JP2001500187A - Polymer composition containing modifier - Google Patents

Abstract

(57) Abstract The novel modifier is a rapidly melting crystalline polymer component, preferably a side-chain crystalline (SCC) moiety, and an active chemical component that physically, but not chemically, binds to the polymer component. And Such modifiers, especially in the form of particles, can be brought into contact with the matrix and do not modify the matrix at temperatures below the crystalline melting point T _P , but rapidly modify the matrix above T _P. The active chemical component can react with the matrix, catalyze the reaction of the matrix, or inhibit the reaction of the matrix. Modifications containing (1) a matrix material, such as an epoxy resin precursor, (2) a rapidly melting crystalline polymer component, and an active chemical component (which can be physically or chemically bonded to the polymer component). Various compositions are described that include agents and (3) additional components that provide the desired properties of the product obtained from the mixture or blend.

Description

DETAILED DESCRIPTION OF THE INVENTION                        Polymer composition containing modifier   No. PCT / US 96/03023, filed on our prior international application no. Was not released, but was released on September 12, 1996 as WO 96/27641. The filed application is   (A) (i) a crystalline polymer portion that melts in a relatively small temperature range, and (ii) a polymer Through a bond, preferably with a strength of at least 10 Kcal / mole A polymer modifier comprising an active chemical moiety attached to the polymer moiety;   (B) (i) a matrix material, and (ii) a polymer bound thereto, as defined in (A). And a mer denaturant;   (C) increasing the degree to which the matrix material comes into contact with the active chemical moiety, and Conditions that cause a physical change in the matrix material that causes a chemical reaction in the modifier Form a chemical compound that exposes the composition as defined in (B) and optionally another material. Method of making, and   (D) a novel product that can be prepared by the method defined in (C) I have.   The polymer modifier (A) is stable under storage conditions for a relatively long time, Increases the contact between matrix and denaturant by other treatments It is particularly useful for preparing a composition (B) that reacts with   As we continue our research in this technical field, we find many Key discoveries, each of which provides a portion of the present invention and These findings can be combined to provide another important part of the present invention.First aspect of the invention   One part of the present invention is a chemical bond between the polymer component of the modifier and the active chemical component. Storage stability, even if the increase in stability is relatively small. Is not desirable, or storage stability should be combined with acceptable activity at the reaction temperature. If this cannot be achieved, this can be very beneficial It is a discovery of the present inventors. Under these circumstances, the active ingredient is converted to a polymer component It is possible to utilize denaturing agents that bind physically but not chemically, and It may be suitable. Such denaturants are referred to herein as "physically bound. Modifiers ". This can be a short delay of a few seconds, or 12 hours or less. A long delay above (compared to the active chemical component of the denaturant itself) can be created. Of this delay As a result, pot-life, cream time (high temperature mode before foaming) Time, response time, or other response index obtain. For example, when making a foam product, for example, polyurethane or other Highly reactive mixtures of polymers are formed by molding, for example by reaction injection molding (RIM). When shaping, physically bound denaturing agents can cause the active chemical ingredient to become very fast. Allowing the polymer mixture to be released quickly Provide sufficient delay to ensure that curing does not start before it is evenly distributed Offer. The physically bound modifier also causes the coating to Useful for curing in place (eg, using a hot wand). The present invention provides a "day batch" that can be used for several hours. To make a coating composition. Physically bound denaturant In this case, the association strength between the components is, for example, Water between component groups, such as sil groups, or other polar groups, or long-chain alkyl groups May be affected by elementary bonds and / or physical interactions.   Accordingly, the present invention provides, in its first aspect,   (1) a matrix material,   (2) distributed in or adjacent to the matrix material,     (a) (i) T_P-T_OIs T_P ^0.7Melting start temperature T_OAnd peak melting temperature T_PA polymer component comprising a crystalline polymer moiety having:        (ii) selected conditions that physically, rather than chemically, bind to the polymer component When contacting the matrix material below, an activity that promotes the chemical reaction of the matrix material And a sex chemical component,     (b) selected from temperature, solvent concentration, electromagnetic radiation, ultrasonic radiation, and pH Exposure to changes in variables causes the denaturant to lose its physical integrity and Is a solid form that undergoes physical changes that increase the extent to which it comes into contact with the active chemical A solid form,         (i) The following properties distributed in the matrix material           (a) an average particle size of 0.1 to 150 microns,           (b) a polymer component having a fusion heat of at least 20 J / g, and           (C) the crystalline polymer portion of the polymer component is a side chain crystalline polymer Solid particles having one or more of them;         (ii) a composition selected from a matrix material and a film in contact with the matrix material. Including.   The physical association between the polymer component and the active chemical component is determined by the Any species that leads to the desired increase in contact between the matrix and the active ingredient) Can be kind. In some embodiments, the components are intimately mixed. Such a blend The compound is prepared by, for example, dissolving the components in a solvent and spray-drying the obtained solution. Or emulsify the components of the heated liquid carrier and then emulsify while shearing It can be prepared by cooling the solution. In another embodiment, the active ingredient is Surrounded by a coating of the polymer component. Such compositions are, for example, active Spray-dry the active chemical component and suspend the spray-dried powder in a solution of the polymer component. And can be prepared by spray drying the suspension or using no solvent. In some systems, it is prepared by forming particles by a milling process. Can be done.   At least a portion of the active ingredient is present as part of a physically bound denaturant. Useful, ie, physically, rather than chemically, attached to the polymer component. In one of the possible cases, the active ingredient is polyurethane, polyurea, or This is the case when it is a catalyst for the preparation of polyisocyanurate. For such a catalyst Is, for example, tin, lead, bismuth, or catalyzes such a reaction. There are other metal-containing compounds known as, for example, Tris (Trib Tyltin) oxide, dibutyltin laurate, tributyltin acetate, dibutyltin Butyltin acetoacetate or tributyltin methacrylate. Another In one embodiment, the curing of unsaturated polyesters (including polyvinyl esters) The catalyst for use in the present invention provides the active chemical component of the modifier. Such a catalyst Include, for example, cobalt, copper, vanadium, manganese, or other transition metals. There are compounds that have In these embodiments, the catalyst containing compound is May interact with groups, hydroxyl groups, or the same or similar groups on the polymer Catalyst containing compounds that can include other polar groups and include long chain alkyl groups are Can interact with similar groups. Therefore, acrylic acid and / or Or by increasing the proportion of units derived from other polar comonomers. It is possible to increase the stability of denaturants containing rimers and metal compounds containing polar groups. Noh. In these embodiments, the denaturing agent may contain another active chemical ingredient. It is also possible. This other active chemical component is another catalyst component or reactive component. Can get. For example, tin compounds (eg, dibutyltin dilaurate (DBTDL)) And a tertiary amine (eg, tetraethylenediamine (TEDA)) containing The agent can be, for example, a tin compound and an amine compound mixed with the molten polymer, cooled and cooled. To form particles. Such modifiers are also foamed It may contain a blowing agent, such as BL from Air Products. Typical denaturant Contains 75% SCC polymer, 10% TEDA, 10% DBTDL and 5% BL. The tin compound can be selected to form a chemical bond with the polymer, for example, Butyltin methacrylate. Alternatively, the amine compound is Can be selected to form a bond, for example, dimethylaminoethyl acrylate It is.   The matrix material is an epoxy resin precursor and the modifiers Especially when it contains a polymer component and an active chemical component that are physically associated Modifiers and / or matrix materials are preferably in the fourth aspect of the invention below. Includes an enhancing group as described in the aspect.Second aspect of the invention   Another part of the invention is the physical combination with the denaturing agents described in the earlier application. The modified modifier is combined with a peroxide initiator and an azo initiator as active chemical components. It is our discovery that both can be used successfully. Therefore, the present invention In a second aspect, the present invention provides:   (1) Matrix that reacts when exposed to peroxide or azo initiators Material and   (2) distributed in the matrix material,     (a) (i) T_P-T_OIs T_P ^0.7Melting start temperature T_OAnd peak melting temperature T_PA polymer component comprising a crystalline polymer moiety having:         (ii) an active chemical component comprising a peroxy group or an azo group; and     (b) when dispersed in a matrix material and heated, enhances the physical integrity of the modifier Loss and increase the extent to which the matrix material contacts the peroxide initiator A modifier that is in the form of solid particles that undergoes a physical change; and Characteristics,         (i) an average particle size of 0.1 to 150 microns,         (ii) a polymer component having a heat of fusion of at least 20 J / g, and         (iii) a polymer component in which the crystalline polymer portion is a side-chain crystalline polymer A composition having one or more of the following:Third aspect of the invention   Another part of the invention is the use of a modifier (where the polymer component and the active ingredient are only chemically bonded). , Can be joined to each other by physical connection only, or both) By using various additives, especially obtained when preparing epoxy resin It is our discovery of the beneficial results obtained.   Therefore, we have found that the active chemical component of the modifier is added to the matrix material. When accelerating the reaction with a selected coreactant, the coagent is preferably Has found one or more of the following features:   1. Reduce the viscosity of the matrix material.   2. Decrease the latency of the denaturant.   3. Not only as co-reactant, but also as co-additive or modifier Works.   4. T of final product_gIncrease.   Suitable co-reactants for epoxy resin curing are anhydrides, especially methyltetrahydrogen. Drophthalic anhydride (MeTHPA). Between about 20% and about 50% by weight, preferred Addition of between about 25% and about 45% by weight of MeTHPA to Epon 828 The viscosity of the resin decreases by more than the order of magnitude of 13,000 cps to 670 cps . If the viscosity of the matrix material is reduced, the viscosity of the mixture will be too high It is much easier to add denaturants to the matrix material before it becomes unmanageable. This can increase the proportion of excipients. Anhydrides also increase the incubation period of the composition, For example, shorten to 30 days at 25-40 ° C. During such incubation periods, curing is rapid at the curing temperature. Such a latency period may be desired to indicate that it occurs quickly.   We also note that the addition of the low surface energy agent, at least, Can be useful in improving the appearance of polymer products obtained from the reaction of materials I discovered that. Therefore, the present inventors have found that the low surface energy agent It has been found to prevent exhibiting rippled surfaces. The formation of this waveform (rippling ) Indicates that the air-epoxy surface is enriched in the modifier and cures fastest, It is believed that this occurs because the oxy phase cures and shrinks more slowly. Low surface The energy agent has a lower surface energy than the modifier, and the air-epoxy resin It is preferentially located at the interface. Therefore, low surface energy agents are used in the air-epoxy Minimizing the accumulation of modifiers on the surface and allowing a more uniform curing process. Suitable Low surface energy agents are fluorocarbon surfactants, such as 3M Fluo rad is a Lodyne product of FC-430 or Ciba-Gelgy.   We also note that the addition of relatively small amounts of certain other co-additives At least enhance the appearance of cured epoxy resin without substantially changing the properties I found it to be. Suitable co-additives for epoxy resins include alkenyl Succinic anhydrides (eg, nonenyl kernels available from Humphrey under the trade name K-9) Acid anhydride), and dodecenylsuccinic anhydride. The amount of auxiliary additives is Generally 0.5 to 10%, preferably 0.5 to 5%, based on the weight of the epoxy resin. %, For example, 2% to 4%. In this weight range, co-additives are often hardened Improves fat uniformity and / or gloss. 20 minutes at 177 ° C, 60 minutes at 120 ° C, And 10 During a 120 minute incubation at 0 ° C, the cured resin is When used as any of the following, showed the least amount of chalking . The incubation period of the denaturant at ambient temperature was not affected. Other suitable auxiliary additives Dodecylbenzenesulfonic acid, available under the trade name Nacure 5076, Letetrahydrophthalic anhydride, nonylphenol, and pentadec-1-yl There is phenol. We have developed a highly filled epoxy and epoxy / Other additives found to be particularly useful for improving the surface gloss of anhydride systems Agents include phosphated polyesters (for example, trade names available from Byk Chemie). Materials sold under BYK-III), and phosphorylated and sulfonated Titanate (eg, isopropyl tri (dodecyl) benzenesulfonylthio) Tanate, and neopentyl (diallyl) oxytri (dioctyl) pyroph Osphatotitanate (for example, the trade names KR95 and Kenrich Petrochemicals) And materials sold under Leica 38).   Generally, co-additives are added to the matrix material before or after the addition of the modifier. Be added. However, some or all of the co-additives may not In some cases, it may be preferable to incorporate the auxiliary additive into the Agent T_PWhen it is heated to a temperature above, it is released from the crystalline polymer component.   Accordingly, a third aspect of the present invention provides:   (1) a matrix material that is an epoxy resin precursor,   (2) distributed in the matrix material,       (A) (a) (i) T_P-T_OIs T_P ^0.7Melting start temperature T_OAnd peak melting Solution temperature T_PA polymer component comprising a crystalline polymer moiety having:             (ii) upon contact with the matrix material under selected conditions, An active chemical component that promotes the formation of an epoxy resin from the matrix material; and          (b) When dispersed in the main material and heated, causes the modifier to lose its physical integrity. And physical changes that increase the degree to which the matrix material comes into contact with the active chemical component. A modifier in the form of a solid particle to receive, wherein the solid particle has the following properties:             (i) an average particle size of 0.1 to 150 microns,             (ii) a polymer component having a heat of fusion of at least 20 J / g, and             (iii) a polymer component in which the crystalline polymer portion is a side-chain crystalline polymer A modifier having one or more of the following components:   Dispersed in the matrix material,     (B1) 20-50% by weight of anhydride based on the weight of the epoxy resin precursor,     (B2) a surfactant having a lower surface energy than the modifier, and     (B3) 0.5 to 10% by weight of an auxiliary additive based on the weight of the epoxy resin precursor Alkenyl succinic anhydride, dodecylbenzene sulfonic acid, methyl tetra Hydrophthalic anhydride, nonylphenol, pentadec-1-ylphenol, Oxidized polyester, phosphorylated titanate, or sulfonated titanate Is an auxiliary additive And a second component selected from the group consisting of:Fourth aspect of the invention   We have also described the auxiliary additives described above and described in the earlier application. Many of the beneficial effects that can be produced by a functional group of a Or by binding to a matrix, or both. I discovered that. Such linking groups are referred to herein as "enhancing" groups. For example, (i) Matrix or matrix chemical reaction after exposure to denaturant Modifiers containing one or more enhancing groups chemically attached to a modifier that are compatible with the product. Matrix, which is compatible with the crystalline polymer component of the modifying agent and / or (ii) the modifier. Use a matrix that contains one or more enhancing groups chemically attached to the matrix. And it is possible.   A particularly beneficial use of enhancing groups is that they contain reactive chemical moieties and are cured epoxy resins. The polymer component of the modifier used in preparing the fat includes a polar group, particularly carboxy. To introduce a thiol group. In the absence of such enhancing groups, the present inventors If the denaturant is not allowed to equilibrate with the matrix before It has been found that functionalized epoxy resins do not have optimal properties. Such equilibrium (also The “conditioning” can be, for example, at 35-40 ° C. for 12-24 hours. We believe that the need for such conditioning can be attributed to crystalline polymers. It can be seen that the introduction or reduction of ruboxyl groups can reduce or eliminate them. Issued. In a preferred embodiment, the crystalline polymer is derived from maleic anhydride. And the resulting anhydride group reacts with an amino compound to form an amic acid. You. Polymers include, for example, one or more long chain α-olefins and maleic anhydride. (Eg, Petrolite X8040) or one or more long-chain acrylic acids It can be a copolymer of an alkyl (eg, C22A) and maleic anhydride. Ami When exposed to a compound, it is exposed to, for example, 1- (2-aminoethyl) -2-methylimidazole And other reactive chemical moieties that participate in the curing of the epoxy matrix. amino It is also possible that the residues of the compound may react further to provide an active chemical moiety, For example, ethanolamine can react with anhydride groups, and the resulting amic acid is 2-E Can react with tyl-4-methylimidazole or 2-methylimidazole.   This type of enhancing group allows the modifier to physically bind to the matrix rather than chemically. It is particularly useful when combining. Because of the conditioning of such denaturants Is likely to cause a reaction with the matrix.   Thus, a preferred embodiment of the fourth aspect of the present invention is:   (1) a matrix material that is an epoxy resin precursor,   (2) distributed in the matrix material,     (a) (i) (A) T_P-T_OIs T_P ^0.7Melting start temperature T_OAnd peak melting Temperature T_PA crystalline polymer portion having           (B) After mixing the matrix material and the modifier, the matrix material A polar group that reduces the time required to reach equilibrium between A polymer component comprising:        (ii) upon contact with the matrix material under selected conditions, An active chemical component that promotes the formation of an epoxy resin from the material; and     (b) when dispersed in a matrix material and heated, enhances the physical integrity of the modifier Physical that causes loss and increases the degree to which the matrix material comes into contact with the active chemical component A modifier that is in the form of solid particles undergoing a change, wherein the solid particles have the following properties,         (i) an average particle size of 0.1 to 150 microns,         (ii) a polymer component having a heat of fusion of at least 20 J / g, and         (iii) the polymer component in which the crystalline polymer portion is a side chain crystalline polymer A composition having one or more of them.   Another way to overcome the need to adjust the denaturant in the final mixture is to use a denaturant Premixed with a relatively low-viscosity epoxy compound, To accept the denaturant. The resulting concentrate is in the final mixture Can be easily dispersed. Suitable low viscosity epoxy compounds are cycloaliphatic epoxy resins. For example, 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane -Carboxylate, vinylcyclohexene dioxide, and bis (3,4-epoxy) (Cyclohexyl) adipate. These are ERL-4221 and ERL, respectively. -4206, and available from Union Carbide under ERL-4299.Units and abbreviations   As used herein, parts and percentages are by weight, units of temperature Is ° C and T_O, T_PAnd heat of fusion are measured with a DSC calorimeter (at a temperature change rate of 10 ° C / min) Is determined using The abbreviation CxA denotes an n-alkyl group in which the n-alkyl group contains x carbon atoms. Used to indicate alkyl acrylate, the abbreviation Cxalkyl is used herein to refer to Used to denote an n-alkyl group containing x carbon atoms, the abbreviation CxIEMA stands for n-alkyl. N-alkyloxycarbonylamidoethyl meta wherein the alkyl group contains x carbon atoms Used to indicate acrylate. Other abbreviations are described below.Matrix material   As used herein, the terms "matrix" and "matrix material" Is used to indicate any material or mixture of materials that the modifier contacts. The matrix comprises at least one solid which provides a continuous phase in which the modifier is distributed. Or liquid material. Such matrices, in addition to denaturants, Distributed in the continuous phase of the matrix (eg, dissolved or dispersed in the continuous phase in the form of particles). (Dispersed) may include one or more other materials. Some such other materials are: This is described in the section entitled "Co-reactants and co-additives" below. Or, for example, The matrix is in the form of particles (e.g., a fine powder) mixed with the particles of the modifier, Ma Or a liquid or liquid that comes in contact with a denaturing agent (eg, one or both sides of a denaturing membrane). Can be in gaseous or solid form (the term “membrane” is used herein to refer to a group Used to include a layer of modifier supported on the board). Matrix in the form of particles The wax may melt at a temperature above or below the melting point of the modifier.   The present invention relates to a method for treating these agents alone or when exposed to the active chemical moiety of a denaturant. Combined with other components to form a matrix material that is polymerized and / or cross-linked Particularly useful. These matrix materials include, for example, cyanoacrylate , Epoxy resin, epoxy novolak, unsaturated polyester (such as vinyl ester) And polyurethane, polyurea, polyisocyanurate, polycyanur Rates, polyacrylics and polyphenols (po lyphenolics). More information on matrix materials For information, see International Application No. PCT / US 96/0323.   The matrix is the only participant in a chemical reaction that is promoted or inhibited by Material. Alternatively, the chemical reaction involves exposing the active chemical moiety to the matrix. Added before or after treating the modifier to change the extent to which it is described below Additional materials such as co-reactants and co-additives may be required.Polymer component   The polymer component of the modifier is a single polymer (or this single polymer Can be obtained from a mixture of polymers. May be a polymer or a random copolymer, a graft copolymer, Two or more comonomers, such as block copolymers and thermoplastic elastomers May be a copolymer of Preferably, at least a portion of the polymer moiety is on the side Although obtained from a chain crystallizable (SCC) polymer, the present invention has the desired properties Including the use of other crystalline polymers.   The molecular weight of the polymer component determines the rate at which the modifier diffuses into the matrix. Is an important factor. Low molecular weight increases the availability of reactive components. Polymer composition The number average molecular weight of the minute (M_n) Is generally between 1,000 and 100,000, preferably between 1,000 and 5 It is 0,000. Another factor in determining the rate at which the denaturant mixes with the matrix is , Differences in the solubility parameters of the matrix and the modifier and the binding of the polymer components Crystallinity (the higher the crystallinity, the lower the speed). Therefore, when the crystallinity increases , In general, T_PAt lower temperatures the stability of the composition increases, but generally T_PThan At higher temperatures, the activity of the denaturing agent does not change. Furthermore, if the crystallinity is higher, Often, the amount of diluent that can be used in the composition is higher. DSC heat of fusion (ΔH) Is at least 10 J / g, especially at least 20 J / g, especially at least 40 J / g Preferred is a degree of crystallinity. Denaturant is T_PAt higher and / or lower temperatures Another factor that determines the rate of mixing with the matrix is one or more matrices, Modifiers and auxiliary additives added to enhance the compatibility of the components of the composition. The presence of a compatibilizing group.   The composition is T_O~ T_PMatrix is activated when heated or cooled in the temperature range The polymer component has a relatively low temperature so that the degree of contact with the It is important to dissolve in the temperature range. T_PAt room temperature (for most compositions, The transition is preferably steeper, the closer (the expected or preferred storage temperature) There must be. Therefore, T_P-T_OIs preferably T_P ^0.7Less than, especially T_P ^0.6Less than Yes, T_OAnd T_PIs in ° C. T_PIs a wide range from 10 ° C to 150 ° C, for example. Can vary. For compositions to be stored at room temperature (typically 20-30 ° C.) T such that the denaturing agent can be activated by moderate heating above room temperature._PIs Preferably, it is at least 40 ° C, especially at least 45 ° C, but not more than 100 ° C, especially Below 85 ° C. T_P-T_OIs preferably less than 10 ° C., especially less than 8 ° C., specifically It is typically less than 6 ° C, especially less than 4 ° C.   The SCC polymer preferably used as a polymer component in the present invention is a substituted polymer. Substituted or unsubstituted acrylates, methacrylates, Rate, vinyl ester, acrylamide, methacrylamide, maleimide, α -Olefin, p-alkylstyrene, alkylvinyl ether, alkylethylene One or more monomers such as oxides, alkyl phosphazenes, and amino acids Polyisocyanate; Polyurethane; Polysilane; Poly obtained from All of these polymers, including siloxanes; Contains a crystallizable group. Suitable SCC polymers include repeating units of the general formula . Here, Y is an organic radical forming a part of the polymer backbone, and Cy is Contains a crystallizable part. The crystallizable moiety can be directly or directly on the polymer backbone. Is a divalent organic or inorganic radical (eg, ester, carbonyl, amide, Via a hydrocarbon (eg, phenylene), amino, or ether linkage Alternatively, an ionic salt bond (eg, carboxyalkylammonium, sulfonium , Or a phosphonium ion pair). Radical Cy is It can be aliphatic or aromatic, for example, consisting of at least 10 carbons Alkyl, fluoroalkyl of at least 6 carbons, or p-alkyl Containing styrene, wherein the alkyl contains 6 to 24 carbons, especially 12 to 50 carbons. Linear polymethylene moieties containing 14 to 22 carbon atoms, or 6 to 50 Perfluorinated or substantially perfluorinated containing carbon atoms Containing a linear polymethylene moiety. Polymers containing such side chains may have one or more The corresponding linear aliphatic acrylate or methacrylate or acrylic By polymerizing an equivalent monomer such as luamide or methacrylamide Can be prepared. The polymer may also optionally contain other alkyl acrylates, Hydroxyalkyl acrylate, alkoxyalkyl acrylate, methacryl Rates (eg, glycidal methacrylate), acrylamide, And methacrylamide; acrylic acid; methacrylic acid; acrylamide; Rylamide; maleic anhydride; and comonomers containing amine groups, preferred Or units derived from one or more other comonomers selected. That's it Such comonomers are generally less than 50%, in particular less than 35%, especially less than 25%, for example Present in a total amount of 0-15%.   Suitable SCC polymers for use in the present invention are alkyl acrylates, Alkyl methacrylate, N-alkyl acrylamide, N-alkyl methacrylamide , Alkyl oxazoline, alkyl vinyl ether, alkyl vinyl ester , Α-olefins, alkyl 1,2-epoxides, and alkyl glycidyl ethers Le (The alkyl group is an n-alkyl group containing 12 to 50 carbon atoms) At least one monomer selected from the group consisting of: And a corresponding fluoroalkyl monomer which is an n-fluoroalkyl group containing 30 to 100%, preferably 40 to 100%, of an alkyl acrylate or an alkyl Methacrylate, N-alkyl acrylamide, alkyl vinyl ether, and And alkyl vinyl esters (an alkyl group is an n-alkyl containing 4 to 12 carbon atoms) Obtained from at least one monomer selected from the group consisting of When the unit is 0 to 20%, acrylic acid, methacrylic acid, itaconic acid, acrylamide, Methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, and At least one polar monomer selected from the group consisting of N-vinylpyrrolidone From 0 to 15%. Such SCC parts are also To increase the percentage of reaction products containing modifiers to alter compatibility with May include units derived from other monomers. For such monomers Include styrene, vinyl acetate, monoacryl functional polystyrene, and the like.   Further information on SCC and other polymer components used in the present invention See International Application No. PCT / US 96/03023 forActive chemical component and denaturing agent containing it   The active chemical component selected may be a catalyst component (including an initiator), a reactive component, or It can be an inhibitory component. How the components behave (i.e., the catalyst component, the reactive component, or (As an inhibitory component) may depend on the matrix material. For example, the amino group In some environments it may be catalytic and in others it may be reactive. The denaturant is Preferably, it contains at least 1% of active chemical ingredient. Modifiers may have two or more different Active chemical components, in which case each active chemical component can be a catalytic component Or each active chemical component is a reactive component, or one or more active chemical components Is a catalyst component and the other active component (s) is a reactive component obtain. The active chemical component may be, for example, nitrogen (eg, primary, secondary, tertiary or tertiary). Is a quaternary amine or imidazole or other cyclic structure containing nitrogen. ), Phosphorus (eg, -PR_ThreeAs a group (where R is an organic radical) , Oxygen (eg, as a carboxyl, ester or amide group), metal or Metal-containing groups such as rhodium, cobalt, vanadium or manganese Transition metals or typical metals such as aluminum, bismuth tin, lead or copper Or a metal, for example, attached to the polymer moiety via one or more ligand groups Alkoxide) or peroxide initiator (eg, benzoylperoxy) Or t-butyl peroxybenzoate or t-butyl peroctoate) May be included.   Particularly useful chemical components in the present invention are amines (primary, secondary, tertiary and tertiary). And quaternary amines, and heterocyclic amines such as imidazole), Xyl group, sulfonate group, phosphine, typical metals (lead, bismuth and tin ), Transition metals (cobalt, copper, manganese, titanium, and rhodium (eg, [( C_TwoH_Four)_TwoRhCl]_TwoAs)) and acetylacetonate esters of transition metals, Enzymes, superacids, metal alkoxides, UV activated moieties (eg, 4-vinyl Benzophenone), Michler ketone, and acetophenone, In addition, there are groups that change to such groups when modifiers are used.   The various parts of the present invention are characterized by the fact that the active chemical component (depending on the relevant part of the invention, Temperature-sensitive polymers, either physically or physically, or both) Any modifier that binds to the components can be utilized. The active ingredient is a catalyst, It can be a reactant or an inhibitor. Reactions that can be catalyzed include polymerization (eg, One or more unsaturated olefin monomers (especially one or more olefins, Polymerization of one or more substituted olefins), ring opening polymerization, hydrogenation, hydro Formylation reaction, enzyme-catalyzed reaction (for example, production of foods and drugs such as cheese) Oxidation, reduction, etc.), in medical diagnostics, and in the treatment of waste.   Examples of reactive chemical components, and monomers from which the reactive chemical components can be obtained, include: Isocyanates, anhydrides, acyl halides, aldehydes, hydroxyl groups, halogenated Alkyl or aryl halides, amides, amines (saturated and unsaturated heterocycles) Formula amines), carboxyl, amine, epoxide, mercaptan, azo and And peroxy, and carbamates and ureas.   For more information on active chemical ingredients and denaturants containing them, See International Application No. PCT / US 96/03023.Physical form of denaturing agent   The modifier is preferably in the form of solid particles that are homogeneously dispersed in the matrix. is there. The matrix can be a solid or a solid that provides a continuous phase containing the system in the form of particles. It may be in the form of a liquid, at least some of the particles, when viewed individually, It comprises a continuous phase of a matrix in which the particles are dispersed. Alternatively, the matrix also , In the form of particles. Smaller particles are easier to disperse and evenly dispersed It becomes easy to maintain the state. On the other hand, the smaller the particle, the more the activity hidden in the particle The ratio of chemical moieties to active chemical moieties exposed on the surface of the particles is reduced, The potential storage stability of the composition is reduced. This ratio is important for smaller particle sizes. Therefore, the size is smaller, and the case of spherical particles is larger than that of particles of other shapes. Is also big. Therefore, 0.1 to 150 microns, more preferably 0.1 to 50 microns, especially 0 .Substantially spherical grains having an average size of 1 to 25 microns, especially 0.1 to 10 microns It is preferred to use a child. Preferably, each of the particles is within these ranges. You. Suitable particles can be produced by known techniques. This technology includes spray drying, Collision milling, and a method of freezing the particle size by cooling after stirring in a fluid, and so on.   Modifiers can also be in the form of films, which can be self-supporting or can be a layer on a support. It may be in a state.Relative amounts of denaturant and matrix   The relative amounts of denaturant and matrix depend on the nature and concentration of the active chemical ingredient of the denaturant. It can vary widely depending on the degree to which the composition is subjected, as well as the desired result. . Generally, the compositions will contain 0.01-50% of a denaturing agent. Active chemical moiety is catalytic moiety When it is, the modifier is preferably contained in an amount of 1 to 40%, particularly 1 to 10%. activation If the chemical moiety is a reactive moiety, preferably the denaturant is at least 5%, more preferably Preferably contains at least 15%, especially at least 20%, for example 15-40%, especially 20-35% It is.Process characteristics   The modifier can be contacted with the matrix in any desired manner. Then, with the result The resulting composition until it is time to accelerate or inhibit the chemical reaction._Pthan Maintain low temperature. Heating and cooling bring the matrix into contact with the active chemical This is a preferred method of changing the degree of change. However, as noted in International Application No.PCT / US 96/03023 As mentioned, in addition to or in place of heating and cooling Alternatively, other means may be used.Auxiliary additive   The composition comprising a matrix material and a modifier used in the present invention comprises: One or more other ingredients that have a useful effect and are referred to herein as co-additives May be contained. For example, such components may be used in (a) solid state transformation in a matrix material. Achieve a good distribution of the active agent and / or separate the solid modifier in the matrix. Can help reduce the time required to fabricate, or (b) May help stabilize the composition before processing, or (c) if the active chemical ingredient (D) have the desired effect on the mode or extent of exposure to the treatment; The desired effect on the chemical reaction that occurs after the treatment, such as increasing the reaction rate And / or reduce the temperature at which the reaction takes place) or (e ) For the products of such chemical reactions (eg, product stability, or The physical properties of the product (such as strength, toughness, flexibility, color, or surface smoothness) And) have the desired effect. A single co-additive may provide more than one of these functions Can play. The total amount of auxiliary additives is based on the "formula weight" , Preferably 0.05 to 50%. The term "prescription weight" is used herein to Used to indicate the combined weight of the active agent and matrix. However, this weight The amount does not include non-reactive (eg, inorganic) fillers.   See International Application No.PCT / US 96/03023 for details of such additives. I want to be.Example   The present invention is illustrated by the following examples. Some of the examples are comparative examples. Real Examples 1-20 illustrate the preparation of denaturants, and Examples AF illustrate the use of denaturants.   In the following description, the following abbreviations are used. C22A is docosanil ack relay G, C18A is octadecyl acrylate, HEA is 2-hydroxyethyl acrylate , C1M is methyl methacrylate, MA is maleic anhydride, AA is acrylic acid, DMAEA is N, N-dimethylaminoethyl acrylate, AMZ is 1- (2-aminoethyl) -2-methylyl Midazole, EMI is 2-ethyl-4-methylimidazole, 2EZ is 2-ethylimidazo , AIBN is azobis (isobutyronitrile), TAP is t-amyl peroxy 2-ethyl Luhexanoate, BPB is t-butylperoxybenzoate, C12SH is dodecant All. Petrolite has an equivalent amount of maleic anhydride and an average of 40 carbon atoms. Copolymer with a mixture of olefins containing, available under the trade name Petrolite 8040 Noh. M_wIs the weight average molecular weight (Dalton), M_nIs the number average molecular weight (Dalton ). DGEBA is a bisphenol A available from Shell under the trade name Epon 828 Kelpoxy G 272-100 is a diglycidyl ether from Reichold Chemicals It is an epoxy resin that can be obtained. Epoxy resin and B.F. Goodrich Of carboxy-terminated polybutadiene and similar materials sold by It is a reaction product with a substance. Pluracol is available from BASF under the trade name Pluracol P1010 Is a functional hydroxy-terminated polyether, and Isonate is Dow under the trade name Isonate143L. 4,4'-methylenebis (phenylisodianate) available from Chemical , Ancamine 1110 is a dimethylamino-methyl available from Air Products Inc. Phenol and DBU is diazobicycloundecene from Air Products. D8 is a hydroxy-terminated linear polymer available from Bayer under the trade name Desmophen 800. An ester polyol, D1150 is available from Bayer under the trade name Desmophen 1150 Olin G36-272 is a functional polyester polyol available from Olln Corp. CB-60N is available from Bayer under the trade name Desmodur CB-60N. A handy toluene diisocyanate polymer, MRS-4 is trade name Desmodur Diphenylmethane diisocyanate polymer available from Bayer under MRS-4 , N-100 is a hexamethylenediamine available from Bayer under the trade name Desmodur N-100 Isocyane G-36-232 is a trihydride available from Olin Chemical Col Roxy-functional polyether-polyol, BTBTO is available from Strem Chem Co. An available bis (tributyltin) oxide, TBT (OAc) is available from Strem Chem Co. DBT (AA) is available from Strem Chem Co. It is a handy dibutyltin bisacetoacetate and DBTDL is available from Strem Chem Co. Is a dibutyltin dilaurate available from Aropol 2036 is a acrylate, styrene, isophthalic acid, glycol And a unsaturated polyester polymer which is a mixture of maleic acid and Liquid resin, CAT is cobalt acetate (II) tetrahydrate, DICY is dicyandiene An amide, 2X viscosity is required for the composition to double the viscosity at the indicated temperature. Time (days unless otherwise noted). Gel times are based on Techne Ins Measured using a Tecam 3 gel timer manufactured by truments. 75g of material sample, Place in a glass bottle maintained at the indicated temperature and place the gel timer plunger in the material. Vibrated. Gel time is what makes a timer "trip" Time (minutes).Example 1   C18A (1925 g), C1M (412 g), AA (412 g), C12SH, and butyl acetate (3 l Turtle). The 20% mixture was placed in a reactor and heated to 100 ° C. The rest of the mixture was added to the reactor over 90 minutes. Then raise the temperature to 110 ° C T-amyl peroxybenzoate (13.8 g, Esperox 5100 available from Witco) ) Was added and heating was continued for 90 minutes. Reduce the resulting polymer (POMA) Dried under pressure and isolated. T of this polymer_OIs 35 ℃, T_PIs 41 ℃, M_WIs 85,0 00, and M_nWas 15,800.   POMA and 4,4'-dimethylaminobenzophenone (Michler's ketone) In a solvent at a ratio corresponding to the amount of POMA carboxyl groups to 0.5 equivalents of ketone. Was. The solvent is removed under vacuum and the dried product is pulverized with an air mill and This provided a modifying agent containing a photoactivatable group.Example 2   A physically bound polymer modifier was made as follows. Petrolite (1 00g) was heated to 65 ° C. Then, ethanolamine (13 g) was added. Temperature After raising to 95 ° C., EMI (28.06 g) was added with stirring.Example 3   M_WIs a copolymer of C22A, AA and C12SH (96/3/1) having a molecular weight of 80,000 to 100,000. Prepared. Prepare a mixture of this copolymer (70 parts) and DBU (30 parts) at 80 ° C And cooled to particles having an average size of less than 20 microns.Example 4   Reaction of C22A (78.6 g), AA (19.6 g) and C12SH (1.7 g) in toluene (100 ml) The mixture was sparged with nitrogen gas for 20 minutes, after which AIBN (1 g) was added. H Close the Lasco and place in a thermostated water bath with stirring at 60 ° C for 20 hours. Was. Slowly add the reaction mixture to 1 liter of acetone with vigorous stirring. To precipitate the polymer. Collect the polymer by filtration and add acetone And washed. The filtrate was dried in a vacuum oven at 50 ° C. for several hours. C22A / AA / C12SH Analysis of the polymer by gel permeation chromatography (GPC)_W23,08 3 and M_W/ M_n= 2.38.   C22A / AA / C12SH polymer (400 g in 800 ml toluene) and DBTDL (100 g) Physically bound by heating with stirring until a homogeneous mixture is obtained. A modified agent was prepared. The mixture is cooled to room temperature and milled to a fine powder. I made it.Examples 5 to 14   Examples 5 to 14 show the preparation of physically bound denaturants.   The components used in these examples and their amounts are shown in Table 1. Each embodiment In the above, the SCC polymer of C22A and AA (the ratio is shown in Table 1 and shown in Table 1) T_O, T_PAnd ΔH values) were mixed with the other components shown in Table 1. . In Examples 5-9 and 11-14, the resulting solution was heated and Spray dried under the conditions shown in Table 2 using a spray dryer from chi laboratory . In Examples 5-7, the components were simply mixed before spray drying. Implementation In Example 10, SCC polymer (8 g) and Ancamine (25 g) were mixed at 92 ° C. to form an oil did. 93% stirred water (1% polyvinyl alcohol (Mowiol 18-188)) The oil was emulsified by adding 50 g) to the oil. Mix the mixture at 2500 rpm for 2 minutes And then cooled to room temperature while shearing at 1200 rpm. As a result The solidified oil microcapsules have a particle size of about 30 microns. This was collected by filtration. After washing with deionized water, dry the particles in air for several days. Let dry. The particles contain about 55% Ancamine and have a T_OIs 47 ℃, T_PIs 50 ℃ , And ΔH were 45 J / G. Product was collected by centrifugation instead of filtration However, the product contained about 27% Ancamine.   In Example 11, the SCC polymer was mixed with DABCO and melted, then Dissolved in loform and spray dried. In Example 12, the components were mixed and 64 Spray dried at 0 ° C. In Examples 13 and 14, 2EZ or AMI-2 was dissolved in water, Then, it was spray-dried to obtain a fine powder. This fine powder (10 g) is mixed with SCC polymer (10 g). g) and mixed with heptane (180 ml) at 80 ° C. and spray dried the suspension, A powder was obtained. In this powder, the particles are surrounded by a coating of SCC polymer. Includes 2EZ or AMI-2. Examples A to D   In Examples A-D, some of the modifiers prepared in Examples 1-14 were used to A bridged polymer resin was prepared.Example A   POMA (20 parts, prepared in Example 1), C1M (50 parts), MA (10 parts), TPGDA (20 parts) Compounded at 50 ° C. in the absence of light, then cooled to room temperature. Resin product (10 Part) in toluene (20 ml) and dry on a polyester membrane with a dry membrane pressure of 48 microns. And then coated with a 38 micron polyethylene film, heat and light Produced a laminable photoresist that could be activated byExample B   Equivalent to about 0.3 parts DBU or about 0.3 parts DMAEA per 100 parts of polyhydric alcohol Polyurethane containing D8 (70 parts), Pluracol (30 parts) and MRS4 (38 parts) In experiments where the modifiers of Examples 6 and 7 were added to the precursor, these modifications The agents were compared to each other and to the unmodified DBU catalyst. 25ml sump Pot life at 25 ° C measured in minutes, and 5 g sample on hot plate The determined gel time (min) is shown in Table 7 below. Example C   A physically bound denaturant containing 26% DBTDL was prepared as in Example 3. However, here, DBTDL was used instead of DBU. This denaturant and DBTDL itself Is used in an amount such that the mixture contains 0.5 phr of DBTDL versus polyhydric alcohol. Used with a cyanate / polyhydric alcohol combination.   The ingredients used, the amount of isocyanate and polyhydric alcohol (in parentheses) The results obtained are shown in Table 4 below. In Table 4, Mod Ag is DBTDL Refers to the contained denaturing agent. Example D   Various modifiers that are the same or similar to the modifiers of Example 4 (ie, different monomers and And / or modifications made from monomer ratios and / or different tin chelates Preparation) with Pluracol (64phr), Isonate (20phr) and G-36-232 (16phr) Mixing gave 0.1 phr tin. By monitoring the gel time, The resulting gel times were tested for reactivity at different temperatures. The following table 5 shows the result. Examples D1-D3 serve as controls. Example D4-D7 use modifiers with tin covalently attached to the polymer moiety . Examples D8-D12 show that tin binds physically, not chemically, to the crystalline polymer. Using a denaturing agent. When tin is covalently bonded, the gel time at 20 ° C Most Slower, but still more effective than the control when tin is physically attached Slow. Other things being equal, the higher the ratio of AA to tin, the more Long gelation time and short gelation time at 80 ° C. Example E   The chemically attached denaturant was made as follows. C22A in 100 g of toluene (89.4g), AA (6.7g), and C12SH (3.8g) were sprayed with nitrogen and Then AIBN (0.1 g) was added. Heat the mixture at 60 ° C. for 24 hours and cool to about 40 ° C. Rejected. 500 ml of methyl alcohol were added with vigorous stirring. By filtration The precipitate was collected and dried in a vacuum oven at 50-60 ° C. for 15 hours. By GPC Analysis revealed that the molecular weight (M_W) Was 100,000. Poly in toluene (355 ml) (175 g) was heated to 50 ° C. and to this was added cobalt (II) in 127 ml of warm water. ) A solution of 40.7 g (0.163 mole) of acetate tetrahydrate was added. The reaction mixture is refluxed Heat for 4 hours, distill the toluene-water azeotrope into the trap and then under reflux Heated for 14 hours. Then vigorously stir the hot reaction mixture into 2 L of acetone. The polymer product was precipitated by slow addition. Collect sediment by filtration And dried in a vacuum oven at 60 ° C. overnight. Elemental analysis revealed a cobalt level Was 5.7 percent. Mill the product to a 4.2 micron average particle size. To a fine powder having a size.   Using the modifier thus produced, Aropol 2036 unsaturated polyester Mixing of resin (100g) and methyl ethyl ketone peroxide (MEKP) (1.25g) The material was cured. Stir 0.67 g of denaturant and mixture vigorously by hand for 5 minutes to denature The agent was dispersed. The gel time of this system at 20 ° C. was 223 minutes. Aropol 2036 (100g), MEKP (1.25g), and cobalt naphthenate in mineral spirits The gelation time for a control mixture of 0.6 g of the solution (containing 6% elemental cobalt) is 16 minutes there were.   Using other cobalt catalysts and other modifiers containing cobalt catalysts, Arop The same mixture of ol 2036 (100 g) and 4EKP (1.25 g) was cured. 30 ° C and 120 All cured systems are measured at 10 ° C⁷dyn / cm^TwoElastic modulus greater than T_gWas between 120 ° C and 125 ° C. Cobalt content and molecules of crystalline polymer components Details of the catalyst, showing the amounts as well as the results obtained, are given in Table 6 below. Implementation Examples E1 to E4 are comparative examples. For the modifiers of Examples E5 and E6, the cobalt catalyst was Attaches physically, not chemically, to the polymer component. In another embodiment, the cobalt The catalyst chemically bonds to the polymer component. Example F   Physically Bound Modifiers of Examples 5-14, and Their Own Active Chemical Ingredients Various matrix materials (for comparison purposes) as shown in Tables 8-10 below And then tested to give the results shown in Table 11 below. Tables 8-10 In, the term "phr amine" indicates the active amine concentration in the mixture.   In Examples F1-F4, denaturant (1.2 g) and Epon 828 (10 g) were added to a 20 ml bath. Put in the vial and mix vigorously with a spatula. Sample at 30 ° C in DSC Testing was performed at a heating rate of 10 ° C./min in the range of 〜300 ° C. In Examples F5 and F6, The modifier or EMI-24 was mixed by hand with the epoxy resin. DSC Day I got it. The viscosity was measured first and after 2 days. 1 x 0.5 inch stacked by 0.5 inch Spread the mixture on a lump aluminum coupon and heat the sample at 120 ° C. And after the indicated time, an Inst equipped with a 1000 lb. load cell at 0.05 inches / minute. The lap shear value is obtained by measuring the lap shear strength with the ron Tensile tester. Was. Viscosity profiles over time of the sample (rheometer, time sweep, 70 ° C., 25 rad / sec, 20% strain) are shown in Table 7 below. * Comparative example   In Examples F7-F10, the ingredients were mixed by hand. In Examples F11 and F12, NCO: OH The components were mixed in amounts such that the ratio was 1: 1. In Examples F13 to F17, the components were mixed by hand. The results of the DSC test show that the initial heat of reaction (300 to 350 J / g in Examples F13 to F15) , In Examples F16-F17 was 400-600 J / g) The residual heat of reaction is shown in Table 11. Example 15   Using the general procedure of Example 1, C18A, C1M, HEA and C12SH were converted to 70:10:20: The reaction was performed at a ratio of 1. T of dried product (POMHA)_PIs about 39 ° C, M_WIs about 8,700 Was. Dissolve POMHA (100 g) in tetrahydrofuran (500 ml) and cool to 5 ° C Rejected. While maintaining the temperature below 10 ° C, butyllithium (hdyrox yl group), 0.9 eq.) was added dropwise, followed by 4-bromobenzene Zofenone (1.2 eq) was added dropwise. The mixture is stirred for 12 hours, and Filtered. The product (POMBP, polymer containing bound benzophenone) , Isolated by precipitation from ethanol and dried.Example 16   C22A (1064 g) and C1M (156.4 g) were dissolved in xylene (1530 g). MA (5 70.7 g) was dissolved in xylene (719 g). C22A / C1M solution over 1.5 hours Add to the MA solution at 110 ° C. while simultaneously adding the initiator (30 g, Esp erox 5100) was measured with a meter. Then the temperature was increased to 130 ° C. 2 After hours, make another solution of the initiator (15 g, Esperox 5100) in xylene (7.5 g). Measured by After 45 minutes, the temperature was reduced to 25 ° C. AMZ (727g) for 1 hour Was measured with a meter. Then, xylene (2300 g) was added and the temperature was raised to 130 ° C. Raised. After heating overnight to remove water of condensation, polymer modification with methanol The agent was allowed to settle.Example 17   C22A (77 parts), vinylimidazole (18 parts) and C12SH (5 parts) The reaction was carried out in xylene at 125 ° C. in the presence of (TAP, 1 part). Two hours later, another opening The initiator (0.5 parts Esperox 5100) is added and the reaction mixture is stirred overnight. At 85 ° C. At this point, the product can be isolated and broken up into small particles . Alternatively, the product is prepared in an equivalent amount of epoxycyclohexyl in a Cowles mixer. (Cylohexyl) methyl-3,4-epoxy-cyclohexanecarboxylate (ERL 4 221) at less than 40 ° C. and then incubated at 40 ° C. overnight, Set To provide a concentrated concentrate.Example 18   By heating C22A (75 g), DMAEA (25 g) and TAP (1%) at 110 ° C. A copolymer was prepared. M of copolymer_WIs 15,000 to 25,000 and T_PIs 63 ° C Was. The copolymer was reduced to particles having an average size of 10 microns.Example 19   In a heated (125 ° C) bath, C22A (924 g) and vinylimidazole (VI) (216 g ), C12SH (60 g) was added along with 1% by weight of Esperox 570. 90 minutes Additional C22A (3700 g), VI (864 g) and C12SH (240 g) with 1% Esperox Added with 570. The reaction proceeded for 1 hour after addition of 0.5% Esperox 5100, The reaction proceeded for 2 hours. Dodecenyl succinic anhydride is added to the hot reaction mixture. (4-12% by weight) was added. The reaction product is then cooled, crushed, and air milled. Into particles having a diameter of less than 10 microns.Example 20   In this example, a solution of the C22A / AA / C12SH polymer prepared in Example 4 (800 ml Was heated with stirring to dissolve the polymer. This solution To this was added 324.3 g of BTBTO. The reaction mixture is steamed using a Dean-Stark water separator. Stayed. Water was collected to indicate the course of the reaction. When 10 g of water is collected, 3.2 liters Slowly add the reaction mixture to the acetone with stirring to precipitate the polymer. I let you go. Collect the precipitate by filtration, wash with acetone and vacuum oven at 50 ° C For several hours. The product has a tin content of 13.1%, T_OIs 37.01 ℃, T_PIs 49 ℃ And ΔH were 39.6 J / g. Mill this product to an average of less than 20 microns Particles having a size were obtained.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, L U, MC, NL, PT, SE), OA (BF, BJ, CF) , CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, S D, SZ, UG, ZW), EA (AM, AZ, BY, KG) , KZ, MD, RU, TJ, TM), AL, AM, AT , AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, F I, GB, GE, HU, IL, IS, JP, KE, KG , KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, N O, NZ, PL, PT, RO, RU, SD, SE, SG , SI, SK, TJ, TM, TR, TT, UA, UG, UZ, VN (72) Inventor Kamp, David A.             United States California 94087,             Sunnyvale, Ticonderoga Drive               886 (72) Inventors Mayers, Paul A.             United States California 94583,             San Raymon, Tahiti Drive 2238 (72) Inventor Taft, David A.             United States California 94027,             Atherton, Melanie Lane 45 (72) Schultz, Donald A.             United States California 94403,             San Mateo, Marshall Avenue             3901

Claims (1)

[Claims] 1. (1) a matrix material; and (2) melting initiation distributed or adjacent to the matrix material such that (a) (i) T _P -T _O is less than T _P ^0.7 a polymer component comprising a crystalline polymer moiety having a temperature T _O and peak melting temperature T _P, (ii) the polymer component chemically physically bound rather than to the, in contact with the matrix material under conditions selected An active chemical component that promotes a chemical reaction of the matrix material, and (b) when exposed to a change in a variable selected from temperature, solvent concentration, electromagnetic radiation, ultrasonic radiation, and pH, A modifier in the form of a solid that undergoes a physical change that destroys the physical integrity of the modifier and increases the degree to which the matrix material contacts the active chemical component, wherein the solid form comprises: i) distributed in the matrix material, (A) an average particle size of 0.1 to 150 microns, (b) a polymer component having a heat of fusion of at least 20 J / g, and (c) a polymer component wherein the crystalline polymer portion is a side chain crystalline polymer. A solid particle having one or more of the following: and (ii) a membrane in contact with the matrix material. 2. The composition of claim 1, wherein the modifier is in the form of solid particles dispersed in a continuous solid or liquid phase of the matrix material. 3. (a) the matrix material, (i) an unsaturated polyester that undergoes a cross-linking reaction when exposed to a metal-containing catalyst, or (ii) reacts with each other when exposed to a metal-containing catalyst to form a polyurethane, polyurea, or The composition of claim 2, comprising: a chemical compound that forms a polyisocyanurate; and (b) the active chemical component is a metal-containing compound that is a catalyst for the reaction of the matrix material. 4. 4. The polymer component of claim 3, wherein the polymer component is an SCC polymer, the SCC polymer and the metal-containing compound both include a polar group, and / or the SCC polymer and the metal-containing compound both include a long chain alkyl group. Composition. 5. The composition of claim 1 or 2, wherein the matrix material is an epoxy resin precursor and the polymer component comprises amic acid groups. 6. The composition according to any one of claims 1 to 4, wherein the process is a process for producing a polyurethane by reacting two or more chemical compounds, the process comprising: (A) a process of mixing the chemical compounds. Preparing a product, wherein at least one of the chemical compounds is the active chemical component of the modifier of claim 1, and (B) heating the mixture of step (A). And increasing the degree to which the matrix material comes into contact with the active chemical component. 7. The process of claim 7, wherein a foamed product is made by a reaction injection molding process. 8. A process of forming a coating of a thermosetting composition on a substrate and heating the coating to cure the composition, thereby producing a coated substrate, wherein the thermosetting composition comprises: A process, which is a composition according to any of the preceding claims. 9. (1) a matrix material that reacts when exposed to a peroxide or azo initiator; (2) distributed in the matrix material, such that (a) (i) T _P -T _O is less than T _P ^0.7 a polymer component containing Do melting start temperature T _O and crystalline polymer segments having a peak melting temperature T _P, wherein the active chemical component comprising (ii) a peroxy group or azo group, and in (b) said matrix material A modifier, which is in the form of solid particles that, when dispersed and heated, undergoes a physical change that causes the modifier to lose physical integrity and increase the degree to which the matrix material comes into contact with the peroxide initiator. Wherein the solid particles comprise the following characteristics: (i) an average particle size of 0.1-150 microns; (ii) a polymer component having a heat of fusion of at least 20 J / g; and (iii) the crystalline polymer portion has side chains. Polymer component that is a crystalline polymer A composition comprising one or more of the following. Ten. (1) a matrix material that is an epoxy resin precursor; and (2) a melting onset temperature T such that (A) (a) (i) T _P -T _O is less than T _P ^0.7 distributed in the matrix material. a polymer component comprising a crystalline polymer moiety having _O and peak melting temperature T _P, upon contact with the matrix material under conditions selected (ii), the active chemical ingredients that promote the formation of the epoxy resin from the matrix material And (b) when dispersed in the matrix material and heated, induces a physical change that causes the modifier to lose physical integrity and increase the extent to which the matrix material comes into contact with the active chemical component. A modifier in the form of a solid particle undergoing, wherein the solid particle has the following properties: (i) an average particle size of 0.1 to 150 microns; (ii) a polymer component having a heat of fusion of at least 20 J / g; and (iii) the crystalline polymer portion is on the side A composition comprising: a modifier having one or more of the polymer components that are chain crystalline polymers; and (B) 20-50% by weight of an anhydride based on the weight of the epoxy resin precursor. 11． (1) a matrix material that is an epoxy resin precursor; and (2) a melting onset temperature T such that (A) (a) (i) T _P -T _O is less than T _P ^0.7 distributed in the matrix material. a polymer component comprising a crystalline polymer moiety having _O and peak melting temperature T _P, upon contact with the matrix material under conditions selected (ii), the active chemical ingredients that promote the formation of the epoxy resin from the matrix material And (b) undergoing a physical change which, when dispersed in the primary material and heated, causes loss of physical integrity of the modifier and increases the degree to which the matrix material comes into contact with the active chemical component A modifier in the form of solid particles, wherein the solid particles have the following properties: (i) an average particle size of 0.1 to 150 microns; (ii) a polymer component having a heat of fusion of at least 20 J / g; and iii) the crystalline polymer portion is a side-chain crystalline poly A composition comprising: a modifier having one or more of the polymer components that is a mer; and (B) a surfactant having a lower surface energy than the modifier. 12． 12. The composition according to claim 11, wherein the surfactant is a fluorocarbon surfactant. 13. (1) a matrix material that is an epoxy resin precursor; and (2) a melting onset temperature T such that (A) (a) (i) T _P -T _O is less than T _P ^0.7 distributed in the matrix material. a polymer component comprising a crystalline polymer moiety having _O and peak melting temperature T _P, upon contact with the matrix material under conditions selected (ii), the active chemical ingredients that promote the formation of the epoxy resin from the matrix material And (b) when dispersed in the matrix material and heated, induces a physical change that causes the modifier to lose physical integrity and increase the extent to which the matrix material comes into contact with the active chemical component. A modifier in the form of a solid particle undergoing, wherein the solid particle has the following properties: (i) an average particle size of 0.1 to 150 microns; (ii) a polymer component having a heat of fusion of at least 20 J / g; and (iii) the crystalline polymer portion is A modifier having one or more of the polymer components that are chain crystalline polymers; and (B) 0.5-10% by weight, based on the weight of the epoxy resin precursor, of an auxiliary additive, wherein the alkenyl succinic anhydride And an auxiliary additive that is dodecylbenzenesulfonic acid, methyltetrahydrophthalic anhydride, nonylphenol, or pentadec-1-ylphenol. 14. (1) a matrix material that is an epoxy resin precursor; and (2) a melting onset temperature T such that (a) (i) (A) T _P -T _O is less than T _P ^0.7 distributed in the matrix material. a crystalline polymer moiety having _O and peak melting temperature T _P, after mixing the (B) the matrix material and the modifying agent is needed to reach equilibrium between the matrix material and the modified agent A polymer component comprising: a time-saving polar group; and (ii) an active chemical component that, upon contact with the matrix material under selected conditions, promotes the formation of an epoxy resin from the matrix material; and (b) solid particles which, upon being dispersed and heated in the matrix material, undergo physical changes that cause the modifier to lose physical integrity and increase the degree to which the matrix material comes into contact with the active chemical component With a denaturant that is in the form The solid particles have the following characteristics: (i) an average particle size of 0.1-150 microns; (ii) a polymer component having a heat of fusion of at least 20 J / g; and (iii) a crystalline polymer moiety having side chain crystals. A composition comprising one or more of the polymer components that is a reactive polymer. 15． A method of making a chemical composition, comprising subjecting the composition of any of claims 1 to 5 and 9 to 14 to a change in a variable that causes the physical integrity of the modifying agent to be lost. ,Method.