stage (A) comprising polymer (A1) made prior to stage (B) comprising polymer (B1).

In a further embodiment, the particle system comprises a mixture of multistage particles in combination with different particles, wherein said different particles are methacrylic polymer (P1) particles, or monomer (M1) particles, or polymethacrylate butadiene / styrene (MBS) particles.

The particulate system is in the range of 0.1% to 15% by weight, preferably in the range of 0.5% to 13%, more preferably 1.5% to 11%, based on the weight of the curable polymer resin composition. %, even more preferably in the range of 2 wt% to 8 wt%, most preferably in the range of 2.5 wt% to 7.5 wt% based on the weight of the curable polymer resin composition, and and/or ranges in any combination of the foregoing ranges.

In a further embodiment, the weighted average particle size based on particle diameter is in the range 15 nm to 900 nm, preferably in the range 20 nm to 800 nm, more preferably in the range 25 nm to 600 nm, even more preferably in the range 30 nm to 550 nm, even more preferably More preferably in the range 40 nm to 400 nm, even more advantageously in the range 75 nm to 350 nm, advantageously in the range 80 nm to 300 nm and/or in combinations of the aforementioned ranges.

In another embodiment, an adhesive is provided comprising a polymer composition as hereinbefore described. The polymer composition may contain fillers. Suitable fillers may be selected from microspheres, glass beads, microballoons, talc and silica.

In a further embodiment, a process for manufacturing a fiber reinforced composite, wherein the fibrous material is laid up in a closed container and the curable epoxy resin composition according to any of the preceding claims is heated to 80°C. A process is provided wherein the reinforcing fibrous material is drawn into the reinforcing fibrous material at a temperature of ~130°C, and once the resin is drawn into the reinforcing material, the temperature is raised to within the range of 150°C to 190°C.

[definition]
By the term "polymer powder", when used, is meant a polymer containing powder grains in the range of at least 1 micrometer (μm) obtained by agglomeration of a primary polymer containing particles in the nanometer range.

By the term "system" ("system"), when used, is meant a single component or a mixture of components. When used, the term "resin system" means a single resin component or a mixture of resin components or resins. By the term "hardener system" is meant a single hardener component or a mixture of hardener components or hardeners, when used. By the term "particle system", when used, is meant a single type of particle or a mixture of particles.

When used, by the term "primary particles" is meant spherical polymer containing particles in the nanometer range. Preferably, the primary particles have a weight average particle size between 20 nm and 800 nm.

When used, the term "particle size" means the volume average diameter of particles that are considered spherical.

When used, the term "copolymer" means that the polymer consists of at least two different monomers.

When used, the term "multi-stage polymer" means a polymer formed in a sequential fashion by a multi-stage polymerization process. One preferred process is where the first polymer is the first stage polymer and the second polymer is the second stage polymer, i.e. the second polymer is is a multi-stage emulsion polymerization process formed by the emulsion polymerization of

By the term "(meth)acrylic" when used is meant all types of acrylic and methacrylic monomers.

When used, the term "(meth)acrylic polymer" means that said (meth)acrylic polymer essentially comprises a polymer comprising (meth)acrylic monomers constituting 50 wt% or more of said (meth)acrylic polymer is meant.

By the term "epoxy resin", when used, is understood any organic compound having at least two functional groups of the oxirane type that can be polymerized by ring opening. Various examples of epoxy resins are described in this application.

By the term "(meth)acrylic resin", when used, adhesives based on acrylic and methacrylic monomers are understood.

By the term "masterbatch", when used, is understood a composition comprising additives in a high concentration in a carrier material. Additives are dispersed in the carrier material.

When used, by the term "impact modifier" is understood a substance that, when incorporated into a polymeric material, increases the impact resistance and toughness of that polymeric material through phase microdomains of a rubbery material or rubbery polymer. .

By the term "rubber" when used is meant the thermodynamic state of a polymer above its glass transition point.

By the term "rubber polymer" is meant a polymer having a glass transition temperature (Tg) of less than 0°C.

The curable polymer composition of the present invention comprises a resin system comprising at least one resin component. This resin component is preferably an epoxy resin component. This component may include one or more epoxy resin components or epoxy resins with a functionality of two (difunctional) or greater (trifunctional, tetrafunctional, etc.).

Suitable epoxy difunctional epoxy resin components used to form the resin component of the polymer composition or polymer matrix can include any suitable difunctional epoxy resin. It will be appreciated that this includes any suitable epoxy resin having two epoxy functionalities. Difunctional epoxy resins can be saturated, unsaturated, cycloaliphatic, cycloaliphatic or heterocyclic. Difunctional epoxies may be used alone or in combination with multifunctional epoxy resins to form the resin component. Resin components containing only multifunctional epoxies are also possible.

Difunctional epoxy resin components include, for example, diglycidyl ethers of bisphenol F, diglycidyl ethers of bisphenol A (optionally brominated), glycidyl ethers of phenol-aldehyde adducts, aliphatic diols. glycidyl ethers, diglycidyl ethers, diethylene glycol diglycidyl ethers, Epikote, Epon, aromatic epoxy resins, epoxidized olefins, brominated resins, aromatic glycidyl amines, heterocyclic glycidyl imidines and glycidyl amides, glycidyl ethers, fluorine based on modified epoxy resins, or any combination thereof. The difunctional epoxy resin is preferably selected from diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol A, diglycidyldihydroxynaphthalene, or any combination thereof. Most preferred is the diglycidyl ether of bisphenol F. Diglycidyl ethers of bisphenol F are commercially available from Huntsman Advanced Materials (Brewster, NY) under the tradenames Araldite GY281 and GY285 and from Ciba-Geigy (located under the tradename LY9703). The difunctional epoxy resin component may be used alone or in any suitable combination with other difunctional or multifunctional epoxies to form the resin system.

The resin system may include one or more epoxy resins with functionality greater than two. Preferred multifunctional epoxy resins are those that are trifunctional or tetrafunctional. A multifunctional epoxy resin may be a combination of a trifunctional epoxy and a multifunctional epoxy. Multifunctional epoxy resins can be saturated, unsaturated, cycloaliphatic, cycloaliphatic or heterocyclic.

Suitable multifunctional epoxy resins include, by way of example, phenolic and cresol epoxy novolaks, glycidyl ethers of phenol-aldehyde adducts, glycidyl ethers of dialiphatic diols, diglycidyl ethers, diethylene glycol diglycidyl ethers, aromatic epoxy resins. , dialiphatic triglycidyl ethers, aliphatic polyglycidyl ethers, epoxidized olefins, brominated resins, aromatic glycidyl amines, heterocyclic glycidyl imidines and glycidyl amides, glycidyl ethers, fluorinated epoxy resins, or any Any combination based on those combinations is included.

A trifunctional epoxy resin will be understood to have three epoxy groups substituted either directly or indirectly in a para or meta orientation on a phenyl ring in the backbone of the compound. A tetrafunctional epoxy resin will be understood to have four epoxy groups substituted either directly or indirectly in a meta or para orientation on the phenyl rings in the backbone of the compound.

The phenyl ring may additionally be substituted with other suitable non-epoxy substituents. Suitable substituents include, for example, hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, alkoxyl, aryl, aryloxyl, aralkyloxyl, aralkyl, halo, nitro or cyano groups. included. Suitable non-epoxy substituents may be attached to the phenyl ring at the para- or ortho-positions, or at meta-positions not occupied by epoxy groups. Suitable tetrafunctional epoxy resins include N,N,N',N'-tetraglycidyl-m-xylenediamine (Tetrad-X from Mitsubishi Gas Chemical Company, Chiyoda-ku, Tokyo, Japan). and under the name Erisys GA-240 (commercially available from CVC Chemicals, Morretown, N.J.) Suitable trifunctional epoxy resins include, for example, phenolic epoxy novolak and cresol epoxy novolaks, glycidyl ethers of phenol-aldehyde adducts, aromatic epoxy resins, dialiphatic triglycidyl ethers, aliphatic polyglycidyl ethers, epoxidized olefins, brominated resins, aromatic glycidylamines and glycidyl ethers, Included are those based on heterocyclic glycidyl imidines and glycidyl amides, glycidyl ethers, fluorinated epoxy resins, or any combination thereof.

One exemplary trifunctional epoxy resin component is triglycidyl meta-aminophenol. Triglycidyl meta-aminophenol is commercially available under the tradename Araldite MY0610 from Huntsman Advanced Materials (Monthey, Switzerland). Another exemplary trifunctional epoxy resin is triglycidyl para-aminophenol. Triglycidyl para-aminophenol is commercially available under the trade name Araldite MY0510 from Huntsman Advanced Materials (Monthey, Switzerland).

Further examples of suitable multifunctional epoxy resin components include, for example, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (Araldite MY720 and MY721 from Huntsman Advanced Materials, Monthey, Switzerland). or from Sumitomo as ELM434), the triglycidyl ether of para-aminophenol (commercially available from Huntsman Advanced Materials as Araldite MY0500 or MY0510), dicyclopentadiene-based epoxy resins such as Tactix 556 (Huntsman Advanced Materials (commercially available from Huntsman Advanced Materials), tris-(hydroxylphenyl), and methane-based epoxy resins such as Tactix 742 (commercially available from Huntsman Advanced Materials). Other suitable multifunctional epoxy resins include DEN438 (obtained from Dow Chemicals, Midland, Mich.), DEN439 (obtained from Dow Chemicals), Araldite ECN1273 (obtained from Huntsman Advanced Materials), and Araldite ECN1299. (obtained from Huntsman Advanced Materials).

Preferred resin systems contain difunctional epoxies, or trifunctional or tetrafunctional epoxies or mixtures of any of these components. Preferably, the difunctional epoxy resin component is present in the range of 12 wt% to 22 wt% based on the total weight of the resin system. More preferably, the difunctional epoxy resin is present in the range of 15 wt% to 19 wt% based on the total weight of the resin system. A trifunctional epoxy resin is present in the range of 15 wt% to 35 wt% based on the total weight of the resin system. Preferably, the trifunctional epoxy resin is present in the range of 20 wt% to 30 wt% based on the total weight of the resin system. More preferably, the trifunctional epoxy resin is present in the range of 24 wt% to 28 wt% based on the total weight of the resin system. A tetrafunctional epoxy resin is present in the range of 5 wt% to 15 wt% based on the total weight of the resin system. Preferably, the tetrafunctional epoxy resin is present in the range of 8 wt% to 12 wt% based on the total weight of the resin system. More preferably, the tetrafunctional epoxy resin is present in the range of 9 wt% to 11 wt% based on the total weight of the resin system. Various preferred range combinations for these three types of epoxy resins in the preferred resin component are possible.

In the most preferred resin component, only tetrafunctional epoxy resins are present in the range of 47 wt% to 87 wt% based on the total weight of the curable composition, preferably in the range of 55 wt% to 65 wt%, more preferably It is present in the range of 58 wt% to 67 wt%.

the dynamic viscosity of the curable liquid composition according to the invention before curing is in the range of 0.1 mPa·s to 200 mPa·s at a temperature of 110° C., preferably in the range of 10 mPa·s to 150 mPa·s; It is conveniently in the range from 50 mPa·s to 100 mPa·s. Viscosity of liquid compositions can be readily measured by a rheometer using shear forces between 0.1 s ⁻¹ and 100 s ⁻¹ . Dynamic viscosity is measured at 25°C. Viscosity is measured at a shear force of 1 s ⁻¹ if shear thinning is observed.

In one embodiment, the (meth)acrylic polymer (P1) has a weight average molecular weight Mw of less than 100000 g/mol, preferably less than 90000 g/mol, more preferably less than 80000 g/mol, even more preferably is less than 70 000 g/mol, advantageously less than 60 000 g/mol, more advantageously less than 50 000 g/mol, even more advantageously less than 40 000 g/mol. Preferred ranges for the weight average molecular weight Mw are from 10000 g/mol to 100000 g/mol, preferably from 20000 g/mol to 90000 g/mol, from 30000 g/mol to 70000 g/mol, even more preferably from 35000 g/mol to 60000 g/mol, conveniently is most preferably from 40,000 g/mol to 50,000 g/mol, and/or combinations of the aforementioned ranges.

In a further embodiment the (meth)acrylic polymer (P1) has a weight average molecular weight Mw of more than 100 000 g/mol, preferably more than 110 000 g/mol, more preferably more than 125 000 g/mol, and More preferably above 140000 g/mol. Preferred ranges for the weight average molecular weight Mw are from 100000 g/mol to 1000000 g/mol, preferably from 120000 g/mol to 190000 g/mol, from 130000 g/mol to 170000 g/mol, even more preferably from 135000 g/mol to 160000 g/mol, advantageously is most preferably from 140,000 g/mol to 150,000 g/mol, and/or combinations of the foregoing ranges.

The (meth)acrylic polymer (P1) has a weight average molecular weight Mw of more than 2000 g/mol, preferably more than 3000 g/mol, more preferably more than 4000 g/mol, even more preferably more than 5000 g/mol. mol, conveniently greater than 6000 g/mol, more conveniently greater than 6500 g/mol, even more conveniently greater than 7000 g/mol, most conveniently greater than 10000 g/mol Exceed.

The (meth)acrylic polymer (P1) has a weight average molecular weight Mw of between 2000 g/mol and 100000 g/mol, preferably between 3000 g/mol and 90000 g/mol, more preferably between 4000 g/mol and 80000 g/mol. mol, conveniently between 5000 g/mol and 70000 g/mol, more conveniently between 6000 g/mol and 50000 g/mol, most conveniently between 10000 g/mol and 40000 g/mol is.

Preferably, the (meth)acrylic polymer (P1) is a copolymer comprising (meth)acrylic monomers. More preferably, the (meth)acrylic polymer (P1) is a (meth)acrylic polymer. Even more preferably, the (meth)acrylic polymer (P1) comprises at least 50 wt% monomers selected from C1-C12 alkyl (meth)acrylates. Conveniently preferably, the (meth)acrylic polymer (P1) comprises at least 50 wt% monomers selected from C1-C4 alkyl methacrylate monomers and C1-C8 alkyl acrylate monomers and mixtures thereof.

Preferably, the glass transition temperature Tg of the (meth)acrylic polymer (P1) is between 30°C and 150°C. The glass transition temperature of the (meth)acrylic polymer (P1) is more preferably between 40°C and 150°C, conveniently between 45°C and 150°C, more conveniently between 50°C and 150°C. is.

Preferably, the polymeric (meth)acrylic polymer (P1) is not crosslinked.

Preferably, the polymeric (meth)acrylic polymer (P1) is not grafted to any other polymer(s).

The (meth)acrylic polymer (P1) comprises 50 wt% to 100 wt% methyl methacrylate, preferably 80 wt% to 100 wt% methyl methacrylate, even more preferably 80 wt% to 99.8 wt% methyl methacrylate, and 0 .2 wt % to 20 wt % C1-C8 alkyl acrylate monomers. Conveniently, the C1-C8 alkyl acrylate monomers are selected from methyl acrylate, ethyl acrylate or butyl acrylate.

In a second preferred embodiment, the (meth)acrylic polymer (P1) comprises between 0 wt% and 50 wt% functional monomers. Preferably, the (meth)acrylic polymer (P1) comprises between 0 wt% and 30 wt% functional monomers, more preferably between 1 wt% and 30 wt%, even more preferably between 2 wt% and between 30 wt% functional monomers, conveniently between 3 wt% and 30 wt% functional monomers, more conveniently between 5 wt% and 30 wt% functional monomers, most conveniently Contains between 5 wt% and 30 wt% functional monomers.

Functional monomers may be (meth)acrylic monomers. Functional monomers have the following formula (1) or formula (2):

with the proviso that in both formula (1) and formula (2), R ₁ is selected from H or CH ₃ and in formula (1) Y is O and R ₅ is H, or C or H and in formula (2) Y is N and _R4 and/or R3 _are H or an aliphatic or aromatic group is the base.

Preferably, functional monomer (1) or functional monomer (2) is glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids (such as dimethylacrylamide), 2-methoxyethyl acrylate. acrylate or 2-methoxyethyl methacrylate, 2-aminoethyl acrylate or 2-aminoethyl methacrylate (optionally quaternized), acrylate or methacrylate monomers containing phosphonate or phosphate groups, alkyl It is selected from imidazolidinone (meth)acrylate and polyethylene glycol (meth)acrylate. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight ranging from 400 g/mol to 10000 g/mol.

A multistage polymer according to the present invention has at least two stages that differ in their polymer composition.

The multistage polymer is preferably in the form of polymer particles, which are considered spherical particles. These particles are also called core-shell particles. The first stage forms the core and the second or all subsequent stages form the respective shells. Such multistage polymers, also called core/shell particles, are preferred.

For the polymer particles according to the invention, which are primary particles, the weight average particle size is between 15 nm and 900 nm. Preferably, the weight average particle size (diameter) of the polymer is between 20 nm and 800 nm, more preferably between 25 nm and 600 nm, even more preferably between 30 nm and 550 nm. and also, even more preferably between 35 nm and 500 nm, advantageously between 40 nm and 400 nm, even more advantageously between 75 nm and 350 nm, advantageously between 80 nm and 300 nm be. The primary polymer particles can be agglomerated, resulting in a polymer powder comprising either a multi-stage polymer or a (meth)acrylic polymer (P1) and a multi-stage polymer.

The polymer particles are obtained by a multi-step process, such as a process comprising two, three or more steps.

The polymer particles comprise at least one layer (A) comprising a polymer (A1) having a glass transition temperature below 0°C and another layer (B) comprising a polymer (B1) having a glass transition temperature above 30°C. It has a multi-layered structure containing

In a first preferred embodiment, the polymer (B1) with a glass transition temperature of at least 30° C. is the outer layer of the polymer particles with said multilayer structure.

In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30° C. is the intermediate layer of the polymer particles with said multilayer structure before the multistage polymer is brought into contact with the monomer (M1). .

Preferably, stage (A) is the first stage and stage (B) comprising polymer (B1) is grafted onto stage (A) comprising polymer (A1) or another intermediate layer. By first stage is meant that stage (A) comprising polymer (A1) is made prior to stage (B) comprising polymer (B1).

A polymer (A1) with a glass transition temperature below 0° C. in layer (A) is not produced during the final stage of the multi-step process. This means that the polymer (A1) is not present in the outer layer of particles with a multilayer structure. In layer (A) the polymer (A1) with a glass transition temperature below 0° C. is present either in the core of the polymer particle or in one of the inner layers.

Preferably, the polymer (A1) having a glass transition temperature of less than 0° C. in layer (A) is used in the first step of a multi-step process for forming the core for polymer particles having a multilayer structure and/or glass It is made prior to the polymer (B1) with a transition temperature above 60°C. Preferably polymer (A1) has a glass transition temperature of less than -5°C, more preferably less than -15°C, advantageously less than -25°C.

In a first preferred embodiment, the polymer (B1) with a glass transition temperature above 60° C. is made in the final stage of a multi-stage process forming the outer layer of polymer particles with a multilayer structure.

In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30° C. is an intermediate layer of polymer particles having a multilayer structure, and in a stage after the polymer (A1) formation stage of the multi-stage process created.

There could be one or more further intermediate layers obtained by one or more intermediate stages.

The glass transition temperature Tg of each polymer can be estimated by dynamic methods such as thermomechanical analysis.

In order to obtain samples of each of polymer (A1) and polymer (B1), these polymers were individually subjected to the It can be prepared alone rather than by a multi-step process.

Regarding polymer (A1), in a first embodiment, polymer (A1) is a (meth)acrylic polymer comprising at least 50 wt % alkyl acrylate-derived monomers.

More preferably, polymer (A1) comprises comonomer(s) copolymerizable with the alkyl acrylate as long as the glass transition temperature is below 0°C.

The comonomer(s) in polymer (A1) are preferably chosen from (meth)acrylic and/or vinyl monomers.

The (meth)acrylic comonomers in polymer (A1) comprise monomers selected from C1-C12 alkyl (meth)acrylates. Even more preferably, the (meth)acrylic comonomers in polymer (A1) comprise C1-C4 alkyl methacrylate monomers and/or C1-C8 alkyl acrylate monomers.

Most preferably, the acrylic or methacrylic comonomers of polymer (A1) are methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert- butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof;

Preferably, polymer (A1) is crosslinked. This means that the crosslinker is added to the other monomer(s). A crosslinker contains at least two groups capable of polymerizing.

In one specific embodiment, polymer (A1) is a homopolymer of butyl acrylate.

In another specific embodiment, polymer (A1) is a copolymer of butyl acrylate and at least one crosslinker. The crosslinker contributes less than 5 wt% of this copolymer.

More preferably, the glass transition temperature Tg of polymer (A1) of the first embodiment is between −100° C. and 0° C., even more preferably between −100° C. and −5° C., conveniently It is between -90°C and -15°C, more conveniently between -90°C and -25°C.

Regarding the polymer (A1), in a second embodiment, the polymer (A1) is a silicone rubber-based polymer. Silicone rubber is, for example, polydimethylsiloxane. More preferably, the glass transition temperature Tg of polymer (A1) of the second embodiment is between −150° C. and 0° C., even more preferably between −145° C. and −5° C., conveniently It is between -140°C and -15°C, more conveniently between -135°C and -25°C.

With respect to polymer (A1), in a third embodiment polymer (A1) having a glass transition temperature below 0° C. comprises at least 50 wt % polymer units derived from isoprene or butadiene, and step (A) comprises a multilayer It is the innermost layer of the structured polymer particles. In other words, stage (A) comprising polymer (A1) is the core of the polymer particle.

By way of example, the polymer (A1) of the core of the second embodiment includes isoprene or butadiene homopolymers, isoprene-butadiene copolymers, copolymers of isoprene with up to 98 wt% vinyl monomers, and up to 98 wt% Copolymers of butadiene with vinyl monomers may be mentioned. Vinyl monomers may be styrene, alkylstyrenes, acrylonitrile, alkyl (meth)acrylates, or butadiene or isoprene. In one embodiment, the core is a butadiene homopolymer.

More preferably, the glass transition temperature Tg of the polymer (A1) of the third embodiment comprising at least 50 wt% polymer units derived from isoprene or butadiene is between -100°C and 0°C, even more preferably - It is between 100°C and -5°C, conveniently between -90°C and -15°C, even more conveniently between -90°C and -25°C.

With respect to polymer (B1), homopolymers and copolymers containing monomers with double bonds and/or vinyl monomers may be mentioned. Preferably, polymer (B1) is a (meth)acrylic polymer.

Preferably, polymer (B1) comprises at least 70 wt% of monomers selected from C1-C12 alkyl (meth)acrylates. Even more preferably, the polymer (B1) comprises at least 80 wt% monomeric C1-C4 alkyl methacrylate and/or C1-C8 alkyl acrylate monomers.

Polymer (B1) can be crosslinked.

Most preferably, the acrylic or methacrylic monomers of polymer (B1) are methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, as long as polymer (B1) has a glass transition temperature of at least 30°C. butyl methacrylate and mixtures thereof.

Conveniently, polymer (B1) comprises at least 50 wt% of monomer units derived from methyl methacrylate, more conveniently at least 60 wt% of monomer units derived from methyl methacrylate, even more conveniently at least 70 wt%. contains a monomer unit derived from methyl methacrylate.

Preferably, the glass transition temperature Tg of polymer (B1) is between 30°C and 150°C. The glass transition temperature of polymer (B1) is more preferably between 50° C. and 150° C., even more preferably between 70° C. and 150° C., advantageously between 90° C. and 150° C., and more Conveniently between 90°C and 130°C.

In another embodiment, the multi-stage polymer as described above has an additional stage, which is a (meth)acrylic polymer (P1). The primary polymer particles according to this embodiment of the invention comprise at least one stage (A) comprising a polymer (A1) having a glass transition temperature below 0°C and a polymer (B1) having a glass transition temperature above 30°C. It has a multilayer structure comprising at least one stage (B) and at least one stage (P) comprising a (meth)acrylic polymer (P1) having a glass transition temperature between 30°C and 150°C.

Preferably, the (meth)acrylic polymer (P1) is not grafted onto either polymer (A1) or polymer (B1).

As regards the process for making the multi-stage polymer according to the invention, the process comprises the following steps:
a) polymerizing by emulsion polymerization of a monomer or mixture of monomers (A _m ) to obtain at least one layer (A) comprising a polymer (A1) having a glass transition temperature below 0° C.,
b) polymerizing by emulsion polymerization of a monomer or mixture of monomers (B _m ) to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30° C.,
Said monomer or monomer mixture (A _m ) and said monomer or monomer mixture (B _m ) are selected from monomers according to the composition for polymer (A1) and polymer (B1) described above.

Preferably step a) is performed prior to step b). More preferably step b) is carried out in the presence of the polymer (A1) obtained in step a), if only two stages are present.

Advantageously, the process for making the multi-stage polymer composition according to the invention comprises the following steps:
a) polymerization by emulsion polymerization of a monomer or mixture of monomers (A _m ) to obtain one layer (A) comprising a polymer (A1) having a glass transition temperature below 0° C.,
b) polymerization by emulsion polymerization of a monomer or mixture of monomers (B _m ) to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30° C. .

Monomers or monomer mixtures (A _m ) and monomers or monomer mixtures (B _m ), respectively, to form layers (A) and layers (B), respectively, comprising polymer (A1) and polymer (B1), respectively, and polymers ( The characteristics of each of A1) and polymer (B1) are the same as defined above.

A process for making a multi-stage polymer can include further steps for further stages between steps a) and b).

The process for making a multi-stage polymer can also include additional steps for additional steps before step a) and step b). Seeds can be used to polymerize a monomer or monomer mixture (A _m ) by emulsion polymerization to obtain a layer (A) comprising a polymer (A1) having a glass transition temperature below 0°C. The seed is preferably a thermoplastic polymer with a glass transition temperature of at least 20°C.

A multistage polymer is obtained as an aqueous dispersion of polymer particles. The solids content of the dispersion is between 10 wt% and 65 wt%.

Regarding the process for producing the (meth)acrylic polymer (P1) according to the invention, the process comprises polymerizing the respective (meth)acrylic monomer (P1 _m ). Each (meth)acrylic monomer (P1 _m ) is the same as defined above for the (meth)acrylic polymer (P1) and the (meth)acrylic polymer (P1) of the two preferred embodiments.

The (meth)acrylic homopolymer or (meth)acrylic copolymer (P1) can be made in a batch or semi-continuous process:
For a batch process, the mixture of monomers is introduced at once immediately before or immediately after introducing one or a portion of the initiator system;
For semi-continuous processes, the monomer mixture is added at multiple times during a given addition period, which can range from 30 minutes to 500 minutes, or continuously in parallel with the addition of the initiator (the initiator is also , applied multiple times or continuously).

A process for preparing a polymer composition comprising a (meth)acrylic polymer (P1) and a multi-stage polymer has two preferred embodiments.

In a first preferred embodiment of the above process, the (meth)acrylic polymer (P1) is polymerized in the presence of a multi-stage polymer. A (meth)acrylic polymer (P1) is made as a further step of the multi-step polymer.

In a second preferred embodiment of the above process, the (meth)acrylic polymer (P1) is polymerized separately and mixed or blended with the multi-stage polymer.

Regarding the process for preparing the polymer composition comprising the (meth)acrylic polymer (P1) and the multi-stage polymer, the process comprises the following steps:
a) polymerizing by emulsion polymerization of a monomer or mixture of monomers (A _m ) to obtain one layer (A) in the stage comprising a polymer (A1) having a glass transition temperature below 0° C.,
b) polymerizing by emulsion polymerization of a monomer or mixture of monomers (B _m ) to obtain a layer (B) during the stage comprising a polymer (B1) having a glass transition temperature of at least 30° C.
c) polymerizing by emulsion polymerization of a monomer or mixture of monomers (P1 _m ) to obtain a layer in this further stage comprising a (meth)acrylic polymer (P1) having a glass transition temperature of at least 30° C.
The (meth)acrylic polymer (P1) is characterized by having a mass average molecular weight Mw of less than 100000 g/mol.

Preferably step a) is performed prior to step b).

More preferably step b) is carried out in the presence of the polymer (A1) obtained in step a).

Advantageously, the process for preparing the polymer composition comprising the (meth)acrylic polymer (P1) and the multi-stage polymer is a multi-stage process, comprising the steps of:
a) polymerizing by emulsion polymerization of a monomer or mixture of monomers (A _m ) to obtain one layer (A) in the stage comprising a polymer (A1) having a glass transition temperature below 0° C.,
b) polymerizing by emulsion polymerization of a monomer or mixture of monomers (B _m ) to obtain a layer (B) during the stage comprising a polymer (B1) having a glass transition temperature of at least 30° C.
c) polymerizing by emulsion polymerization of a monomer or monomer mixture (P1 _m ) to obtain a layer in this further stage comprising a (meth)acrylic polymer (P1) having a glass transition temperature of at least 30° C. ,
The (meth)acrylic polymer (P1) is characterized by having a mass average molecular weight Mw of less than 100000 g/mol.

Monomers or monomer mixtures (A _m ), monomers or monomer mixtures (B _m ), and each of the monomers or monomer mixtures (P1 _m ) are the same as defined above. The characteristics of polymer (A1), polymer (B1) and polymer (P1) are each the same as defined above.

Preferably, the process for producing a polymer composition comprising a (meth)acrylic polymer (P1) and a multistage polymer comprises a further step d) of recovering this multistage polymer composition.

By recovering is meant partial recovery or separation between the aqueous phase and the solid phase comprising the multi-stage polymer composition.

More preferably, according to the invention, recovering the polymer composition is carried out by coagulation or by spray drying.

The polymer (A1) having a glass transition temperature of less than 0° C. contains at least 50 wt % of polymer units derived from an alkyl acrylate, and step (A) is the innermost layer of the polymer particles having a multilayer structure. Spray drying, if any, is the preferred method for recovery and/or drying for the method of making the polymer powder composition according to the present invention.

The polymer (A1) having a glass transition temperature of less than 0° C. contains at least 50 wt % polymer units derived from isoprene or butadiene, and step (A) is the innermost layer of the polymer particles having a multilayer structure. Coagulation, if any, is the preferred method for recovery and/or drying for the method of making the multi-stage polymer powder composition according to the present invention.

A method for producing a polymer composition according to the invention can optionally comprise a further step e) of drying the polymer composition.

Preferably, the drying step e) is performed when the step d) of recovering the polymer composition is performed by coagulation.

Preferably, after the drying step e), the multi-stage polymer composition contains less than 3 wt% humidity or moisture, more preferably less than 1.5 wt% humidity or moisture, advantageously less than 1% humidity or contain water.

The humidity of the polymer composition can be measured using a thermobalance.

Drying of the polymer can be done in an oven or vacuum oven by heating the composition at 50° C. for 48 hours.

Regarding another process for preparing a polymer composition comprising a (meth)acrylic polymer (P1) and a multi-stage polymer, the process comprises the following steps:
a) mixing the (meth)acrylic polymer (P1) and the multi-stage polymer,
b) recovering the mixture obtained in the preceding step in the form of polymer powder,
However, the (meth)acrylic polymer (P1) and the multistage polymer in step a) are in the form of a dispersion in the aqueous phase.

The amount of the aqueous dispersion of (meth)acrylic polymer (P1) and the aqueous dispersion of the multistage polymer is preferably such that the weight proportion of the multistage polymer based only on the solid portion in the resulting mixture is at least 5 wt%. is selected to be at least 10 wt%, more preferably at least 20 wt%, advantageously at least 50 wt%.

The amount of the aqueous dispersion of the (meth)acrylic polymer (P1) and the aqueous dispersion of the multistage polymer is such that the weight proportion of the multistage polymer based only on the solid portion in the resulting mixture is at most 99 wt. It is preferably chosen to be at most 95 wt%, more preferably at most 90 wt%.

The amount of the aqueous dispersion of the (meth)acrylic polymer (P1) and the aqueous dispersion of the multistage polymer is such that the weight proportion of the multistage polymer based only on the solid portion in the resulting mixture is between 5 wt% and 99 wt%. As such, it is preferably chosen to be between 10 wt% and 95 wt%, more preferably between 20 wt% and 90 wt%.

The recovery step b) of the process for producing a polymer composition comprising a (meth)acrylic polymer (P1) and a multistage polymer is preferably carried out by coagulation or by spray drying.

A process for producing a polymer composition comprising a (meth)acrylic polymer (P1) and a multi-stage polymer can optionally comprise a further step c) for drying the polymer composition.

By dry is meant that the polymer composition according to the invention contains less than 3 wt% moisture, preferably less than 1.5 wt% moisture, more preferably less than 1.2 wt% moisture. be done.

Moisture (humidity) can be measured by a thermobalance that heats the polymer composition and measures the weight loss.

A process for producing a polymer composition comprising a (meth)acrylic polymer (P1) and a multi-stage polymer preferably ultimately results in a polymer powder. The polymer powder of the invention is in the form of particles. The polymer powder particles comprise agglomerated primary polymer particles made by a multi-step process and a (meth)acrylic polymer (P1).

For the polymer powder comprising the (meth)acrylic polymer (P1) and the multi-stage polymer according to the two embodiments of the preparation process, the polymer powder has a volume median particle size D50 between 1 μm and 500 μm. Preferably, the volume median particle size of the polymer powder is between 10 μm and 400 μm, more preferably between 15 μm and 350 μm, conveniently between 20 μm and 300 μm.

The D10 of the particle size distribution by volume is at least 7 μm, preferably 10 μm.

The D90 of the particle size distribution by volume is at most 950 μm, preferably at most 500 μm, more preferably at most 400 μm.

The weight ratio r of (meth)acrylic polymer (P1) to the multistage polymer is at least 5 wt%, more preferably at least 7 wt%, even more preferably at least 10 wt%.

According to the invention, the ratio r of (meth)acrylic polymer (P1) to the multistage polymer is at most 95w%.

Preferably, the weight proportion of (meth)acrylic polymer (P1) to the multistage polymer is between 5 wt% and 95 wt%, preferably between 10 wt% and 90 wt%.

Regarding monomer (M1), said monomer (M1) is a liquid monomer at least in the temperature range between 0°C and 60°C. Monomer (M1) contains one carbon C═C double bond.

Monomers (M1) according to the invention are monomers which are solvents for (meth)acrylic polymers (P1). In other words, the (meth)acrylic polymer (P1) is soluble in the monomer (M1).

Soluble means that at a certain time the (meth)acrylic polymer (P1) in contact with the thermodynamically compatible monomer (M1) dissolves and the (meth)acrylic polymer (P1 ) is obtained.

The solubility of the (meth)acrylic polymer (P1) in the monomer (M1) can be easily investigated by mixing these two compounds under stirring at 25°C. Solvents containing monomers as monomers (M1) are known to those skilled in the art for a large number of polymers. On the other hand, solubility parameter values can be found, for example, in Polymer Handbook (4th Edition) (Editors: J. Brandrup, EH Immergut and EA Grulke; Publisher: John Wiley and Sons Inc., 1999, Chapter “ Solubility Parameter Values" (Eric A. Gulke, VII/675 to VII/714)) for a number of polymers and solvents, including a number of monomers.

Monomers (M1) are preferably chosen from (meth)acrylic and/or vinyl monomers and mixtures thereof. If the monomer (M1) is a mixture of several monomers, the (meth)acrylic polymer (P1) is soluble in mixtures containing these monomers (M1).

Monomer (M1) is more preferably selected from C1-C12 alkyl (meth)acrylates, styrenic monomers and mixtures thereof.

Monomer (M1) may comprise at least 50 wt% methyl methacrylate.

Monomer (M1) may be a mixture of monomers comprising at least 50 wt% methyl methacrylate, the balance up to 100 wt% being C2-C12 alkyl (meth)acrylates, alkyl acrylates, styrenic monomers and their selected from a mixture.

Monomer (M1) may comprise at least 80 wt% methyl methacrylate.

Monomer (M1) may be a mixture of monomers comprising at least 80 wt% methyl methacrylate, the balance up to 100 wt% being C2-C12 alkyl (meth)acrylates, alkyl acrylates, styrenic monomers and their selected from a mixture.

Monomer (M1) may comprise at least 90 wt% methyl methacrylate.

Monomer (M1) may be a mixture of monomers comprising at least 90 wt% methyl methacrylate, the balance up to 100 wt% being C2-C12 alkyl (meth)acrylates, alkyl acrylates, styrenic monomers and their selected from a mixture.

Monomer (M1) may be methyl methacrylate only.

[Evaluation method]
Viscosity Measurement Viscosity is measured using an MCR301 rheometer from Anton Paar. A Couette arrangement is used. The temperature is 25° C. and the shear rate is 0.1 s−1 to 100 s−1.

Glass Transition Temperature The glass transition temperature (Tg) of a polymer is measured using an instrument capable of performing thermomechanical analysis. The RDAII "RHEOMETRICS DYNAMIC ANALYSER" proposed by Rheometrics Company is used. Thermomechanical analysis precisely measures the viscoelastic change of a sample as a function of temperature, applied strain or deformation. The instrument continuously records the deformation of the sample while maintaining a fixed strain during a controlled program of temperature changes.
Results are obtained by plotting the elastic modulus (G'), loss modulus and tangent delta as a function of temperature. Tg is the hot side temperature value read in the tangent delta curve when the derivative of tangent delta equals zero.

Molecular Weight The weight average molecular weight (Mw) of a polymer is determined by size exclusion chromatography (SEC).

Particle Size Analysis The particle size of primary particles after multi-stage polymerization is measured using a Zetasizer.
The particle size of the recovered polymer powder is measured using a Malvern Mastersizer 3000 from MALVERN.
A Malvern Mastersizer 3000 instrument with a 300 mm lens measuring the range from 0.5 μm to 880 μm is used to estimate weight average powder particle size, particle size distribution and fine particle fraction.
GIc
Gic is the critical strain energy release rate measured according to ASTM D5045-99 (2007) e1.
KIc
KIc is the critical stress intensity factor determined according to ASTM D5045-99 (2007) e1.
Compressive Modulus Compressive modulus was determined using ASTM D790 on an Instron mechanical tester for neat resin tubing machined into parallel end faces.
Dry E'Tg Dry and Wet Tg
Dry E'Tg Dry and wet Tg are measured by dynamic mechanical analysis (DMA) according to ASTM D7028. A wet test was performed on the samples after two weeks of immersion in water at a temperature of 70°C.
Water Absorption Water absorption was determined by immersing a pre-weighed neat resin sample (40 mm x 8 mm x 3 mm) in water at a temperature of 70°C. Samples were taken after two weeks. Excess water was removed with a paper towel and the sample was weighed after which it was determined how much water had been taken up.
The invention will now be described by way of example only.

Synthesis of the multistage polymer (core-shell particles) is carried out according to the example of Sample 1 of WO2012/038441 to obtain the multistage polymer CS1. The multi-stage polymer CS1 comprises stage (A) comprising a polymer (A1) having a glass transition temperature below 0° (made essentially of butyl acrylate) and (made essentially of methyl methacrylate) and (B) comprising a polymer (B1) having a glass transition temperature of at least 30°C. Multistage polymer CS1 is stored as an aqueous dispersion for further use.

The synthesis of the (meth)acrylic polymer type (P1) is carried out according to two embodiments: first the (meth)acrylic polymer (P1) is polymerized in the presence of the multi-stage polymer CS1. A (meth)acrylic polymer (P1) is made as a further stage of the multi-stage polymer CS. In a second embodiment, the (meth)acrylic polymer (P1) is polymerized separately and mixed or blended with the multi-stage polymer after the polymerization of (meth)acrylic polymer (P1) is complete.

Particle 1 (Comparative): This particle is a multi-stage polymer particle comprising a butyl acrylate core (Tg about -45°C) and a polymethyl methacrylate (PMMA) shell (Tg greater than 50°C). The particles are available from Arkema Inc. It is commercially available as Durastrength 480 from .

Particle 2: A (meth)acrylic polymer (P1) is made as a further step on multi-stage polymer CS1 to form multi-stage particle 2. A semi-continuous process is used: 6400 g multistage polymer (CS1), 0.01 g _FeSO4 and 0.032 g sodium salt of ethylenediaminetetraacetic acid (in 10 g deionized water) in deionized water with stirring in the reactor. dissolved), 3.15 g sodium formaldehyde sulfoxylate dissolved in 110 g deionized water, and 21.33 g emulsifier, potassium salt of tallow fatty acid (dissolved in 139.44 g water). and the mixture was stirred until all the added ingredients, except the core-shell polymer, were completely dissolved. Three vacuum-nitrogen purges were performed in succession to place the reactor under a slight vacuum. The reactor was then heated. At the same time, a mixture containing 960.03 g methyl methacrylate, 106.67 g dimethylacrylamide and 10.67 g n-octyl mercaptan was nitrogen degassed for 30 minutes. The reactor is heated to 63° C. and maintained at that temperature. This monomer mixture was then introduced into the reactor in 180 minutes using a pump. In parallel, a solution of 5.33 g of ter-butyl hydroperoxide (dissolved in 100 g of deionized water) is introduced (same addition time). These lines were washed with 50g and 20g water. The reaction mixture was then heated at a temperature of 80° C., after which the polymerization was left to complete for 60 minutes after the end of the monomer addition. The reactor was cooled to 30°C. The weight average molecular weight of the (meth)aryl polymer P1 is M _w =28000 g/mol.
The final polymer composition was then recovered and the polymer composition was dried by spray drying to obtain multistage particles 2 .

Particle 3: The (meth)acrylic polymer (P1) is polymerized separately and mixed or blended with the multi-stage polymer CS1. Synthesis of (meth)acrylic polymer (P1): Semi-continuous process: 1700 g deionized water, 0.01 g _FeSO4 and 0.032 g sodium salt of ethylenediaminetetraacetic acid (10 g deionized water) were added to the reactor with stirring. ), 3.15 g sodium formaldehyde sulfoxylate dissolved in 110 g deionized water, and 21.33 g emulsifier, potassium salt of tallow fatty acid (dissolved in 139.44 g water). The mixture was stirred until completely dissolved. Three vacuum-nitrogen purges were performed in succession to place the reactor under a slight vacuum. The reactor was then heated. At the same time, a mixture containing 960.03 g methyl methacrylate, 106.67 g dimethylacrylamide and 10.67 g n-octyl mercaptan was nitrogen degassed for 30 minutes. The reactor is heated to 63° C. and maintained at that temperature. This monomer mixture was then introduced into the reactor in 180 minutes using a pump. In parallel, a solution of 5.33 g of ter-butyl hydroperoxide (dissolved in 100 g of deionized water) is introduced (same addition time). These lines were washed with 50g and 20g water. The reaction mixture was then heated at a temperature of 80° C., after which the polymerization was left to complete for 60 minutes after the end of the monomer addition. The reactor was cooled to 30°C. The solids content obtained is 34.2%. The weight average molecular weight of the (meth)aryl polymer P1 is M _w =28000 g/mol.

The aqueous dispersion of multistage polymer CS1 and (meth)acrylic polymer (P1) was added in an amount such that the weight ratio based on solid polymer between (meth)acrylic polymer (P1) and multistage polymer CS1 was 15/85. to mix. The mixture was recovered as a powder by spray drying to obtain multistage particles 3.

Particle 4: Repeat the process for Particle 3. However, the weight ratio based on solid polymer between (meth)acrylic polymer (P1) and multistage polymer CS1 is 25/75. Thus, multistage particles 4 are obtained after the mixture is recovered as a powder by spray drying.

Particle 5 (Comparative): This particle is a commercial multistage polymer called MBS (polymethylmethacrylate butadiene/styrene) impact modifier, having a poly(butadiene/styrene) core with a polymethylmethacrylate shell. particles. The particles are sold under the tradename Clearstrength® E950 and are available from Arkema Inc.; available from

The performance of Particle 1 and Particle 3 was tested with MY721 (provided by Huntsman) in the form of methylene-bis(diethylaniline) (MDEA) and 4,4-methylenebis(isopropyl-6-methylaniline) (MMIPA). and a curing agent system comprising the two curing agent components of 2:1 MDEA to MMIPA in a resin formulation (RF). The hardener system made up 40 wt% based on the total weight of resin component MY721 and hardener system.
Formulation RF was prepared by blending Particle 1 and Particle 3 into MY721 at different concentrations as shown in the table below using a speed mixer (Hauschild DAC 600 FVZ) at a speed of 2,500 rpm for 3 minutes. bottom. This process was repeated two more times resulting in a total mixing time of 9 minutes.

From visual inspection of the dispersion, particle 1 remained present as agglomerates at RF, regardless of concentration, whereas particle 3 was uniformly distributed, regardless of the concentration of particle 3 at RF, indicating that no agglomerates were present. It was noted that nothing was visible.

The viscosity of each liquid composition is measured. The viscosity of RF modified by particle 1 is greater than that of RF modified by particle 3 for comparable concentrations of multi-stage polymer particles.

The particles 3 of the multistage core-shell particles are more efficiently dispersed and have a lower effective volume in the liquid epoxy resin composition.

Particle 5 was dispersed in RF in the same manner as Particle 1 and Particle 3 described herein at loading levels of 5 wt%, 7.5 wt% and 10 wt% based on the total weight of the formulation. rice field. No change in RF reactivity was observed. However, Particle 5 was poorly dispersed at RF and evidence of Particle 5 aggregation was seen both visually and by electron microscopy. Although the toughness of the resin decreased, no significant decrease in E'Tg(dry) was found.

（式中、Ｒ _１ 、Ｒ _２ 、Ｒ _３ 、Ｒ _４ 、Ｒ _１’ 、Ｒ _２’ 、Ｒ _３’ およびＲ _４’ は独立して、
水素；
Ｃ _１ ～Ｃ _６ アルコキシ、好ましくはＣ _１ ～Ｃ _４ アルコキシ（ただし、前記アルコキシ基は直鎖状または分岐型であり得る：例えば、メトキシ、エトキシおよびイソプロポキシであってよい）；
Ｃ _１ ～Ｃ _６ アルキル、好ましくはＣ _１ ～Ｃ _４ アルキル（ただし、前記アルキル基は直鎖状または分岐型であってよく、任意選択で置換されていてよい：例えば、メチル、エチル、イソプロピルおよびトリフルオロメチルであってよい）；
ハロゲン（例えば、塩素）
から選択され、
Ｒ _１ 、Ｒ _２ 、Ｒ _３ 、Ｒ _４ 、Ｒ _１’ 、Ｒ _２’ 、Ｒ _３’ およびＲ _４’ の少なくとも１つがＣ _１ ～Ｃ _６ アルキル基である）
を有する、上記項目３に記載の組成物。
［５］．
前記アミン型硬化剤が、アルキルアルカノアニリンから選択され、好ましくはメチレン－ビス（ジエチルアニリン）（ＭＤＥＡ）、４，４－メチレンビス（イソプロピル－６－メチルアニリン）（ＭＭＩＰＡ）、メチレン－ビス－（クロロジエチルアニリン）（ＭＣＤＥＡ）またはビスメチルエチルアニリン－ビス（クロロジエチルアニリン）（ＭＭＥＡＣＤＥＡ）から選択される、上記項目１～４のいずれかに記載の組成物。
［６］．
前記アミン型硬化剤がメチレン－ビス（ジエチルアニリン）（ＭＤＥＡ）および４，４－メチレンビス（イソプロピル－６－メチルアニリン）（ＭＭＩＰＡ）の混合物であり、ＭＤＥＡ対ＭＭＩＰＡの比が２：１である、上記項目１～５のいずれかに記載の組成物。
［７］．
前記硬化剤系がアルキルベンゼンジアミンを含む、上記項目１または２に記載の組成物。
［８］．
前記アルキルベンゼンジアミンが、１つもしくは複数のアルキル基または１つもしくは複数のチオアルキル基を有するトルエンジアミンを含む、上記項目６に記載の組成物。
［９］．
前記アルキルベンゼンジアミンが、下記の式：
［化２］

（式中、Ｙは、１個～４個の炭素原子を含有するアルキル基であり、Ｘは、水素、または１個～４個の炭素原子を含有するアルキル基であり、ＲおよびＲ’はアルキル基またはアルキルチオ基であり、好ましくは１個～４個の炭素原子を含有するアルキル基またはアルキルチオ基である）
である、上記項目６または７に記載の組成物。
［１０］．
アルキルベンゼンジアミンが混合物として存在し、前記構造成分（ｉ）対構造成分（ｉｉ）の比が９０：１０～７０：３０であり、好ましくは８０：２０である、上記項目８に記載の組成物。
［１１］．
硬化剤系が、前記硬化剤系の重量に基づいて１０ｗｔ％～５０ｗｔ％の前記ジアルキルチオアルキルベンゼンジアミンを含み、好ましくは２０ｗｔ％～４０ｗｔ％の前記ジアルキルチオアルキルベンゼンジアミンを含み、より好ましくは１８ｗｔ％～２５ｗｔ％を含む、上記項目８または９に記載の組成物。
［１２］．
前記ジアルキルチオアルキルベンゼンジアミンが、
［化３］

から構成される混合物である、上記項目８～１０のいずれかに記載の組成物。
［１３］．
前記ジアルキルチオアルキルベンゼンおよび前記アミン成分がともに室温において液体である、上記項目７～１０のいずれかに記載の組成物。
［１４］．
前記アミン系硬化剤が、２種以上の異なるアルキレン架橋芳香族アミンの混合物である、上記項目１～１３のいずれかに記載の組成物。
［１５］．
前記アミン系硬化剤が、ビスアニリン系芳香族アミンおよびアルキルベンゼンジアミンを含む成分から選択される混合物である、上記項目１３に記載の組成物。
［１６］．
前記アミン型硬化剤がアミノ－フェニルフルオレン型硬化剤を含む、上記項目１に記載の組成物。
［１７］．
前記硬化剤が、下記の構造式：
［化４］

（式中、それぞれのＲ ^０ は独立して、水素、ならびにエポキシド基含有化合物の重合において不活性である基で、好ましくはハロゲン、１個～６個の炭素原子を有する直鎖状アルキル基および分岐型アルキル基、フェニル、ニトロ、アセチルならびにトリメチルシリルから選択される基から選択される；
それぞれのＲは独立して、水素、ならびに１個～６個の炭素原子を有する直鎖状アルキル基および分岐型アルキル基から選択される；かつ
それぞれのＲ ^１ は独立して、Ｒ、水素、フェニルおよびハロゲンから選択される）
を有する、上記項目１または２に記載の組成物。
［１８］．
前記硬化剤がハロゲン置換アミノ－フェニルフルオレン型硬化剤を含む、上記項目１６または１７のいずれかに記載の組成物。
［１９］．
前記樹脂成分が、グリシジルエーテルエポキシ樹脂を含む第１の樹脂ポリマーａ）と、ナフタレン系エポキシ樹脂を含む第２の樹脂ポリマーｂ）とから少なくともなる混合物であり、前記エポキシ樹脂ポリマーａ）およびエポキシ樹脂ポリマーｂ）が、ポリマーａ）およびポリマーｂ）の総重量に基づいて前記第２の樹脂ポリマーｂ）の最大でも３３ｗｔ％を含有する、上記項目１６～１８のいずれかに記載の組成物。
［２０］．
前記第２の樹脂ポリマーｂ）が、ビスフェノール－Ａ（ＢＰＡ）ジグリシジルエーテルおよび／またはビスフェノール－Ｆ（ＢＰＦ）ジグリシジルエーテルならびにそれらの誘導体の少なくとも１つを含む、上記項目２３に記載の組成物。
［２１］．
前記第２のポリマー樹脂ｂ）が１０ｗｔ％以上の量で存在し、好ましくは１５ｗｔ％以上の量で存在し、より好ましくは２０ｗｔ％以上の量で存在する、上記項目２３または２４のいずれかに記載の組成物。
［２２］．
上記項目２３～２５のいずれかに記載の組成物において、前記組成物の非ナフタレン成分が、前記組成物の総重量に基づいて１０ｗｔ％～９０ｗｔ％の範囲での量で、好ましくは２０ｗｔ％～４５ｗｔ％の範囲での量で、より好ましく６５ｗｔ％～８０ｗｔ％の範囲での量で、および／または前記前述範囲の組合せの範囲での量で存在する、組成物。
［２３］．
前記ポリマー粒子が、ガラス転移温度が０℃未満であるポリマー（Ａ１）を含む少なくとも１つの層（Ａ）と、ガラス転移温度が３０℃を超えるポリマー（Ｂ１）を含む別の層（Ｂ）とを含む多段階ポリマーによって形成される多層構造を有する、上記項目１～２２のいずれかに記載の組成物。
［２４］．
前記ポリマー（Ｂ１）が少なくとも３０℃のガラス転移温度を有し、前記ポリマー粒子の外側層を形成する、上記項目１５に記載の組成物。
［２５］．
少なくとも３０℃のガラス転移温度を有する前記ポリマー（Ｂ１）が、前記多段階ポリマーがモノマー（Ｍ１）と接触させられる前に前記ポリマー粒子の中間層を形成する、上記項目１６に記載の組成物。
［２６］．
前記段階（Ａ）が第１の段階であり、ポリマー（Ｂ１）を含む前記段階（Ｂ）が、ポリマー（Ａ１）または別の中間層を含む段階（Ａ）にグラフト化され、前記第１の段階が、ポリマー（Ｂ１）を含む段階（Ｂ）に先立って作成されるポリマー（Ａ１）を含む段階（Ａ）として定義される、上記項目１７に記載の組成物。
［２７］．
前記ポリマー粒子が、ガラス転移温度が０℃未満であるポリマー（Ａ１）を含む少なくとも１つの段階（Ａ）と、ガラス転移温度が３０℃を超えるポリマー（Ｂ１）を含む少なくとも１つの段階（Ｂ）と、ガラス転移温度が３０℃～１５０℃の間である（メタ）アクリルポリマー（Ｐ１）を含む少なくとも１つの段階（Ｐ１）とを含む多層構造を有する、上記項目１６～１９のいずれかに記載の組成物。
［２８］．
前記（メタ）アクリルポリマー（Ｐ１）が前記ポリマー（Ａ１）およびポリマー（Ｂ１）のいずれにもグラフト化されない、上記項目２０に記載の組成物。
［２９］．
前記（メタ）アクリルポリマー（Ｐ１）が前記ポリマー（Ａ１）およびポリマー（Ｂ１）の一方に、またはそれらの両方にグラフト化される、上記項目２０に記載の組成物。
［３０］．
前記粒子の直径に基づく加重平均粒子サイズが、１５ｎｍ～９００ｎｍの範囲、好ましくは２０ｎｍ～８００ｎｍの範囲、より好ましくは２５ｎｍ～６００ｎｍの範囲、一層より好ましくは３０ｎｍ～５５０ｎｍの範囲、さらにまたより好ましくは４０ｎｍ～４００ｎｍの範囲、一層より好都合には７５ｎｍ～３５０ｎｍの範囲、好都合には８０ｎｍ～３００ｎｍの範囲、および／または前記前述範囲の組合せの範囲である、上記項目１～２９のいずれかに記載の組成物。
［３１］．
前記樹脂成分が、官能性が少なくとも２であるエポキシ樹脂成分を含み、好ましくは官能性が少なくとも４であるエポキシ樹脂成分を含む、上記項目１～３０のいずれかに記載の組成物。
［３２］．
前記樹脂成分が、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－４，４’－ジアミノジフェニルメタン（ＴＧＤＤＭ）を含むエポキシ樹脂である、上記項目１～３１のいずれかに記載の組成物。
［３３］．
前記多段階粒子が、前記硬化性ポリマー樹脂組成物の重量に基づいて０．１重量％～１５重量％の範囲で、好ましくは０．５％～１３％の範囲で、より好ましくは１．５％～１１％の範囲で、一層より好ましくは２重量％～８重量％の範囲で、最も好ましくは前記硬化性ポリマー樹脂組成物の重量に基づいて２．５重量％～７．５重量％の範囲で、および／または前記前述範囲のいずれかの組合せの範囲で存在する、上記項目１～３２のいずれかに記載の組成物。
［３４］．
前記粒子系が、異なる粒子との組合せでの多段粒子の混合物を含み、前記異なる粒子が、メタクリルポリマー（Ｐ１）粒子、またはモノマー（Ｍ１）粒子、またはポリメタクリラートブタジエン／スチレン（ＭＢＳ）粒子から選択される、上記項目１～３３のいずれかに記載の組成物。
［３５］．
前記粒子系が、前記硬化性ポリマー樹脂組成物の重量に基づいて０．１重量％～１５重量％の範囲で、好ましくは０．５％～１３％の範囲で、より好ましくは１．５％～１１％の範囲で、一層より好ましくは２重量％～８重量％の範囲で、最も好ましくは前記硬化性ポリマー樹脂組成物の重量に基づいて２．５重量％～７．５重量％の範囲で、および／または前記前述範囲のいずれかの組合せの範囲で存在する、上記項目１～３４のいずれかに記載の組成物。
［３６］．
前記硬化剤系が、前記硬化性ポリマー樹脂組成物の重量に基づいて５重量％～８０重量％の範囲で、好ましくは１０％～６０％の範囲で、より好ましくは１５％～５０％の範囲で、一層より好ましくは１８％～４２％の範囲で、最も好ましくは前記硬化性ポリマー樹脂組成物の重量に基づいて３５重量％～４０重量％の範囲で、および／または前記前述範囲のいずれかの組合せの範囲で存在する、上記項目１～３５のいずれかに記載の組成物。
［３７］．
前記樹脂成分と前記硬化剤系との比率が１：１～５：２の範囲であり、好ましくは２：１～４：３の範囲であり、より好ましくは３：２である、上記項目１～３６のいずれかに記載の組成物。
［３８］．
繊維状強化材を上記項目１～３７のいずれかで定義されるような組成物との組合せで含む複合材料または複合部品。
［３９］．
繊維強化複合材を製造するためのプロセスであって、繊維状材料が閉鎖容器においてレイアップされ、上記項目１～２５のいずれかに記載される硬化性エポキシ樹脂組成物が８０℃～１３０℃の温度で前記強化用繊維状材料に引き込まれ、いったん前記樹脂が前記強化用材料に引き込まれたら、温度が１５０℃～１９０℃の範囲内に上昇させられる、プロセス。
［４０］．
前記繊維強化複合材の製造における前記硬化性樹脂としての上記項目１～２８のいずれかに記載の組成物の使用。
［４１］．
上記項目３０の前記注入プロセスによる前記繊維強化複合材の製造における上記項目３１に記載の使用。 Poor dispersion of particles 5 appeared to affect the desired properties of the resin formulation RF.
Aspects or embodiments that can be included in the present invention are summarized as follows.
[1].
a. a resin system comprising at least one resin component;
b. a curing agent system comprising at least one component in the form of an amine-based curing agent; and
c. Particulate system containing multi-stage polymer particles
A curable polymer resin composition comprising
The particles are present in the range of 2% to 10% by weight, preferably in the range of 2% to 8% by weight, based on the weight of the curable polymer resin composition, and the viscosity of the composition is is 10 mPa.s at a temperature of 110°C. s to 130 mPa.s. s, preferably 40 mPa.s. s to 100 mPa.s. s range of curable polymer resin compositions.
[2].
2. The composition according to item 1 above, wherein the amine-based curing agent is an aromatic amine including an alkylene-bridged aromatic amine.
[3].
3. The composition according to item 1 or 2 above, wherein the amine curing agent comprises methylenebisaniline, preferably 4,4-methylenebisaniline.
[4].
The methylenebisaniline is liquid at 20° C. and has the formula:
[Chemical 1]

(wherein R ₁ , R ₂ , R ₃ , R ₄ , R _1′ , R _2′ , R _3′ and R _4′ are independently
hydrogen;
C ₁ -C ₆ alkoxy, preferably C ₁ -C ₄ alkoxy (wherein said alkoxy group may be linear or branched: for example methoxy, ethoxy and isopropoxy);
C ₁ -C ₆ alkyl, preferably C ₁ -C ₄ alkyl, provided said alkyl groups may be linear or branched and optionally substituted: for example methyl, ethyl, isopropyl and may be trifluoromethyl);
Halogen (e.g. chlorine)
is selected from
at least one of R ₁ , R ₂ , R ₃ , R ₄ , R _1′ , R _2′ , R _3′ and R _4′ is a C ₁ -C ₆ alkyl group)
3. The composition according to item 3 above, having
[5].
Said amine-type curing agent is selected from alkylalkanoanilines, preferably methylene-bis(diethylaniline) (MDEA), 4,4-methylenebis(isopropyl-6-methylaniline) (MMIPA), methylene-bis-(chloro 5. The composition according to any of the preceding items 1-4, wherein the composition is selected from: diethylaniline) (MCDEA) or bismethylethylaniline-bis(chlorodiethylaniline) (MMEACDEA).
[6].
the amine-type curing agent is a mixture of methylene-bis(diethylaniline) (MDEA) and 4,4-methylenebis(isopropyl-6-methylaniline) (MMIPA) with a ratio of MDEA to MMIPA of 2:1; The composition according to any one of items 1 to 5 above.
[7].
3. The composition of item 1 or 2 above, wherein the curing agent system comprises an alkylbenzene diamine.
[8].
7. The composition of item 6 above, wherein the alkylbenzenediamine comprises toluenediamine having one or more alkyl groups or one or more thioalkyl groups.
[9].
The alkylbenzenediamine has the formula:
[Chemical 2]

wherein Y is an alkyl group containing 1 to 4 carbon atoms, X is hydrogen or an alkyl group containing 1 to 4 carbon atoms, and R and R' are an alkyl or alkylthio group, preferably an alkyl or alkylthio group containing 1 to 4 carbon atoms)
8. The composition according to item 6 or 7 above, wherein
[10].
A composition according to item 8 above, wherein the alkylbenzenediamine is present as a mixture and the ratio of said structural component (i) to structural component (ii) is from 90:10 to 70:30, preferably 80:20.
[11].
The curing agent system comprises from 10 wt% to 50 wt% of said dialkylthioalkylbenzenediamine based on the weight of said curing agent system, preferably from 20wt% to 40wt% of said dialkylthioalkylbenzenediamine, more preferably from 18wt% to A composition according to item 8 or 9 above, comprising 25 wt%.
[12].
The dialkylthioalkylbenzenediamine is
[Chemical 3]

11. The composition according to any one of items 8 to 10 above, which is a mixture consisting of
[13].
11. The composition according to any one of items 7 to 10 above, wherein both the dialkylthioalkylbenzene and the amine component are liquid at room temperature.
[14].
14. The composition according to any one of items 1 to 13 above, wherein the amine curing agent is a mixture of two or more different alkylene-bridged aromatic amines.
[15].
14. The composition according to item 13 above, wherein the amine-based curing agent is a mixture selected from components including bisaniline-based aromatic amines and alkylbenzenediamines.
[16].
2. The composition of item 1 above, wherein the amine-type curing agent comprises an amino-phenylfluorene-type curing agent.
[17].
The curing agent has the following structural formula:
[Chemical 4]

(wherein each R ⁰ is independently hydrogen and a group that is inert in the polymerization of the epoxide group-containing compound, preferably halogen, a linear alkyl group having 1 to 6 carbon atoms, and selected from a group selected from branched alkyl groups, phenyl, nitro, acetyl and trimethylsilyl;
each R is independently selected from hydrogen, and linear and branched alkyl groups having 1 to 6 carbon atoms; and
each R ¹ is independently selected from R, hydrogen, phenyl and halogen)
3. The composition according to item 1 or 2 above, having
[18].
18. The composition of any of items 16 or 17 above, wherein the curing agent comprises a halogen-substituted amino-phenylfluorene type curing agent.
[19].
The resin component is a mixture comprising at least a first resin polymer a) containing a glycidyl ether epoxy resin and a second resin polymer b) containing a naphthalene-based epoxy resin, and the epoxy resin polymer a) and the epoxy resin 19. The composition of any of the preceding items 16-18, wherein polymer b) contains at most 33 wt% of said second resinous polymer b) based on the total weight of polymer a) and polymer b).
[20].
24. The composition according to item 23 above, wherein said second resinous polymer b) comprises at least one of bisphenol-A (BPA) diglycidyl ether and/or bisphenol-F (BPF) diglycidyl ether and derivatives thereof. .
[21].
25. Any of items 23 or 24 above, wherein said second polymer resin b) is present in an amount of 10 wt% or greater, preferably 15 wt% or greater, more preferably 20 wt% or greater. The described composition.
[22].
26. The composition according to any of the above items 23-25, wherein the non-naphthalene component of said composition is in an amount ranging from 10 wt% to 90 wt%, preferably from 20 wt% to A composition present in an amount in the range of 45 wt%, more preferably in an amount in the range of 65 wt% to 80 wt%, and/or in an amount in any combination of the foregoing ranges.
[23].
At least one layer (A) comprising a polymer (A1) in which said polymer particles have a glass transition temperature below 0°C and another layer (B) comprising a polymer (B1) with a glass transition temperature above 30°C 23. The composition according to any of the above items 1 to 22, having a multi-layered structure formed by a multi-stage polymer comprising
[24].
16. The composition according to item 15, above, wherein the polymer (B1) has a glass transition temperature of at least 30° C. and forms the outer layer of the polymer particles.
[25].
17. The composition according to item 16 above, wherein said polymer (B1) having a glass transition temperature of at least 30° C. forms an intermediate layer of said polymer particles before said multi-stage polymer is brought into contact with monomer (M1).
[26].
said step (A) is the first step, said step (B) comprising polymer (B1) is grafted onto step (A) comprising polymer (A1) or another intermediate layer, said first step 18. The composition of item 17 above, wherein the step is defined as step (A) comprising polymer (A1) made prior to step (B) comprising polymer (B1).
[27].
At least one stage (A) wherein the polymer particles comprise a polymer (A1) having a glass transition temperature below 0°C and at least one stage (B) comprising a polymer (B1) having a glass transition temperature above 30°C and at least one stage (P1) comprising a (meth)acrylic polymer (P1) having a glass transition temperature between 30°C and 150°C. composition.
[28].
21. The composition according to item 20 above, wherein the (meth)acrylic polymer (P1) is not grafted to either the polymer (A1) or the polymer (B1).
[29].
21. The composition according to item 20 above, wherein said (meth)acrylic polymer (P1) is grafted to one or both of said polymer (A1) and polymer (B1).
[30].
The weighted average particle size based on the diameter of said particles is in the range of 15 nm to 900 nm, preferably in the range of 20 nm to 800 nm, more preferably in the range of 25 nm to 600 nm, even more preferably in the range of 30 nm to 550 nm, even more preferably 30. Any of the above items 1-29, in the range 40 nm to 400 nm, even more advantageously in the range 75 nm to 350 nm, advantageously in the range 80 nm to 300 nm, and/or in any combination of said ranges. Composition.
[31].
31. The composition according to any of the preceding items 1-30, wherein the resin component comprises an epoxy resin component with a functionality of at least 2, preferably an epoxy resin component with a functionality of at least 4.
[32].
32. The composition according to any one of items 1 to 31 above, wherein the resin component is an epoxy resin containing N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (TGDDM).
[33].
The multistage particles are in the range of 0.1% to 15% by weight, preferably in the range of 0.5% to 13%, more preferably 1.5% by weight based on the weight of the curable polymer resin composition. % to 11%, even more preferably 2% to 8%, most preferably 2.5% to 7.5%, based on the weight of the curable polymer resin composition. 33. The composition of any of the preceding items 1-32, present in a range and/or in any combination of the preceding ranges.
[34].
The particle system comprises a mixture of multistage particles in combination with different particles, the different particles being from methacrylic polymer (P1) particles, or monomer (M1) particles, or polymethacrylate butadiene/styrene (MBS) particles. 34. A composition according to any one of items 1 to 33 above, which is selected.
[35].
The particulate system is in the range of 0.1% to 15% by weight, preferably in the range of 0.5% to 13%, more preferably 1.5%, based on the weight of the curable polymer resin composition. in the range of ~11%, even more preferably in the range of 2% to 8% by weight, and most preferably in the range of 2.5% to 7.5% by weight based on the weight of said curable polymer resin composition and/or in any combination of the preceding ranges.
[36].
The curing agent system is in the range of 5% to 80% by weight based on the weight of the curable polymer resin composition, preferably in the range of 10% to 60%, more preferably in the range of 15% to 50%. even more preferably in the range of 18% to 42%, most preferably in the range of 35% to 40% by weight based on the weight of said curable polymer resin composition, and/or any of said ranges 36. The composition according to any one of items 1 to 35 above, present in a range of combinations of
[37].
Item 1 above, wherein the ratio of said resin component to said curing agent system is in the range of 1:1 to 5:2, preferably in the range of 2:1 to 4:3, more preferably 3:2. 37. The composition according to any one of 1-36.
[38].
A composite material or composite part comprising a fibrous reinforcement in combination with a composition as defined in any of items 1-37 above.
[39].
A process for producing a fiber reinforced composite, wherein the fibrous material is laid up in a closed container and the curable epoxy resin composition described in any of the above items 1-25 is heated at 80°C to 130°C. A process wherein a temperature is drawn into said reinforcing fibrous material, and once said resin is drawn into said reinforcing material, the temperature is raised to within the range of 150°C to 190°C.
[40].
Use of the composition according to any one of the above items 1 to 28 as the curable resin in the production of the fiber-reinforced composite material.
[41].
32. Use according to item 31 above in the manufacture of said fiber reinforced composite by said infusion process of item 30 above.

Claims (29)

a. a resin system comprising at least one resin component;
b. a curing agent system comprising at least one component in the form of an amine-based curing agent; and c. A curable polymer resin composition comprising: a particulate system comprising multi-stage polymer particles,
The particulate system is present in the range of 2% to 10% by weight based on the weight of the curable polymer resin composition, and the viscosity of the composition is 10 mPa.s at a temperature of 110°C. s to 130 mPa.s. is the range of s,
wherein the amine-based curing agent comprises a mixture of two or more different alkylene-bridged aromatic amines;
The amine-based curing agent contains methylenebisaniline,
The methylenebisaniline is liquid at 20° C. and has the formula:

(wherein R ₁ , R ₂ , R ₃ , R ₄ , R _1′ , R _2′ , R _3′ and R _4′ are independently
hydrogen;
C ₁ -C ₆ alkoxy, provided said alkoxy group may be linear or branched;
C ₁ -C ₆ alkyl, wherein said alkyl group may be linear or branched and optionally substituted;
selected from Halogen,
at least one of R ₁ , R ₂ , R ₃ , R ₄ , R _1′ , R _2′ , R _3′ and R _4′ is a C ₁ -C ₆ alkyl group)
has
The multi-stage polymer particles comprise at least one stage (A) comprising a polymer (A1) having a glass transition temperature below 0°C and at least one stage comprising a polymer (B1) having a glass transition temperature above 30°C ( B) and at least one stage (P1) comprising a (meth)acrylic polymer (P1) having a glass transition temperature between 30° C. and 150° C.,
said resin system comprising an epoxy resin component having a functionality of at least 2;
the curing agent system is present in the range of 5% to 80% by weight based on the weight of the curable polymer resin composition;
wherein the ratio of said resin system to said hardener system is in the range of 1:1 to 5:2;
A curable polymer resin composition. The amine curing agent is methylene-bis(diethylaniline) (MDEA), 4,4-methylenebis(isopropyl-6-methylaniline) (MMIPA), methylene-bis-(chlorodiethylaniline) (MCDEA) or bismethyl A composition according to claim 1, selected from ethylaniline-bis(chlorodiethylaniline) (MMEACDEA). the amine curing agent is a mixture of methylene-bis(diethylaniline) (MDEA) and 4,4-methylenebis(isopropyl-6-methylaniline) (MMIPA), the ratio of MDEA to MMIPA being 2:1; 3. A composition according to claim 1 or 2. 2. The composition of claim 1, wherein said curing agent system comprises an alkylbenzenediamine. 5. The composition of claim 4, wherein said alkylbenzenediamine comprises toluenediamine having one or more alkyl groups or one or more thioalkyl groups. The alkylbenzenediamine has the formula:

wherein Y is an alkyl group containing 1 to 4 carbon atoms, X is hydrogen or an alkyl group containing 1 to 4 carbon atoms, and R and R' are an alkyl group or an alkylthio group , wherein Y is an alkyl group containing 1 to 4 carbon atoms, X is hydrogen, and in formula (i) above and/or formula (ii) above When R and R' are alkylthio groups, said alkylbenzenediamines are referred to as dialkylthioalkylbenzenediamines. )
6. The composition of claim 4 or 5, wherein 7. The composition of claim 6, wherein the alkylbenzenediamine is present as a mixture and the ratio of structural component (i) to structural component (ii) is from 90:10 to 70:30. A composition according to claims 6 or 7, wherein the curing agent system comprises from 10 wt% to 50 wt% of said dialkylthioalkylbenzenediamine based on the weight of said curing agent system. The dialkylthioalkylbenzenediamine is

The composition according to any one of claims 6 to 8, which is a mixture composed of 2. The composition of claim 1, wherein the amine-based curing agent is a mixture selected from components including bisaniline-based aromatic amines and alkylbenzenediamines. The composition of claim 1, wherein said amine-based curing agent comprises an amino-phenylfluorene-type curing agent. The curing agent has the following structural formula:

(wherein each R ⁰ is independently hydrogen, and halogen, which is a group that is inert in the polymerization of epoxide group-containing compounds, linear alkyl groups having 1 to 6 carbon atoms, and branched selected from groups selected from alkyl groups, phenyl, nitro, acetyl and trimethylsilyl;
each R is independently selected from hydrogen, and linear and branched alkyl groups having 1 to 6 carbon atoms; and each R ¹ is independently R, hydrogen, phenyl and halogen)
12. The composition of claim 11 , comprising: A composition according to claim 11 or 12 , wherein said curing agent comprises a halogen-substituted amino-phenylfluorene type curing agent. The resin system is a mixture consisting of at least a first resin polymer a) comprising a glycidyl ether epoxy resin and a second resin polymer b) comprising a naphthalene-based epoxy resin, wherein the epoxy resin polymer a) and the epoxy resin 2. The composition of claim 1, wherein polymer b) contains at most 33 wt% of said second resinous polymer b) based on the total weight of polymer a) and polymer b). 15. The composition of claim 14 , wherein said second resinous polymer b) comprises at least one of bisphenol-A (BPA) diglycidyl ether and/or bisphenol-F (BPF) diglycidyl ether and derivatives thereof. . 16. The composition of any of claims 14 or 15, wherein said second polymeric resin b) is present in an amount of 10 wt% or greater. A composition according to any of claims 14-16 , wherein the non-naphthalene component of said composition is present in an amount ranging from 10 wt% to 90 wt% based on the total weight of said composition. A composition according to claim 1, wherein said polymer (B1) with a glass transition temperature above 30°C forms an intermediate layer of said polymer particles before said multi-stage polymer is brought into contact with monomer (M1). said step (A) is the first step, said step (B) comprising polymer (B1) is grafted onto step (A) comprising polymer (A1) or another intermediate layer, said first step 2. The composition of claim 1, wherein step is defined as step (A) comprising polymer (A1) made prior to step (B) comprising polymer (B1). 2. The composition according to claim 1, wherein said (meth)acrylic polymer (P1) is not grafted to either said polymer (A1) or polymer (B1). 2. The composition according to claim 1, wherein said (meth)acrylic polymer (P1) is grafted to one or both of said polymer (A1) and polymer (B1). A composition according to any preceding claim , wherein the weighted average particle size based on diameter of the particle system ranges from 15 nm to 900 nm. A composition according to any preceding claim , wherein the resin system is an epoxy resin comprising N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (TGDDM). A composition according to any preceding claim , wherein the multistage polymer particles are present in the range of 0.1% to 10 % by weight based on the weight of the curable polymer resin composition. said particle system comprises a mixture of multi-stage polymer particles in combination with different particles, said different particles being selected from methacrylic polymer (P1) particles or polymethacrylate butadiene/styrene (MBS) particles; A composition according to any preceding claim . A composite material or composite part comprising a fibrous reinforcement in combination with a composition as defined in any one of claims 1-25. A process for producing fiber reinforced composites, wherein the fibrous material is laid up in a closed container and the curable epoxy resin composition according to any of claims 1-25 is heated at a temperature of 80°C to 130°C. A process wherein a temperature is drawn into said reinforcing fibrous material, and once said resin is drawn into said reinforcing material, the temperature is raised to within the range of 150°C to 190°C. Use of the composition according to any of claims 1-25 as said curable resin in the manufacture of said fiber reinforced composites. 29. Use according to claim 28 in the manufacture of said fiber reinforced composites by said infusion process of claim 27 .