JPH1112426A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition capable of forming a coating film and an adhesive layer which have high hardness and are excellent in wear resistance and solvent resistance. SOLUTION: This composition contains inorganic particles having oxazoline groups and a carboxylated acrylic resin (having an acid value of about 2-200 mg.KOH/g), and it is useful as a coating agent and an adhesive. The inorganic particles having oxazoline groups are obtained by treating inorganic particles (A) with a silane coupling agent to introduce a reactive group and reacting the group with a bisoxazoline compound. For example, the inorganic particles are represented by the formula [C-(B)m ]n -A (wherein A is an inorganic particle; C is an oxazoline group; B is an organic group; n is an integer of 2 or greater; and m is 0 or 1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing
The present invention relates to a resin composition useful as a coating resin composition for forming a coating film having excellent wear resistance.

[0002]

2. Description of the Related Art In a resin composition, for example, a resin composition for coatings, various powders as additives or fillers are used in order to improve the properties of the film (for example, hardness, heat resistance, solvent resistance, etc.). For example, an inorganic powder (eg, silica, mica, talc, diatomaceous earth, calcium carbonate, silicon oxide, aluminum oxide, titanium oxide, calcium hydroxide, etc.) is added. However, if the affinity between these powders and the resin is poor, the mechanical strength of the coating is greatly reduced. In order to improve the affinity of the granules, granules treated with a surface treating agent have been used. For example, powders and granules treated with a resin, powders and granules treated with a surface treatment agent, and powders and granules treated with a surfactant are known. However, these powders do not have reactivity, and there is a limit in improving the mechanical and chemical properties of the coating.

[0003] Japanese Patent Application Laid-Open No. Hei 4-363313 discloses a reactivity in which a shell part having an ethylenically unsaturated bond is formed on the surface of a core particle of a three-dimensionally crosslinked organic resin having a specific degree of crosslinking. Have been proposed. JP-A-5-170845 discloses organic polymer fine particles having amino groups on the surface of core particles composed of a polymer of an ethylenically unsaturated monomer. These fine particles have a reactive functional group on the surface, but the reactivity of the functional group is low, and the coating film formed by the resin composition to which the fine particles are added still has hardness and abrasion resistance. , Low solvent resistance.

JP-A-6-184224 discloses a polymer having a functional group containing an active hydrogen atom such as a carboxyl group at a terminal or a side chain of a hydrophobic main chain (for example, a modified olefin polymer) and oxazoline. A method for producing reactive particles by reacting is disclosed. The reactive particles obtained by this method are useful for obtaining a polymer alloy by adding a small amount to a polymer composition incompatible with each other. However, when the reactive particles are applied to a resin composition for coating, the transparency, saturation, and the like of the coating film are impaired, and in addition, reinforcement, filling properties cannot be imparted, and hardness, abrasion resistance, and Low solvent properties. The same applies to coating agents and printing inks. Further, even when polymer fine particles or reactive fine particles are applied to an adhesive or a pressure-sensitive adhesive, it is difficult to impart high adhesion.

[0005] It should be noted that the literature, ACS Polymer Material Science and Engineering (ACS Polyme)
r Mater. Sci. & Eng.) 76 , Apr. 1997, 2-
Hydrosilylation of (10-decene-1-yl) -1,3-oxazoline with trialkoxysilane produces a compound having an oxazoline group and an alkoxysilyl group, and the reaction of this compound with silica particles produces oxazoline. It has been reported to obtain silica particles having groups. This document describes that silica particles having an oxazoline group are used for reaction processing in order to functionalize a polymer together with a function as a filler.
However, there is no description in the above document about using such silica particles in combination with an acrylic resin suitable for an adhesive or a coating agent.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resin composition which can improve hardness, abrasion resistance, solvent resistance and the like. Another object of the present invention is to provide a resin composition having improved chemical resistance such as adhesion and alkali resistance in addition to the above-mentioned properties. Still another object of the present invention is to provide a resin composition useful as a coating agent (paint, coating agent, printing ink, etc.), an adhesive (including an adhesive) and the like.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, specific inorganic particles having an oxazoline group have high dispersibility and storage stability, and a carboxyl group or a salt thereof is used. By adding specific inorganic particles having an oxazoline group to a coating resin composition containing an acrylic resin having, it has been found that the hardness, solvent resistance, abrasion resistance, etc. of the coating film can be effectively improved, and the present invention has been completed. .
That is, the resin composition of the present invention is composed of (1) an inorganic particle having an oxazoline group and (2) an acrylic resin having a carboxyl group or a salt thereof. In the inorganic particles having an oxazoline group, the oxazoline group may be bonded to the inorganic particles by a residue of a silane coupling agent. The usage ratio of the inorganic particles having an oxazoline group is about 0.1 to 120 parts by weight per 100 parts by weight of the solid content of the acrylic resin, and the acrylic resin having a carboxyl group or a salt thereof has a glass transition temperature of −60 ° C. -50 ° C and acid value 2-200mg KO
An acrylic resin of about H / g can be used. In the acrylic resin, based on the total amount of all the constituent monomer units of the acrylic resin having a carboxyl group, the proportion of the (meth) acrylate monomer unit is 50% by weight or more and has a carboxyl group or a salt thereof. The ratio of monomer units is 0.2
About 30% by weight. The inorganic particles having an oxazoline group (1) include (1a) inorganic particles having a reactive group.
(A) a method of reacting a compound having an oxazoline group (C), (1b) treating an inorganic particle (A) with a coupling agent or a coordinating compound (B) to introduce a reactive group, A method of reacting with a compound (C) having an oxazoline group, (1c) a coupling agent or a coordinating compound (B) formed by a reaction of a compound (C) having an oxazoline group, and an oxazoline group and a reactive functional group. A compound having the inorganic particles (A)
At least one type of oxazoline group-containing inorganic particles obtained by the method of treating is used.

In the present specification, the inorganic particles (A)
May be referred to as “carrier particles (A)” or “carrier (A)”. An organic group connecting the inorganic particles (A) and the oxazoline group may be simply referred to as a “connected organic group”. Further, “acrylic” monomers and “methacrylic” monomers are collectively referred to as “(meth) acrylic” monomers. “Organic group” refers to a linear, branched or cyclic carbon skeleton as a main skeleton. In addition to carbon atoms, oxygen, nitrogen, sulfur, boron, silicon, phosphorus, and metal atoms (Titanium atom, germanium atom, tin atom, selenium atom, arsenic atom and antimony atom) at least one atom selected from the group consisting of a main skeleton (main chain) or a side chain which may have at least one atom selected from the group consisting of: means. "Linking",
The term “bond” is used to include a covalent bond, an ionic bond, and a hydrogen bond.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

[Reactive inorganic particles] The reactive inorganic particles are obtained at least by a reaction between the inorganic particles (A) and the compound (C) having an oxazoline group, for example, by any one of the following methods (1a) to (1c). Can be. (1a) Method of reacting inorganic particles (A) having a reactive group with compound (C) having an oxazoline group (1b) Coupling agent or coordinating compound of inorganic particles (A)
Method of introducing a reactive group by treating with (B) and reacting with a compound (C) having an oxazoline group (1c) a coupling agent or a coordinating compound (B) and a compound having an oxazoline group (C) A compound formed by the reaction of and having an oxazoline group and a reactive functional group,
Method for Treating Inorganic Particles (A) The reactive inorganic particles thus obtained seem to have, for example, a structure represented by the following formula (II). [C- (B) _m ] _n -A (II) (where A is an inorganic particle, C is an oxazoline group, and B is an organic group connecting the inorganic particle A and the oxazoline group C.
n is an integer of 2 or more; m is an integer of 0 or 1;
M is an integer of 0 or 1 corresponding to the presence or absence of the linking organic group B, n
Is an integer of 2 or more corresponding to the amount of oxazoline group introduced, and m may be different depending on n. [Carrier particles (A)] Inorganic substances forming the carrier particles (A) include metals (eg, aluminum, nickel, tungsten, gold, silver, copper, platinum, cadmium, zinc, lead, etc.), carbon (eg, Carbon black, graphite, fullerene, etc.), metal compounds and ceramics. The inorganic substances can be used alone or in combination of two or more.

Examples of the metal compound include naturally occurring inorganic compounds (eg, silica sand, quartz, glass, mica, talc, clay, diatomaceous earth, etc.), carbonates (eg, calcium carbonate, magnesium carbonate, etc.), metal sulfates Salts (eg, barium sulfate, etc.), metal oxides [eg,
Silicon oxide such as silicon dioxide, glass, aluminum oxide (alumina), titanium oxide, copper oxide, silver oxide, iron oxide (such as _{Fe 2 O 3, Fe 3 O} 4), zinc oxide, zirconium oxide, magnesium oxide, etc.], Examples include metal hydroxides (eg, aluminum hydroxide), metal sulfides (eg, cadmium sulfide, zinc sulfide, molybdenum disulfide, etc.), potassium titanate, aluminum borate, and inorganic pigments. Ceramics include oxide ceramics (for example, silicon oxide, alumina, titanium oxide, zirconia, etc.), non-oxide ceramics (for example, carbides such as silicon carbide and boron carbide, titanium nitride, boron nitride, aluminum nitride, and nitride). Nitrides such as silicon, silicides, borides, and the like).

As the carrier particles (A), for example, when using silicon dioxide, calcium carbonate, magnesium carbonate, barium sulfate, titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, aluminum hydroxide, inorganic pigment, carbon black, etc. There are many.

The shape of the carrier particles (A) is not particularly limited.
It may be spherical, elliptical, flat, or rod-shaped. The average particle diameter of the inorganic particles is a wide range depending on the application, for example,
It can be selected from a range of about 1 nm to 100 μm, preferably about 2 nm to 50 μm, and more preferably about 2 nm to 20 μm.

[Compound (B) Having Linking Organic Group] The carrier particles (A) are prepared as long as the oxazoline group C can be introduced.
The carrier (A1) having a reactive group itself (for example, carbon black or the like) may be used, and the carrier (A) having a reactive group introduced therein by reaction with a compound (B) having a linking organic group may be used.
2). In addition, even if the carrier (A1) itself has a reactive group, a reactive group may be further introduced by the compound (B) having the linking organic group. In the present invention, a carrier particle (A) into which a reactive group has been introduced by treatment or reaction of a compound (B) having a linking organic group is often used. As the compound (B) having a linking organic group,
Usually, a reactive functional group (b1) for the carrier particles (A),
A reactive agent having a reactive group (b2) for the compound (C) having an oxazoline group C can be used, and the reactive functional group (b1) and the reactive group (b2) may be the same or different. Good.

The organic linking group is a polar group such as an ester bond (-OOC-), an amide bond (-NHCO-), a urea bond (-
NHCONH-), urethane bond (-OCONH-, -SCONH-), ether bond (-O-), thioether bond (-S-), bond formed by reaction of epoxy group with active hydrogen atom (-COOCH
(OH) CH _2- , -NHCH (OH) CH _2- ) and the like.

Preferred compounds (B) include a condensable or hydrolyzable group (for example, a halo-substituted silyl group, a hydroxy-substituted silyl group, an alkoxy-substituted silyl group) and a reactive group [for example, a halogen atom, a hydroxyl group, A mercapto group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, a (meth) acryloyloxy group, etc.] (silane coupling agent). The organosilicon compound is generally used as a carrier (A)
Has a condensable or hydrolyzable group (hydrolyzable silyl group) as a reactive functional group (b1) and a reactive group (b2) for the compound (C). Preferred reactive groups of the silane coupling agent include a hydroxyl group, a mercapto group, a carboxyl group, an amino group (particularly a carboxyl group) and the like. The silane coupling agent may have one or two or more reactive groups.

The halogen atom includes chlorine, bromine and iodine atoms, and the epoxy group is an unsaturated bond of a hydrocarbon group (for example, an unsaturated bond of a cycloalkenyl group such as a cyclopentenyl group or a cyclohexenyl group). It may be composed of an epoxy ring generated by oxidation of a (heavy bond) or an epoxy ring of a glycidyl group. The amino group may be substituted with one or two lower C _1-4 alkyl groups (for example, methyl, ethyl, propyl, isopropyl, butyl group, etc.), and the (meth) acryloyl group is (meth) acryloyloxy It may be composed of groups. The alkoxy group of the silane coupling agent includes, for example, C _1-4 alkoxy groups such as methoxy, ethoxy, flopoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, and t-butoxy groups. Preferred alkoxy groups are hydrolyzable alkoxy groups (particularly methoxy groups or ethoxy groups). In the silane coupling agent, the number of the reactive groups is about 1 to 3 (particularly 1 or 2), and the number of the alkoxy groups is about 1 to 3 (particularly 2 or 3).

Specific examples of the silane coupling agent include:
For example, silane coupling agents having the following reactive groups (b-1) to (b-8) can be exemplified. The silane coupling agents may be used alone or in combination of two or more.

(B-1) Halogen atom: containing halogen atom
Examples of the silane coupling agent include 2-chloroethyl
Trimethoxysilane, 2-chloroethyltriethoxy
Orchid, 3-chloropropyltrimethoxysilane, 3-c
Halogenated C such as loropropyltriethoxysilane
_1-4 Alkyl tri C_1-4 Including alkoxysilane
You.

(B-2) Hydroxyl group: Examples of the silane coupling agent containing a hydroxyl group include 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, and 3-hydroxypropyl. Examples thereof include hydroxy C _1-4 alkyltri C _1-4 alkoxysilane such as propyltriethoxysilane.

(B-3) Mercapto group: Mercapto group-containing silane coupling agents include, for example, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercapto trimethoxysilane, include a mercapto C _1-4 alkyl tri C _1-4 alkoxysilane such as 3-mercaptopropyl triethoxysilane.

(B-4) Carboxyl group: Examples of the carboxyl group-containing silane coupling agent include carboxymethyltrimethoxysilane, carboxymethyltriethoxysilane, 2-carboxyethyltrimethoxysilane, and 2-carboxyethyltriethoxysilane. , 3-carboxypropyl trimethoxysilane, etc. carboxy C _1-4 alkyl tri C _1-4 alkoxysilane such as 3-carboxypropyl triethoxysilane and the like.

(B-5) Amino group: The amino group-containing silane coupling agent includes, for example, 2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane, 3-aminopropyl and an amino C _1-4 alkyl tri C _1-4 alkoxysilane methyl diethoxy silane, 2- [N- (2- aminoethyl) amino] ethyltrimethoxysilane, 3-
[N-(2-aminoethyl) amino] propyltrimethoxysilane, 3- (2-aminoethyl) amino] [N-(amino C _1-4 alkyl) propyl triethoxysilane amino] C _1-4 alkyl tri such as C _1-4 alkoxy silane, and the like amino C _1-4 alkyl trihydroxy silane, such as aminopropyl silane triol.

(B-6) Epoxy group: Epoxy group-containing silane coupling agents include, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
-(3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl)
Such as propyl trimethoxysilane (epoxy C _5-8 cycloalkyl) C _1-4 alkyl tri C _1-4 alkoxy silanes; 2-glycidyloxy ethyltrimethoxysilane, 2- glycidyloxy triethoxysilane,
3-glycidyloxypropyltrimethoxysilane, 3
- glycidyl oxy C _1-4 alkyl tri C _1-4 alkoxysilane such as glycidyl trimethoxy silane can be exemplified.

(B-7) Isocyanate group: The isocyanate group-containing silane coupling agent includes, for example, 2-isocyanatoethyltrimethoxysilane, 2-isocyanatoethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, Isocyanate C _1-4 alkyltri C _1-4 alkoxysilane such as 3-isocyanatopropyltriethoxysilane; isocyanate C such as 3-isocyanatopropyldimethylchlorosilane
_1-4 alkyl di C _1-4 alkyl chlorosilanes and the like are included.

(B-8) (Meth) acryloyl group: (meth) acryloyl group-containing silane coupling agents include, for example, 2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyl (Meth) acryloyloxy C _1-4 alkyltri C _1-4 alkoxy such as oxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane And silane.

A compound (B) having a silane coupling agent, a reactive functional group for the reactive group of the silane coupling agent and a reactive group for the compound (C)
By reacting with 1), a functional group to be reacted with the carrier (A) can be appropriately selected. For example, when the reactive group of the silane coupling agent is a reactive group such as a halogen atom, an epoxy group, an isocyanate group, a vinyl group and a (meth) acryloyl group, the reactive group is reacted with the compound (B1) to form a carrier (A ) To hydroxyl, mercapto,
You may convert into a carboxyl group and an amino group (especially a carboxyl group). The combination of the reactive groups (b1) to (b-8) of such a silane coupling agent with the compound (B1) is, for example, as follows.

(B-1) Halogen atom: (B1-1) Hydroxyl group-containing compound, mercapto group-containing compound Amino group-containing compound (b-2) Hydroxyl group: (B1-2) Carboxyl group-containing compound, acid anhydride Group-containing compound, ester group or cyclic ester group-containing compound, isocyanate group-containing compound (b-3) mercapto group: (B1-2) carboxyl group-containing compound, acid anhydride group-containing compound ester group or cyclic ester group-containing compound, Isocyanate group-containing compound (b-4) Carboxyl group: (B1-4) hydroxyl group-containing compound, mercapto group-containing compound, ester group or cyclic ester group-containing compound, amino group-containing compound, cyclic ether group-containing compound, isocyanate group-containing Compound (b-5) amino group: (B1-5) carboxyl group-containing compound, acid anhydride group-containing compound, formyl group or Is an alkylcarbonyl group-containing compound, an ester group or a cyclic ester group-containing compound, a cyclic ether group-containing compound, an isocyanate-containing compound (b-6) an epoxy group: (B1-6) a carboxyl group-containing compound, an acid anhydride group-containing compound, Amino group-containing compound (b-7) Isocyanate group: (B1-7) Hydroxyl group-containing compound, mercapto group-containing compound, carboxyl group-containing compound, amino group-containing compound (b-8) (meth) acryloyl group: ( B1-8) Vinyl group-containing compound, (meth) acryloyl group-containing compound The hydroxyl group-containing compound includes diols [for example, aliphatic diols (eg, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, Polypropylene glycol, tetramethylene glycol Coal, polytetramethylene glycol, hexanediol, etc.), alicyclic diols (eg, 1,4-cyclohexanediol, hydrogenated bisphenol A, etc.), aromatic diols (eg, bisphenol A, alkylene oxide adduct of bisphenol A, etc.) ) And the like, and polyhydric alcohols (for example, aliphatic polyhydric alcohols such as glycerin and trimethylolpropane). The hydroxyl group-containing compound also includes an ester group-containing compound such as an acetyloxy group. Examples of the mercapto group-containing compound include dithiols corresponding to the above diols.

Examples of the amino group-containing compound include aliphatic diamines (for example, alkylenediamines such as ethylenediamine, diaminopropane, tetramethylenediamine, hexamethylenediamine, and 2,2,4-trimethylhexamethylenediamine), and aliphatic diamines. Polyamines (eg, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, etc.), alicyclic diamines [eg, isophoronediamine, bis (aminomethyl) cyclohexane, bis (4-amino-3-methylcyclohexyl) methane, etc.], aromatics Examples thereof include diamines (for example, m- or p-phenylenediamine, diaminotoluene, xylylenediamine, 4,4'-diaminodiphenylmethane, and the like). The amino group-containing compound may have a hydroxyl group or a carboxyl group. Examples of the compound having an amino group and a hydroxyl group include amino alcohol (for example, 2-aminoethanol, diethanolamine, 2-aminoisopropanol, etc.), aminophenol, and the like. Examples of the compound having an amino group and a carboxyl group include, for example, amino acids (eg, glycine, alanine, valine, leucine, isoleucine, lysine, serine, threonine, phenylalanine, aspartic acid, glutamic acid, methionine, arginine, tryptophan, histidine, proline , Oxyproline, cystine, etc.) or an active ester thereof, an aliphatic aminocarboxylic acid (for example,
Examples thereof include aminocaproic acid and aminoundecanoic acid) or corresponding lactams and aromatic aminocarboxylic acids (eg, aminobenzoic acid and the like).

Examples of the compound containing a carboxyl group or an acid anhydride group include dicarboxylic acids (saturated fatty acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid). Aliphatic dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and hexahydrophthalic acid, phthalic acid, isophthalic acid and terephthalic acid Aromatic dicarboxylic acids), polyvalent carboxylic acids (eg, trimellitic acid, pyromellitic acid) or derivatives (eg, methyl esters) of these acid anhydrides (eg, maleic anhydride, phthalic anhydride, etc.) or esters Lower alkyl esters, carboxylic acid halides, active esters, etc.) Murrell. The carboxyl group-containing compound may have a hydroxyl group. Examples of the compound having a hydroxyl group and a carboxyl group include aliphatic oxycarboxylic acids (eg, glycolic acid, lactic acid, oxypropionic acid, malic acid, tartaric acid, citric acid, etc.),
Aromatic oxycarboxylic acids (e.g., p-hydroxybenzoic acid, salicylic acid, etc.) and the like are included. Compounds having a hydroxyl group and a carboxyl group include oxycarboxylic acids having about 6 to 18 carbon atoms such as oxyhexanoic acid, oxyoctanoic acid, and oxydecanoic acid, and corresponding cyclic ester group-containing compounds (for example, γ-caprolactone, γ −
Lactones such as laurolactone, δ-valerolactone and δ-caprolactone).

In these compounds, the hydroxyl group may be protected with a protecting group (for example, a benzylcarbonyl group, a substituted benzylcarbonyl group, a t-butylcarbonyl group, a tetrahydropyranylcarbonyl group, etc.), and the amino group may be protected. And a carboxyl group may be protected with a protecting group (eg, a benzyloxy group, a substituted benzyloxy group, a t-butyloxy group, a phenacyloxy group). Etc.).

Examples of the isocyanate group-containing compound include aromatic diisocyanates (for example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc.) and alicyclic diisocyanates [for example, isophorone diisocyanate, 4,4 ' -Methylenebis (cyclohexyl isocyanate), methylcyclohexane diisocyanate, etc.], aliphatic diisocyanates (eg, hexamethylene diisocyanate, lysine diisocyanate, etc.).

Examples of the cyclic ether group-containing compound include alkylene oxide (eg, ethylene oxide, propylene oxide, etc.), epichlorohydrin, glycidyl ether (eg, bisphenol A type epoxy compound, alkylene glycol diglycidyl ether, polyoxyalkylene glycol dialkyl) Glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, etc.), glycidyl esters (for example,
Diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl ester of dimer acid, etc., glycidylamine (eg, diglycidylaniline, diglycidyltoluidine, N, N-diglycidyl-4-glycidyloxyaniline), etc. Can be exemplified.

Examples of the compound containing a formyl group or an alkylcarbonyl group include dialdehyde (eg, glyoxal, methylglyoxal, succinaldehyde), diketone (eg, dioxime derivatives such as diacetyl and dimethylglyoxime, and acetylacetone). Aldehydic acid (for example, glyoxalic acid), ketone acid (for example, pyruvic acid) and the like can be exemplified.

The compound containing a vinyl group or a (meth) acryloyl group includes, for example, a compound having a hydroxyl group [for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate. C _2-10 alkylene glycol mono (meth) acrylate such as acrylate, polyoxy C _2-4 alkylene glycol mono (meth) acrylate, allyl alcohol, etc.), a compound having a carboxyl group or an acid anhydride group [eg, (meth) acrylic Acid, itaconic acid, maleic anhydride, etc.], a compound having an amino group (for example, aminostyrene, vinylamine,
Examples thereof include compounds having an epoxy group [e.g., allyl glycidyl ether and glycidyl (meth) acrylate], and compounds having an isocyanate group (e.g., vinyl isocyanate).

When the carrier (A) is a metal, the compound (B) may be a compound having a functional group capable of coordinating with at least the metal (coordinating compound). Examples of such a coordinating compound include mercapto alcohol (for example, mercaptoethanol), and a sulfur or nitrogen-containing compound (for example, cysteine and histidine). When the coordinating compound is, for example, mercaptoethanol, the mercapto group forms a coordination bond with the exemplified metal (eg, gold, platinum, etc.), and the remaining hydroxyl group is used for the reaction with the compound (C). it can.

[Oxazoline group-containing compound (C)] As the oxazoline group-containing compound (C), a bisoxazoline compound represented by the following formula (I) can be used.

[0037]

Embedded image (In the formula, E is an alkylene group which may have a substituent,
Substituted have a good cycloalkylene group or a substituent shown also arylene group, R ^1, R
² , R ³ and R ⁴ are the same or different and are each a hydrogen atom,
Represents an alkyl group which may have a substituent or an aryl group which may have a substituent) In the bisoxazoline compound, the alkylene group of E is, for example, a C _1-10 alkylene group (for example, Methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, etc.). Cycloalkylene groups include, for example, C
_5-10 cycloalkylene groups (for example, 1,3-cyclopentylene, 1,3-cyclohexylene, 1,4-cyclohexylene group, etc.) and the like are included. Arylene groups include
C _6-12 arylene group (for example, 1,3-phenylene,
1,4-phenylene, 1,5-naphthylene, 2,5-naphthylene group and the like). The alkylene group,
The cycloalkylene group and the arylene group may have a substituent. Examples of such a substituent include a halogen atom (eg, fluorine, chlorine, bromine atom, etc.), an alkyl group (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl group, etc.) And an alkoxy group having about 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy and butoxy groups. Desirable E includes an aryl group which may have a substituent, particularly a phenylene group which may have a substituent (for example, a 1,3-phenylene group, a 1,4-phenylene group and the like). .

In the above formula, the alkyl groups represented by R ¹ , R ² , R ³ and R ⁴ include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s
-Butyl, t-butyl, pentyl, hexyl, etc.
Examples are _1-10 alkyl groups. Preferred alkyl groups are
A lower alkyl group having about 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms
Lower alkyl group (for example, especially methyl group, ethyl group,
Propyl group, isopropyl group, etc.). R ¹ , R
^The aryl group represented by ² , R ³ and R ⁴ includes a phenyl, 1-naphthyl, 2-naphthyl group and the like.

The alkyl group and the aryl group may have a substituent. Examples of the alkyl group having a substituent include dichloromethyl, trichloromethyl, trifluoromethyl, 2,2,2-trichloroethyl, 2,2,2-
And halogenated C _1-4 alkyl groups such as trifluoroethyl and pentafluoroethyl groups. Aryl groups having a substituent include, for example, 2-chlorophenyl, 3
Phenyl group having a halogen atom such as -chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 3,5-dichlorophenyl group, 2-methylphenyl, 3
A C _1-4 alkyl-phenyl group such as -methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 4-ethylphenyl group, 2-methoxyphenyl, 3-methoxyphenyl, C _1-4 such as -methoxyphenyl, 2,4-dimethoxyphenyl, 3,5-dimethoxyphenyl, 4-ethoxyphenyl, etc.
An alkoxy-phenyl group and the like.

Particularly preferred bisoxazoline compounds can be represented by the following formula (Ia).

[0041]

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represent a hydrogen atom or a C _1-4 alkyl group.) In particular, at least one of R ¹ and R ² (particularly R ² ) is It is preferable that at least one of the hydrogen atom, R ³ and R ⁴ (particularly R ⁴ ) is a hydrogen atom. More preferably, R
¹ , R ² , R ³ and R ⁴ are all hydrogen atoms.

Specific examples of preferred bisoxazoline compounds include, for example, 1,6-bis (1,3
-Oxazoli-2-yl) hexane, 1,8-bis (1,3-oxazoli-2-yl) octane, 1,10
-Bis (1,3-oxazoli-2-yl) decane, 1,
3-bis (1,3-oxazoli-2-yl) cyclohexane, 1,4-bis (1,3-oxazoli-2-yl)
Cyclohexane, 2,2 '-(1,3-phenylene)-
Bis (2-oxazoline), 2,2 '-(1,4-phenylene) -bis (2-oxazoline), 2,2'-
(1,2-phenylene) -bis (2-oxazoline),
2,2 '-(1,3-phenylene) -bis (4-methyl-2-oxazoline), 2,2'-(1,4-phenylene) -bis (4-methyl-2-oxazoline), 2,
2 '-(1,2-phenylene) -bis (5-methyl-2
-Oxazoline), 2,2 '-(1,3-phenylene)
-Bis (5-methyl-2-oxazoline), 2,2'-
(1,4-phenylene) -bis (5-methyl-2-oxazoline), 2,2 ′-(1,3-phenylene) -bis (4-methylphenyl-2-oxazoline), 2,2 ′
-(1,4-phenylene) -bis (4-methylphenyl-2-oxazoline), 2,2 '-(1,3-phenylene) -bis (4-chlorophenyl-2-oxazoline), 2,2'- (1,4-phenylene) -bis (4-
Chlorophenyl-2-oxazoline) and the like. One or two or more bisoxazoline compounds can be used.

The bisoxazoline compound can be produced by a conventional method, for example, by reacting a fatty acid or its methyl ester with ethanolamine in the presence of a catalyst to form a 5-membered heterocyclic compound (“Plastic Age”, 11).
4, Mar. 1995), by reacting a dicarboxylic acid or its lower alkyl ester corresponding to E in the above formula with ethanolamine or a derivative thereof to form a 5-membered heterocyclic compound. .

Preferred reactive inorganic particles are represented by the following formula (i)
Can be represented by

[0045]

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A,
(B, E, and n are the same as described above.) The reactive particles represented by the formula (i) correspond to the reactive particles using a bisoxazoline compound as the compound (C).

In the above formula (i), R¹ , R^Two , R^Three 
And R^Four Is the same as above. Preferred R¹ , R^Two ,
R^Three And R^Four Is a hydrogen atom, C_1-4 An alkyl group
And alkyl groups include methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, s-butyl, t-
Butyl group and the like. More preferred alkyl group
Includes a methyl and an ethyl group (especially a methyl group).
Particularly preferred R¹ And R ^Three Is a hydrogen atom or C_1-4 Al
A kill group (particularly a methyl group),^Two And R^Four 
Is a hydrogen atom.

Further, among the reactive particles represented by the above formula (i), preferred reactive particles can be represented by the following formula (ia).

[0048]

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a C _1-4 alkyl group, at least one of R ¹ and R ² is a hydrogen atom, and at least one of R ³ and R ⁴ is (A, B, E, and n are the same as described above.) [Method for Producing Reactive Particles] Reactive particles can be obtained by the above-mentioned production methods (1a) to (1c). In the production method (1a), the reactive particles are obtained by directly reacting an inorganic particle (A) having a reactive group such as carbon black with a compound (C) having an oxazoline group (particularly, two or more oxazoline groups). Can be obtained.

In the production method (1b), first, the inorganic particles (A) are treated or reacted with a coupling agent (particularly, a silane coupling agent) or a coordinating compound (B) to give the inorganic particles (A). Introduce a reactive group. This carrier particle (A)
Is reactive with the oxazoline group. Thus, the reactive inorganic particles can be obtained by reacting the reactive group of the carrier particles (A) with the compound (C) having an oxazoline group (particularly two or more oxazoline groups). In this method, the inorganic particles (A) subjected to the reaction with the compound (B) may not have a reactive group,
It may have a reactive group.

In the production method (1c), a coupling agent (particularly a silane coupling agent) or a coordinating compound (B) and a compound (C) having an oxazoline group (particularly two or more oxazoline groups) are previously prepared. The reaction produces a compound having an oxazoline group and a reactive functional group. In this compound, the reactive functional groups can react with the inorganic particles (A). Therefore, reactive inorganic particles can be obtained by treating or reacting the inorganic particles (A) with the compound having the oxazoline group and the reactive functional group. At this time, as the reactive functional group, a condensable or hydrolyzable group of a silane coupling agent can be used. In addition, the inorganic particles (A) may not have a reactive group, and may have a reactive group.

In the carrier (A) other than the carrier having a reactive group such as carbon black, a preferred method is to select a silane coupling agent [for example, a hydroxyl group, a mercapto group, a carboxyl group, an amino group (particularly a carboxyl group). Silane coupling agent having at least one type of reactive group], and then using a powdery carrier (A) having a reactive group introduced by surface treatment.

For example, the method for producing the reactive particles (1b)
In the above, for the reaction between the carrier (A) and the silane coupling agent, an ordinary condensation reaction of the coupling agent can be used.
The proportion of each component can be selected from a wide range according to the type and surface area of the carrier. The ratio of the compound (B) is, for example,
0 to 1000 parts by weight (for example, 0.1 to 1000 parts by weight), preferably 0 to 1000 parts by weight, per 100 parts by weight of the carrier (A)
500 parts by weight (for example, 0.1 to 500 parts by weight), more preferably 0.2 to 200 parts by weight (for example, 0.2 to 500 parts by weight)
150 parts by weight). The reaction may be performed in the presence or absence of a catalyst. The reaction may be carried out in the presence or absence of an organic solvent, and a poor solvent that does not solubilize the carrier is often used as the organic solvent. The reaction temperature can be selected, for example, from a range of about 20 to 150 ° C. according to the type of the carrier (A) or the compound (B). The particulate reaction product is separated by filtration or the like,
It may be washed with an appropriate solvent and subjected to a subsequent reaction.

More specifically, the reaction between the carrier (A) and the silane coupling agent is performed, for example, in an organic solvent inert to the reaction of water, alcohols (eg, methanol, ethanol, isopropanol, etc.). The reaction can be carried out by reacting the dispersed carrier (A) with a silane coupling agent. The reaction temperature is, for example, 30 ° C.
It can be selected from the range of the reflux temperature of the solvent.

The compound (C) (bisoxazoline compound) reacts with the reactive group introduced into the carrier (A) by the compound (B).
Can be carried out by a usual ring-opening reaction of an oxazoline group. The ratio of the compound (C) is usually 1 to the reactive group introduced into the carrier (A) by the compound (B).
Equivalent or more (especially excess), for example, compound (B)
The amount of the compound (C) is 0.5 to 5 mol, preferably 0.7 to 3 mol, more preferably about 0.8 to 2 mol, per 1 mol of the reactive group introduced into the carrier (A). Since the weight ratio of the compound (C) depends on the molecular weight [for example, the molecular weight of the compound (B) or the compound (C), etc.], it cannot be unambiguously determined, but for example, the reactive group introduced by the compound (B) To 100 parts by weight of the carrier (A) having
1 to 200 parts by weight, preferably 0.1 to 150 parts by weight,
More preferably, it can be selected from the range of about 0.1 to 100 parts by weight.

The ring-opening reaction of the oxazoline group may be performed in the presence or absence of a catalyst. The reaction may be carried out in a suspension or dispersion system in the presence of a solvent inert to the reaction. Examples of the solvent include alcohols such as methanol, ethanol and isopropanol; aliphatic hydrocarbons such as pentane, hexane and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene. Hydrogen; halogenated hydrocarbons such as methyl chloride, methylene chloride, chloroform, and trichloroethylene; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran; Nitrogen-containing compounds such as pyrrolidone, acetonitrile, and dimethylformaldehyde; or a mixed solvent thereof. The solvent is often a poor solvent for the carrier (A). The reaction temperature may be selected, for example, from the range of 20 to 250 ° C.

In the production method (1a), the carrier (A)
Is reacted with the oxazoline group-containing compound (C) in the above-mentioned production method (1b) by reacting the reactive group introduced into the carrier (A) by the compound (B) with the oxazoline group-containing compound (C). )). The ratio of the oxazoline group-containing compound (C) can be selected from the range of the ratio of the compound (C) to the reactive group introduced into the carrier (A) by the compound (B) in the above method (1b).

In the above production method (1c), the reaction between the silane coupling agent and the oxazoline group-containing compound (C) is carried out by the reaction introduced into the carrier (A) by the compound (B) in the production method (1b). The reaction can be carried out in the same manner as in the reaction of the compound (C) with the reactive group. The ratio of the oxazoline group-containing compound (C) can be selected from the range of the ratio of the compound (C) to the reactive group introduced into the carrier (A) by the compound (B) in the above method (1b). The reaction between the compound having an oxazoline group and a reactive functional group obtained by the reaction of the silane coupling agent and the oxazoline group-containing compound (C) with the carrier (A) is performed by the silane coupling with the carrier (A). The reaction can be carried out in the same manner as in the reaction with the agent. Compound (B) and oxazoline group-containing compound (C)
The ratio of the reaction product with the compound (compound having an oxazoline group and a reactive functional group) can be selected from the range of the ratio of the compound (B) to the carrier (A) in the method (1b).

The above-mentioned reactions (condensation reaction of silane coupling agent, ring-opening reaction of oxazoline, etc.)
In an atmosphere of an inert gas such as nitrogen, helium, or argon,
It can be performed with stirring. After completion of the reaction, if necessary, reactive particles can be obtained by a conventional separation method such as filtration, washing, concentration, and drying.

The average particle diameter of the reactive inorganic particles is, for example, from 1 nm to 100 μm depending on the amount of the oxazoline group introduced.
m, preferably 2 nm to 10 μm, more preferably 2 nm to 10 μm.
It can be selected from a range of about nm to 1 μm (for example, 5 to 500 nm).

[Acrylic Resin] In the present invention, an acrylic resin having a carboxyl group or a salt thereof (hereinafter, simply referred to as an acrylic resin) is used together with the inorganic particles. The acrylic resin in the present invention includes alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, aminoalkyl (meth) acrylate and (meth) acrylate.
It is a polymer having a monomer unit composed of a (meth) acrylate such as glycidyl acrylate as a main component and having a carboxyl group or a salt thereof.

The acrylic resin is used together with the (meth) acrylic acid ester and a comonomer to be described later,
It can be produced by copolymerizing a carboxyl group-containing monomer such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid or maleic anhydride, or a salt thereof. In the present invention, the preferred acrylic resin contains 50% by weight or more (preferably 60 to 100% by weight) of a monomer unit composed of a (meth) acrylate based on the total amount of all monomer units constituting the acrylic resin. And 0.2 to 30% by weight (preferably 1 to 20% by weight) of a monomer unit having a carboxyl group or a salt thereof.

Further preferred acrylic resin has an acid value of 2
~ 200mg KOH / g (preferably 10-100m
g · KOH / g).

Specific examples of the (meth) acrylate constituting the acrylic resin include alkyl (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Isobutyl meth) acrylate, t-butyl (meth) acrylate,
C _1-10 alkyl (meth) acrylates such as hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate] Hydroxyalkyl (meth) acrylate [such as hydroxy C _2-4 alkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate]; (meth) acrylic acid 2 Aminoalkyl (meth) acrylates such as dimethylaminoethyl and 2-diethylaminoethyl (meth) acrylate; benzyl (meth) acrylate, glycidyl (meth) acrylate and the like.

The acrylic resin may contain, in addition to the (meth) acrylic acid ester monomer unit and the monomer unit containing a carboxyl group or a salt thereof, a unit composed of the following copolymer monomers. Good. As the comonomer, aromatic vinyls (styrene, α-methylstyrene,
Vinyl ester (vinyl acetate, vinyl propionate, etc.), (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N-alkoxymethyl (meth) acrylamide [N-methoxymethyl ( Meth) acrylamide, etc.].

The preferred weight average molecular weight of the acrylic resin is, for example, about 1,000 to 1,000,000, preferably about 3,000 to 500,000, and more preferably about 5,000 to 100,000. Further, the glass transition temperature of the acrylic resin can be selected according to the application, and generally -60 ° C to 50 ° C is appropriate. Specifically, an acrylic resin having a glass transition temperature of about −10 ° C. to 50 ° C. is preferable for paints, coating agents, and printing inks, and a glass transition temperature of −20 ° C. to 30 ° C. for adhesives.
An acrylic resin having a glass transition temperature of about -60 ° C to about 10 ° C is preferable for an adhesive.

As a base for forming a salt of a carboxyl group in the acrylic resin, for example, an organic base (dimethylamine, trimethylamine, triethylamine,
Amines such as diethanolamine, triethanolamine, and morpholine); and inorganic bases (such as ammonia, sodium hydroxide, and potassium hydroxide). Further, in the present invention, not only all of the carboxyl groups but also an acrylic resin partially converted into a salt may be used.

The form of the acrylic resin may be a solution (organic solvent solution, aqueous solution) or a dispersion (aqueous emulsion or the like) depending on the use of the resin composition. In the organic solvent solution of the acrylic resin, as the organic solvent, for example, alcohols (eg, methanol, ethanol,
Propanol, isopropanol, n-butanol, etc.), aliphatic hydrocarbons (e.g., hexane, heptane, octane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., benzene, toluene , Xylene, etc.), esters (eg,
Ethyl acetate, n-butyl acetate, isobutyl acetate, n-acetic acid
-Butyl, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ethers (e.g., diethyl ether, dioxane, tetrahydrofuran, etc.), cellosolves [e.g., methylcellosolve (ethylene glycol monomethyl ether),
Ethylcellosolve, propylcellosolve, butylcellosolve, phenylcellosolve, benzylcellosolve, etc.], carbitols [eg, diethylene glycol monomethyl ether, carbitol (diethylene glycol monoethyl ether), diethylene glycol monopropyl ether, etc.], or these And the like can be used.

The aqueous acrylic resin solution can be prepared by dissolving a carboxyl group-containing acrylic resin using an alkali. Examples of the alkali include an organic base [aliphatic amine (eg, trimethylamine, triethylamine,
Ethylenediamine, etc.), alkanolamines (ethanolamine, etc.), heterocyclic amines (eg, morpholine, etc.), and inorganic bases [ammonia, alkali metal compounds (sodium hydroxide, potassium hydroxide, etc.)].

The aqueous emulsion can be prepared by a conventional method, for example, a method of neutralizing and dispersing a part of the carboxyl groups of the acrylic resin with the above alkali, or a conventional emulsion polymerization method. In the emulsion polymerization, a conventional emulsifier (for example, an anionic surfactant,
Nonionic surfactants, protective colloids such as vinyl alcohol and water-soluble polymers, etc.) may be used. In addition,
The emulsion may be pH adjusted.

The solid content concentration of the acrylic resin such as an organic solvent solution, an aqueous solution and an aqueous emulsion is not particularly limited.
For example, it can be selected from the range of about 10 to 70% by weight, preferably about 25 to 50% by weight.

[Resin Composition] A feature of the present invention is that the reactive particles and the acrylic resin constitute a resin composition (particularly, a crosslinked or curable resin composition). Reactive particles consist of multiple active sites with high reactivity (oxazoline groups)
Therefore, when the resin composition is used as a coating agent (paint, printing ink, coating agent, etc.) and the substrate is coated to form a coating layer, a coating film having a high crosslinking density can be formed. Therefore, the coating film has excellent mechanical strength such as hardness, and can also improve characteristics such as abrasion resistance and solvent resistance. In addition, the chemical resistance (alkali resistance), durability, and adhesion to the substrate (adhesion) of the coating film
Can also be improved. In particular, since the reactive particles have a large number of oxazoline groups, even if the reactive particles are small,
A coating layer having a high crosslinking density can be formed. In addition, since it contains inorganic particles (particularly, silica particles), a high filling effect can be provided. Furthermore, when the resin composition is used as an adhesive (including a pressure-sensitive adhesive), the adhesion to an adherend can be greatly improved, and a high adhesion can be maintained over a long period of time.

As the substrate or the adherend, for example, metal, ceramics, glass, plastic, stone (for example, marble), wood, and the like can be used. These substrates or adherends may be subjected to a pretreatment depending on the type. A coating agent or an adhesive composed of a resin composition is applied to a substrate or an adherend by coating or the like, and is heated and dried as necessary to form a coating film (coating layer) or an adhesive layer. it can. The coating is
It can be performed by a conventional method such as spray coating, roll coating, knife coating, bar coater coating, dip coating, or a coating method using a brush. The thickness of the coating layer is, for example, 0.
It can be selected from the range of about 1 to 1000 μm, preferably about 0.2 to 500 μm, more preferably about 0.3 to 300 μm, and the thickness of the adhesive layer is, for example, 1 to 10000 μm, preferably, depending on the type of the adherend. 5-5000μ
m, more preferably in the range of about 10 to 3000 μm.

The drying and curing of the coating film and the adhesive can be performed, for example, by the following steps:
It can be carried out at 0 to 200 ° C, preferably about 20 to 150 ° C, and usually about 50 to 120 ° C.

The resin composition of the present invention can be prepared by mixing reactive inorganic particles and an acrylic resin. The resin composition may be a powder, but is usually a solution or dispersion (emulsion) using an organic solvent or water as a solvent in many cases. A preferred resin composition usually contains an organic solvent and is useful as a coating agent or an adhesive.

The resin composition can be prepared by a conventional method, for example, using a mixing and dispersing machine.
Reactive inorganic particles, additives (eg, fillers, pigments, etc.) may be dispersed with a disperser (eg, ball mill, ultrasonic disperser, etc.).

The proportion of the reactive particles used cannot be determined unconditionally because it depends on the molecular weight of the reactive particles, the amount of the oxazoline group introduced, the molecular weight of the acrylic resin, the acid value, and the like. It can be selected from the range of about 0.1 to 120 parts by weight, preferably about 0.5 to 100 parts by weight (for example, 1 to 50 parts by weight) based on 100 parts by weight of the resin.

The resin composition may contain other thermoplastic resins (for example, acrylic resin and polyester resin containing no carboxyl group) and thermosetting resins (for example, urethane resin, amino resin, etc.) depending on the use. ), Stabilizers such as antioxidants, ultraviolet absorbers, heat stabilizers, plasticizers, antistatic agents, dispersants, anti-skinning agents, viscosity modifiers such as thickeners, leveling agents, anti-sagging agents, Additives such as fungicides, preservatives, fillers, dyes and pigments may be added.

[0078]

As described above, the resin composition of the present invention comprises reactive particles and an acrylic resin, so that the coating film formed from this resin composition has high hardness, abrasion resistance and resistance to abrasion. Excellent solvent properties. Further, the chemical resistance of the coating film and the adhesion to the substrate and the adherend can be improved. Therefore, the resin composition is useful as a coating agent or an adhesive.

[0079]

The present invention will be described below in more detail with reference to examples. The present invention is not limited by these examples. [Preparation Example 1 of Particles Having Oxazoline Group] (1) Amino group-containing silicon dioxide Ethanol / water mixed solvent [5/1 (weight ratio)] 60 g
1.2 g of 3-aminopropyltriethoxysilane [Silas s330, manufactured by Chisso Corp .; hereinafter, referred to as “amino group-containing silane”] was added thereto, and the mixture was stirred at room temperature (20 ° C.) for 10 minutes. Silicon dioxide [Aerosil # 50, manufactured by Nippon Aerosil Co., Ltd., average particle size: 30]
nm, specific surface area: 50 m ² / g, unit surface area (nm ² )
Number of hydroxyl groups per unit: 2, hereinafter referred to as “silicon dioxide”] 2 g was added and dispersed using an ultrasonic disperser for 10 minutes, and then the particles were sedimented by a centrifuge (2000 rpm, 10 minutes). And collected. After the collected particles were air-dried, they were heated at 100 ° C. for 10 minutes. After the heat treatment, the particles were dispersed in ethanol (30 ml) using an ultrasonic disperser (10 minutes), and then subjected to centrifugation, and the separated particles were placed in tetrahydrofuran (THF) (30 ml).
In addition, silica particles dispersed with an ultrasonic disperser (10 minutes), sedimented with a centrifugal separator, washed and collected, subsequently dried under reduced pressure, and treated with amino group-containing silane-treated silica particles (hereinafter, “amino Referred to as "group-containing silicon dioxide").
Using FT-NMR GSX270 manufactured by JEOL Ltd., solid-state ¹³ C-NMR (C
(P / MAS) spectrum, the following (1-
The result shown in a) was obtained. (1-a) ¹³ C-NMR (CP / MAS) spectrum 7.9 ppm (Cα), 27.4 ppm (Cβ), 45.1 pp
m (Cγ) (2) Carboxyl group-containing silicon dioxide 5 g of the amino group-containing silicon dioxide is added to THF100m
and added with 0.81 g (0.0083 mol) of maleic anhydride, followed by stirring at room temperature for 2 days. The particles in THF were washed twice with 200 ml of methanol (400 ml in total), once with 200 ml of acetone, and twice with 100 ml of THF each (200 ml in total) using a centrifuge (3000 rpm, 15 minutes). Particles treated with maleic anhydride (hereinafter referred to as "carboxyl group-containing silicon dioxide") were obtained. The solid-state ¹³ C-NMR (CP / MAS) spectrum of the carboxyl group-containing silicon dioxide was measured, and the result shown in the following (2-a) was obtained. (2-a) Solid ¹³ C-NMR (CP / MAS) spectrum δ (ppm): 7.9, 22.3, 43.6, 134.1, 166.5 From the comparison between the data (1-a) and the data (2-a), It can be observed that the carboxyl group-containing silicon dioxide has a carboxyl group and an organic group corresponding to maleic anhydride introduced.

(3) Oxazoline group-containing silicon dioxide 4.8 g of the carboxyl group-containing silicon dioxide was added to N,
Dispersed in 60 ml of N-dimethylformaldehyde (DMF), 0.05 g of triphenylphosphine and 2,2- (1,3-phenylene) -bis (2-oxazoline) [manufactured by Takeda Pharmaceutical Co., Ltd .; 1.75 g was added and stirred at 100 ° C. for 3 hours. After the reaction, centrifuge (3000 rpm, 15
), The obtained particles are each dissolved in methanol for 20 minutes.
2 times with 0 ml (total 400 ml), 1 with 200 ml of acetone
The mixture was washed twice with 100 ml each of THF (200 ml in total) and dried under reduced pressure. The resulting particles (hereinafter referred to as “oxazoline group-containing silicon dioxide”) were hydrophobic and did not disperse in water at all. When the solid state ¹³ C-NMR (CP / MAS) spectrum of this oxazoline group-containing silicon dioxide was measured, the result shown in the following (3-a) was obtained. (3-a) Solid ¹³ C-NMR (CP / MAS) spectrum δ (ppm): 7.9, 22.3, 43.6, 51.8, 60.3, 129.1, 13
5.3, 168.1 From the comparison between the data (2-a) and the data (3-a), it can be observed that oxazoline groups are introduced into the oxazoline group-containing silicon dioxide.

The solid-state NMR spectra of ¹³ C and ²⁹ Si of bisoxazoline and oxazoline group-containing silicon dioxide were measured using a JEEOL JMM 270GX solid probe, and the following (3-b) to (3-d) Were obtained. (3-b) Solid ¹³ C-NMR (CP / MAS) spectrum δ (ppm): 57.5, 59.8, 130.0, 164.7 From the above data (3-b), the oxazoline group-containing silicon dioxide had an oxazoline group introduced. Particles are observed.

(3-c) Solid ²⁹ Si-NM of silicon dioxide
R spectrum No significant signal was observed. (3-d) Solid ²⁹ Si of oxazoline group-containing silicon dioxide
-NMR spectrum A broad signal was observed at about -70 ppm (half-width 15 to 20 ppm). This signal corresponds to the silica layer formed by the amino group-containing silane (silane coupling agent).

Further, a sample pellet obtained by molding silicon dioxide and oxazoline group-containing silicon dioxide into a tablet having a diameter of 1 cm, a sample pellet of a mixture obtained by wet-mixing silicon dioxide and bisoxazoline at an arbitrary ratio, and a zirconium oxide (reference sample) ) And the reflection amount at 256 nm (benzene ring) was measured using an object color spectrophotometer UV-350A manufactured by Shimadzu Corporation. A calibration curve was prepared using the data of these reflection UV spectra, and the oxazoline group content of the oxazoline group-containing silicon dioxide was determined to be 2.4% by weight.

Comparative Example 1 Carboxyl group-containing acrylic resin [Composition: isobutyl acrylate / methyl methacrylate / styrene / 2-hydroxyethyl methacrylate / acrylic acid = 40/24/5]
/ 23/8 (% by weight), solid content concentration: 65% (solvent: isopropyl alcohol), weight average molecular weight: about 15.0
00, acid value: 40.5 mg-KOH / g, hereinafter referred to as “acrylic resin A”] with methanol and a solid content of 50
% By weight. A predetermined amount of triethylamine (hereinafter referred to as “TEA”) is added to the diluted resin solution to neutralize 33 mol% of the carboxyl groups of the acrylic resin A, and the neutralized solution is added to distilled water while stirring. An emulsion having a solid content of 30% by weight was prepared.

Comparative Example 2 A mixture of acrylic resin A and bisoxazoline (addition amount: 0.72% by weight based on the resin solid content of acrylic resin A) was diluted with methanol to a solid content concentration of 50% by weight. . A predetermined amount of TEA was added to the diluted solution to neutralize 33 mol% of the carboxyl groups of the acrylic resin A, and the neutralized solution was added to distilled water while stirring to obtain a solid content of 3%.
A 0% by weight emulsion was prepared.

Comparative Example 3 Acrylic resin A was diluted with methanol to give a solid content of 50%.
% By weight. 33 mol% of the carboxyl groups of the acrylic resin A in this diluted resin solution was neutralized using TEA. To the neutralized resin solution, silicon dioxide was added at 30% by weight of the acrylic resin solids, and dispersed using an ultrasonic disperser. This dispersion was added to distilled water with stirring to prepare a dispersion having a solid content of 30% by weight.

Example 1 Acrylic resin A was diluted with methanol to obtain a solid content of 50%.
% By weight. 33 mol% of the carboxyl groups of the acrylic resin A in this diluted solution was neutralized using TEA. Oxazoline group-containing silicon dioxide was added to the neutralized resin solution in an amount of 30% by weight of the solid content of the acrylic resin, and dispersed using an ultrasonic dispersing machine. This dispersion was added to distilled water with stirring to prepare a dispersion having a solid content of 30% by weight.

Then, the above Comparative Examples 1 to 3 and Example 1
Using the bar coater #
Apply to a stainless steel plate using
After drying for a minute, a coating film having a thickness of about 30 μm was formed. The pencil hardness, acetone rubbing resistance and alkali resistance of this coating film [5
% Aqueous potassium hydroxide solution at room temperature (about 20 ° C.)
2 hours], the results shown in Table 1 were obtained.
In the table, the evaluation criteria for acetone rubbing resistance and alkali resistance are as follows.

○: excellent, △: good, ×: not good

[0090]

[Table 1] Comparative Example 4 Carboxyl group-containing acrylic resin [Composition: styrene / methyl methacrylate / isobutyl acrylate / methacrylic acid = 7/56/27/10 (% by weight), solid content concentration: 5
5.6% (solvent: xylene / isobutyl acetate), weight average molecular weight: about 12,500, hereinafter referred to as “acrylic resin B”] with isobutyl acetate;
A 5% by weight coating was prepared.

Comparative Example 5 Acrylic resin B was diluted with isobutyl acetate to a solid content of 27.5% by weight. Bisoxazoline was added to this diluted solution at 0.72% by weight of the solid content of the acrylic resin and dissolved to prepare a coating agent.

Comparative Example 6 Acrylic resin B was diluted with isobutyl acetate to a solid content of 27.5% by weight. To this diluted solution, silicon dioxide was added at 30% by weight of the solid content of the acrylic resin, and dispersed using an ultrasonic disperser to prepare a coating agent.

Example 2 Acrylic resin B was diluted with isobutyl acetate to a solid content of 27.5% by weight. Oxazoline group-containing silicon dioxide is added to this diluted solution at 30% by weight of the solid content of the acrylic resin.
In addition, it was dispersed using an ultrasonic disperser to prepare a coating agent.

Then, the above Comparative Examples 4 to 6 and Example 2
Was applied to a stainless steel plate using a bar coater # 40 and dried at 120 ° C. for 20 minutes to form a coating film having a thickness of about 31 μm. When the acetone rubbing resistance, alkali resistance, and pencil hardness of the coating film were examined in the same manner as described above, the results shown in Table 2 were obtained.

[0095]

[Table 2] [Preparation Example 2 of Particles Having Oxazoline Group] To 80 ml of chloroform, 30 g of 3-aminopropyltriethoxysilane (manufactured by Chisso Corp., Siraace S330) and 13.6 g of succinic anhydride were added, and reacted at room temperature for 1 hour. Was. When the reaction product was confirmed by ¹ H-NMR, the reaction proceeded quantitatively, and an equimolar addition reaction product of the silane coupling agent and succinic anhydride was generated. This product was very unstable to moisture.

After chloroform was distilled off from the reaction mixture, 2,2 '-(1,3-phenylene) -bis (2-oxazoline) (manufactured by Takeda Pharmaceutical Co., Ltd., 3-BPO), 44.1 g, and 155
The reaction was carried out at a temperature of 1 hour. The reaction product was treated with ethyl acetate 250
The resulting solution was dissolved in ml, and the insoluble material was separated by filtration. The filtrate was concentrated to 50 ml, and the precipitate was separated by filtration. The residue was purified by silica gel column chromatography (eluent: ethyl acetate) to obtain a compound represented by the following formula (oxazoline group-containing silicon compound) (colorless oil, 3.88 g).

[0097]

Embedded image (1) ¹³ C-NMR (ppm, CDCl ₃ ) (JEOL Ltd.)
Ltd., JMM270): δ 173 (C OO), 171.5 (NH C O), 167 (NH C OC 6 H 4), 164 (C
H ₂ CH ₂ C NO), 126.7, 127.8, 128.2, 130.0, 130.6, 13
_{4.6 (C 6 H 4),} 67.8 (C H 2 CH 2 CNO), 63.5 (COO C H 2 CH 2 NHC
O), 58.5 (CH ₃ CH ₂ O), 55.0 (CH ₂ CH ₂ CNO), 42.0 (CH ₂ CH ₂ CNO)
_{CH 2 C H 2 NHCO),} 39.0 (COOCH 2 C H 2 NHCO), 31.0, 30.0 (C
_{H 2 C H 2 COO),} 22.8 (CH 2 C H 2 CH 2 NHCO), 18.2 (C H 3 CH
_{2 O), 7.9 (C H} 2 CH 2 CH 2 NHCO) (2) Mass spectrum (Shimadzu Corp., laser ionization time-of-flight mass spectrometer COMPACT MALDI) calcd _{C 25 H 39 N 3 O 8} Si = 537 Measurement values: 560 (M + Na), 576 (M + K) 3.33 g of fine particle silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex methanol silica sol), 0.85 g of the above oxazoline group-containing silicon compound, and methanol 3
The mixture with 8.3 g was stirred for 15 hours. 20 ml of toluene was added to the reaction mixture, followed by centrifugation, and the supernatant was removed. This operation of centrifugation and removal of the supernatant is repeated a total of three times to remove the unreacted oxazoline group-containing silicon compound, followed by drying under reduced pressure at 100 ° C. for 0.5 hour to obtain the silica particles into which the oxazoline group has been introduced. I got
The reaction of the oxazoline group-containing silicon compound is carried out by a solid ¹³ C-
Confirmed by NMR.

Solid state ¹³ C-NMR (CP / MAS) spectrum (JMM270, manufactured by JEOL Ltd.) δ (ppm): 173, 162, 130, 62, 53, 44, 41, 32, 24,
19, 8 The resulting oxazoline group-containing inorganic reactive particles were dispersed in ethanol to prepare a dispersion having a solid content of 2.35% by weight.

Comparative Example 7 and Examples 3 to 5 Acrylic resin A was diluted with methanol to give a solid content of 50%.
% By weight. A predetermined amount of triethylamine (hereinafter referred to as “TEA”) was added to the diluted resin solution to neutralize 33 mol% of the carboxyl groups of the acrylic resin A.

The dispersion of the oxazoline group-containing inorganic reactive particles obtained in Preparation Example 2 was added to 4 g (solid content: 2 g) of the obtained acrylic resin A solution in terms of solid content of 0 g (Comparative Example 7). 0.05 g (Example 3), 0.10 g (Example 4), and 0.20 g (Example 5) were added and mixed to prepare a resin composition for coating.

The above resin composition for coating was applied to a stainless steel plate degreased with ethanol, dried at room temperature for 1 day at room temperature, and then dried at 120 ° C. for 20 minutes. Then, the film thickness, gloss (60 °), and pencil hardness were examined. Further, the residual liquid of the prepared resin composition for paint was stored at room temperature, and the stability (usability of use) after 2 days was examined by observing the solution state. Table 3 shows the results.

[0102]

[Table 3]

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Michihiro Kawai 1 Nagoya Research Institute, Nagoya Aichi

Claims (7)

[Claims] 1. A resin composition comprising (1) an inorganic particle having an oxazoline group, and (2) an acrylic resin having a carboxyl group or a salt thereof. 2. The resin composition according to claim 1, wherein the oxazoline group is bonded to the inorganic particles by a residue of a silane coupling agent. 3. The use ratio of the inorganic particles having an oxazoline group is as follows:
The resin composition according to claim 1, wherein the amount is 0.1 to 120 parts by weight. 4. The resin composition according to claim 1, wherein the acrylic resin having a carboxyl group or a salt thereof has a glass transition temperature of −60 ° C. to 50 ° C. and an acid value of 2 to 200 mg · KOH / g. Stuff. 5. A monomer having a (meth) acrylate monomer unit ratio of 50% by weight or more and a carboxyl group or a salt thereof based on the total amount of all constituent monomer units of the acrylic resin. 0.2-30% by weight of monomer unit
The resin composition according to claim 1, 2, 3, or 4. 6. Inorganic particles having oxazoline groups (1)
Is a method of reacting (1a) an inorganic particle (A) having a reactive group with a compound (C) having an oxazoline group, (1b) a coupling agent or a coordinating compound (B) with the inorganic particle (A) A compound having an oxazoline group by introducing a reactive group
(1c) a coupling agent or a compound having a oxazoline group and a reactive functional group, which is produced by reacting a coordinating compound (B) with a compound (C) having an oxazoline group. The resin composition according to claim 1, which is at least one kind of oxazoline group-containing inorganic particles obtained by a method of treating the inorganic particles (A). 7. A compound having an oxazoline group (C)
Has the following formula (I): (In the formula, E is an alkylene group which may have a substituent,
Substituted have a good cycloalkylene group or a substituent shown also arylene group, R ^1, R
² , R ³ and R ⁴ are the same or different and are each a hydrogen atom,
And a substituted or unsubstituted alkyl group or an aryl group which may have a substituent).