JP6392045B2 - Composite resin particle and composite resin particle aqueous dispersion - Google Patents

Description

  The present invention relates to a composite resin particle and a composite resin particle aqueous dispersion containing a vinyl resin and a polyurethane resin. More specifically, the present invention relates to composite resin particles and aqueous composite resin particle dispersions that are excellent in the flexibility, mechanical strength, weather resistance, solvent resistance, and water resistance of the film because of excellent affinity between the vinyl resin and the polyurethane resin.

  In recent years, many resin particle aqueous dispersions are used from the viewpoints of environmental problems and safety. Among these, acrylic resin particle aqueous dispersions are generally used for coating agents that require mechanical strength, weather resistance, water resistance, and the like. When an acrylic resin particle aqueous dispersion is used, since the film is generally inferior in flexibility, a method of using the acrylic resin particle aqueous dispersion and the polyurethane resin particle aqueous dispersion in combination as a method for improving flexibility. It has been proposed (see, for example, Patent Document 1). However, since acrylic resin and polyurethane resin are generally not compatible, when acrylic resin particle aqueous dispersion and polyurethane resin particle aqueous dispersion are used in combination, mechanical strength, weather resistance, solvent resistance, water resistance, etc. There was a problem that the performance deteriorated.

Japanese Patent Laid-Open No. 06-192616

  This invention is made | formed in view of the said problem, The objective of this invention contains the vinyl resin and polyurethane resin which are excellent in the flexibility of a film | membrane, mechanical strength, a weather resistance, solvent resistance, and water resistance. It is to provide composite resin particles and an aqueous dispersion thereof.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to achieve the above object. That is, in the present invention, part or all of the surface of the resin particles (Pa) containing the polyurethane resin (P) is obtained by polymerizing the monomer component containing the monomer (X) represented by the general formula (1). Resin particles (Va) containing vinyl resin (V) and / or composite resin particles coated with a coating (Vf) of vinyl resin (V ), containing monomer (X) in the monomer component the amount is 1 to 42.7% by weight, based on the weight of the monomer component, the composite resin particles having a volume average particle diameter of 0.01 to 1 [mu] m; composite resin particles containing said composite resin particles child and an aqueous medium An aqueous dispersion; a paint, composite coating containing a composite resin particle, a rust preventive coating agent, a fiber processing agent or an adhesive.

Wherein, M ¹ represents a residue obtained by removing the c-number of active hydrogen from the hydroxyl or 20-valent active hydrogen-containing organic compound; c, if M ¹ is a hydroxyl group is 1, M ¹ is In the case of a residue obtained by removing c active hydrogens from an organic compound containing 1 to 20 valent active hydrogens, it represents an integer satisfying 1 ≦ c ≦ (M ¹ valence); R ¹ contains an ethylenically unsaturated bond R ^{1 in the} case where there are plural groups may be the same or different; M ² represents a residue obtained by removing one active hydrogen from a hydroxyl group or an organic compound containing 1-20 valent active hydrogens; In some cases, M ² may be the same or different, and M ² and M ¹ may be the same or different; L is a residue obtained by removing all carboxyl groups from a trivalent or higher valent aromatic polycarboxylic acid. The aromatic ring of L is composed of carbon atoms, and the carbon The atom may be bonded to a substituent other than a carboxyl group and / or a halogen atom, but at least one carbon atom is bonded to a hydrogen atom; a and b each represent an integer of 0 or more; 2 ≦ a + b ≦ d−2 is satisfied, and a in the case where there are a plurality may be the same or different, and at least one of c a is not 0, and b in the case where there are a plurality may be the same D may be different; d is the number of hydrogen atoms bonded to carbon atoms constituting the aromatic ring when all the substituents including the carboxyl group of the aromatic polycarboxylic acid are substituted with hydrogen atoms, that is, on the aromatic ring Represents the number of sites that can be replaced with. ]

  Since the composite resin particle (K) of the present invention has excellent affinity between the vinyl resin (V) and the polyurethane resin (P), the flexibility of the dry film, mechanical strength, weather resistance, solvent resistance, water resistance, etc. Excellent performance.

  The composite resin particle (K) of the present invention is a resin particle (Va) in which a part or all of the surface of the core particle composed of the resin particle (Pa) containing the polyurethane resin (P) contains the vinyl resin (V). And / or coated with a film (Vf) containing the vinyl resin (V). One composite resin particle (K) contains one resin particle (Pa) containing a polyurethane resin (P), and resin particles containing a plurality of (Pa) are included in the composite resin particle (K). Absent.

  The coverage of the surface of the resin particles (Pa) by the resin particles (Va) and / or the coating (Vf) is from the viewpoint of the flexibility, mechanical strength, weather resistance, solvent resistance and water resistance of the coating. It is preferably 20% or more, more preferably 40% or more, particularly preferably 60% or more, and most preferably 80% or more.

The surface coverage of (Pa) in the present invention is calculated based on the following formula from an image projected on a two-dimensional image obtained by a scanning electron microscope (SEM) for any 100 composite resin particles. Is the average value.
Surface coverage (%) = [projected area of the portion covered with the resin particles (Va) containing the vinyl resin (V) and / or the film (Vf) of the vinyl resin (V)] / [vinyl Of the portion covered with the resin particles (Va) containing the resin (V) and / or the coating (Vf) of the vinyl resin (V) + the portion where the polyurethane resin (P) is exposed Projected area] × 100

In a scanning electron microscope (SEM), as a method for distinguishing between the portion covered with the coating (Vf) of the vinyl resin (V) and the portion where the polyurethane resin (P) is exposed, for example, composite resin particles ( There is a method in which the polyurethane resin (P) is selectively dyed by dyeing K) with phosphotungstic acid to cause contrast in the SEM image.

When the surface coverage is 100%, it is difficult to determine the distinction between the part covered with the vinyl resin (V) film (Vf) and the part where the polyurethane resin (P) is exposed. In such a case, the composite resin particles (K) are encapsulated in an epoxy resin and cured, and then a slice cross section is cut out, and the polyurethane resin (P) is selectively stained by the above-described method, and then scanned with a scanning electron microscope. By observing, it can be confirmed that the surface coverage is 100%.

  The surface of the polyurethane resin (P) is covered with the resin particles (Va) containing the vinyl resin (V) and / or the coating (Vf) of the vinyl resin (V), so that the composite resin is formed into a film. In this case, the polyurethane resin (P) can be prevented from agglomerating, so that the resulting film has excellent flexibility, mechanical strength, weather resistance, solvent resistance and water resistance.

  The weight ratio [(V) :( P)] of the vinyl resin (V) and the polyurethane resin (P) is preferably 1:99 to 99: 1, more preferably from the viewpoint of impact resistance and film strength of the film. Is 10:90 to 90:10, particularly preferably 20:80 to 80:20, most preferably 25:75 to 75:25.

  The vinyl resin (V) of the present invention can be obtained by polymerizing a monomer component having the monomer (X) represented by the general formula (1) as an essential component. Since the vinyl resin (V) has a structural unit introduced by the monomer (X) represented by the general formula (1), the affinity between the vinyl resin (V) and the polyurethane resin (P) is improved. In the dry film, it becomes possible to finely disperse the polyurethane resin (P) in the vinyl resin (V) or the vinyl resin (V) in the polyurethane resin (P), and the flexibility, mechanical strength, A film excellent in weather resistance, solvent resistance, water resistance and the like can be obtained.

M ¹ in the general formula (1) represents a residue obtained by removing c active hydrogens from a hydroxyl group or an organic compound containing 1 to 20 valent active hydrogens.

  Examples of the active hydrogen-containing organic compound include a hydroxyl group-containing compound, ammonia, an amino group-containing compound, and a thiol group-containing compound. An active hydrogen containing organic compound may be used individually by 1 type, or may use 2 or more types together.

  Examples of the hydroxyl group-containing compound include monovalent alcohols having 1 to 20 carbon atoms, polyhydric alcohols and phenols having 2 to 20 carbon atoms; adducts of these alkylene oxides (hereinafter abbreviated as AO); ammonia and amino group-containing compounds. And AO adducts of thiol group-containing compounds.

  Examples of monohydric alcohols having 1 to 20 carbon atoms include alkanols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), and those having 2 to 20 carbon atoms. Alkenol (oleyl alcohol, linoleyl alcohol, etc.), aromatic aliphatic alcohol having 7 to 20 carbon atoms (benzyl alcohol, naphthyl ethanol, etc.) and the like can be mentioned.

  The polyhydric alcohol having 2 to 20 carbon atoms includes a dihydric alcohol having 2 to 20 carbon atoms [aliphatic diol (ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol). , Neopentyl glycol, 1,2- or 1,10-decanediol and 1,2- or 1,12-dodecanediol), alicyclic diol (1,2-, 1,3- or 1,4- Cyclohexanediol and cyclohexanedimethanol), araliphatic diol {1-phenylethane-1,2-diol and 1,4-bis (hydroxyethyl) benzene, etc.}, ether group-containing diol {3-butoxy-1,2 -Propanediol, 3- (2-ethylhexoxy) -1,2-propanediol, 3-phenoxy-1,2-propanedio And 3- (p-tert-butylphenoxy) -1,2-propanediol, etc. and halogen group-containing diols (3-chloro-1,2-propanediol, etc.)], trivalent having 3 to 20 carbon atoms Alcohol [aliphatic triol (such as glycerin and trimethylolpropane)] and 4 to 8 carbon number alcohol [aliphatic polyol (such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin and dipentaerythritol)] Sugars (sucrose, glucose, mannose, fructose, methylglucoside and derivatives thereof)] and the like.

  Examples of the phenols include monovalent phenols (phenol, 1-hydroxynaphthalene, anthrol, 1-hydroxypyrene, etc.) and polyhydric phenols (phloroglucin, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1 , 3,6,8-tetrahydroxynaphthalene, 1,4,5,8-tetrahydroxyanthracene, a condensate of phenol and formaldehyde (novolak) and polyphenols described in US Pat. No. 3,265,641].

  Examples of amino group-containing compounds include monohydrocarbylamines having 1 to 20 carbon atoms [alkylamines (such as butylamine), benzylamine and aniline], aliphatic polyamines having 2 to 20 carbon atoms (ethylenediamine, hexamethylenediamine, diethylenetriamine, etc.) ), Alicyclic polyamines having 6 to 20 carbon atoms (such as diaminocyclohexane, dicyclohexylmethanediamine and isophoronediamine), aromatic polyamines having 2 to 20 carbon atoms (such as phenylenediamine, tolylenediamine and diphenylmethanediamine), and 2 carbon atoms. ~ 20 heterocyclic polyamines (such as piperazine and N-aminoethylpiperazine), alkanolamines (such as monoethanolamine, diethanolamine and triethanolamine), dicarboxylic acids and excess polyamines Polyamide polyamine, polyether polyamine obtained by condensation, hydrazine (such as hydrazine and monoalkylhydrazine), dihydrazide (such as succinic acid dihydrazide and terephthalic acid dihydrazide), guanidine (such as butylguanidine and 1-cyanoguanidine) and dicyandiamide .

  Examples of the thiol group-containing compound include monovalent thiol compounds having 1 to 20 carbon atoms (alkanethiol such as ethanethiol, benzenethiol and phenylmethanethiol) and polyvalent thiol compounds (1,2-ethanedithiol and 1,6 -Hexanedithiol etc.).

  Examples of AO used in the hydroxyl group-containing compound include AO having 2 to 4 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene. Examples thereof include oxide, 1,2-, 1,3- or 2,3-butylene oxide and tetrahydrofuran (hereinafter abbreviated as THF). Among these, EO, PO, and THF are preferable from the viewpoint of mechanical strength and water resistance of the composite resin. AO may be used alone or in combination of two or more. As an addition method when two or more of AO are used in combination, block addition or random addition may be used. It may be used in combination.

  The added mole number of AO is preferably 8 to 100, more preferably 10 to 80, from the viewpoint of water resistance and solvent resistance of the composite resin. The hydroxyl value of the AO adduct is preferably 18 to 360 mgKOH / g. In the present invention, the hydroxyl value is measured according to JIS K1557-1.

  In addition, as an active hydrogen containing organic compound, the compound which has 2 or more types of active hydrogen containing functional groups (a hydroxyl group, an amino group, a thiol group etc.) in a molecule | numerator can also be used.

As the active hydrogen-containing organic compound for introducing M ¹ into the monomer (X), preferred from the viewpoint of mechanical strength, solvent resistance and water resistance of the composite resin are a hydroxyl group-containing compound and an amino group-containing compound. Preferred are polyhydric alcohols having 2 to 20 carbon atoms, polyether polyols obtained by adding AO to polyhydric alcohols having 2 to 20 carbon atoms and aliphatic polyamines having 2 to 20 carbon atoms, and particularly preferred are those having 2 to 2 carbon atoms. Polyether polyols obtained by adding AO to 20 polyhydric alcohols and C2-20 polyhydric alcohols, most preferred are C2-20 polyhydric alcohols.

  The valence of active hydrogen of the active hydrogen-containing organic compound is usually 1 to 20, preferably 1 to 8, more preferably 1 to 4, particularly from the viewpoint of mechanical strength, solvent resistance and water resistance of the composite resin. Preferably it is 1-2.

C in the general formula (1) represents an integer satisfying 1 to 20 and 1 ≦ c ≦ (M ¹ valence), and preferably 1 to 8 from the viewpoint of mechanical strength and water resistance of the composite resin. Preferably it is 1 to 2, particularly preferably 1.

M ² in the general formula (1) represents a residue obtained by removing one active hydrogen from a hydroxyl group or a 1-20 valent active hydrogen-containing organic compound, and when there are a plurality of M ^{2 s} , they may be the same or different. Good.
Examples of the active hydrogen-containing organic compound used for constituting M ² include the same as the active hydrogen-containing organic compound represented by M ¹ , and preferred examples thereof are also the same. M ² and M ¹ may be the same or different.
In addition, the valence of M ² is usually 1 to 20, preferably 1 to 8, more preferably 1 to 4, particularly preferably 1 to 2, from the viewpoint of mechanical strength and water resistance of the composite resin.

M ¹ and M ² can be introduced into the monomer (X) by reacting the active hydrogen-containing organic compound with a trivalent or higher polycarboxylic acid used to constitute L described later. In the case where the organic compound is a polyether polyol having 2 to 4 carbon atoms in the repeating unit, an equivalent residue may be introduced by adding the AO having 2 to 4 carbon atoms to the carboxyl group of the polycarboxylic acid. Can do.

  Further, when the active hydrogen-containing organic compound is a diol compound having 2 to 20 carbon atoms in which a hydroxyl group is bonded to an adjacent carbon atom, a ring-opening addition reaction of an epoxy compound having 2 to 20 carbon atoms to the carboxyl group of the polycarboxylic acid Can also introduce a residue equivalent to the case of using the diol compound. For example, when the active hydrogen-containing organic compound is ethylene glycol, a residue obtained by removing one active hydrogen from ethylene glycol can be introduced by reacting 1 mol of EO with a carboxyl group of a polycarboxylic acid. Further, when the active hydrogen-containing organic compound is 3-phenoxypropane-1,2-diol, by reacting 1 mol of phenylglycidyl ether with the carboxyl group of the polycarboxylic acid, the 3-phenoxypropane-1,2-diol can be reacted. Residues with one active hydrogen removed can be introduced.

Examples of the epoxy compound having 2 to 20 carbon atoms include AO having 2 to 4 carbon atoms, glycidol, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, and 1,2-epoxy. Examples include decane, 1,2-epoxide decane, cyclohexene oxide, styrene oxide, and epichlorohydrin.
Of these, epoxy compounds having 2 to 15 carbon atoms are preferred from the viewpoints of the mechanical strength, solvent resistance and water resistance of the composite resin.

R ¹ in the general formula (1) represents an ethylenically unsaturated bond-containing group, and when there are a plurality of R ^{1 s} , they may be the same or different. R ¹ is preferably at least one substituent selected from the group consisting of substituents represented by the following general formulas (2) to (6) from the viewpoint of water resistance of the composite resin.

R ² , R ⁴ and R ⁶ in the general formulas (2) to (6) are each independently a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms which may be substituted with a hydroxyl group, and R ³ and R ⁵ each independently represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom, a methyl group or an ethyl group, and * represents an oxycarbonyl group in the general formula (1) by a bond to which R ⁵ is attached. Represents bonding to the oxygen atom.

  L in General formula (1) represents the residue remove | excluding all the carboxyl groups from trivalent or more aromatic polycarboxylic acid. The aromatic ring of L is composed of a carbon atom, and a substituent other than a carboxyl group and / or a halogen atom may be bonded to the carbon atom, but at least one carbon atom is not bonded to a substituent. Must be bonded to a hydrogen atom.

  Examples of the substituent other than the carboxyl group include an alkyl group, vinyl group, allyl group, cycloalkyl group, amino group, hydroxyl group, hydroxyamino group, nitro group, thiol group, aryl group, and cyano group.

  Examples of the trivalent or higher valent aromatic polycarboxylic acid used for constituting L include aromatic polycarboxylic acids having 9 to 30 carbon atoms such as trimellitic acid, 1,2,3-benzenetricarboxylic acid, trimesic acid, Hemicitic acid, 1,2,4-, 1,3,6- or 2,3,6-naphthalenetricarboxylic acid and tricarboxylic acids such as 2,3,6-anthracentricarboxylic acid; pyromellitic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid, 2,3,3 ′, 4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′- Biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 4,4′-oxybisphthalic acid, Phenylmethanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid and 4,4′- (Hexafluoroisopropylidene) tetracarboxylic acid such as bisphthalic acid; and the like. Aromatic polycarboxylic acid may be used individually by 1 type, and may use 2 or more types together.

  In producing the monomer (X), these ester-forming derivatives [acid anhydrides, lower alkyl (carbon number 1 to 4) esters (methyl esters, ethyl esters, isopropyl esters, etc.) and acid halides (acid chlorides) Etc.)] can also be used.

  Among these aromatic polycarboxylic acids, from the viewpoint of the mechanical strength and water resistance of the composite resin, it is preferable that the two carbon atoms adjacent to the carbon atom constituting the aromatic ring and not bonded to the substituent are carboxyl. Having a structure in which a carboxyl group is further bonded to at least one of carbon atoms different from the carbon atom adjacent to the carbon atom to which the carboxyl group is bonded and the substituent is not bonded. is there.

  For example, when the aromatic ring of the aromatic polycarboxylic acid is a benzene ring and the position of the carbon atom to which the substituent is not bonded is the 1st position, a carboxyl group is bonded to the 2nd position and the 6th position, and the 3rd position and / or Those having a structure in which a carboxyl group is bonded to the 5-position are preferred.

  From the viewpoint of the mechanical strength and water resistance of the composite resin, the aromatic polycarboxylic acid used to constitute L is particularly preferably a monocyclic compound, and most preferably trimellitic acid and / or pyromellitic acid. is there.

  In the general formula (1), a and b each represent an integer of 0 or more and satisfy 2 ≦ a + b ≦ d−2. When c is 2 or more and a plurality is present, a may be the same or different, and when c is 2 or more and a plurality is present, b may be the same or different. However, at least one of c a's is not 0, that is, the monomer (X) has at least one ethylenically unsaturated bond-containing group.

  d is the number of hydrogen atoms bonded to the carbon atom constituting the aromatic ring when all the substituents including the carboxyl group of the aromatic polycarboxylic acid are substituted with hydrogen atoms, that is, the number of sites that can be substituted on the aromatic ring. Represents a number. For example, when the aromatic ring is a benzene ring composed of 6 carbon atoms, d is 6, a + b can take a value of 2 to 4, and when the aromatic ring is a naphthalene ring composed of 10 carbon atoms, d is 8, and a + b can take a value of 2-6. When the aromatic ring is a monocyclic aromatic ring, a + b is preferably 2 or 3 from the viewpoint of mechanical strength and water resistance of the composite resin. Moreover, from the viewpoint of mechanical strength and water resistance of the composite resin, a is preferably 1 or 2, and 1 is particularly preferable.

The hydroxyl value of the monomer (X) in the present invention is preferably 0 to 500 mgKOH / g, more preferably 0 to 350 mgKOH / g, from the viewpoints of elongation at break, breaking strength and water resistance of the composite resin. In addition, the hydroxyl value of the monomer (X) being 0 means that M ¹ , M ² and L in the general formula (1) all have no hydroxyl group.

  The concentration of L in the monomer (X) means the number of millimoles of the residue L in 1 g of the monomer (X). From the viewpoint of elongation at break, breaking strength and water resistance of the composite resin, preferably 0.5 to 10 mmol / g, more preferably 0.5 to 8 mmol / g, particularly preferably 0.5 to 7.5 mmol / g.

  The carbonyl group concentration in the monomer (X) is preferably from 1.5 to 30 mmol / g, more preferably from 1.5 to 24 mmol / g, and particularly preferably from 1.5 to 24, from the viewpoint of mechanical strength and water resistance of the composite resin. 22.5 mmol / g. The carbonyl group at the carbonyl group concentration in the present invention is a carbonyl group bonded to L in the general formula (1), that is, a carboxyl group of an aromatic polycarboxylic acid having a valence of 3 or more used for introducing L, and derived therefrom. A carbonyl group in a functional group such as an ester group, a thioester group and an amide group.

Monomer (X) is, for example, an active hydrogen-containing organic compound constituting M ¹ or M ² and the like and a compound having an ethylenically unsaturated bond and a hydroxyl group constituting R ¹ [hydroxyalkyl (meth) acrylate, hydroxyalkylpropenyl ether , Allyloxyalkanol, (meth) allyl alcohol, etc.] and a trivalent or higher valent aromatic polycarboxylic acid.

  The said reaction can be performed in the below-mentioned organic solvent (J), and the used organic solvent (J) may be distilled off at the final stage of manufacture of monomer (X), or without distilling ( X) and (J) can also be used for the production of composite resins. Moreover, when it uses for manufacture of composite resin as a mixture of (X) and (J), it can also distill off after manufacture of composite resin. Furthermore, the reaction for obtaining the monomer (X) may be carried out in a monomer other than (X) [for example, monomers (m1) to (m16) described later] and used as a monomer component for obtaining a composite resin as it is. it can.

  The content of the monomer (X) in the monomer component at the time of obtaining the vinyl resin (V) is preferably 1 to 40% by weight based on the weight of the monomer component, from the viewpoint of the film forming property and water resistance of the composite resin. More preferably, it is 2 to 35% by weight, and particularly preferably 3 to 30% by weight.

  Examples of the monomer component other than the monomer (X) used for the production of the vinyl resin (V) include the following vinyl monomers (m1) to (m16). Vinyl monomers other than (X) may be used alone or in combination of two or more.

(1) Hydroxyl group-containing vinyl monomer (m1):
C2-C12 alkenols such as vinyl alcohol, (meth) allyl alcohol, 1-buten-3-ol and 2-buten-1-ol; C4-C12 alkene diols such as 2-butene-1, 4-diol; hydroxyl group-containing aromatic vinyl monomer such as hydroxystyrene; hydroxyalkyl (meth) acrylate having 5 to 8 carbon atoms such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; alkenyl having 3 to 30 carbon atoms Ethers such as 2-hydroxyethylpropenyl ether and sucrose allyl ether;

(2) Carboxyl group-containing vinyl monomer (m2):
C3-C30 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and anhydrides thereof, monoalkyl (C1-24) esters and neutralized salts thereof such as (meth) acrylic acid, (anhydrous) maleic acid , Maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoester, citraconic acid, citraconic acid monoalkyl ester, cinnamic acid and neutralization thereof salt.

  The neutralized salt of (m2) is neutralized with a neutralizing agent such as ammonia, an amine compound having 1 to 20 carbon atoms, or an alkali metal hydroxide (such as sodium hydroxide, potassium hydroxide, and lithium hydroxide). Salt.

  Examples of the amine compound having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine and monoethanolamine, secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine, diisopropanolamine and methylpropanolamine. Examples include amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine and triethanolamine.

  Among these salts, compounds having a high vapor pressure at 25 ° C. such as ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine are preferable from the viewpoint of water resistance of the resulting composite resin film. More preferred are ammonia, monoethylamine, dimethylamine and diethylamine, particularly preferred is ammonia.

(3) Sulfo group-containing vinyl monomer (m3):
Alkene sulfonic acids having 2 to 14 carbon atoms and neutralized salts thereof such as vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid; styrene sulfonic acid and alkyl substituents having 1 to 24 carbon atoms such as α- Methyl styrene sulfonic acid, etc .; sulfo (hydroxy) alkyl (C1-8)-(meth) acrylate or (meth) acrylamide, for example, sulfopropyl (meth) acrylate, 2- (meth) acryloyloxyethanesulfonic acid, 3 -(Meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid; alkyl (3 to 18 carbon atoms) (Meth) allylsulfosuccinate and the same Such as the neutralized salt.

  Examples of the neutralizing agent used in the salt of (m3) include the same neutralizing agents as those used in the salt of (m2), and preferred ones are also the same.

(4) Ester group-containing vinyl monomer (m4):
Esters of unsaturated alcohols or hydroxystyrenes with mono- or polycarboxylic acids having 1 to 12 carbon atoms such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, methyl-4 -Vinyl benzoate, vinyl methoxyacetate, vinyl benzoate and acetoxystyrene; unsaturated carboxylic alcohol (1-30 carbon atoms) ester such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth ) Acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrelane , Cyclohexyl (meth) acrylate, methylnorbornene (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, ethyl-α-ethoxy (meth) acrylate, di (cyclo) alkyl fumarate (two alkyl groups are , A linear or branched group having 2 to 8 carbon atoms) and di (cyclo) alkyl maleate (two alkyl groups are a linear or branched group having 2 to 8 carbon atoms); Polyvalent (2-3) alcohol unsaturated carboxylic acid ester, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate and polyethylene Glycol di (meth) acrylate; polyoxyalkylene (2 to 4 carbon) mono- or poly (2-3) ol unsaturated carboxylic acid ester having a degree of polymerization of 5 to 50, such as poly (oxyalkylene) glycol chain (of alkelene) Vinyl monomers having 2 to 4 carbon atoms [poly (oxyethylene) glycol (degree of polymerization 7) mono (meth) acrylate, poly (oxypropylene) glycol (degree of polymerization 9) mono (meth) acrylate, methyl alcohol ethylene oxide 10 Mole adduct (meth) acrylate and lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate and the like.

(5) Vinyl hydrocarbon (m5):
(5-1) Aliphatic vinyl hydrocarbons: alkenes having 2 to 20 carbon atoms such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, and other α-olefins An alkadiene having 4 to 20 carbon atoms, such as butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene and 1,7-octadiene;
(5-2) Alicyclic vinyl hydrocarbons: mono- or dicycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and vinylnorbornene; terpenes such as pinene and limonene.
(5-3) Aromatic vinyl hydrocarbons (8 to 20 carbon atoms): Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products such as α-methylstyrene, vinyltoluene, 2 , 4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene and trivinylbenzene; vinylnaphthalene.

(6) Amino group-containing vinyl monomer (m6):
Aminoalkyl (meth) acrylate having 5 to 20 carbon atoms, such as 7-amino-3,7-dimethyloctyl (meth) acrylate, monomethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, t-octyl Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and the like; N-aminoalkyl (meth) acrylamide having 5 to 20 carbon atoms such as N- (2-aminoethyl) (meta ) Acrylamide, N- (1-methyl-2-aminoethyl) (meth) acrylamide, N- (3-aminopropyl) (meth) acrylamide, N- (4-aminobutyl) (meth) acrylamide, N- (5 -Aminopentyl) (meth) acrylamide, N- ( 6-aminohexyl) (meth) acrylamide, N- (3-methylaminopropyl) (meth) acrylamide, N- (2-isopropylaminoethyl) (meth) acrylamide, N- (3-isopropylaminopropyl) (meth) Acrylamide, N- (3-tert-butylaminopropyl) (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and the like.

(7) Epoxy group-containing vinyl monomer (m7):
C6-C20 glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate; 4-vinyl-1,2-epoxycyclohexane and 5-vinyl-2,3-epoxy C6-20 alicyclic epoxy group-containing vinyl monomers such as norbornane.

(8) Silanol group or alkoxysilyl group-containing vinyl monomer (m8):
C4-C20 silanol group-containing vinyl monomers such as dimethylvinylsilanol, divinylsilanol and 1,4-phenylenebisdivinylsilanol; 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3- C8-C15 alkoxysilyl group-containing vinyl monomers such as methacryloyloxypropyltrimethoxysilane and p-styryltrimethoxysilane.

(9) Isocyanate group-containing vinyl monomer (m9):
Isocyanatoethyl-containing vinyl monomers having 5 to 15 carbon atoms such as isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and 4-vinylphenyl isocyanate.

(10) Oxazoline group-containing vinyl monomer (m10):
2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl- C5-C15 vinyl monomers having an oxazoline skeleton such as 2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and 5-decyl-2-vinyl-2-oxazoline.

(11) Carbodiimide group-containing vinyl monomer (m11):
1-vinylcarbodiimide, N-ethyl-N ′-[(E) -1-methyl-2- (methoxycarbonyl) vinyl] carbodiimide, N-propyl-N ′-[(E) -1-methyl-2- ( Methoxycarbonyl) vinyl] carbodiimide, 1-cyclohexyl-3- (1-phenylvinyl) carbodiimide, 1-phenyl-3- (1-phenylvinyl) carbodiimide, N-phenyl-N ′-(4-vinylphenyl) carbodiimide and C3-C30 carbodiimide group-containing vinyl monomers such as N-phenyl-N′-ethenylcarbodiimide.

(12) Blocked isocyanate group-containing vinyl monomer (m12):
The isocyanate group of the isocyanate group-containing vinyl monomer (m9) is converted into a known blocking agent (phenol, thiophenol, chlorophenol, cresol, resorcinol, p-sec-butylphenol, p-tert-butylphenol, p-sec-amylphenol). Phenols such as p-octylphenol and p-nonylphenol; secondary or tertiary alcohols such as isopropyl alcohol and tert-butyl alcohol; oximes such as acetoxime, methylethylketoxime and cyclohexanone oxime; dimethylamine, diethylamine, di -Secondary amine bonded to primary carbon such as n-propylamine, ethylmethylamine, diisopropylamine, di-sec-butylamine, dicyclohexylamine, Carbon number 2 such as secondary amine bonded to secondary carbon such as sopropylcyclohexylamine, secondary amine bonded to tertiary carbon such as di-t-butylamine, and other secondary amines such as isopropylethylamine ~ 15 aliphatic secondary amines; aromatic secondary amines such as diphenylamine and xylidine; phthalic imides; lactams such as ε-caprolactam and δ-valerolactam; dialkyl esters of malonic acid, acetylacetone and acetoacetic acid Active methylene compounds such as alkyl esters; pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3, Such as 5-dimethylpyrazole and 3-methyl-5-phenylpyrazole Razoru compounds; acidic sodium sulfite, etc.); those that have been blocked by such like.

(13) Keto group-containing vinyl monomer (m13):
Any monomer having a double bond polymerizable with at least one keto group (not including a keto group in a carboxyl group, an ester group and an amide group) in the molecule can be used without any particular limitation. Diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, (meth) acryloxyalkylpropanal, acetonyl acrylate, diacetone (meth) acrylamide and the like.

(14) Aldehyde group-containing vinyl monomer (m14):
Any monomer having at least one aldehyde group in the molecule and a polymerizable double bond can be used without particular limitation. For example, acrolein, formylstyrene, (meth) acrylamide pivalin aldehyde, 2-hydroxypropyl Acrylate acetyl acetate, acetoacetoxyethyl (meth) acrylate, butanediol-1,4-acrylate-acetyl acetate, acrylamide methyl anisaldehyde, and the like.

(15) Vinyl monomer having urethane group or urea group (m15):
Reaction product of the isocyanate group-containing vinyl monomer (m9) and a monoalcohol having 1 to 8 carbon atoms or monoamines having 1 to 10 carbon atoms described in the reaction terminator (a4) described later; polyurethane resin (described later) A part of the active hydrogen component (A) for forming P) is a vinyl functional group added to the polyurethane resin using the hydroxyl group-containing vinyl monomer (m1) and / or the amino group-containing vinyl monomer (m6). Introduced; UF-8001G, DAUA-167 [manufactured by Kyoeisha Chemical Co., Ltd.], U-200PA, UA-4200 [manufactured by Shin-Nakamura Chemical Co., Ltd.], New Frontier R-, as commercially available urethane acrylate products 1235, R-1220, R-1301, R-1304, R-1214 [Daiichi Kogyo Seiyaku Co., Ltd.], KUA-4I, KUA-6I [Ke M Co., Ltd.] urethane acrylate such as.

(16) Other vinyl monomers (m16):
Vinyl sulfones such as vinyl ethyl sulfone, divinyl sulfone; divinyl sulfoxide and the like.

  As a manufacturing method of vinyl-type resin (V), the method of radical-polymerizing the above-mentioned monomer (X) and the vinyl-type monomers (m1)-(m16) etc. as needed is mentioned.

Polymerization initiators that can be used for radical polymerization include persulfate initiators such as potassium persulfate and ammonium persulfate; azo initiators such as azobisisobutyronitrile; benzoyl peroxide, cumene hydroperoxide Ordinary radical polymerization initiators such as organic peroxides such as tertiary butyl peroxybenzoate; hydrogen peroxide; and the like may be used alone or in combination of two or more. May be used. Moreover, the usage-amount of a polymerization initiator is used in 0.05-5 weight% with respect to the total weight of the monomer component used for superposition | polymerization.
A necessary amount of these initiators may be used in a lump at the start of polymerization, or may be divided and added every arbitrary time.

  Moreover, you may use a reducing agent for the radical polymerization with the said polymerization initiator as needed. Such reducing agents include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose and formaldehyde sulfoxylate metal salts, and reducing properties such as sodium thiosulfate, sodium sulfite, sodium bisulfite and sodium metabisulfite. An inorganic compound etc. are mentioned.

  Moreover, you may use a chain transfer agent for radical polymerization as needed. Examples of such chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid and α-methylstyrene dimer. It is done.

  The polymerization reaction in the production of the vinyl resin (V) is preferably performed in a range of 20 ° C to 150 ° C, more preferably 40 ° C to 100 ° C. When temperature is less than 20 degreeC, a polymerization rate may become slow. Moreover, when temperature exceeds 150 degreeC, it may become difficult to control a polymerization reaction. The reaction time is preferably 1 minute to 50 hours. The polymerization reaction is preferably performed in the presence of an inert gas.

  The polyurethane resin (P) in this invention is not specifically limited, For example, the polyurethane resin obtained by making an active hydrogen component (A) and an organic polyisocyanate component (B) react is mentioned.

  The active hydrogen component (A) contains the polyol (a1) and, if necessary, a compound (a2) having a hydrophilic group and active hydrogen, a chain extender (a3) and a reaction terminator (a4).

  Examples of the polyol (a1) include a high molecular polyol (a11) having a chemical formula weight or number average molecular weight (hereinafter abbreviated as Mn) of 300 or more and a low molecular polyol (a12) having a chemical formula weight or Mn of less than 300.

The Mn of the polyol in the present invention can be measured, for example, under the following conditions using gel permeation chromatography (hereinafter abbreviated as GPC).
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 each connected one” [all manufactured by Tosoh Corporation]
Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection amount: 10 μl
・ Flow rate: 0.6 ml / min ・ Measurement temperature: 40 ° C.
・ Detection device: Refractive index detector ・ Reference material: Standard polyethylene glycol

  Examples of the polymer polyol (a11) having a chemical formula amount or Mn of 300 or more include polyether polyol (a111), polyester polyol (a112), and acrylic polyol (a113).

  Examples of the polyether polyol (a111) include aliphatic polyether polyols and aromatic ring-containing polyether polyols.

  Examples of the aliphatic polyether polyol include polyoxyethylene polyol (PEG and the like), polyoxypropylene polyol [poly (oxypropylene) glycol and the like], polyoxyethylene / propylene polyol and poly (oxytetramethylene) glycol and the like. .

  Commercial products of aliphatic polyether polyols include PTMG1000 [poly (oxytetramethylene) glycol with Mn = 1,000, manufactured by Mitsubishi Chemical Corporation], PTMG2000 [poly (oxytetramethylene) glycol with Mn = 2,000. , Manufactured by Mitsubishi Chemical Co., Ltd.], PTMG3000 [poly (oxytetramethylene) glycol with Mn = 3,000, manufactured by Mitsubishi Chemical Co., Ltd.], and Sanniks Triol GP-3000 [poly (oxypropylene with Mn = 3,000). ) Triol, manufactured by Sanyo Chemical Industries, Ltd.].

  Examples of aromatic polyether polyols include EO addition products of bisphenol A [EO 2 mol addition product of bisphenol A, EO 4 mol addition product of bisphenol A, EO 6 mol addition product of bisphenol A, EO 8 mol addition product of bisphenol A, and bisphenol A. EO 10 mol adduct and bisphenol A EO 20 mol adduct, etc.] and bisphenol A PO adduct [PO2 mol adduct of bisphenol A, PO3 mol adduct of bisphenol A, PO5 mol adduct of bisphenol A, etc.] Examples thereof include a polyol having a bisphenol skeleton and an EO or PO adduct of resorcin.

  Examples of the polyester polyol (a112) include condensed polyester polyols, polylactone polyols, polycarbonate polyols, and castor oil-based polyols.

  The condensed polyester polyol is a polyester polyol obtained by reacting a low molecular weight (chemical formula amount or Mn is less than 300) polyhydric alcohol with a polyhydric carboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof.

  The polyhydric alcohol having a low molecular weight (chemical formula amount or Mn is less than 300) includes a divalent to octavalent or higher aliphatic polyhydric alcohol having a chemical formula amount or Mn of less than 300 and a chemical formula amount or Mn of less than 300. AO low-mole adducts of valence to octavalence or higher. Among these, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, EO or PO low-mole adducts of bisphenol A and combinations thereof are preferred.

  Examples of the polyvalent carboxylic acid having 2 to 10 carbon atoms or ester-forming derivatives thereof that can be used in the condensed polyester polyol include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc.) , Alicyclic dicarboxylic acids (such as dimer acid), aromatic dicarboxylic acids (such as terephthalic acid, isophthalic acid and phthalic acid), trivalent or higher polycarboxylic acids (such as trimellitic acid and pyromellitic acid), these Anhydrides (succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), acid halides thereof (adipic acid dichloride, etc.), low molecular weight alkyl esters thereof (dimethyl succinate, dimethyl phthalate, etc.) These combinations are listed.

  Specific examples of the condensed polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene Hexamethylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene seba Kate diol and polyneopentyl terephthalate diol It is.

  Commercially available condensed polyester polyols include San Ester 2610 [polyethylene adipate diol with Mn = 1,000, manufactured by Sanyo Chemical Industries, Ltd.], San Ester 2620 [Polyethylene adipate diol with Mn = 2,000, Sanyo Chemical Industries, Ltd. Manufactured by Co., Ltd.] and Sanester 5620 [polyneopentylene adipate diol with Mn = 2,000, manufactured by Sanyo Chemical Industries, Ltd.].

A polylactone polyol is a polyadduct of a lactone to a polyhydric alcohol having the low molecular weight (chemical formula or Mn is less than 300). As the lactone, a lactone having 4 to 12 carbon atoms (for example, γ-butyrolactone, γ- Valerolactone and ε-caprolactone).
Specific examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

  As the polycarbonate polyol, the low molecular weight (chemical formula amount or Mn is less than 300) polyhydric alcohol, a low molecular carbonate compound (for example, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 2 to 6 carbon atoms). And a polycarbonate polyol produced by condensing a dialkyl carbonate having 6 to 9 carbon atoms and a diaryl carbonate having an aryl group having 6 to 9 carbon atoms with a dealcoholization reaction. Two or more low molecular weight polyhydric alcohols and alkylene carbonates may be used in combination.

  Specific examples of the polycarbonate polyol include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, poly (tetramethylene / hexamethylene) carbonate diol (for example, 1,4-butanediol and 1,6-hexane). Diol obtained by condensing a diol with a dialkyl carbonate while subjecting it to a dealcoholization reaction) and poly [cyclohexylenebis (methylene) / hexamethylene] carbonate diol (for example, 1,4-cyclohexanedimethanol and 1,6-hexanediol are dialkyl) And a diol obtained by condensation while causing a dealcoholization reaction with carbonate).

  Examples of commercially available polycarbonate polyols include NIPPOLAN 980R [polyhexamethylene carbonate diol with Mn = 2,000, manufactured by Nippon Polyurethane Industry Co., Ltd.], NIPPOLAN 981 [polyhexamethylene carbonate diol with Mn = 1,000, Nippon Polyurethane Industry DURANOL G4672 [poly (tetramethylene / hexamethylene) carbonate diol with Mn = 2,000, manufactured by Asahi Kasei Chemicals Corporation], etanacol UH-200 [polyhexamethylene carbonate diol with Mn = 2,000] , Manufactured by Ube Industries, Ltd.] and etanacol UM-90 [poly [cyclohexylenebis (methylene) / hexamethylene] carbonate diol of Mn = 900, manufactured by Ube Industries, Ltd.].

  The castor oil-based polyol includes castor oil and modified castor oil modified with polyol or AO. Modified castor oil can be produced by transesterification of castor oil and polyol and / or AO addition. Castor oil-based polyols include castor oil, trimethylolpropane-modified castor oil, pentaerythritol-modified castor oil, and EO (4 to 30 mol) adduct of castor oil.

  Of the polyester polyol (a112), preferred are a condensed polyester polyol and a polycarbonate polyol from the viewpoint of the mechanical strength and solvent resistance of the composite resin.

  The acrylic polyol (a113) is a copolymer (m1) to (m17) of the vinyl monomer, wherein the hydroxyl group-containing vinyl monomer (m1) is an essential constituent monomer, and (meth) acrylic in the constituent monomer. Examples include those having a weight of 50% by weight or more of the system monomer. Examples of commercially available products (a113) include ARUFUON UH-2000, UH-2032, UH-2041, UH-2012 [manufactured by Toa Gosei Co., Ltd.], Takelac W, WS, E [manufactured by Mitsui Chemicals, Inc.] and the like. Can be mentioned.

  Mn of (a11) is usually 300 or more, preferably 300 to 10,000, more preferably 300 to 6,000, from the viewpoint of the mechanical strength of the composite resin.

  Examples of the low molecular polyol (a12) having a chemical formula amount or Mn of less than 300 include divalent aliphatic alcohols, trivalent aliphatic alcohols, and tetravalent or higher aliphatic alcohols. Among (a1), from the viewpoint of physical properties such as breaking strength and breaking elongation, a divalent or trivalent aliphatic alcohol is preferable. Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol, 1,4- Butanediol, neopentyl glycol and 1,6-hexanediol are particularly preferred, and trimethylolpropane is particularly preferred as the aliphatic trihydric alcohol.

  Examples of the compound (a2) having a hydrophilic group and active hydrogen include a compound (a21) having an anionic group and active hydrogen, a compound (a22) containing a nonionic hydrophilic group (for example, polyoxyethylene chain) and active hydrogen, and the like. Is mentioned.

  As the compound (a21) having an anionic group and active hydrogen, for example, a compound having a carboxyl group as an anionic group and having 2 to 10 carbon atoms [dialkylol alkanoic acid (for example, 2,2-dimethylolpropionic acid) 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid and 2,2-dimethyloloctanoic acid), tartaric acid and amino acids (for example, glycine, alanine and valine)], a sulfo group as an anionic group A compound having 2 to 16 carbon atoms [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and sulfoisophthalic acid di (ethylene glycol) ester, etc.], containing a sulfamic acid group as an anionic group And a compound having 2 to 10 carbon atoms [N, N-bis (2-hydroxylethyl) sulfamic acid, etc.], etc. Neutralized salts of these compounds with a neutralizing agent to the beauty.

  As a neutralizing agent used for the salt of (a21), the same thing as the neutralizing agent used for the salt of said (m2) is mentioned, A preferable thing is also the same.

  Among (a21), 2,2-dimethylolpropionic acid and 2,2-dimethylol are preferable from the viewpoint of the resin properties of the obtained composite resin and the dispersion stability of the aqueous dispersion of composite resin particles (K). Butanoic acid and salts thereof are more preferable, and neutralized salts of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid with ammonia or amine compounds having 1 to 20 carbon atoms.

  Examples of the compound (a22) containing a nonionic hydrophilic group and active hydrogen include, in addition to the polyoxyethylene polyol (eg, PEG) and polyoxyethylene / propylene polyol mentioned in the polyether polyol (a111), 2 , 2-dimethylolpropionic acid carboxylic acid 4 to 30 mol of EO compound, diethylenetriamine secondary amine 4 to 30 mol of EO compound.

  Examples of the chain extender (a3) include water, diamines having 2 to 10 carbon atoms (for example, ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, toluene diamine and piperazine), poly (n = 2 to 6) alkylene (carbon number). 2-6) poly (n = 3-7) amine (diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, etc.), hydrazine or derivatives thereof ( And dibasic acid dihydrazides such as adipic acid dihydrazide and the like, and amino alcohols having 2 to 10 carbon atoms (such as ethanolamine, diethanolamine, 2-amino-2-methylpropanol and triethanolamine).

  As the reaction terminator (a4), monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.), monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, mono Mono- or dialkylamines such as butylamine, dibutylamine and monooctylamine, and mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine).

  As the organic isocyanate component (B) in the present invention, those conventionally used for the production of polyurethane can be used, and an aromatic polyisocyanate having 8 to 26 carbon atoms having 2 to 3 or more isocyanate groups (b1). ), C4-C22 aliphatic polyisocyanate (b2), C8-C18 alicyclic polyisocyanate (b3), C10-C18 araliphatic polyisocyanate (b4), and these polyisocyanates And the modified product (b5). An organic isocyanate component (B) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter referred to as tolylene diisocyanate as TDI). Abbreviation), crude TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenyl Methane triisocyanate and m- or p-isocyanatophenylsulfonyl Cyanate and the like.

  Examples of the aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-diisocyanatohexanoate is mentioned.

  Examples of the alicyclic polyisocyanate (b3) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, and methyl. Examples include cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic polyisocyanate (b4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

  As the modified polyisocyanate (b5) of (b1) to (b4), the modified polyisocyanate (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group) Or modified product containing oxazolidone group, etc .; free isocyanate group content is usually 8 to 33% by weight, preferably 10 to 30% by weight, especially 12 to 29% by weight), such as modified MDI (urethane modified MDI, carbodiimide modified MDI) And modified products of polyisocyanates such as urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI.

  Of the organic polyisocyanate component (B), from the viewpoint of solvent resistance and yellowing resistance of the resulting composite resin, (b2) and (b3) are preferable, (b3) is more preferable, and IPDI and particularly preferable are Hydrogenated MDI.

  Polyol (a1), chain extender (a3) and / or organic polyisocyanate component (B) used in the polyurethane resin (P) are trivalent or higher polyols [poly (oxypropylene) triol, polyester triol, etc.], trivalent or higher. Chain extenders [poly (n = 2-6) alkylene (carbon number 2-6) poly (n = 3-7) amine, etc.], trivalent or higher organic isocyanate compounds (isocyanurate-modified HDI and isocyanurate-modified IPDI) Etc.) can be introduced into the polyurethane resin (P) to improve the mechanical strength, water resistance and solvent resistance of the composite resin.

  Part or all of the surface of the resin particle (Pa) containing the polyurethane resin (P) in the present invention is a resin particle (Va) containing the vinyl resin (V) and / or a coating of the vinyl resin (V). In order to obtain the aqueous dispersion of composite resin particles (K) coated with (Vf), it is necessary to make the hydrophilicity of the vinyl resin (V) higher than the hydrophilicity of the polyurethane resin (P).

The hydrophilicity of the vinyl resin (V) and the polyurethane resin (P) can be adjusted by the type and amount of the hydrophilic group of each resin. In the present invention, the vinyl resin (V) and the polyurethane resin (P) can be adjusted. The value of F calculated by the following mathematical formula (1) derived based on various examination results, with the content of the hydrophilic group in the polyurethane resin (P) as a variable, is 1 to 40 (preferably 2 to 20, further Preferably, by being in the range of 3 to 10), composite resin particles (K) in which a part or all of the surface of (Pa) is coated with (Va) and / or before (Vf) are stably produced. it can.
F = (N _V + C _V × 10 + S _V × 20) − (N _P + C _P × 10 + S _P × 20) (1)
However, the meanings of the symbols in the formula (1) are as follows.
N _V : Numerical value representing the content of nonionic hydrophilic groups in the vinyl-based resin (V) in wt%;
C _V : Numerical value representing the content of carboxyl groups in the vinyl resin (V) in weight%;
S _V : a numerical value representing the content of sulfo group in the vinyl resin (V) in% by weight;
N _P : Numerical value representing the content of nonionic hydrophilic groups in the polyurethane resin (P) in wt%;
C _P : Numerical value representing the content of carboxyl group in the polyurethane resin (P) in wt%;
S _P : A numerical value representing the content of the sulfo group in the polyurethane resin (P) in wt%.

The content of the nonionic hydrophilic group in each resin is the content based on the weight of the resin of the polyoxyalkylene group [(—CH ₂ CH ₂ O—) n: n is a number of 4 or more] of the resin. (% By weight). Further, when the hydrophilic group is a carboxyl group or a sulfo group, it represents the content (% by weight) based on the weight of the resin of the carboxyl group and sulfo group of the resin, and these groups are basic compounds such as amines. In the case of being neutralized with, the weight of the cation moiety in the neutralized salt is not included, and represents the respective content when calculated as a carboxyl group (—COOH) and a sulfo group (—SO ₃ H).

  As a method of adjusting the surface coverage of (Pa) in the present invention, for example, the weight ratio of the polyurethane resin (P) to be used and the vinyl resin (V) [the higher the ratio of (V), the higher the coverage] Alternatively, a method of adjusting the above-described F value [the higher the F value, the higher the coverage ratio] may be mentioned.

  From the viewpoint of water resistance of the resulting composite resin, the content of the hydrophilic group in the composite resin particle (K), that is, the total amount of the hydrophilic group (V) and the hydrophilic group (P) ( The weight ratio of K) to the weight is preferably 0.01 to 10% by weight, more preferably 0.1 to 6% by weight, and particularly preferably 0.5 to 3% by weight. In this case, the content of the hydrophilic group is the same as the content of the hydrophilic group defined in the mathematical formula (1).

The glass transition temperature (Tg) of the vinyl resin (V) is usually −60 to 100 ° C., preferably −40 to 70 ° C., particularly preferably from the viewpoint of the film forming property, heat resistance, and mechanical properties of the composite resin. -20 to 40 ° C. The Tg of (V) can be appropriately adjusted by adjusting the type of monomer constituting (V) and the constituent ratio.
In addition, Tg in this invention is the differential scanning calorimetry method prescribed | regulated to ASTM D3418-82 using differential scanning calorimeters, such as "Q-20" by TA Instruments Japan Co., Ltd. (for example). DSC method).

  The Tg of the polyurethane resin (P) is usually from −80 to 60 ° C., preferably from −70 to 40 ° C., particularly preferably from −60 to 20 ° C., from the viewpoint of the film forming property, heat resistance, and mechanical properties of the composite resin. is there. The Tg of (P) can be appropriately adjusted depending on the type of polyol (a1) constituting (P).

Part or all of the surface of the resin particles (Pa) containing the polyurethane resin (P) are resin particles (Va) containing the vinyl resin (V) and / or the coating (Vf) of the vinyl resin (V). The aqueous dispersion of the composite resin particles (K) coated with is made of, for example, the following [1] to [4] using a raw material in which F calculated by the mathematical formula (1) becomes a predetermined preferable value. ] Can be obtained.
[1] A method in which the constituent monomer of the vinyl resin (V) is dropped in the aqueous dispersion (PE) of the polyurethane resin (P), or the whole amount of the constituent monomer is charged all at once and polymerized.
[2] A urethane prepolymer having an isocyanate group as a precursor of the polyurethane resin (P) is dispersed in an aqueous medium, and the constituent monomer of the vinyl resin (V) is dropped, or the whole amount of monomers is charged all at once. Polymerization is performed, and further, during the polymerization reaction of this monomer and / or after the polymerization reaction step, a chain extender (a3) is added to carry out a chain extension reaction of the urethane prepolymer, and if necessary, a termination reaction is performed with a reaction terminator (a4). Method.
[3] A method of dispersing a mixture of a polyurethane resin (P), a vinyl resin (V), and an organic solvent (J) if necessary in an aqueous medium, and removing the solvent if necessary.
[4] A mixture of a urethane prepolymer having an isocyanate group as a precursor of the polyurethane resin (P) and the vinyl resin (V), and if necessary, an organic solvent (J) or the urethane prepolymer and (V) and organic A mixture with the solvent (J) is dispersed in an aqueous medium, a chain extension reaction of the urethane prepolymer is performed using the chain extender (a3), and if necessary, a termination reaction and a desolvation with the reaction terminator (a4) are performed. How to do.

Of the methods [1] to [4], [1] is preferable because the amount of the organic solvent to be added is small and the labor for removal is reduced.

  Examples of the organic solvent (J) in the present invention include ketone solvents [for example, acetone and methyl ethyl ketone (hereinafter abbreviated as MEK)], ester solvents (for example, ethyl acetate and γ-butyrolactone), ether solvents (for example, THF), amides. Solvents (eg N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N-methylcaprolactam), alcohol solvents (eg isopropyl alcohol) and aromatic hydrocarbon solvents (eg toluene) And xylene). These organic solvents (J) may be used individually by 1 type, and may use 2 or more types together.

  The aqueous medium in the present invention means water and a mixture of water and the organic solvent (J). The organic solvent (J) used in the aqueous medium is preferably a water-soluble organic solvent from the viewpoint of dispersibility. When (J) is used, it may be distilled off if necessary during and / or after the production of the aqueous dispersion of composite resin particles (K).

  Examples of the method for producing the aqueous dispersion (PE) of the polyurethane resin (P) in the production method [1] include, among the active hydrogen components (A), a polyol (a1) and a compound containing a hydrophilic group ( a2) and, if necessary, the chain extender (a3), the reaction terminator (a4), and the organic polyisocyanate component (B), have an isocyanate group in one or more stages in the presence or absence of the organic solvent (J). A urethane prepolymer is formed, and then, if necessary, the hydrophilic group portion introduced by (a2) of the prepolymer is neutralized to form a salt as an organic solvent (J), surfactant (C), chain extender (a3 ) And / or the reaction terminator (a4) in the presence or absence of an aqueous medium and the reaction [chain extension by (a3) and, if necessary, (a4) until the isocyanate groups are substantially absent. A method of reacting Stop is due and the like.

  In this method, the urethane prepolymer includes a polyol (a1), a compound (a2) containing a hydrophilic group, and optionally a chain extender (a3), a reaction terminator (a4), among the active hydrogen components (A). The equivalent ratio of the isocyanate group to the active hydrogen-containing group (excluding carboxyl group, sulfo group and sulfamic acid group) in the presence or absence of the organic polyisocyanate component (B) in the presence or absence of the organic solvent (J) is preferably 1. It is formed by urethanization reaction at a ratio of 0.01 to 3, more preferably 1.1 to 2.

The urethane prepolymerization reaction is preferably performed at a reaction temperature of 20 ° C. to 150 ° C., more preferably 60 ° C. to 110 ° C., and the reaction time is preferably 2 to 15 hours. The content of isocyanate groups in the urethane prepolymer is preferably 0.1 to 5% by weight.
In order to accelerate the reaction in the urethane prepolymerization reaction, a catalyst usually used in the urethanization reaction may be used if necessary.

  The obtained urethane prepolymer or an organic solvent solution thereof is converted into a salt by neutralizing the hydrophilic group part introduced by (a2) of the prepolymer, if necessary, to form an organic solvent (J), a surfactant (C), a chain. It is dispersed in an aqueous medium in the presence or absence of the extender (a3) and / or the reaction terminator (a4) and reacted until the isocyanate group is substantially eliminated [by chain extension by water and, if necessary, by (a3) The polyurethane resin aqueous dispersion (PE) in the present invention can be obtained by chain extension and reaction termination by (a4).

  From the viewpoint of the water resistance of the composite resin of the polyurethane resin (P), it is preferable not to use the surfactant (C), but the amount used when (C) is used is based on the weight of the polyurethane resin (P). It is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 1 to 5% by weight. (C) is added at any time before the urethanization reaction of the polyurethane resin (P), during the urethanization reaction, after the urethanization reaction, before the aqueous medium dispersion step, during the aqueous medium dispersion step, or after the aqueous medium dispersion. However, from the viewpoint of the dispersibility of (P) and the stability of the aqueous medium dispersion, it is preferably added before or during the aqueous medium dispersion process.

  As surfactant (C), nonionic surfactant (C1), anionic surfactant (C2), cationic surfactant (C3), amphoteric surfactant (C4) and other emulsifying dispersants ( C5). Further, if necessary, sodium acetate, sodium citrate, sodium bicarbonate and the like can be used as buffering agents, and water-soluble cellulose derivatives and alkali metal salts of polymethacrylic acid can be used in appropriate amounts as protective colloids.

  Examples of (C1) include AO addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants. As the AO addition type, EO adduct of aliphatic alcohol having 10 to 20 carbon atoms, EO adduct of phenol, EO adduct of nonylphenol, EO adduct of alkylamine having 8 to 22 carbon atoms, and poly (oxypropylene) Examples of the polyhydric alcohol type include fatty acid (carbon number 8-24) ester (for example, glycerin mono) of polyhydric (3 to 8 valence or higher) alcohol (carbon number 2 to 30). Stearate, glycerin monooleate, sorbitan monolaurate and sorbitan monooleate) and alkyl (4 to 24 carbon atoms) poly (degree of polymerization 1 to 10) glycosides.

  Examples of (C2) include ether carboxylic acids having a hydrocarbon group having 8 to 24 carbon atoms or salts thereof [sodium lauryl ether acetate and (poly) oxyethylene (addition mole number 1 to 100) sodium lauryl ether acetate, etc.]; Sulfate ester or ether sulfate ester having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof [sodium lauryl sulfate, (poly) oxyethylene (addition mole number 1 to 100) sodium lauryl sulfate, (poly) oxyethylene (addition) Mole number 1 to 100) lauryl sulfate triethanolamine and (poly) oxyethylene (addition mole number 1 to 100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.]; sulfonate having a hydrocarbon group having 8 to 24 carbon atoms [Sodium dodecylbenzenesulfonate, etc.]; carbon number 8-2 Sulfosuccinates having 1 or 2 hydrocarbon groups; phosphate esters or ether phosphate esters having 8 to 24 carbon atoms and their salts [sodium lauryl phosphate and (poly) oxyethylene ( Addition mole number 1 to 100) sodium lauryl ether phosphate and the like]; fatty acid salt having a hydrocarbon group having 8 to 24 carbon atoms [sodium laurate and triethanolamine laurate and the like]; hydrocarbon group having 8 to 24 carbon atoms Coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L -Sodium glutamate and lauroylmethyl-β-a Lanine sodium, etc.].

  Examples of (C3) include quaternary ammonium salt type [stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyl dimethyl ammonium, etc.] and amine salt type [diethylamino stearate. Ethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

  Examples of (C4) include betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl. Hydroxysulfobetaine and lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropyl sodium phosphate etc.] and amino acid type amphoteric surfactants [sodium β-laurylaminopropionate etc.].

  (C5) is, for example, a reactive activator (C51) [not particularly limited as long as it has radical reactivity, and specifically, ADEKA rear soap {registered trademark, manufactured by ADEKA Corp.} SE-10N, SR-10, SR-20, SR-30, ER-20, ER-30, Aqualon {registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.} HS-10, KH-05, KH-10, KH-1025, Eleminor {registered trademark, manufactured by Sanyo Chemical Industries, Ltd.} JS-20, Latemuru (registered trademark, manufactured by Kao Corporation) PD-104, PD-420, PD-430, Ionette {registered trademark, Sanyo Chemical Industries, Ltd. )} MO-200], polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethylcellulose, methylcellulose and hydroxyethylcellulose; An emulsifying dispersant having a carboxyl group-containing (co) polymer such as sodium acrylate and a urethane group or an ester group described in US Pat. No. 5,906,704 (for example, polycaprolactone polyol and polyether diol are linked with polyisocyanate). Etc.).

  The method of the apparatus for emulsifying and dispersing the urethane prepolymer or its organic solvent solution in an aqueous medium is not particularly limited. For example, (1) vertical stirring method, (2) rotor-stator method [for example, Ebara Milder ( (3) Line mill method [for example, line flow mixer], (4) Static tube mixing type [for example, static mixer], (5) Vibration type [for example, "VIBRO MIXER" Manufactured)], (6) ultrasonic impact type [for example, ultrasonic homogenizer], (7) high pressure impact type [for example, Gaurin homogenizer (manufactured by Gaurin)], (8) membrane emulsification type [for example, membrane emulsification module], and ( 9) An emulsifier such as a centrifugal thin film contact type [for example, “Fillmix” (manufactured by Primix)] or the like. Of these, (2) is preferable.

  The volume average particle size of the aqueous polyurethane resin dispersion (PE) in the present invention is preferably 0.01 to 1 μm, more preferably 0.02 to 0, from the viewpoint of dispersion stability of the aqueous polyurethane resin dispersion (PE). 0.7 μm, particularly preferably 0.03 to 0.5 μm.

  In the production method [1], in the polyurethane resin aqueous dispersion (PE) thus obtained, the monomer component containing the monomer (X) is subjected to emulsion polymerization (drop polymerization, batch polymerization, etc.), thereby producing the present invention. An aqueous dispersion of composite resin particles (K) can be obtained.

  In the emulsion polymerization, the surfactant (C) may be used in combination. The amount of the surfactant (C) used in the emulsion polymerization is usually 0.5 to 10% by weight, preferably 1 with respect to the total amount of vinyl monomers used in the polymerization, from the viewpoint of water resistance and emulsion stability of the composite resin. ~ 5% by weight.

Polymerization initiators that can be used in emulsion polymerization include persulfate initiators such as potassium persulfate and ammonium persulfate; azo initiators such as azobisisobutyronitrile; benzoyl peroxide, cumene hydroperoxide Ordinary radical polymerization initiators such as organic peroxides such as tertiary butyl peroxybenzoate; hydrogen peroxide; and the like may be used alone or in combination of two or more. May be used. Moreover, the usage-amount of a polymerization initiator is used in 0.05-5 weight% with respect to the total weight of the monomer component used for superposition | polymerization.
A necessary amount of these initiators may be used in a lump at the start of polymerization, or may be divided and added every arbitrary time.

  Moreover, in emulsion polymerization, you may use a reducing agent with the said polymerization initiator as needed. Such reducing agents include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose and formaldehyde sulfoxylate metal salts, and reducing properties such as sodium thiosulfate, sodium sulfite, sodium bisulfite and sodium metabisulfite. An inorganic compound etc. are mentioned.

In the emulsion polymerization, a chain transfer agent may be used as necessary. Examples of such chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid and α-methylstyrene dimer. It is done.
Further, if necessary, sodium acetate, sodium citrate, sodium bicarbonate and the like can be used as a buffering agent, and polyvinyl alcohol, water-soluble cellulose derivatives and polymethacrylic acid alkali metal salts and the like can be used as protective colloids.

  The polymerization reaction in the emulsion polymerization is preferably performed in the range of 20 ° C to 150 ° C, more preferably 40 ° C to 100 ° C. When temperature is less than 20 degreeC, a polymerization rate may become slow. Moreover, when temperature exceeds 150 degreeC, it may become difficult to control a polymerization reaction. The reaction time is preferably 1 minute to 50 hours. The polymerization reaction is preferably performed in the presence of an inert gas.

  The production method of the urethane prepolymer having an isocyanate group as a precursor of the polyurethane resin (P) in the production method [2] is the same as the production method of the urethane prepolymer in the production method [1]. The methods such as the elongation reaction according to (a3) and the termination reaction according to (a4) are the same as in the production method [1].

  The method for batch polymerization of the constituent monomers in the production method [2] by dropping polymerization or charging the whole amount of monomers is the same as the monomer polymerization method in the case of the production method [1].

  As a method for producing the polyurethane resin (P) in the production method [3], for example, the urethane prepolymer is added to the chain extender (a3) and / or in the presence or absence of the organic solvent (J). Or the method of reacting with the reaction terminator (a4), the active hydrogen component (A), the polyol (a1), the compound (a2) containing a hydrophilic group, and the chain extender (a3) if necessary, the reaction termination In the presence or absence of the organic solvent (J), the agent (a4) and the organic polyisocyanate component (B) are mixed with an active hydrogen-containing group (excluding carboxyl group, sulfo group and sulfamic acid group). A method in which the urethanization reaction is carried out at a ratio of preferably 0.8 to 1.01, more preferably 0.9 to 1.0 is given.

  As a method for producing the vinyl resin (V) in the production method [3], for example, the monomer component containing the monomer (X) is polymerized in the presence or absence of the organic solvent (J). be able to.

  Examples of the polymerization initiator used for the polymerization include those exemplified as the polymerization initiator used in the emulsion polymerization. One kind may be used alone, or two or more kinds may be mixed. May be used. Moreover, it is preferable that the usage-amount of a polymerization initiator is 0.05 to 5 weight% with respect to the total weight of the monomer component used for superposition | polymerization.

  In the polymerization, if necessary, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid, α-methylstyrene dimer, etc. The chain transfer agent may be used.

  The temperature of the polymerization reaction is preferably 20 ° C. to 150 ° C., more preferably 40 ° C. to 100 ° C. from the viewpoint of the polymerization rate and the ease of reaction control. The reaction time is preferably 1 minute to 50 hours. The polymerization reaction is preferably performed in the presence of an inert gas.

  In the production method [4], a urethane prepolymer is used instead of the polyurethane resin (P) in the production method [3] and dispersed in an aqueous medium, and then (a3) is used to chain-extend the urethane prepolymer. And, if necessary, a termination reaction and a solvent removal using a reaction terminator (a4). The method for producing the urethane prepolymer, the elongation reaction of the urethane prepolymer by (a3), the termination reaction by (a4) and the like are the same as the method in the production method [1].

  The method of the apparatus for emulsifying and dispersing the polyurethane resin (P), the urethane prepolymer, the vinyl resin (V), and these organic solvent solutions in the production methods [1] to [4] in an aqueous medium is not particularly limited. (1) Vertical stirring system, (2) Rotor-stator system [for example, TK homomixer (manufactured by Primix) and Ebara Milder (manufactured by Ebara Corporation)], (3) Line mill system [for example Line flow mixer], (4) Static tube mixing type [for example, static mixer], (5) Vibration type [for example, "VIBRO MIXER" (manufactured by Chilling Industries Co., Ltd.)], (6) Ultrasonic impact type [for example, ultrasonic homogenizer ], (7) High-pressure impact type [for example, Gaurin homogenizer (manufactured by Gaurin)], (8) Membrane emulsification type [for example, membrane emulsification module], and (9) Centrifugal thin film contact [For example, "Filmics" (manufactured by plies mix Co., Ltd.)], and the like of the emulsifier and the like. Of these, (2) is preferable.

  When emulsifying and dispersing the polyurethane resin (P), the urethane prepolymer, the vinyl resin (V), and these organic solvent solutions in the production methods [1] to [4] in an aqueous medium, the surfactant (C) Can be used in combination.

  By removing the aqueous medium from the aqueous dispersion of composite resin particles (K) produced by the above method, solid composite resin particles (K) can be obtained.

  When the composite resin particle (K) of the present invention does not have a crosslinked structure and is soluble in an organic solvent and Mn can be measured, the Mn is preferably 5,000 from the viewpoint of mechanical strength, solvent resistance and water resistance. To 1,000,000, more preferably 8,000 to 800,000, and particularly preferably 10,000 to 500,000.

Mn of the composite resin particle (K) of the present invention can be measured using GPC, for example, under the following conditions.
・ Device: “HLC-8120GPC” [manufactured by Tosoh Corporation]
Column: “Guardcolumn H _XL- H” (1), “TSKgel GMH _XL ” (2) [both manufactured by Tosoh Corporation]
Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection amount: 100 μl
・ Flow rate: 1 ml / min ・ Measurement temperature: 40 ° C.
・ Detection device: Refractive index detector ・ Reference material: Standard polystyrene

  The composite resin particle (K) of the present invention may contain additives such as an antioxidant, an anti-coloring agent, an ultraviolet absorber, a hindered amine light stabilizer, a plasticizer, and a release agent as necessary. Moreover, the aqueous dispersion of the composite resin particles (K) of the present invention can also contain these additives. In the case of an aqueous dispersion, these additives may be contained in the composite resin particles (K). Both the aqueous medium and the aqueous medium may contain. The amount of these additives used is usually 10% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, based on the weight of the composite resin particles (K).

  The aqueous dispersion of the composite resin particles (K) of the present invention may contain the organic solvent (J), but from the viewpoint of odor, stability over time, environmental load, safety, production cost, etc. The content of the solvent is preferably 10,000 ppm or less, more preferably 8,000 ppm or less, particularly preferably 5,000 ppm or less, based on the weight of the aqueous dispersion.

  The volume average particle diameter of the composite resin particles (K) of the present invention is preferably 0.01 to 1 μm, more preferably 0.02 to 0.7 μm, and particularly preferably 0.03 from the viewpoint of dispersion stability and the like. ˜0.5 μm.

  The volume average particle diameter of the composite resin particles (K) can be controlled by the type and amount of the hydrophilic group in the composite resin and the type and amount of the dispersant. The volume average particle diameter of the composite resin particles (K) in the present invention is diluted with ion-exchanged water so that the solid content of the resin becomes 0.01% by weight, and then the light scattering particle size distribution measuring device [ELS-8000 { Otsuka Electronics Co., Ltd.}].

  The composite resin particles (K) of the present invention can be used in combination with polyurethane resin particles and vinyl resin particles other than the polyurethane resin (P) and vinyl resin (V) constituting the composite resin particles (K). The vinyl resin (V) in the composite resin particle (K) of the present invention has a structural unit introduced by the monomer (X) represented by the general formula (1), thereby improving the affinity with the polyurethane resin. The polyurethane resin can be finely dispersed in the vinyl resin or the vinyl resin can be finely dispersed in the polyurethane resin, and a film excellent in flexibility, mechanical strength, weather resistance, solvent resistance, water resistance and the like can be obtained. can get.

  Since the composite resin particle (K) of the present invention is excellent in performance such as mechanical strength, water resistance and solvent resistance of the coating, it can be used for paints, coating agents (rust preventive coating agent, waterproof coating agent, water repellent coating agent and Stain coating agents, etc.), adhesives, fiber processing agents (binders for pigment printing, binders for nonwoven fabrics, binders for reinforcing fibers, binders for antibacterial agents, raw materials for artificial leather and synthetic leather, etc.), paper treatment agents, inks, etc. In particular, it can be suitably used as a resin for aqueous paints, aqueous anticorrosive coating agents, aqueous fiber processing agents and aqueous adhesives.

  When used in these applications, other additives such as coating forming auxiliary resins, crosslinking agents, catalysts, pigments, pigment dispersants, viscosity modifiers, antifoaming agents, leveling agents, preservatives, anti-degradation are necessary. One, two or more agents, stabilizers, antifreezing agents and the like can be added.

  When the composite resin particle (K) of the present invention is used in an aqueous paint, in addition to (V) and (P), other aqueous medium-dispersible resins or A water-soluble resin may be used in combination.

  Examples of other aqueous medium-dispersible resins or water-soluble resins used in water-based paints include aqueous medium-dispersible or water-soluble polyurethane resins other than the aqueous dispersion of composite resin particles (K) in the present invention, and vinyl resins. And polyester resin. These other resins can be appropriately selected from those commonly used in each application for each application of the water-based paint.

  The content of the composite resin particles (K) of the present invention in the aqueous paint is preferably 0.1 to 100% by weight, more preferably 1 to 100% by weight, based on the weight of the resin solid content in the aqueous paint.

  The water-based paint may further contain one or more of a crosslinking agent, a pigment, a pigment dispersant, a viscosity modifier, an antifoaming agent, an antiseptic, a deterioration preventing agent, a stabilizer, an antifreezing agent, water, and the like. it can.

  Examples of the pigment include inorganic pigments having a solubility in water of 1 or less (for example, white pigment, black pigment, gray pigment, red pigment, brown pigment, yellow pigment, green pigment, blue pigment, purple pigment and metallic pigment) and organic pigments ( For example, natural organic pigment synthetic organic pigments, nitroso pigments, nitro pigments, pigment dye-type azo pigments, azo lakes made from water-soluble dyes, azo lakes made from poorly soluble dyes, lakes made from basic dyes, lakes made from acid dyes, xanthan lakes , Anthraquinone lake, pigments from vat dyes and phthalocyanine pigments). The content of the pigment is preferably 50% by weight or less, more preferably 30% by weight or less, based on the weight of the aqueous paint.

  As the pigment dispersant, the surfactant (C) can be used, and the content of the pigment dispersant is preferably 20% by weight or less, more preferably 15% by weight or less based on the weight of the pigment.

Viscosity modifiers include thickeners such as inorganic viscosity modifiers (such as sodium silicate and bentonite), cellulose viscosity modifiers (such as methylcellulose, carboxymethylcellulose and hydroxymethylcellulose with Mn of 20,000 or more), protein viscosity Conditioners (casein, casein soda, casein ammonium, etc.), acrylic viscosity modifiers (such as sodium polyacrylate and ammonium polyacrylate with Mn of 20,000 or more), vinyl viscosity modifiers (Mn of 20,000 or more) Polyvinyl alcohol, etc.) and associative viscosity modifiers.
Examples of antifoaming agents include long-chain alcohols (such as octyl alcohol), sorbitan derivatives (such as sorbitan monooleate), and silicone oils (such as polymethylsiloxane and polyether-modified silicone).

Examples of the preservative include organic nitrogen sulfur compound preservatives and organic sulfur halide preservatives.
Deterioration inhibitors and stabilizers (such as UV absorbers and antioxidants) include hindered phenol-based, hindered amine-based, hydrazine-based, phosphorus-based, benzophenone-based and benzotriazole-based deterioration inhibitors and stabilizers. .
Examples of the antifreezing agent include ethylene glycol and propylene glycol.
The contents of the viscosity modifier, antifoaming agent, antiseptic, deterioration preventing agent, stabilizer and antifreezing agent are each preferably 5% by weight or less, more preferably 3% by weight or less, based on the weight of the aqueous paint. is there.

  A solvent may be further added to the water-based paint for the purpose of improving the appearance of the coating film after drying. Examples of the solvent to be added include monohydric alcohols having 1 to 20 carbon atoms (such as methanol, ethanol, propanol and 2-ethylhexanol), glycols having 1 to 20 carbon atoms (such as ethylene glycol, propylene glycol and diethylene glycol), and the number of carbon atoms. Alcohols having 1 to 20 or more valences (such as glycerin) and cellosolves having 1 to 20 carbon atoms (such as methyl and ethyl cellosolve) can be used. The content of the solvent to be added is preferably 20% by weight or less, more preferably 15% by weight or less, based on the weight of the aqueous paint.

The aqueous paint using the composite resin particles (K) of the present invention is produced by mixing and stirring the composite resin particles (K) of the present invention or an aqueous dispersion thereof and the components described above. When mixing, all the components may be mixed at the same time, or each component may be added stepwise and mixed.
The solid content concentration of the water-based paint is preferably 10 to 70% by weight, more preferably 15 to 60% by weight.

  When the composite resin particle (K) of the present invention is used in an aqueous rust-proof coating agent, the resin used is an aqueous medium-dispersible or water-soluble polyurethane resin other than the composite resin particle (K) of the present invention, a vinyl resin and a polyester. Resin etc. can be used together.

  The content of the composite resin particles (K) of the present invention in the aqueous rust preventive coating agent is preferably 0.1 to 100% by weight, more preferably 1 to 1%, based on the weight of the resin solid content in the aqueous rust preventive coating agent. 100% by weight.

  In addition, auxiliary materials and additives used in ordinary aqueous anticorrosive coating agents within a range not impairing the performance of the aqueous anticorrosive coating agent containing the composite resin particles (K) of the present invention, such as crosslinking agents and plasticizers It is also possible to use fillers, pigments, thickeners, antioxidants, ultraviolet absorbers, surfactants and flame retardants.

  When the composite resin particle (K) of the present invention is used in an aqueous fiber processing agent, known antifoaming agents, wetting agents, various aqueous medium dispersible or water-soluble resins [vinyl resins, water-soluble polyurethane resins, and SBR as necessary. Latex etc.] and softeners can be blended. In the case of an aqueous resin dispersion, these blending amounts are preferably 30% by weight or less, more preferably 20% by weight or less based on the weight of the composite resin particles (K) of the present invention in terms of solid content. In the case of an agent, it is preferably 1% by weight or less, more preferably 0.1 to 0.5% by weight. Moreover, a pH adjuster can also be added as needed. Examples of pH adjusters include alkaline substances such as salts of strong bases (alkali metals, etc.) and weak acids (acids with a pKa exceeding 2.0, such as carbonic acid and phosphoric acid) (sodium bicarbonate, etc.) and acidic substances (acetic acid, etc.). Can be mentioned.

  The solid content (nonvolatile content) concentration of the aqueous fiber processing agent of the present invention is not particularly limited, but is preferably 10 to 50% by weight, more preferably 15 to 45% by weight. The viscosity (25 ° C.) is preferably 10 to 100,000 mPa · s.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. In the following, parts represent parts by weight.

Production Example 1 [Production of Monomer (X-1)]
A stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 210 parts of trimellitic acid, 142 parts of glycidyl methacrylate, 417.3 parts of isobutyl methacrylate, and 1.8 parts of an alkali catalyst (N-ethylmorpholine). By reacting for 1 hour, a compound in which 1 mol of glycidyl methacrylate was reacted with 1 mol of trimellitic acid was obtained. Subsequently, 900 parts of EO are added dropwise over 5 hours under a nitrogen atmosphere at 100 ± 10 ° C. while controlling the pressure to be 0.50 MPa or less, and then aged at 100 ± 10 ° C. for 1 hour. An isobutyl methacrylate solution of the monomer (X-1) in which EO was added to the carboxyl group was obtained.

Production Example 2 [Production of Monomer (X-2)]
Monomer (X-2) in the same manner as in Production Example 1, except that 142 parts of glycidyl methacrylate are replaced with 130 parts of 2-hydroxyethyl methacrylate, 417.3 parts of isobutyl methacrylate are replaced with 339.3 parts of acetone, and 900 parts of EO are replaced with PO696 parts. An acetone solution of was obtained.

Production Example 3 [Production of Monomer (X-3)]
A monomer solution (X-3) in acetone as in Production Example 1 except that 210 parts of trimellitic acid are replaced with 254 parts of pyromellitic acid, 417.3 parts of isobutyl methacrylate are replaced with 480 parts of acetone, and 900 parts of EO are replaced with PO1044 parts. Got.

Production Example 4 [Production of Monomer (X-4)]
A stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 210 parts of trimellitic acid, 142 parts of glycidyl methacrylate, 15.6 parts of alkali catalyst (triethylamine), and 313 parts of acetone, and reacted at 90 ° C. for 5 hours. A compound obtained by reacting 1 mol of trimellitic acid with 1 mol of glycidyl methacrylate was obtained. Subsequently, under a nitrogen atmosphere, 900 parts of EO was added dropwise at 100 ± 10 ° C. over 5 hours while controlling the pressure to be 0.50 MPa or less, and then aged at 100 ± 10 ° C. for 1 hour. Then, the monomer (X-4) which EO added to the carboxyl group of the said compound was obtained by distilling acetone off at 80 +/- 10 degreeC and gauge pressure -0.05MPa.

Production Example 5 [Production of Monomer (X-5)]
In a stainless steel autoclave equipped with a stirrer and a temperature controller, 192 parts of trimellitic anhydride, 130 parts of 2-hydroxyethyl methacrylate, 207.3 parts of styrene, and an alkaline catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1, 7.8 parts of 5-diazabicyclo [4.3.0] -5-nonene} was added and reacted at 85 ° C. for 6 hours to half-esterify the acid anhydride group part. A compound obtained by reacting 1 mol of hydroxyethyl methacrylate was obtained. Subsequently, 300 parts of phenyl glycidyl ether was charged and reacted at 90 ° C. for 10 hours to obtain a styrene solution of monomer (X-5) in which 2 mol of phenyl glycidyl ether was reacted with 1 mol of the compound.

Production Example 6 [Production of Monomer (X-6)]
A stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 210 parts of trimellitic acid, 142 parts of glycidyl methacrylate, 217.3 parts of acetone, and 1.8 parts of an alkali catalyst (N-ethylmorpholine) at 90 ° C. for 5 hours. A compound obtained by reacting 1 mol of glycidyl methacrylate with 1 mol of trimellitic acid was obtained. Subsequently, 300 parts of phenylglycidyl ether was charged and reacted at 90 ° C. for 10 hours to obtain an acetone solution of a monomer (X-6) in which 2 mol of phenylglycidyl ether was reacted with 1 mol of the compound.

Production Example 7 [Production of Monomer (X-7)]
192 parts of trimellitic anhydride, 130 parts of 2-hydroxyethyl methacrylate and 107.3 parts of acetone were charged into a stainless steel autoclave equipped with a stirrer and a temperature controller, and reacted at 85 ° C. for 6 hours to obtain an acid anhydride group part. Then, an acetone solution of a monomer (X-7) obtained by reacting 1 mol of trimellitic anhydride with 1 mol of 2-hydroxyethyl methacrylate was obtained.

Production Example 8 [Production of Monomer (X-8)]
In the same manner as in Production Example 5, except that 192 parts of trimellitic anhydride was replaced with 218 parts of pyromellitic anhydride, 207.3 parts of styrene was replaced with 272 parts of acetone, and the amount of phenylglycidyl ether charged was 450 parts. An acetone solution of 8) was obtained.

Production Example 9 [Production of Monomer (X-9)]
In a stainless steel autoclave equipped with a stirrer and a temperature controller, 192 parts of trimellitic anhydride and 130 parts of 2-hydroxyethyl methacrylate, alkali catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1,5-diazabicyclo [4.3 0.0] -5-nonene} and 156 parts of acetone, and reacted at 85 ° C. for 6 hours to half-esterify the acid anhydride group, and 2-hydroxyethyl to 1 mol of trimellitic anhydride A compound obtained by reacting 1 mol of methacrylate was obtained. Subsequently, 300 parts of phenylglycidyl ether was charged and reacted at 90 ° C. for 10 hours. Thereafter, acetone was distilled off at 80 ± 10 ° C. and a gauge pressure of −0.05 MPa to obtain a monomer (X-9) in which 2 mol of phenylglycidyl ether was reacted with 1 mol of the compound.

Production Example 10 [Production of Monomer (X-10)]
A stainless steel autoclave equipped with a stirrer and a temperature controller was charged with 62 parts of ethylene glycol, 384 parts of trimellitic anhydride, 262 parts of acetone, and 15.6 parts of an alkali catalyst (triethylamine) and reacted at 85 ° C. for 6 hours. Then, the acid anhydride group portion was half-esterified to obtain an esterified product in which 2 mol of trimellitic anhydride was reacted with 1 mol of ethylene glycol. Subsequently, 284 parts of glycidyl methacrylate was charged and reacted at 90 ° C. for 5 hours to obtain a compound in which 2 mol of glycidyl methacrylate reacted with 1 mol of the compound. Subsequently, 216 parts of benzyl alcohol was added and reacted for 5 hours while distilling off water generated at 120 ° C. to obtain an acetone solution of a monomer (X-10) in which 2 mol of benzyl alcohol was reacted with 1 mol of the compound.

Production Example 11 [Production of Monomer (X-11)]
In a stainless steel autoclave equipped with a stirrer and a temperature controller, 62 parts of ethylene glycol, 384 parts of trimellitic anhydride, 343.3 parts of acetone, and an alkali catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1,5-diazabicyclo [4.3.0] -5-Nonene} 7.8 parts was charged and reacted at 85 ° C. for 6 hours to half-esterify the acid anhydride group, and 2 mol of trimellitic anhydride was added to 1 mol of ethylene glycol. A molar reaction esterified product was obtained. Subsequently, 284 parts of glycidyl methacrylate was charged and reacted at 90 ° C. for 5 hours to obtain a compound in which 2 mol of glycidyl methacrylate reacted with 1 mol of the compound. Subsequently, 300 parts of phenyl glycidyl ether was added and reacted at 90 ° C. for 10 hours to obtain an acetone solution of a monomer (X-11) in which 2 mol of phenyl glycidyl ether was reacted with 1 mol of the compound.

Production Example 12 [Production of Monomer (X-12)]
In a stainless steel autoclave equipped with a stirring device and a temperature control device, 62 parts of ethylene glycol, 436 parts of pyromellitic anhydride, 272 parts of acetone, and an alkali catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1,5-diazabicyclo [4 .3.0] -5-nonene} 7.8 parts, reacted at 85 ° C. for 6 hours to half-esterify the acid anhydride group, and 2 mol of pyromellitic anhydride reacts with 1 mol of ethylene glycol. An esterified product was obtained. Subsequently, 230 parts of ethanol was charged and reacted at 100 ° C. for 5 hours to obtain a compound in which 1 mol of the compound reacted with 5 mol of ethanol. Subsequently, 142 parts of glycidyl methacrylate was charged and reacted at 90 ° C. for 5 hours to obtain an acetone solution of a monomer (X-12) in which 1 mol of glycidyl methacrylate was reacted with 1 mol of the compound.

Production Example 13 [Production of Monomer (X-13)]
Ethylene glycol 62 parts, sucrose 342 parts, trimellitic anhydride charge from 384 parts to 1536 parts, acetone charge from 262 parts to 803 parts, glycidyl methacrylate 284 parts, 2-hydroxyethyl methacrylate 130 parts In addition, an acetone solution of the monomer (X-13) was obtained in the same manner as in Production Example 10 except that the amount of benzyl alcohol charged was changed from 160 parts to 1203 parts.

Production Example 14 [Production of Monomer (X-14)]
In a stainless steel autoclave equipped with a stirrer and a temperature controller, 192 parts of trimellitic anhydride, 130 parts of 2-hydroxyethyl methacrylate, 207.3 parts of acetone and an alkaline catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1,5 -7.8 parts of diazabicyclo [4.3.0] -5-nonene} were reacted at 85 ° C for 6 hours to half-esterify the acid anhydride group, A compound obtained by reacting 1 mol of hydroxyethyl methacrylate was obtained. Subsequently, 300 parts of phenyl glycidyl ether was added and reacted at 90 ° C. for 10 hours to obtain an acetone solution of a monomer (X-14) in which 2 mol of phenyl glycidyl ether was reacted with 1 mol of the compound.

Production Example 15 [Production of Monomer (X-15)]
130 parts of 2-hydroxyethyl methacrylate was added to 102 parts of 2-hydroxyethyl propenyl ether, and the amount of acetone charged was changed from 207.3 parts to 198.0 parts. Alkaline catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1,5- An acetone solution of the monomer (X-15) was obtained in the same manner as in Production Example 14 except that the amount of diazabicyclo [4.3.0] -5-nonene} was changed from 7.8 parts to 7.4 parts.

Production Example 16 [Production of Monomer (X-16)]
130 parts of 2-hydroxyethyl methacrylate was added to 102 parts of 2- (allyloxy) ethanol, the amount of acetone charged was 207.3 parts to 198.0 parts, an alkaline catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1,5- An acetone solution of the monomer (X-16) was obtained in the same manner as in Production Example 14 except that the amount of diazabicyclo [4.3.0] -5-nonene} was changed from 7.8 parts to 7.4 parts.

Production Example 17 [Production of Monomer (X-17)]
130 parts of 2-hydroxyethyl methacrylate was added to 72 parts of 2-buten-1-ol, the amount of acetone charged was 207.3 parts to 188.0 parts, an alkaline catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1,5 An acetone solution of the monomer (X-17) was obtained in the same manner as in Production Example 14, except that the amount of -diazabicyclo [4.3.0] -5-nonene} was changed from 7.8 parts to 7.1 parts. .

Production Example 18 [Production of Monomer (X-18)]
130 parts of 2-hydroxyethyl methacrylate are added to 58 parts of allyl alcohol, the amount of acetone charged is 207.3 parts to 183.3 parts, an alkaline catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1,5-diazabicyclo [4. 3.0] -5-nonene}, an acetone solution of the monomer (X-18) was obtained in the same manner as in Production Example 14 except that the amount charged was changed from 7.8 parts to 6.9 parts.

Production Example 19 [Production of Monomer (X-19)]
300 parts of phenyl glycidyl ether was added to 412 parts of p- (tert-butyl) phenyl glycidyl ether, the amount of acetone charged was changed from 207.3 parts to 244.7 parts, alkaline catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1, An acetone solution of the monomer (X-19) was obtained in the same manner as in Production Example 14 except that the amount of 5-diazabicyclo [4.3.0] -5-nonene} was changed from 7.8 parts to 9.2 parts. It was.

Production Example 20 [Production of Monomer (X-20)]
In a stainless steel autoclave equipped with a stirrer and a temperature controller, 192 parts of trimellitic anhydride, 130 parts of 2-hydroxyethyl methacrylate, 136.7 parts of MEK, and an alkali catalyst {"DBN" manufactured by San Apro Co., Ltd .: 1,5 -Diazabicyclo [4.3.0] -5-nonene} 5.1 parts was charged and reacted at 90 ° C. for 5 hours to obtain a compound in which 1 mol of 2-hydroxyethyl methacrylate was reacted with 1 mol of trimellitic acid. Subsequently, 88 parts of EO are controlled at 100 ± 10 ° C. under a nitrogen atmosphere while controlling the pressure to be 0.50 MPa or less, followed by aging at 100 ± 10 ° C. for 1 hour. A MEK solution of the monomer (X-20) in which EO was added to the carboxyl group of the compound was obtained.

  Table 1 shows the analysis results of the monomers (X-1) to (X-20) obtained in Production Examples 1 to 20.

Production Example 21 [Production of aqueous polyurethane resin dispersion (PE-1)]
A simple pressure reactor equipped with a stirrer and a heating device was charged with the raw materials for prepolymer shown in Table 2 and stirred at 85 ° C. for 10 hours to conduct a urethanization reaction, and an acetone solution of a urethane prepolymer having an isocyanate group Manufactured. The isocyanate content per solid content of the acetone solution of the urethane prepolymer was 0.46 mmol / g. 399 parts of an acetone solution of the obtained urethane prepolymer was charged into a simple pressure reactor, and 6 parts of triethylamine (neutralizing agent) and 509 parts of water were added while stirring at 40 ° C. After stirring for 3 minutes at 60 rpm, 6 parts of a 10% by weight aqueous solution of diethylenetriamine as a chain extender was added, and acetone was distilled off at 65 ° C. under reduced pressure for 8 hours to obtain an aqueous polyurethane resin dispersion (PE-1). Obtained.

Production Example 22 [Production of aqueous polyurethane resin dispersion (PE-2)]
A polyurethane resin aqueous dispersion (PE-2) was obtained in the same manner as in Production Example 21 except that the charged raw materials were changed to those shown in Table 2.

In addition, the composition of the raw material represented by the trade name in Table 2 is as follows.
Duranol G4672: Mn = 2,000 poly (tetramethylene / hexamethylene) carbonate diol [manufactured by Asahi Kasei Chemicals Corporation]
Ethanacol UH-200: Polyhexamethylene carbonate diol with Mn = 2,000 [manufactured by Ube Industries, Ltd.]
PTMG2000: Poly (oxytetramethylene) glycol with Mn = 2,000 [Mitsubishi Chemical Corporation]

Production Example 23 [Production of polyurethane resin MEK solution (PJ-1)]
In a four-necked flask equipped with a thermometer and a stirrer, PTMG2000 [Mit = 2,000 poly (oxytetramethylene) glycol manufactured by Mitsubishi Chemical Corporation] 139.8 parts, polyethylene glycol 21. 0 parts, 26.2 parts of 1,6-hexanediol, 3.6 parts of 2,3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid sodium, 58.7 parts of HDI and 249.3 parts of MEK, Under stirring, the urethanization reaction was carried out by stirring at 90 ° C. for 6 hours to prepare a MEK solution of urethane prepolymer having an isocyanate group. The isocyanate content per solid content of the urethane prepolymer MEK solution was 0.25 mmol / g. After the obtained urethane prepolymer was cooled to 40 ° C., 1.5 parts of ethylenediamine was added to this MEK solution to perform chain elongation, and a polyurethane resin MEK solution (PJ-1) having a resin concentration of 50% was obtained.

Production Example 24 [Production of MEK solution of vinyl resin (VJ-1)]
Into a separable flask equipped with a dropping funnel for monomer solution, a dropping funnel for initiator solution, a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 200.0 parts of MEK were charged and stirred while blowing nitrogen gas. The temperature was raised to ° C.

  Next, 90.3 parts of 2-ethylhexyl acrylate, 84.5 parts of isobutyl methacrylate, 44.8 parts of styrene, 9.6 parts of acrylic acid, a styrene solution of monomer (X-5) obtained in Production Example 5 20. A monomer mixture consisting of 8 parts was prepared and added to the dropping funnel for monomer solution.

  Next, an initiator solution composed of 1.8 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) [“V-65” manufactured by Wako Pure Chemical Industries, Ltd.] and 50.0 parts of MEK was prepared. In addition to the dropping funnel for the initiator solution, the monomer solution and the initiator solution were dropped at a constant rate over 4 hours while maintaining the temperature in the reaction system at 80 ± 2 ° C. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 2 hours, and further, the temperature was raised from 80 ° C. to 85 ° C. and stirring was continued for 2 hours. Then, the mixture was cooled to room temperature, and a vinyl resin having a resin concentration of 50% was obtained. A MEK solution (VJ-1) was obtained.

Example 1 [Production of aqueous composite resin particle dispersion (PV-1)]
In a separable flask equipped with a dropping funnel for monomer dispersion, a dropping funnel for initiator solution, a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 1500 parts of (PE-1) polyurethane ion and ion 337.8 parts of exchange water was charged, stirred while blowing nitrogen, and heated to 70 ° C.

  Next, 84.2 parts of ion-exchange water, 20.0 parts (solid content: 5.0 parts) of Aqualon KH-1025 [Daiichi Kogyo Seiyaku Co., Ltd.] as a reactive surfactant, Production Example 1 250.4 parts of an isobutyl methacrylate solution of monomer (X-1) obtained in 1), 18.6 parts of 2-ethylhexyl acrylate, 157.0 parts of i-butyl methacrylate, 37.9 parts of n-butyl acrylate, 25.0 styrene A monomer dispersion consisting of 5.0 parts of methacrylic acid and 5.0 parts of 1,6-hexanediol dimethacrylate was prepared and charged into a dropping funnel for monomer dispersion.

  Next, an initiator solution consisting of 1.0 part of ammonium persulfate and 49.0 parts of ion-exchanged water was prepared and placed in a dropping funnel for the initiator solution, 5.0 parts of which were added to a separable flask, While maintaining the temperature in the system at 70 ± 2 ° C., the monomer dispersion and the remaining initiator solution were added dropwise at a constant rate over 3 hours. Thereafter, stirring was continued for 90 minutes at the same temperature, and then cooled to room temperature, and 4.8 parts of 25 wt% aqueous ammonia solution was added and stirred for 30 minutes, whereby composite resin particle aqueous dispersion (PV-1) was obtained. Obtained.

Examples 2-38
Composite resin particle aqueous dispersions (PV-2) to (PV-38) were obtained in the same manner as in Example 1 except that the raw materials used were changed to those shown in Tables 3 to 5.

Example 39
After mixing 500 parts of the polyurethane resin MEK solution (PJ-1) obtained in Production Example 23 and 500 parts of the vinyl resin MEK solution (VJ-1) obtained in Production Example 24, triethylamine 13.5 was mixed. After neutralization with a part, TK homomixer (manufactured by Primix) is dispersed in 750 parts of ion-exchanged water to form an aqueous dispersion, and then MEK is distilled over 15 hours at 70 ° C. under reduced pressure. To obtain a composite resin particle aqueous dispersion (PV-39).

Comparative Example 1
A comparative vinyl resin aqueous dispersion (PV′-1) was obtained in the same manner as in Example 1 except that the charged raw materials were changed to those shown in Table 5.

  The physical property values of the composite resin particle aqueous dispersions (PV-1) to (PV-39) obtained in Examples 1 to 39 and the composite resin particle aqueous dispersion (PV′-1) obtained in Comparative Example 1 are as follows. It shows in Tables 6-8.

  Furthermore, about the composite resin particle aqueous dispersions (PV-1) to (PV-39) obtained in Examples 1 to 39 and the composite resin particle aqueous dispersion (PV′-1) obtained in Comparative Example 1. Table 9 shows the results of evaluation of dispersibility, water resistance and solvent resistance by the following evaluation methods.

<Method for evaluating dispersibility of vinyl resin and polyurethane resin in composite resin>
The composite resin particle aqueous dispersion was coated on a 10 cm × 20 cm polyethylene terephthalate film with a bar coater, heated at 80 ° C. for 3 minutes, and then heated at 140 ° C. for 30 minutes to prepare a coating film having a thickness of 10 μm. This polyethylene terephthalate film with a coating film is cut to 3 mm × 10 mm and cut to a width of 100 nm while cooling to −80 ° C. with an ultramicrotome, and the coating film cross section is 10000 times using a transmission electron microscope. The dispersibility was evaluated according to the following evaluation criteria.
A: The size of the polyurethane resin domain is 500 nm or less.
○: The size of the polyurethane resin domain exceeds 500 nm and is 1 μm or less.
X: The size of the polyurethane resin domain exceeds 1 μm.

<Water resistance of film>
Pour 10 parts of the composite resin particle aqueous dispersion into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, and after drying for 12 hours at room temperature, air circulation dryer. The film obtained by heating and drying at 80 ° C. for 3 hours was immersed in ion exchange water at 80 ° C. for 30 days, and then the surface state of the film was visually observed. The case where there was no change was marked with ◯, and the case where whitening occurred was marked with ×.

<Solvent resistance of film>
10 parts of the composite resin particle aqueous dispersion was applied to a steel sheet 10 cm long by 20 cm wide so that the film thickness after drying was 200 μm, dried at room temperature for 12 hours, and then 3 ° C. at 100 ° C. with a circulating dryer. The test piece obtained by heating and drying for a period of time was immersed in dimethylformamide at 25 ° C. for 1 hour, then removed and wiped lightly, the surface state of the film was observed, and visually evaluated according to the following evaluation criteria. .
A: There is no change in the film surface before and after immersion.
○: After immersion, the number of swellings present on the surface of the coating is less than 10.
(Triangle | delta): After immersion, the number of the swelling which exists in the membrane | film | coat surface is ten or more, but resin is not melt | dissolving.
X: After immersion, 10 or more bulges exist on the surface of the film, and the resin is dissolved in the solution.

Example 40 and Comparative Example 2 [Evaluation as water-based paint]
90 parts of deionized water, 70 parts of thickener [Sanyo Chemical Industries Co., Ltd. “Biserizer AP-2”], pigment dispersant [Sanyo Chemical Industries Co., Ltd. “Caribbon L-400”] 10 parts, oxidation 140 parts of titanium ["CR-93" manufactured by Ishihara Sangyo Co., Ltd.], carbon black ["FW200P" manufactured by Degussa Co., Ltd.] and 160 parts of calcium carbonate were mixed and dispersed for 30 minutes by a paint conditioner. Here, 20 parts of 1-nonanol, 200 parts of “Polytron Z330” [Acrylic resin aqueous dispersion manufactured by Asahi Kasei Co., Ltd.] and the aqueous resin dispersion (PV-1) obtained in Example 1 or Comparative Example 1 were obtained. The resin aqueous dispersion (PV′-1) 50 parts obtained was charged, mixed and dispersed for 10 minutes, and further adjusted with ion-exchanged water so that the viscosity at 25 ° C. was 150 mPa · s. E-1) and a comparative water-based paint (E′-1) were obtained.

  Table 10 shows the results of evaluating the film-forming properties of the coatings and the water resistance and solvent resistance of the coatings of the obtained water-based coatings (E-1) and (E'-1) based on the following test methods.

<Method for evaluating film-forming properties of paint>
A water-based paint was spray-coated on a 10 cm × 20 cm steel plate and heated at 80 ° C. for 3 minutes to produce a coating film having a thickness of 20 μm. This coated steel sheet was immersed in 25 ° C. ion-exchanged water for 10 minutes, then taken out, gently wiped with a cloth, and visually evaluated according to the following evaluation criteria.
○: Color does not transfer to the cloth.
X: Color transfer is observed on the cloth.

<Water resistance evaluation method of coating film>
The aqueous paint was spray-coated on a 10 cm × 20 cm steel plate and heated at 80 ° C. for 10 minutes to produce a coating film having a thickness of 20 μm. This coated steel sheet was immersed in ion exchange water at 80 ° C. for 30 days, then taken out and lightly wiped, and the surface of the coating film was visually evaluated according to the following evaluation criteria.
○: There is no change in the coating film surface before and after immersion.
X: After immersion, a part of the coating film is peeled off.

<Method for evaluating solvent resistance of coating film>
The aqueous paint was spray-coated on a 10 cm × 20 cm steel plate and heated at 140 ° C. for 30 minutes to prepare a coating film having a thickness of 20 μm. The coated steel sheet was immersed in a 25% by weight butyl cellosolve aqueous solution at 25 ° C. for 15 minutes, and then taken out, the surface was lightly wiped, and the coating film surface was visually evaluated according to the following evaluation criteria.
○: There is no change in the coating film surface before and after immersion.
X: After immersion, there is peeling off of the coating film.

Example 41 and Comparative Example 3 [Evaluation as an aqueous rust preventive coating agent]
The aqueous resin dispersion (PV-1) obtained in Example 1 and the comparative aqueous resin dispersion (PV′-1) obtained in Comparative Example 1 were “gin coated” (galvanized steel sheet manufactured by Engineering Test Service Co., Ltd.). , Size: vertical 10 cm × horizontal 5 cm × thickness 0.08 cm) obtained by applying using a bar coater so that the film thickness after drying is 5 μm, and drying with a dryer at 150 ° C. for 1 minute. Table 11 shows the results of evaluating the rust prevention properties of the coating film based on the following test method using the test pieces.

<Method for evaluating rust resistance of paint>
A salt spray test was performed according to JIS Z 2371 using the test piece, and the appearance after 45 hours was visually evaluated according to the following evaluation criteria.
○: No rusting ×: Rusting

Example 42 and Comparative Example 4 [Evaluation as aqueous fiber processing agent]
For each 100 parts of the aqueous resin dispersion (PV-1) obtained in Example 1 and the comparative aqueous resin dispersion (PV′-1) obtained in Comparative Example 1, a viscoelasticity modifier [ "SN thickener 618" manufactured by San Nopco Co., Ltd., 8.9 parts, silicone antifoaming agent ["SN deformer 777" manufactured by San Nopco Co., Ltd.] 0.9 parts, water 35 parts, titanium oxide 44.6 parts, and pigment [19.9 parts of “NL Red FR3R-D” manufactured by Yamagata Kogyo Co., Ltd.] was mixed to obtain a pigment printing paste (H-1) and a comparative pigment printing paste (H′-1). . Table 12 shows the results obtained by testing the water resistance of the pigment-printed fiber cloth and the film-forming property of the pigment-printed paste for the obtained pigment-printed paste based on the following test methods.

<Method for evaluating water resistance of textile fabric printed with pigment>
The pigment printing paste was applied onto a cotton-plated mold using a bar coater so that the film thickness was 2 cm × 10 cm and the film thickness was 0.2 mm. This was dried for 5 minutes with a tenter temperature-controlled at 140 ° C. to obtain a textile fabric printed with pigment. This pigment-printed fiber cloth was immersed in ion-exchanged water at 60 ° C. for 3 days, then taken out, and the surface was lightly wiped with a non-printed fiber cloth, and visually evaluated according to the following evaluation criteria.
○: No color transfer to a textile fabric that has not been printed.
X: Color transfer is observed in the fiber cloth not subjected to the printing process.

<Method for evaluating film forming property of pigment printing paste>
The pigment printing paste was applied onto a cotton-plated mold using a bar coater so that the film thickness was 2 cm × 10 cm and the film thickness was 0.2 mm. This was dried for 3 minutes with a tenter temperature-controlled at 120 ° C. to obtain a textile fabric printed with pigment. The surface of the textile fabric printed with the pigment was lightly wiped with a textile fabric not subjected to textile printing, and visually evaluated according to the following evaluation criteria.
○: No color transfer to a textile fabric that has not been printed.
X: Color transfer is observed in the fiber cloth not subjected to the printing process.

Example 43 and Comparative Example 5 [Evaluation as water-based adhesive]
The solid content concentration of the aqueous resin dispersion (PV-1) obtained in Example 1 and the comparative aqueous resin dispersion (PV′-1) obtained in Comparative Example 1 was 40 wt.% Using ion-exchanged water. % Of acrylic emulsion (Asahi Kasei Co., Ltd., trade name: Polytron U-154, solid content 60% by weight) 158 parts (solid content 94.8 parts) was added to and mixed with 474 parts of a solid content of 45% by weight. % Aqueous adhesive (G-1) and a comparative aqueous adhesive (G′-1) were obtained. Table 13 shows the results of evaluating the adhesive strength to the flexible board by the following evaluation method for each aqueous adhesive.

<Evaluation method for normal adhesion to flexible board>
The obtained aqueous adhesive was applied to a canvas and a flexible board (width 25 mm, length 125 mm, thickness 2.5 mm) by brush coating. The coating amount, solid content 100 g / ^{m 2} for the canvas was a solid content 60 g / ^{m 2} for a flexible board. After applying the aqueous adhesive, it was dried in an air-drying oven at 80 ° C. for 4 minutes, and then the aqueous adhesive-applied surfaces of the canvas and flexible board were roll-bonded at a pressure of 60 kg / 25 mm to prepare a test piece. The obtained test piece was cured at 23 ° C. for a week, and then a 90 ° peel test was conducted at 23 ° C. at a pulling speed of 50 mm / min, and the following evaluation criteria were evaluated.
○: Adhesive strength is 3.0 kg / 25 mm or more.
Δ: Adhesive strength is 1.5 kg / 25 mm or more and less than 3.0 kg / 25 mm.
X: Adhesive strength is less than 1.5 kg / 25 mm.

  Since the composite resin particle (K) of the present invention is excellent in performance such as mechanical strength, water resistance and solvent resistance of the coating, it can be used for paints, coating agents (rust preventive coating agent, waterproof coating agent, water repellent coating agent and anti-proofing agent). Stain coating agents, etc.), adhesives, fiber processing agents (binders for pigment printing, binders for nonwoven fabrics, binders for reinforcing fibers, binders for antibacterial agents, raw materials for artificial leather and synthetic leather, etc.), paper treatment agents, inks, etc. Can be used widely, but because of its excellent film-forming properties and water resistance, it is particularly suitable for use as an aqueous polyurethane resin dispersion for water-based paints, water-based anti-corrosion coating agents, water-based fiber processing agents, and water-based adhesives. can do.

Claims (15)

Vinyl resin (V) in which part or all of the surface of the resin particles (Pa) containing the polyurethane resin (P) is polymerized with the monomer component containing the monomer (X) represented by the general formula (1) ) Containing resin particles (Va) and / or composite resin particles coated with the vinyl resin (V) coating (Vf) , wherein the monomer component content of the monomer component is Composite resin particles having a volume average particle size of 0.01 to 1 μm, based on the weight of 1 to 42.7% by weight .

Wherein, M ¹ represents a residue obtained by removing the c-number of active hydrogen from the hydroxyl or 20-valent active hydrogen-containing organic compound; c, if M ¹ is a hydroxyl group is 1, M ¹ is In the case of a residue obtained by removing c active hydrogens from an organic compound containing 1 to 20 valent active hydrogens, it represents an integer satisfying 1 ≦ c ≦ (valence of M ¹ ); R ¹ contains an ethylenically unsaturated bond A plurality of R ^{1 s} may be the same or different; and M ² represents a residue obtained by removing one active hydrogen from a hydroxyl group or an organic compound containing 1 to 20 valent active hydrogens. In some cases, M ² may be the same or different, and M ² and M ¹ may be the same or different; L is a residue obtained by removing all carboxyl groups from a trivalent or higher valent aromatic polycarboxylic acid. The aromatic ring of L is composed of carbon atoms, A substituent other than a xyl group and / or a halogen atom may be bonded, but a hydrogen atom is bonded to at least one carbon atom; a and b each represents an integer of 0 or more, and 2 ≦ When a + b ≦ d−2 is satisfied and a plurality of a's are present, the a's may be the same or different, and at least one of c a's is not 0, and when there are a plurality of a's, the b's are the same or different. D is the number of hydrogen atoms bonded to the carbon atoms constituting the aromatic ring when all the substituents including the carboxyl group of the aromatic polycarboxylic acid are replaced with hydrogen atoms, that is, can be substituted on the aromatic ring. This represents the number of sites. ]   2. The composite resin particle according to claim 1, wherein a surface coverage of the resin particle (Pa) by the resin particle (Va) and / or the coating film (Vf) is 20 to 100%. The ethylenically unsaturated bond-containing group in the general formula (1) is at least one substituent selected from the group consisting of substituents represented by the following general formulas (2) to (6). 2. Composite resin particles according to 2.

[Wherein R ² , R ⁴ and R ⁶ are each independently a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms which may be substituted with a hydroxyl group, and R ³ and R ⁵ are each independently A hydrogen atom or a methyl group; R ⁷ is a hydrogen atom, a methyl group or an ethyl group; and * is a bond to which the substituent is bonded to the oxygen atom of the oxycarbonyl group in the general formula (1). Represents that. ]   The trivalent or higher valent aromatic polycarboxylic acid in the general formula (1) has a carboxyl group bonded to two carbon atoms adjacent to the carbon atom that constitutes the aromatic ring and has no substituent group bonded thereto, The composite resin according to any one of claims 1 to 3, wherein the composite resin has a structure in which a carboxyl group is further bonded to at least one of carbon atoms different from the carbon atom to which the substituent is not bonded and adjacent to the carbon atom to which the group is bonded. particle.   The composite resin particle according to any one of claims 1 to 3, wherein the trivalent or higher aromatic polycarboxylic acid in the general formula (1) is trimellitic acid and / or pyromellitic acid.   The composite resin particle according to any one of claims 1 to 5, wherein a in the general formula (1) is 1 and c is 1.   The composite resin particles according to any one of claims 1 to 6, wherein the monomer (X) has a hydroxyl value of 0 to 500 mgKOH / g.   The composite resin particle according to any one of claims 1 to 7, wherein a concentration of L in the monomer (X) is 0.5 to 10 mmol / g.   The composite resin particle according to any one of claims 1 to 8, wherein the monomer (X) has a carbonyl group concentration of 1.5 to 30 mmol / g. The composite resin particle according to any one of claims 1 to 9, wherein the F value calculated from the following mathematical formula (1) is 1 to 40.
F = (N _V + C _V × 10 + S _V × 20) − (N _P + C _P × 10 + S _P × 20) (1)
[However, N _V is the numerical representation of the content of the nonionic hydrophilic group in the vinyl resin (V) in% by weight of formula (1); the content of C _V is vinyl resin (V) Medium carboxyl group the content of the nonionic hydrophilic group in the N _P is a polyurethane resin (P); S _V is vinyl resin numerical content expressed in weight percent of the sulfo group in (V); numerical value representing the weight% C _P is a numerical value representing the content of carboxyl groups in the polyurethane resin (P) in weight percent; S _P is the content of sulfo groups in the polyurethane resin (P) in weight percent Represents the numerical value represented. ] Composite resin particle aqueous dispersion containing a composite resin particle child and an aqueous medium according to any one of claims 1 to 10.   The coating material containing the composite resin particle in any one of Claims 1-10.   The antirust coating agent formed by containing the composite resin particle in any one of Claims 1-10.   The fiber processing agent formed by containing the composite resin particle in any one of Claims 1-10.   The adhesive agent containing the composite resin particle in any one of Claims 1-10.