JP2011016980A - Acrylic emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an acrylic emulsion composition which has good storage stability and also good affinity and the wettability to a material to be treated with, and exhibiting necessary and sufficient mechanical strength and adhesive force even on the treatment at relatively low temperature.SOLUTION: The acrylic emulsion composition comprises 2-50 wt.% of an acrylic copolymer and 50-98 wt.% of water, where the acrylic copolymer contains 0.3-50 wt.% of a chemical structure (P1) in the molecule where an acrylic monomer (P) having a functional group in the molecule is radically polymerized, and the cohesive energy CE(P1) of the chemical structure (P1) is ≥500 MPa. Alternatively, the acrylic emulsion composition comprises 2-50 wt.% of an acrylic copolymer and 50-98 wt.% of water, where the acrylic copolymer contains 0.3-50 wt.% of a chemical structure (P2) in the molecule which is generated after the functional group of the chemical structure (P1), where an acrylic monomer (P) having a functional group in the molecule is radically polymerized, is further reacted, and the cohesive energy CE(P2) of the chemical structure (P2) is ≥450 MPa.

Description

  The present invention relates to an acrylic emulsion composition, and in particular, to an acrylic emulsion composition used for paints, pressure-sensitive adhesives, adhesives, binders and sizing agents, paper strength enhancers, compatibilized polymers of polymer composite materials, and the like.

  Acrylic emulsions are widely used as paints, pressure-sensitive adhesives, adhesives and the like because of their low VOC and low environmental impact. On the other hand, since acrylic emulsion is produced by emulsion polymerization using water as a medium, an emulsifier remains in the polymer even after film formation, and since there is no appropriate curing agent because water is used as a medium, sufficient crosslinking reaction The mechanical strength was low, and the chemical resistance such as water resistance and solvent resistance was inferior.

  A method for crosslinking an acrylic emulsion has been proposed (see Patent Document 1). Patent Document 1 mixes a high acid value acrylic emulsion derived from a carboxyl group and an emulsion of a vinyl compound having an oxazonyl group in the molecule. The technology proposed by Patent Document 1 is basically a two-component mixed type consisting of an acrylic emulsion and an emulsion of a vinyl compound having an oxazonyl group, which is inconvenient and has sufficient performance in the field where continuous processing is performed. In order to draw out, a curing reaction and a crosslinking reaction at a high temperature of 200 ° C. or higher are necessary, and the heat resistance is not so much, for example, it cannot be applied to plastics.

  Carbon fiber treatment methods using polyamine compounds as binders have been proposed (see Patent Document 2 and Patent Document 3). The technique proposed in Patent Document 2 or 3 relates to a carbon fiber chopped strand in which a carbon fiber bundle is produced with polyethyleneimine or polyallylamine and then dispersed in a matrix resin. In the technique proposed in Patent Document 2 or 3, the polyethyleneimine aqueous solution or the polyallylamine aqueous solution has poor affinity with carbon fiber, insufficient wettability, and the molecular weights of polyethyleneimine and polyallylamine are low. At most, it is as small as several thousand to less than tens of thousands. Polyethyleneimine and polyallylamine are not crosslinked, and the necessary and sufficient mechanical strength, heat resistance, chemical resistance, etc. expected as carbon fiber composite material (CFRP) are not exhibited. I guess that.

Japanese Patent Laid-Open No. 9-328656 Japanese Patent Laid-Open No. 3-65311 JP-A-7-266462

  The problem to be solved by the present invention is to obtain an acrylic emulsion composition that has good storage stability, good affinity for the object to be processed, good wettability, and exhibits necessary and sufficient mechanical strength and adhesive strength. It is.

  In the present invention, the molecule has a chemical structure (P1) obtained by radical polymerization of an acrylic monomer (P) having a functional group in the molecule, and the cohesive energy CE (P1) of the chemical structure (P1) is 500 MPa or more. An acrylic emulsion composition containing 2 to 50% by weight of an acrylic copolymer containing 0.3 to 50% by weight of a chemical structure and 50 to 98% by weight of water.

  The present invention further provides a chemical structure (P2) generated after further reaction of a functional group in the chemical structure (P1) obtained by radical polymerization of an acrylic monomer (P) having a functional group in the molecule. And an acrylic copolymer containing 2 to 50% by weight of an acrylic copolymer containing 0.3 to 50% by weight of a chemical structure having a cohesive energy CE (P2) of the chemical structure (P2) of 450 MPa or more and 50 to 98% by weight of water It is an emulsion composition.

  The acrylic emulsion composition of the present invention has good storage stability and is excellent in affinity to various materials and wettability. The acrylic emulsion composition of the present invention exhibits necessary and sufficient mechanical strength such as elastic modulus, tensile strength, elongation, tensile shear strength, bending stress, bending elastic modulus even at a relatively low temperature treatment of about 150 ° C. or less.

  In addition, the acrylic emulsion composition of the present invention is useful for paints, pressure-sensitive adhesives, and adhesives. Acrylonitrile-styrene-butadiene resin (ABS), polycarbonate resin (PC), polypropylene resin (PP), nylon resin (NY), polyphenylene sulfide resin (PPS), polypropylene resin (PP) and other plastics, iron, aluminum alloy, magnesium alloy and other metals, excellent adhesion, adhesion, corrosion resistance, chemical resistance, weather resistance Demonstrate balanced performance.

  The acrylic emulsion composition of the present invention is excellent as a binder or sizing agent for high-performance fibers such as glass fiber, carbon fiber, titanium whisker, and aramid fiber because the cohesive energy of the acrylic copolymer is appropriately selected and controlled. It exhibits excellent performance, firmly adheres to high-performance fibers such as glass fiber, carbon fiber, titanium whisker, and aramid fiber, and acts to uniformly disperse glass fiber, carbon fiber, titanium whisker, and aramid fiber in the matrix resin. is there. With this function, the acrylic emulsion composition of the present invention can be used for elastic modulus, tensile strength, elongation, tensile strength of glass fiber reinforced plastic (GFRP) and carbon fiber reinforced plastic (CFRP), titanium whisker reinforced plastic, aramid fiber reinforced plastic, It has an effect of remarkably improving heat resistance such as an increase in mechanical strength such as shear strength, interfacial shear strength, bending stress, flexural modulus, and heat distortion temperature (HDT).

  In the acrylic emulsion composition of the present invention, as an acrylic monomer (P) having a functional group in the molecule, carboxyl groups such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, β-carboxyethyl acrylate, etc. Containing acrylic monomer, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glycerin mono Methacrylate, glyceryl-1-methacryloyloxyethyl urethane, 3,4-dihydroxybutyl-1-methacryloyloxyethyl urethane, α-hydroxymethyl acrylate, α-hydroxyethyl acrylate, diethylene glycol Noacrylate, Triethylene glycol monoacrylate, Polyethylene glycol glycol monoacrylate, Dipropylene glycol monoacrylate, Tripropylene glycol monoacrylate, Polypropylene glycol monoacrylate, Dibutanediol monoacrylate, Tributanediol monoacrylate, Polytetramethylene glycol monoacrylate , Diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, polyethylene glycol glycol monomethacrylate, dipropylene glycol monomethacrylate, tripropylene glycol monomethacrylate, polypropylene glycol monomethacrylate, dibutanediol monomethacrylate, tributanediol Hydroxyl group-containing acrylic monomers such as polymethacrylate, polytetramethylene glycol monomethacrylate, amino group-containing acrylic monomers such as N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, glycidyl acrylate, methyl glycidyl acrylate , Glycidyl methacrylate, methyl glycidyl methacrylate, vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate and other epoxy group-containing acrylic monomers, acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropyl Acrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N-methylol Amide group-containing acrylic monomers such as acrylamide, N- (2-hydroxyethyl) acrylamide, N- (3-hydroxypropylacrylamide), N- (4-hydroxybutyl) acrylamide, N- (2-methacryloyloxyethyl) Urea group-containing acrylic monomers such as ethylene urea and N- (2-methacrylamidoethyl) ethylene urea, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxy methacrylate Acrylic monomer having methoxy group or ethoxy group such as ethyl, carbonyl group-containing acrylic monomer such as N-vinyl-2-pyrrolidone, diacetone acrylamide, zinc acrylate, zinc methacrylate, hybrid polyester acrylate oligomer Metal atoms (Zn, Al, etc.) in molecules such as “Sartomer CN-2402” (Zarter-containing acrylic oligomer of Sartomer Co., Ltd.) and hybrid polyurethane oligomer “Sartomer 2405” (Zinc-containing acrylic oligomer of Sartomer Co., Ltd.) Examples thereof include monomers, oligomers and the like containing Ca, Mg, Zr, Cu and the like. In the acrylic emulsion composition of the present invention, the acrylic monomer (P) having a functional group in the molecule may be used alone or in a mixture of two or more.

  In the acrylic emulsion composition of the present invention, the acrylic monomer (P) having a functional group in the molecule is composed of an acrylic monomer having a functional group in the molecule and another acrylic monomer capable of radical copolymerization. The total amount is preferably 100% by weight, preferably 0.3 to 50% by weight, more preferably 0.5 to 40% by weight, and still more preferably 0.8 to 35% by weight. In the acrylic emulsion composition of the present invention, when the amount of the acrylic monomer (P) having a functional group in the molecule is less than 0.3% by weight, the mechanical strength of the acrylic copolymer is reduced, Sufficient tensile shear strength and interfacial shear strength may not be exhibited. When the amount of the acrylic monomer (P) having a functional group in the molecule exceeds 50% by weight, it becomes difficult to produce an acrylic emulsion composition due to high viscosity and high thixotropy during the acrylic emulsion production process. It may be.

  In the acrylic emulsion composition of the present invention, methyl acrylate, ethyl acrylate, n-butyl acrylate are used as other acrylic monomers capable of radical copolymerization with an acrylic monomer (P) having a functional group in the molecule. , Isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, benzyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylate Butyl, t-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, benzyl methacrylate, isobornyl methacrylate, trifluoroethyl (Meth) acrylic acid (fluoro) alkyl ester such as tacrylate, acrylic monomer having dicyclopentyl group such as dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, styrene And acrylic monomers such as vinyl compounds such as vinyl acetate. In the acrylic emulsion composition of the present invention, the acrylic monomer (P) having a functional group in the molecule and other acrylic monomers capable of radical copolymerization may be used alone or in a mixture of two or more. May be.

  In the present invention, the molecule has a chemical structure (P1) obtained by radical polymerization of an acrylic monomer (P) having a functional group in the molecule, and the cohesive energy CE (P1) of the chemical structure (P1) is 500 MPa or more. An acrylic emulsion composition containing 2 to 50% by weight of an acrylic copolymer containing 0.3 to 50% by weight of a chemical structure and 50 to 98% by weight of water. The acrylic copolymer containing 0.3 to 50% by weight of a chemical structure having a chemical structure (P1) cohesive energy CE (P1) of 500 MPa or more is preferably 5 to 45% by weight, more preferably 5 to 30% by weight. It is desirable to contain. In the acrylic emulsion composition of the present invention, the content of the acrylic copolymer containing 0.3 to 50% by weight of the chemical structure having a cohesive energy CE (P1) of the chemical structure (P1) of 500 MPa or more is less than 2% by weight. In this case, the processing efficiency of the acrylic copolymer with respect to the adherend is deteriorated, processing unevenness is generated, and sufficient adhesive strength is not exhibited. In addition, when the content of the acrylic copolymer containing 0.3 to 50% by weight of the chemical structure having a cohesive energy CE (P1) of the chemical structure (P1) of 500 MPa or more exceeds 50% by weight, the acrylic emulsion composition The viscosity and thixotropy of the product are increased, and the adherend cannot be uniformly treated with the acrylic copolymer, and the adhesive strength is not exhibited.

  In the acrylic emulsion composition of the present invention, if the chemical structure (P1) is glycidyl methacrylate (GMA) as an example of an acrylic monomer (P) having a functional group in the molecule, the chemical structure (P1) is functional in the molecule. Glycidyl methacrylate (GMA) which is an acrylic monomer (P) having a group is

The chemical structure (P1) obtained by radical polymerization of glycidyl methacrylate (GMA), which is an acrylic monomer (P) having a functional group in the molecule, is

Indicated by

  In the acrylic emulsion composition of the present invention, the cohesive energy CE (P1) of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule is 500 MPa or more. When the cohesive energy CE (P1) of the chemical structure (P1) is less than 500 MPa, necessary and sufficient tensile shear strength and interfacial shear strength are not exhibited, and the adhesive force is insufficient. When the cohesive energy CE (P1) of the chemical structure (P1) is less than 500 MPa, the tensile strength, elastic modulus, heat resistance and the like of the polymer composite material reinforced with high-functional fibers are insufficient.

  In the acrylic emulsion composition of the present invention, the cohesive energy CE (P1) of the chemical structure (P1) is CE (P1) = δ × E / M (where δ is an acrylic monomer having a functional group in the molecule) (P) represents the density (g / cc), E represents the sum of the cohesive energies Ecoh (J / mol) of the atomic groups constituting the chemical structure (P1), and M represents the molecular weight of P1. Is done.

  In the acrylic emulsion composition of the present invention, when determining the cohesive energy CE (P1) of the chemical structure (P1), the density (g / cc) δ of the acrylic monomer (P) having a functional group in the molecule, and The molecular weight M is an acrylic monomer (P) having a functional group in the molecule, and is commercially available. For example, Mitsubishi Rayon Co., Ltd., Osaka Organic Chemical Co., Ltd., Nippon Shokubai Co., Ltd., NOF ( The manufacturer's catalog values were used, such as Co., Ltd., Toagosei Co., Ltd., Kyoeisha Chemical Co., Ltd., Kojin Co., Ltd., Reine Co., Ltd., and Sartomer Co., Ltd.

  Table 1 shows an example of the acrylic monomer (P) having a functional group in the molecule in the acrylic emulsion composition of the present invention.

  In the acrylic emulsion composition of the present invention, E (J / mol) is the sum of the cohesive energies Ecoh (J / mol) of the atomic groups constituting the chemical structure (P1). That is, in the acrylic emulsion composition of the present invention, E = ΣEcoh (J / mol).

In the acrylic emulsion composition of the present invention, the cohesive energy Ecoh (J / mol) of the atomic group constituting the chemical structure (P1), for example, —CH ₃ , —CH ₂ —,> C <, —COOH, etc. References: (1) RFFedors: “A Method for Estimating Both the Solubility Parameters and Molar Volumes of Liquids”, Polm. Eng. Sci., 14 (2) .147-154 (1974), and References: (2 ) "SP value Basic / application and calculation method" (Information Organization Co., Ltd.), 6th edition, p69, 2008, using the cohesive energy Ecoh (J / mol) of the atomic group proposed by RFFedors . An example of the cohesive energy Ecoh (J / mol) of the atomic group proposed by RFFedors is shown in Table 2.

  In the acrylic emulsion composition of the present invention, when a plurality of acrylic monomers (P) having different functional groups are copolymerized with the acrylic copolymer, the acrylic monomers (P) having functional groups are radically polymerized. As the cohesive energy CE (P1) of the chemical structure (P1), the largest one among the plural cohesive energies CE (P1) is adopted. Similarly, when a plurality of CE (P1) are simultaneously present in the acrylic copolymer molecule, the largest one of CE (P1) and CE (P2) is employed.

  That is, in the acrylic emulsion composition of the present invention, if the acrylic monomer (P) having a functional group is A, B, C..., The acrylic monomer (P) having a functional group is a radical. Assuming that the polymerized chemical structure (P1) is (A), (B), (C), each cohesive energy CE (P1) (A) = CE (P1) (B)> CE (P1) (C ), The cohesive energy of the acrylic copolymer is CE (P1) (A) or CE (P1) (B).

  A calculation example of the cohesive energy CE (P1) is explained by taking glycidyl methacrylate (GMA) (molecular weight M = 142, density δ = 1.07 g / cc) as an example of the acrylic monomer (P) having a functional group in the molecule. To do.

The chemical structure (P) in which glycidyl methacrylate (GMA) is radically polymerized has, as an atomic group in the molecule, one —CH ₃ (Ecoh = 4710), three —CH ₂ — (Ecoh = 4940),> CH -(Ecoh = 3430), 1> C <(Ecoh = 1470), -COO- (Ecoh = 18000), 1 -O- (Ecoh = 3350), 1 ΣEcoh = 4710 (= 4710 × 1) +14820 (= 4940 × 3) +3430 (= 3430 × 1) +1470 (= 1470 × 1) +18000 (= 18000 × 1) +3350 (= 3350 × 1) = 45780. Since the molecular weight M of glycidyl methacrylate (GMA) is 142 and the density δ = 1.07 (g / cc), CE (P1) = δ × E / M = 1.07 × 45780/142 = 345 MPa.

  In the acrylic emulsion composition of the present invention, a functional group is present in the molecule where the cohesive energy CE (P1) of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule is 500 MPa or more. As acrylic monomers (P) having, acrylic acid (CE (P1) = 530), itaconic acid (CE (P1) = 844), maleic acid (CE (P1) = 851), 2-hydroxyethyl acrylate ( CE (P1) = 556), 2-hydroxyethyl methacrylate (CE (P1) = 501), glycerin monomethacrylate (CE (P1) = 513), N- (2-methacryloyloxyethyl) ethylene urea (CE (P1) ) = 513), N- (2-hydroxyethyl) acrylamide (CE (P1) = 717) and the like.

  In the acrylic emulsion composition of the present invention, the cohesive energy CE (P1) of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule is preferably 500 MPa to 900 MPa, more preferably. Is preferably 500 to 880 MPa. In the acrylic emulsion composition of the present invention, the cohesive energy CE (P1) of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule is preferably 500 MPa to 900 MPa. There is a tendency to improve the chemical properties such as water resistance and alkali resistance of the acrylic copolymer itself, and mechanical properties such as tensile strength and elongation. At the same time, the adhesive properties such as tensile shear strength and interfacial shear strength are improved. There is a tendency to improve.

  The second invention according to the present invention is a chemical structure formed after further reaction of a functional group in a chemical structure (P1) in which an acrylic monomer (P) having a functional group in the molecule undergoes radical polymerization. An acrylic emulsion composition containing 2 to 50% by weight of an acrylic copolymer containing 0.3 to 50% by weight of a chemical structure having a cohesive energy CE (P2) of (P2) of 450 MPa or more and 50 to 98% by weight of water is there.

  In the acrylic emulsion composition of the present invention, the acrylic copolymer containing 0.3 to 50% by weight of a chemical structure having a chemical structure (P2) cohesive energy CE (P2) of 450 MPa or more is preferably 5 to 45% by weight. %, More preferably 5 to 30% by weight.

  In the acrylic emulsion composition of the present invention, the content of the acrylic copolymer containing 0.3 to 50% by weight of the chemical structure having a chemical structure (P2) cohesive energy CE (P2) of 450 MPa or more is less than 2% by weight. In this case, the processing efficiency of the acrylic copolymer with respect to the adherend is deteriorated, processing unevenness is caused, and sufficient adhesive strength is not exhibited. When the content of the acrylic copolymer containing 0.3 to 50% by weight of the chemical structure having a chemical structure (P2) cohesive energy CE (P2) of 450 MPa or more exceeds 50% by weight, an acrylic emulsion The viscosity and thixotropy of the composition are increased, and the adherend cannot be uniformly treated with the acrylic copolymer, and the adhesive strength is not exhibited.

  In the acrylic emulsion composition of the present invention, the chemical structure (P2) represents a chemical structure (P2) that is generated after the functional group of the chemical structure (P1) further reacts. In the acrylic emulsion composition of the present invention, even if the chemical structure (P2) is a new chemical structure (P2) generated by the self-reaction of the chemical structure (P1), the chemical structure (P1) and the functional group of the chemical structure (P1) It may be a chemical structure (P2) generated after reaction with a compound having a functional group that reacts with. In the acrylic emulsion composition of the present invention, the chemical structure (P2) is a chemical structure (P2) generated by a covalent bond such as a covalent bond between a carbon atom and a carbon atom or a covalent bond between a carbon atom and an oxygen atom. However, for example, a hydrogen bond between a hydroxyl group and a hydroxyl group, a hydrogen bond between a hydroxyl group and an amino group, a hydrogen bond such as a hydrogen bond between a hydroxyl group and a carboxyl group, for example, a carboxyl group and a metal atom such as Zn, Cu, Fe or the like It may be a chemical bond (P2) by an ionic bond such as an ionomer with a compound containing a metal atom.

  In the acrylic emulsion composition of the present invention, when the chemical structure (P1) does not react or the chemical structure does not change due to the reaction, the chemical structure (P2) becomes the chemical structure (P1).

  In the acrylic emulsion composition of the present invention, when the chemical structure (P1) is changed by the reaction to become the chemical structure (P2), the reaction mechanism and the chemical structure (P2) to be generated are described in, for example, Document: Polymer Experimentals Volume 6 “Polymer Reaction”, edited by the Society of Polymer Science, edited by the Committee on Polymer Experimental Studies, Kyoritsu Shuppan, 1978.

  For the chemical structure (P2), glycidyl methacrylate (GMA) is selected as an example of the acrylic monomer (P) having a functional group in the molecule, and the functional structure of the chemical structure (P1) obtained by radical polymerization of glycidyl methacrylate (GMA). As an example of a compound that reacts with an epoxy group that is a group, a case where “Epomin SP-012” (polyethyleneimine manufactured by Nippon Shokubai Co., Ltd.) that is a polyamine compound is selected will be described as an example.

  Glycidyl methacrylate (GMA) which is an acrylic monomer (P) having a functional group in the molecule is

The chemical structure (P1) obtained by radical polymerization of glycidyl methacrylate (GMA), which is an acrylic monomer (P) having a functional group in the molecule, is

The chemical structure (P2) formed after the reaction of the epoxy group, which is a functional group of the chemical structure (P1), with “Epomin SP-012” is

It is illustrated by.

  In the acrylic emulsion composition of the present invention, when a plurality of acrylic monomers (P) having different functional groups are copolymerized with the acrylic copolymer, the acrylic monomers (P) having functional groups are radically polymerized. As the cohesive energy CE (P2) of the chemical structure (P2) formed by further reaction of the functional group of the chemical structure (P1), the largest one among the plurality of cohesive energies CE (P2) is adopted. Similarly, when a plurality of CE (P2) are present in the acrylic copolymer molecule at the same time, the largest one of CE (P2) is adopted.

  That is, in the acrylic emulsion composition of the present invention, if the acrylic monomer (P) having a functional group is A, B, C..., The acrylic monomer (P) having a functional group is a radical. Assuming that the polymerized chemical structure (P1) is (A), (B), (C), the chemical structure (P2) formed by further reaction of the functional groups (A), (B), (C) is ( Assuming that AA), (BB), and (CC), the respective cohesive energies CE (P2) (AA) <CE (P2) (BB)> CE (P2) (CC) and CE (P2) ( When CC)> CE (P1) (A) = CE (P1) (B), the cohesive energy of the acrylic copolymer is CE (P2) (CC).

  Glycidyl methacrylate (GMA) is selected as the acrylic monomer (P) having a functional group in the molecule, and the chemical structure (P1) in which glycidyl methacrylate is radically polymerized and the chemical structure (P1) in which glycidyl methacrylate is radically polymerized are As a chemical structure (P2) produced when “PAA-03” (polyallylamine from Nittobo Co., Ltd.), which is a polyamine, is selected as a compound that reacts with an epoxy group that is a functional group of the chemical structure (P1). Table 3 exemplifies methods for calculating the respective cohesive energies CE (P1) and CE (P2).

  Examples of acrylic monomers (P) having functional groups in the molecule include acrylic acid (AA), methacrylic acid (MAA), itaconic acid (IA), maleic acid (MA) 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), glycerin monomethacrylate (GLM), glycidyl methacrylate (GMA), vinylbenzyl glycidyl ether (VBGE), N- (2-methacryloyloxyethyl) ethylene urea (MEEU), N- (2 Table 4 illustrates the cohesive energy CE (P1) of the chemical structure (P1) produced by radical polymerization of the acrylic monomer (P) having a functional group in the molecule by selecting -hydroxyethyl) acrylamide (HEAA). .

  In the acrylic emulsion composition of the present invention, among the examples shown in Table 4, functional groups in the molecule are preferable from the viewpoint of the cohesive energy CE (P1) MPa of the chemical structure (P1), 500 MPa to 900 MPa. Preferably, the acrylic monomer (P) having an acrylic acid (AA) (CE (P1) = 530), itaconic acid (IA) (CE (P1) = 844), maleic acid (MA) (CE ( Acrylic monomers having a carboxyl group in the molecule such as P1) = 851), 2-hydroxyethyl acrylate (HEA) (CE (P1) = 556), 2-hydroxyethyl methacrylate (HEMA) (CE (P1 ) = 501), acrylic monomers having a hydroxyl group in the molecule such as glycerin monomethacrylate (GLM) (CE (P1) = 624), N- (2 An acrylic monomer having a urea group in the molecule such as methacryloyloxyethyl) ethylene urea (MEEU) (CE (P1) = 513), N- (2-hydroxyethyl) acrylamide (HEAA) (CE (P1) = 717 An acrylic monomer having an amide group in the molecule is desirable.

  In the acrylic emulsion composition of the present invention, the chemical structure (P1) contained in the acrylic copolymer preferably contains at least one of a hydroxyl group, a carboxyl group, an amide group, and a urea group as a functional group in the molecule. It is recommended.

  In the acrylic emulsion composition of the second invention of the present invention, the cohesive energy CE (P2) of the chemical structure (P2) is CE (P2) = δ × E / M (where δ is a functional group in the molecule). The density (g / cc) of the acrylic monomer (P) is represented, E is the sum of the cohesive energies Ecoh of the atomic groups constituting the chemical structure (P2), and M is the molecular weight of P2. Is done.

  Examples of acrylic monomers (P) having functional groups in the molecule include radical polymerization of acrylic acid (AA), methacrylic acid (MAA), itaconic acid (IA), maleic acid (MA), and glycidyl methacrylate (GMA). The chemical structure (P1) generated by reacting the generated chemical structure (P1) with polyallylamine, and the chemical structure (P1) generated by radical polymerization of N- (2-hydroxyethyl) acrylamide (HEAA) are generated by self-reaction. Table 5 shows the cohesive energy CE (P2) of the chemical structure (P2).

  In the acrylic emulsion composition of the second invention of the present invention, the cohesive energy CE (P2) of the chemical structure (P2) is 450 MPa or more. When CE (P2) is less than 450 MPa, the necessary and sufficient tensile shear strength and interfacial shear strength are not exhibited, the adhesive strength becomes insufficient, and the tensile strength and elasticity of the polymer composite material reinforced with high-performance fibers. Rate, heat resistance, etc. are insufficient.

  In the acrylic emulsion composition of the present invention, the cohesive energy CE (P2) of the chemical structure (P2) is preferably 450 MPa to 1200 MPa, more preferably 480 MPa to 1180 MPa. In the acrylic emulsion composition of the present invention, when the cohesive energy CE (P2) of the chemical structure (P2) is preferably 450 MPa to 1200 MPa, the acrylic copolymer itself has chemical properties such as water resistance and alkali resistance, tensile strength, and the like. There is a tendency that mechanical properties such as strength and elongation are improved, and at the same time, there is a tendency that adhesiveness such as tensile shear strength and interfacial shear strength is improved.

  In the acrylic emulsion composition of the present invention, among the examples shown in Table 5, the acrylic monomer (P) having a functional group in the molecule is preferably acrylic acid (AA) (CE (P2 ) = 634), methacrylic acid (MAA) (CE (P2) = 542), itaconic acid (IA) (CE (P2) = 1004), maleic acid (MA) (CE (P2) = 1030), glycidyl methacrylate ( GMA) (CE (P2) = 489), vinylbenzyl glycidyl ether (VBGE) (CE (P2) = 476), N- (2-hydroxyethyl) acrylamide (HEAA) (CE (P2) = 541) is desirable.

  In the acrylic emulsion composition of the present invention, it is recommended that the chemical structure (P2) preferably contains at least one of a carboxyl group, an epoxy group, and an amide group as a functional group in the molecule. In the acrylic emulsion composition of the present invention, more preferably, the functional group having the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule is an epoxy group.

  In the acrylic emulsion of the present invention, the cohesive energy CE (P1) of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule is further reacted with the chemical structure (P1). In the cohesive energy CE (P2) of the chemical structure (P2), the functional group capable of reacting with the functional group of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule The chemical compound (Q) having a chemical structure (Q1) formed after reaction of the acrylic monomer (P) having a functional group in the molecule with the functional group of the chemical structure (P1) obtained by radical polymerization of the chemical structure (Q1) When the cohesive energy of Q1) is CE (Q1), when CE (Q1)> CE (P1) or CE (Q1)> CE (P2), the cohesive energy of the acrylic copolymer Over to the CE (Q1).

  In the acrylic emulsion composition of the present invention, “PAA” is a compound having a functional group capable of reacting with the functional group of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule. Taking "-03" (polyallylamine from Nittobo Co., Ltd.) and "Epomin SP-012" (polyethyleneimine from Nippon Shokubai Co., Ltd.) as an example of CE (Q1), "PAA-03" In this case, CE (Q1) = 499 MPa, and in the case of “Epomin SP-012,” CE (Q1) = 561 MPa.

  In the acrylic emulsion composition of the present invention, preferably, a compound having a functional group that reacts with a functional group of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule is used. can do.

  In the acrylic emulsion composition of the present invention, the compound having a functional group that interacts with the functional group of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule is preferably, N, N-dimethylethanolamine, 1,6-hexamethylenediamine, polyallylamine, polyethyleneimine and other compounds having amino groups or amide groups in the molecule, phthalic acid, maleic anhydride, tetrahydrophthalic anhydride, trimellitic acid Polybasic acids or acid anhydrides such as glycerin, pentaerythritol, dipentaerythritol, polyhydric alcohols such as ethylene glycol, polyisocyanates such as tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate Isocyanates temporarily deactivated with blocking agents such as methyl ethyl ketone oxime, organic peroxides such as benzoyl peroxide and cumene hydroperoxide, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxy Examples include silane coupling agents such as silane, γ-isocyanatopropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane, tetraisopropoxy titanate, aluminum monoacetylacetonate bis (metal-containing organic compounds such as ethyl acetoacetate, etc. In the acrylic emulsion composition of the present invention, the compound having a functional group that reacts with the functional group of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule is used alone. Shi It may also be used in mixture of two or more.

  In the acrylic emulsion composition of the present invention, among the compounds having a functional group that reacts with the functional group of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule, Preferably, an oligomer or polymer having a primary amino group in the molecule such as polyallylamine and polyethyleneimine and having a molecular weight of 200 to 50,000 is recommended.

  In the acrylic emulsion composition of the present invention, the compound having a functional group that reacts with the functional group of the acrylic monomer (P) having a functional group in the molecule is more preferably a molecule such as polyallylamine or polyethyleneimine. When an oligomer or polymer having a primary amino group in the molecular weight of 200 to 50,000 is used, the acrylic emulsion tends to be stabilized, and at the same time, acrylonitrile-styrene-butadiene resin (ABS), polycarbonate resin ( PC), polypropylene resin (PP), nylon resin (NY), polyphenylene sulfide resin (PPS), polypropylene resin (PP) and other plastics, iron, aluminum alloys, magnesium alloys and other metals are improved. There is a tendency to improve adhesion.

  In the acrylic emulsion composition of the present invention, the compound having a functional group that reacts with the functional group of the acrylic monomer (P) having a functional group in the molecule, more preferably polyallylamine, polyethyleneimine, etc. When an oligomer or polymer having a primary amino group in the molecule and having a molecular weight of 200 to 50,000 is used, the wettability, affinity, and adhesion to high-performance fibers such as glass fiber, aramid fiber, carbon fiber, and titanium whisker The interfacial shear strength between these high-functional fibers and polymer materials is greatly improved, and the tensile strength, elongation, flexural modulus, and heat resistance of thermoplastics and thermosetting plastics reinforced with high-functional fibers There is a tendency to improve mechanical strength and thermal properties such as property.

  In the acrylic emulsion composition of the present invention, the polyallylamine can be arbitrarily selected from, for example, “PAA series”, “PAS series”, and “amphoteric series” marketed by Nittobo Co., Ltd. The products of the “PAA series” on the market include “PAA-01” (weight average molecular weight of about 1000), “PAA-03” (weight average molecular weight of about 3000), “PAA-05” (weight average molecular weight of about 5000). ), “PAA-08” (weight average molecular weight of about 8000), “PAA-15” (weight average molecular weight of about 15000), “PAA-15C” (weight average molecular weight of about 15000), “PAA-25” (weight average molecular weight) About 25000). In the acrylic emulsion composition of the present invention, among the commercially available “PAA series”, “PAA-01” (weight average molecular weight of about 1000) and “PAA-03” (weight average molecular weight of about 3000) having a small weight average molecular weight. ), “PAA-05” (weight average molecular weight of about 5000) is desirable since it has a tendency to improve the reactivity with the acrylic copolymer and to give a tough cured product. The products of the “PAS series” on the market include “PAS-21CL” (weight average molecular weight of about 110,000), “PAS-21” (weight average molecular weight of about 4000), “PAS-92” (weight average molecular weight of about 5000). And the like. “PAS-410”, “PAS-84” (weight average molecular weight of about 23000), “PAS-2451” (weight average molecular weight of about 3000) and the like are exemplified as products of the “amphoteric series” on the market.

  In the acrylic emulsion composition of the present invention, the polyethyleneimine can be arbitrarily selected from, for example, polyethyleneimine “Epomin” marketed by Nippon Shokubai Co., Ltd. “Epomin” on the market is “SP-300” (molecular weight about 300), “SP-006” (molecular weight about 600), “SP-012” (molecular weight about 1200), “SP-018” (molecular weight). About 1800), "SP-200" (molecular weight about 10,000), and the like. In the acrylic emulsion composition of the present invention, “SP-300” (molecular weight of about 300), “SP-006” (molecular weight of about 600), “SP-012” having a small molecular weight among the commercially available “epomines”. (Molecular weight of about 1200) and “SP-018” (molecular weight of about 1800) are desirable because the reactivity with the acrylic copolymer is improved and a tendency to give a tough cured product is seen.

  In the acrylic emulsion composition of the present invention, polyallylamine and / or polyethyleneimine is preferably used in an amount of 2 to 35 parts by weight with respect to 100 parts by weight of the acrylic copolymer. More preferably, polyallylamine and / or polyethyleneimine is used in an amount of 5 to 30 parts by weight, more preferably 5 to 25 parts. In the acrylic emulsion composition of the present invention, when the amount of polyallylamine and / or polyethyleneimine used is preferably 2 to 35 parts by weight with respect to 100 parts by weight of the acrylic copolymer, storage of the acrylic emulsion composition is possible. Good stability, improved adhesion to high-performance fibers such as glass fiber, carbon fiber and aramid fiber, mechanical strength such as tensile strength, elongation, flexural modulus, heat resistance of high-performance fiber composite material There is a tendency for thermal properties to improve.

  In the acrylic emulsion composition of the present invention, it is preferable to use a nonionic emulsifier when the acrylic emulsion composition and polyallylamine and / or polyethyleneimine are mixed. In the acrylic emulsion composition of the present invention, the nonionic emulsifier may be contained in the acrylic emulsion composition or in the polyallylamine and / or polyethyleneimine, and the acrylic emulsion composition and the polyallylamine and / or You may add when mixing a polyethyleneimine.

  In the acrylic emulsion composition of the present invention, the acrylic emulsion is preferably a method in which an acrylic copolymer is produced by solution polymerization and then desolvated, and preferably emulsified in ion-exchanged water, and the acrylic copolymer is bulk polymerized. Then, preferably, any method such as a method of emulsifying in ion-exchanged water, a method of directly producing an acrylic emulsion by emulsion polymerization, or a method of performing aqueous solution polymerization in ion-exchanged water when the acrylic copolymer is water-soluble. It may be manufactured.

In the acrylic emulsion composition of the present invention, when the acrylic emulsion is produced by emulsion polymerization, it is preferably produced using ion-exchanged water. In the acrylic emulsion composition of the present invention, the acrylic emulsion is preferably manufactured and manufactured using an anionic emulsifier and / or a nonionic emulsifier. In the acrylic emulsion composition of the present invention, the acrylic emulsion In the production of the anionic emulsifier, the anionic emulsifier used in the emulsion polymerization is preferably an anionic emulsifier such as sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, sodium alkyldiphenyletherdisulfonate. In the acrylic emulsion composition of the present invention, the anionic emulsifier that is preferably used when producing the acrylic emulsion may be used alone or in a mixture of two or more.

  In the acrylic emulsion composition of the present invention, as the nonionic emulsifier used for emulsion polymerization in producing the acrylic emulsion, preferably polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene Nonionic emulsifiers such as ethylene oleyl ether are exemplified. In the acrylic emulsion composition of the present invention, the nonionic emulsifier that is preferably used when producing the acrylic emulsion may be used alone or in a mixture of two or more.

  In the acrylic emulsion composition of the present invention, it is more preferable to use a reactive emulsifier as an emulsifier when producing the acrylic emulsion. In the acrylic emulsion composition of the present invention, as a reactive emulsifier, “Latemul PD-104” (polyoxyalkylene alkenyl ether ammonium sulfate), “Latemul PD-420” (polyoxyalkylene alkenyl ether) (above, Kao ( Product of Co., Ltd.) “Adekariasorb SR-1025” (α-sulfo-ω- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium Salt aqueous solution) (product of Asahi Denka Kogyo Co., Ltd.), “Aqualon KH-1025” (product of Daiichi Kogyo Seiyaku Co., Ltd.), and the like. In the acrylic emulsion composition of the present invention, the reactive emulsifier that is more preferably used when the acrylic emulsion is produced may be used alone or in a mixture of two or more.

  In the acrylic emulsion composition of the present invention, when an acrylic emulsion is produced, preferably, a reactive emulsifier is used as an emulsifier, so that stability during emulsion polymerization and storage of the acrylic emulsion is improved, water resistance, There is a tendency to improve chemical resistance such as alkali resistance.

  In the acrylic emulsion composition of the present invention, examples of the polymerization initiator preferably used for producing the acrylic emulsion include water-soluble polymerization initiators such as ammonium persulfate and potassium persulfate. In the acrylic emulsion composition of the present invention, the polymerization initiator may be used alone or in a mixture of two or more.

  In the acrylic emulsion composition of the present invention, the acrylic emulsion is preferably produced by radical polymerization at a polymerization temperature of 50 to 100 ° C. after ion-exchanged water is used and the polymerization system is replaced with an inert gas with nitrogen gas or the like. .

  In the acrylic emulsion composition of the present invention, a known emulsion polymerization method such as a monomer dropping method, a pre-emulsion method, a pre-charge method, a seed emulsion polymerization, or a power feed method can be preferably used for the production of the acrylic emulsion. In the acrylic emulsion composition of the present invention, the acrylic emulsion may be produced by any known method, but the particle diameter measured by the laser scattering method of the produced acrylic emulsion is preferably 40 to 250 nm, more Preferably, it is 50 to 200 nm, and more preferably 60 to 160 nm. In the acrylic emulsion composition of the present invention, when the particle size of the acrylic emulsion is 40 to 250 nm, the viscosity, concentration, and thixotropy of the acrylic emulsion are appropriate, and the production of the acrylic emulsion composition is facilitated, and the wettability and adhesiveness are improved. There is a tendency to improve.

  In the acrylic emulsion composition of the present invention, the particle size of the acrylic emulsion was measured using a concentrated particle size analyzer “FPAR-1000” (analyzer manufactured by Otsuka Electronics Co., Ltd.).

  In the acrylic emulsion composition of the present invention, the acrylic monomer having a functional group in the molecule has high solubility in water, that is, when the distribution coefficient is small, the acrylic monomer having a functional group in the molecule ( The acrylic monomer containing P) is subjected to bulk polymerization (acrylic prepolymer) in the presence of α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-pentene), and then in the presence of the acrylic prepolymer. Furthermore, a method of emulsion polymerization of an acrylic monomer is recommended.

  In the acrylic emulsion composition of the present invention, the acrylic monomer (P) having a functional group in the molecule is preferably transferred to the aqueous phase and is not polymerized in the aqueous phase. It is easy to incorporate the acrylic monomer (P) having a functional group into the acrylic copolymer by copolymerization, and there is a tendency that the wettability and the adhesive strength are improved. In the acrylic emulsion composition of the present invention, it tends to be a block copolymer at the same time, and the adhesive strength with the matrix resin is further improved and improved.

  Here, in the acrylic emulsion composition of the present invention, the distribution coefficient is a numerical value representing the hydrophobicity of the compound. The partition coefficient is a value obtained by actually measuring the equilibrium solubility ratio when the compound is dissolved in two phases of water and an organic solvent (n-octanol is commonly used). Generally, the partition coefficient P = (concentration of organic solvent phase) / It is expressed by (concentration of aqueous phase). The higher the value, the higher the fat solubility. That is, in the acrylic emulsion composition of the present invention, the distribution coefficient means the ratio of the acrylic monomer (P) having a functional group in the molecule remaining in the micelle during the emulsion polymerization and the ratio of shifting to the aqueous phase. It is shown. When the distribution coefficient is small, the proportion of the acrylic monomer incorporated into the polymer by copolymerization is low, and the proportion of homopolymer in the aqueous phase is increased. In the acrylic emulsion composition of the present invention, examples of the partition coefficient include partition coefficient log Pow = 0.31 for acrylic acid, partition coefficient log Pow = 0.93 for methacrylic acid, and partition coefficient log Pow = for N-methylolacrylamide. -1.81 and acrylamide are exemplified by log Pow = −1.65 to −0.67 (see above, International Chemical Safety Card (ICSC): published by National Institute of Pharmaceutical Health).

  In the acrylic emulsion composition of the present invention, when the acrylic emulsion is produced by emulsion polymerization, it is preferable to use, for example, potassium persulfate, persulfate as a polymerization initiator in ion-exchanged water previously deoxygenated by nitrogen gas bubbling or the like. Water-soluble polymerization initiators such as ammonium sulfate and 2,2-azobis (2- (2-imidazolin-2-yl) propane (water-soluble organic azo polymerization initiator “VA-061” from Wako Pure Chemical Industries, Ltd.) As an emulsifier, an anionic emulsifier such as dodecylbenzenesulfonic acid, a nonionic emulsifier such as polyoxyethylene alkyl ether, or “Adekariasorb SR-1025” (reactive emulsifier of Adeka Corp.), “ Laterum PD-104 "(Reactive emulsifier of Kao Corporation) is used at a polymerization temperature of 50 to 100 ° C. Acrylic monomer having a functional group in the molecule an acrylic monomer containing (P) can be produced by emulsion polymerization.

  In the acrylic emulsion composition of the present invention, when the distribution coefficient of the acrylic monomer (P) having a functional group in the molecule is small, the acrylic monomer (P) having a functional group in the molecule is preferably used. After the acrylic prepolymer is produced, it is desirable to produce an acrylic emulsion by emulsion polymerization of an acrylic monomer in the presence of the acrylic prepolymer. In the acrylic emulsion composition of the present invention, the acrylic prepolymer is preferably 0.02 to 1.00 mol of 1.0 mol of α-methylstyrene dimer in the presence of α-methylstyrene dimer. For example, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate (“Perbutyl O” from NOF Corporation), 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd. oil-soluble organic azo polymerization initiator "V-65"), 2,2'-azobis (2-methylbutyronitrile) (Wako Pure Chemical Industries Ltd. oil-soluble organic azo polymerization start The polymer is produced by radical polymerization of an acrylic monomer containing an acrylic monomer having a functional group in the molecule at a polymerization temperature of 80 to 100 ° C. using a polymerization initiator such as an agent “V-59”).

  In the acrylic emulsion composition of the present invention, the acrylic emulsion is preferably used as a polymerization initiator, for example, potassium persulfate, peroxygen, in ion-exchanged water previously deoxygenated by nitrogen gas bubbling or the like in the presence of an acrylic prepolymer. Water-soluble polymerization initiators such as ammonium sulfate and 2,2-azobis (2- (2-imidazolin-2-yl) propane (water-soluble organic azo polymerization initiator “VA-061” from Wako Pure Chemical Industries, Ltd.) As an emulsifier, an anionic emulsifier such as dodecylbenzenesulfonic acid, a nonionic emulsifier such as polyoxyethylene alkyl ether, or “Adekariasorb SR-1025” (reactive emulsifier of Adeka Corp.), “ Latemul PD-104 "(reactive emulsifier of Kao Corporation), etc., and a polymerization temperature of 50 to 10 ℃ In can be prepared by emulsion polymerization of acrylic monomers.

  In the acrylic emulsion composition of the present invention, the acrylic emulsion is more preferably ion-exchanged water deoxygenated in advance by nitrogen gas bubbling or the like in the presence of the acrylic prepolymer using an acrylic prepolymer as an emulsifier and a polymerization initiator. Thus, it can be produced by emulsion polymerization of an acrylic monomer at a polymerization temperature of 50 to 100 ° C.

  In the acrylic emulsion composition of the present invention, as the nonionic emulsifier, preferably, HLB13 to HLB19, more preferably HLB15 to 19, and still more preferably HLB16 to 19 nonionic emulsifiers are recommended. In the acrylic emulsion composition of the present invention, preferably, when non-ionic emulsifiers of HLB13 to HLB19 are used, when the acrylic emulsion composition is mixed with polyallylamine and / or polyethyleneimine, there is no generation of aggregates and stable. There is a tendency that a simple acrylic emulsion composition can be produced.

  In the acrylic emulsion composition of the present invention, polyoxyethylene alkyl ether is preferably recommended as the nonionic emulsifier for HLB 13-19. In the acrylic emulsion composition of the present invention, when polyoxyethylene alkyl ether is preferably used as a nonionic emulsifier, agglomerates are generated when the acrylic emulsion composition is mixed with polyallylamine and / or polyethyleneimine. There is a tendency that a stable acrylic emulsion composition can be produced.

  In the acrylic emulsion composition of the present invention, preferably the nonionic emulsifier of HLB13 to HLB19 is preferably 0.02 to 20 parts by weight of the nonionic emulsifier of HLB13 to HLB19 per 100 parts by weight of the acrylic emulsion. It is desirable to do. In the acrylic emulsion composition of the present invention, when the amount of the nonionic emulsifier of HLB13 to HLB19 is preferably 0.02 to 20 parts by weight, mixing of the acrylic emulsion with polyallylamine and / or polyethyleneimine is possible. It tends to be stable without the formation of agglomerates and without thickening or separation even during storage.

  In the production of the acrylic emulsion, preferably, a nonionic emulsifier of HLB13 to HLB19 is used, or a nonionic emulsifier of HLB13 to HLB19 is preferably added to the produced acrylic emulsion, so that Allylamine and / or polyethyleneimine can be easily mixed.

  In the acrylic emulsion composition of the present invention, preferably, as an polyoxyethylene alkyl ether of HLB13 to HLB19, “Emulgen 1108” (HLB13.4), “Emulgen 1118S-70” (HLB16.4), “ Examples include “Emulgen 1135S-70” (HLB17.9), “Emulgen 1150S-60” (HLB18.5) (which is a nonionic emulsifier of Kao Corporation), and the like. In the acrylic emulsion composition of the present invention, the polyoxyethylene alkyl ether may be used alone or in a mixture of two or more.

  The details of the present invention will be described in the following examples. In the following examples, the evaluation method, measurement method, and the like were as follows.

1) Heating residue (%)
The heating residue was measured according to JIS K 5407: 1997. The measurement was performed by heating and drying at 140 ° C. for 60 minutes. The heating residue (%) was the acrylic copolymer content (% by weight) in the acrylic emulsion composition.

2) pH (25 ° C)
Measurement was performed at 25 ° C. using a pH meter.

3) Particle size (nm)
Measurement was performed at 25 ° C. using a dense particle size analyzer “FPAR-1000” (analyzer manufactured by Otsuka Electronics Co., Ltd.).

4) Storage stability The acrylic emulsion composition was placed in a 100 mL glass bottle, sealed, and allowed to stand at 23 ° C. for 1 month. The state (appearance, thickening) was visually observed, and a product that did not change immediately after production was regarded as acceptable.

5) Acid value (mgKOH)
Measured according to JIS K 5407: 1997.

6) Tensile shear strength (MPa)
A test piece made of an aluminum alloy (thickness 1 mm) (JIS A-2017P: 1999) was immersed in the acrylic emulsion composition for 5 minutes, and heated at 140 ° C. for 30 minutes at the same time as pulling up. A polypropylene plate (thickness 1 mm) was pressure-bonded to the treated test piece at 200 ° C. for 10 seconds, and the tensile shear strength was measured at 23 ° C. according to JIS K-6850: 1999. A tensile shear strength of 10 MPa or more was considered acceptable.

Example 1
100 g of ion-exchanged water, SR-1025 (25% aqueous solution), deoxygenated by bubbling nitrogen gas through a 1-liter four-necked flask equipped with a stirrer, temperature sensor, reflux condenser, and monomer dropping port in advance. 0.8 g of Adeka Co., Ltd. reactive emulsifier, concentration 25% was charged and heated to 80 ° C.

  Methyl methacrylate 79.5g, n-butyl methacrylate 20.0g, itaconic acid 0.5g acrylic monomer mixture 100g, Adekariasorb "SR-1025" (25% aqueous solution) 3.2g, nitrogen gas bubbling in advance Deionized and deoxygenated ion exchange water 39.5 g for emulsifying acrylic monomer was put into an emulsifier and emulsified at 10,000 rpm for 5 minutes (monomer emulsion).

  Into the flask, 0.2 g of ammonium persulfate was added, followed by 20% (28.6 g) of the monomer emulsion, and emulsion polymerization was performed for 30 minutes. Thereafter, the remaining 80% (114.5 g) of the monomer emulsion was dropped into the flask in 3 hours. After completion of the dropwise addition, emulsion polymerization was further continued for 1 hour, and then 5.9 g of ion exchange water for dilution was added and cooled to 40 ° C. or lower to produce an acrylic emulsion.

  While stirring the acrylic emulsion, 416.7 g of ion-exchanged water was added to prepare an acrylic emulsion composition (AE-1) of Example 1 having a concentration adjusted to 15%.

  As shown in Table 6, the acrylic emulsion composition (AE-1) had a heating residue of 15.3% and a pH (25 ° C.) of 2.4. Moreover, the storage stability was also good.

  In Table 6, (1) is initially charged ion-exchanged water, (2) and (5) are reactive emulsifiers ADEKA rear sorb “SR-1025” (25% aqueous solution) (reactive emulsifiers of ADEKA Corporation) Concentration 25%), (3) is polymerization initiator ammonium persulfate, (4) is an acrylic monomer containing an acrylic monomer having a functional group in the molecule, (6) is for acrylic monomer emulsification and dilution (7) is ion-exchanged water for dilution, (8) is the cohesive energy CE (MPa) of the chemical structure (P1) contained in the acrylic copolymer, and (9) is the acrylic emulsion composition. The characteristic values are shown.

Example 2 to Example 6
Acrylic emulsion compositions AE-2 to AE-6 of Examples 2 to 5 were produced in the same manner as in Example 1 with the compositions shown in Table 6. As shown in Table 6, the acrylic emulsion compositions of Examples 2 to 6 could be produced without any problems, and the storage stability was also good.

Example 7
100 g of ion-exchanged water, SR-1025 (25% aqueous solution), deoxygenated by bubbling nitrogen gas through a 1-liter four-necked flask equipped with a stirrer, temperature sensor, reflux condenser, and monomer dropping port in advance. 0.8 g of Adeka Co., Ltd. reactive emulsifier, concentration 25% was charged and heated to 80 ° C.

Methyl methacrylate 69.0 g, n-butyl methacrylate 20.0 g, itaconic acid 1.0 g, acrylic acid monomer mixture 100 g of 2-hydroxyethyl methacrylate 10.0 g, Adeka Resorb “SR-1025” (25% aqueous solution) 3.2 g of ion exchanged water for emulsification of acrylic monomer, which was deoxygenated by bubbling with nitrogen gas in advance, was put into an emulsifier and emulsified at 10,000 rpm for 5 minutes. (Monomer emulsion)
Into the flask, 0.2 g of ammonium persulfate was added, followed by 20% (28.6 g) of the monomer emulsion, and emulsion polymerization was performed for 30 minutes.

  Thereafter, the remaining 80% (114.5 g) of the monomer emulsion was dropped into the flask in 3 hours. After completion of the dropwise addition, emulsion polymerization was further continued for 1 hour, and then 5.9 g of ion exchange water for dilution was added and cooled to 40 ° C. or lower to produce an acrylic emulsion.

  While stirring the acrylic emulsion, 5.0 g of nonionic emulsifier Emulgen “1135S-70” (emulsifier of Kao Corporation, HLB 17.9) and 433.3 g of ion-exchanged water were added and stirred for 30 minutes. Thereafter, 50.0 g of a polyallylamine aqueous solution (Nittobo “PAA-03” (20% aqueous solution)) was added, and the mixture was further stirred for 60 minutes to adjust the concentration to 15%. An emulsion composition (AE-7) was prepared.

  As shown in Table 7, the acrylic emulsion composition (AE-7) had a heating residue of 15.2% and a pH (25 ° C.) of 10.8. Moreover, the storage stability was also good.

  In Table 7, (1) is initially charged ion-exchanged water, (2) and (5) are reactive emulsifiers ADEKA rear sorb “SR-1025” (25% aqueous solution) (Adeka Co., Ltd. reactive emulsifiers, Concentration 25%), (3) is polymerization initiator ammonium persulfate, (4) is an acrylic monomer containing an acrylic monomer having a functional group in the molecule, (6) is for acrylic monomer emulsification and dilution (7) is a nonionic emulsifier Emulgen “1135S-70” (emulsifier of Kao Corporation, HLB17.9) and ion-exchanged water for dilution, (8) is a polyamine compound (polyallylamine “ PAA-03 "(Nittobo Co., Ltd.), polyethyleneimine" Epomin SP-012 "(Nippon Shokubai Co., Ltd.)," PAA-03 "uses a 20% aqueous solution as it is," SPA-03 " "012" was previously diluted with ion-exchanged water to a concentration of 20%.), (9) Cohesive energy CE (MPa) of the chemical structure (P2) contained in the acrylic copolymer, (10) Shows the characteristic values of the acrylic emulsion composition.

Example 8 to Example 11
Acrylic emulsion compositions AE-8 to AE-11 of Examples 8 to 11 were produced in the same manner as in Example 7 with the compositions shown in Table 7. As shown in Table 8, the acrylic emulsion compositions of Examples 8 to 11 could be produced without any problems, and the storage stability was also good.

Production of acrylic prepolymer AP-1 In a 500 ml four-necked flask equipped with a stirrer, temperature sensor, reflux condenser, and monomer dropping port, 82.0 g of cyclohexyl acrylate, 3.0 g of acrylic acid, 2-hydroxy acrylate 100 g of an acrylic monomer containing an acrylic monomer having a functional group in a molecule of 15.0 g of ethyl, 47.6 g of α-methylstyrene dimer, 2,2-azobis (2,4-dimethylvaleronitrile) (Wako Pure) "V-65" of Yakuhin Kogyo Co., Ltd. 20.0 g (20.0 parts by weight per 100 parts by weight of an acrylic monomer containing an acrylic monomer having a functional group in the molecule, α-methylstyrene dimer 0.400 mol) with respect to 1.0 mol).

  Nitrogen gas bubbling was performed for 30 minutes to deoxygenate the polymerization system, and then the system was changed to nitrogen gas blowing, and the temperature was raised to 90 ° C. in 90 minutes. Polymerization was carried out at 90 ° C. for 16 hours to produce an acrylic prepolymer AP-1 used for the acrylic emulsion composition of Examples (Table 8).

  During the production of the acrylic prepolymer AP-1, no abnormal heat generation, sudden increase in viscosity, etc. occurred, and it was possible to produce without problems. Further, during the production, sampling was performed every 2 hours, and the heating residue and the number average molecular weight were measured, and it was confirmed that the number average molecular weight increased in direct proportion to the heating residue.

  In Table 8, (1) is an acrylic monomer containing an acrylic monomer having a functional group in the molecule, and (2) is α-methylstyrene which is a RAFT agent (reversible addition-cleavage chain transfer agent). Dimer, (3) is a polymerization initiator, (4) is the cohesive energy CE (MPa) of the chemical structure (P1) contained in the acrylic prepolymer, and (5) is a characteristic value of the acrylic prepolymer.

Production of acrylic prepolymers AP-2 to AP-4 Acrylic prepolymers AP-2 to AP-4 were produced in the same manner as the acrylic prepolymer AP-1 except that the composition was changed as shown in Table 8. During the production of the acrylic prepolymers AP-2 to AP-4, no abnormal heat generation or sudden viscosity increase occurred, and the production was possible without any problems. Further, during the production, sampling was performed every 2 hours, and the heating residue and the number average molecular weight were measured, and it was confirmed that the number average molecular weight increased in direct proportion to the heating residue.

Production of Acrylic Prepolymer AP-5 A 500 ml four-necked flask equipped with a stirrer, a temperature sensor, a reflux condenser, and a monomer dropping port was charged with 100 g of acrylic prepolymer (AP-1) and 2 g of cyclohexyl acrylate.

  Nitrogen gas bubbling was performed for 30 minutes to deoxygenate the polymerization system, and then the system was changed to nitrogen gas blowing, and the temperature was raised to 90 ° C. in 90 minutes. Polymerization was carried out at 90 ° C. for 8 hours to produce an acrylic prepolymer AP-5 used in the acrylic emulsion composition of the example.

  During the production of the acrylic prepolymer AP-5, no abnormal heat generation or sudden viscosity increase occurred, and the production was possible without problems. Further, during the production, sampling was performed every 2 hours, and the heating residue and the number average molecular weight were measured, and it was confirmed that the number average molecular weight increased in direct proportion to the heating residue.

  In Table 9, (1) is the raw acrylic prepolymer and acrylic monomer used for the acrylic prepolymer, and (2) is either the chemical structure (P1) or chemical structure (P2) contained in the acrylic prepolymer. The cohesive energy CE (MPa) having the larger value, (3) is 28% ammonia water used as a neutralizing agent for water-solubilizing the acrylic prepolymer, and (4) shows the characteristic values of the acrylic prepolymer. It was.

Production of acrylic prepolymers AP-6 to AP-8 Acrylic prepolymers AP-6 to AP-8 were produced in the same manner as the acrylic prepolymer AP-5 except that the composition was changed as shown in Table 9. During the production of the acrylic prepolymers AP-6 to AP-8, no abnormal heat generation or sudden increase in viscosity occurred, and the production was possible without problems. Further, during the production, sampling was performed every 2 hours, and the heating residue and the number average molecular weight were measured, and it was confirmed that the number average molecular weight increased in direct proportion to the heating residue.

Example 12
120 g of ion-exchanged water, SR-1025 (25% aqueous solution), deoxygenated by bubbling nitrogen gas in advance into a 1-liter four-necked flask equipped with a stirrer, temperature sensor, reflux condenser, and monomer dropping port. 1.0 g (Adeka Co., Ltd., reactive emulsifier, concentration 25%) was charged, and the temperature was raised to 83 ° C.

  Acrylic prepolymer (AP-1) 20 g, isobornyl methacrylate 5.0 g, dicyclopentenyloxyethyl methacrylate (Hitachi Chemical Co., Ltd. FANCYRY “FA-512M”) 85.0 g, glycidyl methacrylate 10.0 g acrylic 100 g of body mixture, 3.8 g of Adeka Resorb “SR-1025” (25% aqueous solution), 47.8 g of ion-exchanged water for emulsifying acrylic monomer deoxygenated by bubbling nitrogen gas in advance and emulsifying for 5 minutes at 10,000 rpm (Monomer emulsion).

  Into the flask, 0.2 g of ammonium persulfate was added, and then 20% (34.3 g) of the monomer emulsion was added and emulsion polymerization was performed for 30 minutes. Thereafter, the remaining 80% (137.3 g) of the monomer emulsion was dropped into the flask in 3 hours. After completion of the dropwise addition, emulsion polymerization was further continued for 1 hour, and then 7.1 g of ion-exchanged water for dilution was added and cooled to 40 ° C. or lower to produce acrylic emulsion AE-12.

  While stirring the acrylic emulsion, 6.0 g of nonionic emulsifier Emulgen “1135S-70” (Emulsifier of Kao Corporation, HLB17.9) and 520.0 g of ion-exchanged water were added and stirred for 30 minutes. Thereafter, 60.0 g of a polyallylamine aqueous solution (Nittobo “PAA-03” (20% aqueous solution)) was added, and the mixture was further stirred for 60 minutes to adjust the concentration to 15%. An emulsion composition (AE-12) was prepared. As shown in Table 10, the acrylic emulsion composition (AE-12) had a heating residue of 15.5% and a pH (25 ° C.) of 11.0. Moreover, the storage stability was also good.

  In Table 10, (1) is initially charged ion-exchanged water, (2) and (5) are reactive emulsifiers ADEKA rear sorb “SR-1025” (25% aqueous solution) (Adeka Co., Ltd. reactive emulsifiers, (3) is a polymerization initiator ammonium persulfate, (4) is an acrylic prepolymer and an acrylic monomer, (6) is ion-exchanged water for emulsifying and diluting the acrylic monomer, (7) Is a nonionic emulsifier Emulgen “1135S-70” (emulsifier of Kao Corporation, HLB 17.9) and ion-exchanged water for dilution. (8) is a polyamine compound (polyallylamine “PAA-03” (Nittobo Co., Ltd.) )), Polyethyleneimine “Epomin SP-012” (Nippon Shokubai Co., Ltd.), “PAA-03” uses a 20% aqueous solution as it is, “SP-012” (9) Cohesive energy CE (MPa) of chemical structure (P2) contained in the acrylic copolymer (10) is acrylic. The characteristic values of the emulsion composition are shown.

Example 13 to Example 15
Acrylic emulsion compositions AE-13 to AE-15 of Examples 13 to 15 were produced in the same manner as in Example 12 with the compositions shown in Table 10. As shown in Table 10, the acrylic emulsion compositions of Examples 13 to 15 could be produced without any problems and had good storage stability.

Example 16
A 1-liter four-necked flask equipped with a stirrer, a temperature sensor, a reflux condenser, and a monomer dropping port was charged with 120 g of ion-exchanged water previously deaerated by bubbling nitrogen gas, and the temperature was raised to 83 ° C.

  Acrylic prepolymer (AP-5) 20 g, isobornyl methacrylate 5.0 g, dicyclopentenyloxyethyl methacrylate (Hitachi Chemical Co., Ltd. FANCYL “FA-512M”) 85.0 g, glycidyl methacrylate 10.0 g acrylic 100 g of the body mixture and 51.4 g of ion-exchanged water for emulsifying acrylic monomer that had been deoxygenated by bubbling nitrogen gas in advance were emulsified and emulsified for 10 minutes at 10,000 revolutions (monomer emulsion).

  Into the flask, 20% (34.3 g) of the monomer emulsion was charged, and emulsion polymerization was performed for 30 minutes. Thereafter, the remaining 80% (137.1 g) of the monomer emulsion was dropped into the flask in 3 hours. After completion of the dropwise addition, emulsion polymerization was further continued for 1 hour, and then 8.6 g of ion-exchanged water for dilution was added and cooled to 40 ° C. or lower to produce acrylic emulsion AE-16.

  While stirring the acrylic emulsion, 6.0 g of an ionic emulsifier Emulgen “1135S-70” (Emulsifier of Kao Corporation, HLB 17.9) and 520.0 g of ion-exchanged water were added and stirred for 30 minutes. Thereafter, (5) 60.0 g of polyallylamine aqueous solution (Nittobo Co., Ltd. “PAA-03” (20% aqueous solution)) was added, and the mixture was further stirred for 60 minutes to adjust the concentration to 15%. Sixteen acrylic emulsion compositions (AE-16) were produced.

  As shown in Table 11, the acrylic emulsion composition (AE-16) had a heating residue of 15.3% and a pH (25 ° C.) of 11.0. Moreover, the storage stability was also good.

  In Table 11, (1) is initially charged ion exchange water, (2) is acrylic prepolymer and acrylic monomer, (3) is ion exchange water for emulsification and dilution of acrylic monomer, (4 ) Is a nonionic emulsifier Emulgen “1135S-70” (emulsifier of Kao Corporation, HLB 17.9) and ion-exchanged water for dilution, and (5) is a polyamine compound (polyallylamine “PAA-03” (Nittobo) ), Polyethyleneimine “Epomin SP-012” (Nippon Shokubai Co., Ltd.), “PAA-03” uses a 20% aqueous solution as it is, and “SP-012” is pre-ionized water. (6) Cohesive energy CE (MPa) of chemical structure (P2) contained in the acrylic copolymer, (7) is active. It showed characteristic values of Le emulsion composition.

Example 17 to Example 19
Acrylic emulsion compositions AE-17 to AE-19 of Examples 17 to 19 were produced in the same manner as in Example 12 with the compositions shown in Table 11. As shown in Table 11, the acrylic emulsion compositions of Examples 17 to 19 could be produced without any problems and had good storage stability.

Comparative Example 1
100 g of ion-exchanged water, SR-1025 (25% aqueous solution), deoxygenated by bubbling nitrogen gas through a 1-liter four-necked flask equipped with a stirrer, temperature sensor, reflux condenser, and monomer dropping port in advance. 0.8 g of Adeka Co., Ltd. reactive emulsifier, concentration 25% was charged and heated to 80 ° C.

  Methyl methacrylate 75.0 g, n-butyl methacrylate 20.0 g, acrylic monomer mixture 100 g of methacrylic acid 5.0 g, Adekariasorb "SR-1025" (25% aqueous solution) 3.2 g, nitrogen gas bubbling in advance Deionized and deoxygenated ion exchange water 39.5 g for emulsifying acrylic monomer was put into an emulsifier and emulsified at 10,000 rpm for 5 minutes (monomer emulsion).

  Into the flask, 0.2 g of ammonium persulfate was added, followed by 20% (28.6 g) of the monomer emulsion, and emulsion polymerization was performed for 30 minutes. Thereafter, the remaining 80% (114.5 g) of the monomer emulsion was dropped into the flask in 3 hours. After completion of the dropwise addition, emulsion polymerization was further continued for 1 hour, and then 5.9 g of ion exchange water for dilution was added and cooled to 40 ° C. or lower to produce an acrylic emulsion.

  While stirring the acrylic emulsion, 416.7 g of ion-exchanged water was added and stirred for 30 minutes without adding the nonionic emulsifier Emulgen “1135S-70” (emulsifier of Kao Corporation, HLB 17.9). The acrylic emulsion composition (AE-20) of Comparative Example 1 was prepared without adding polyallylamine and polyethyleneimine and stirring for 60 minutes to adjust the concentration to 15%.

  As shown in Table 12, the acrylic emulsion composition (AE-20) had a heating residue of 15.0% and a pH (25 ° C.) of 2.3. Moreover, the storage stability was also good.

  In Table 12, (1) is initially charged ion-exchanged water, (2) and (5) are reactive emulsifiers ADEKA rear sorb “SR-1025” (25% aqueous solution) (Adeka Co., Ltd. reactive emulsifiers, Concentration 25%), (3) is polymerization initiator ammonium persulfate, (4) is an acrylic monomer containing an acrylic monomer having a functional group in the molecule, (6) is for acrylic monomer emulsification and dilution (7) is a nonionic emulsifier Emulgen “1135S-70” (emulsifier of Kao Corporation, HLB17.9) and ion-exchanged water for dilution, (8) is a polyamine compound (polyallylamine “ PAA-03 "(Nittobo Co., Ltd.), polyethyleneimine" Epomin SP-012 "(Nippon Shokubai Co., Ltd.)," PAA-03 "uses a 20% aqueous solution as it is, and" S “−012” used in advance was ion-exchanged water having a concentration of 20%.), (9) Cohesive energy CE (MPa) of chemical structure (P1) contained in the acrylic copolymer, (10) Shows the characteristic values of the acrylic emulsion composition.

Comparative Example 2 to Comparative Example 4
Acrylic emulsion compositions AE-21 to AE-23 of Comparative Examples 2 to 4 were produced in the same manner as in Comparative Example 1 with the compositions shown in Table 12. As shown in Table 13, the acrylic emulsion compositions of Comparative Examples 2 to 4 could be produced without any problems and had good storage stability.

Adhesion Test of Acrylic Emulsion Compositions of Examples and Comparative Examples Adhesion tests were conducted using the acrylic emulsion compositions of Examples (1-19) and Comparative Examples (1-4).

  As seen in Table 13, when the cohesive energy CE (P1) of the chemical structure (P1) contained in the acrylic copolymer is 500 MPa to 900 MPa, good adhesiveness was exhibited. On the other hand, the acrylic emulsion composition of the comparative example not satisfying this condition resulted in insufficient adhesive strength.

  As seen in Table 14, when a polyamine compound (polyallylamine or polyethyleneimine) was used, even better adhesion was exhibited.

  As seen in Table 16, after an acrylic monomer containing an acrylic monomer having a functional group in the molecule is radically polymerized to produce an acrylic prepolymer, the functional group is further added to the molecule in the presence of the acrylic prepolymer. An acrylic emulsion composition obtained by radical polymerization of an acrylic monomer containing an acrylic monomer having a higher viscosity had further excellent adhesiveness.

Claims (5)

A chemical structure in which a molecule has a chemical structure (P1) obtained by radical polymerization of an acrylic monomer (P) having a functional group in the molecule, and the cohesive energy CE (P1) of the chemical structure (P1) is 500 MPa or more. An acrylic emulsion composition comprising 2 to 50% by weight of an acrylic copolymer containing 0.3 to 50% by weight and 50 to 98% by weight of water. The functional group of the chemical structure (P1) obtained by radical polymerization of an acrylic monomer (P) having a functional group in the molecule is any one of a hydroxyl group, a carboxyl group, an amide group, and a urea group. Acrylic emulsion composition. The molecule has a chemical structure (P2) generated after further reaction of the functional group of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule, and the chemical structure ( An acrylic emulsion composition comprising 2 to 50% by weight of an acrylic copolymer containing 0.3 to 50% by weight of a chemical structure having a cohesive energy CE (P2) of P2) of 450 MPa or more and 50 to 98% by weight of water. The acrylic emulsion composition according to claim 3, wherein the functional group of the chemical structure (P1) obtained by radical polymerization of the acrylic monomer (P) having a functional group in the molecule is an epoxy group. The acrylic emulsion according to any one of claims 1 to 4, wherein the cohesive energy CE (P1) of the chemical structure (P1) is 500 MPa to 900 MPa, and the cohesive energy CE (P2) of the chemical structure (P2) is 450 MPa to 1200 MPa. Composition.