JP2686902B2 - Curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a curable fat composition. More specifically, it relates to a curable resin composition comprising a vinyl resin containing a specific carboxyl group and a hydrolyzable silyl group.

[0002]

2. Description of the Related Art A paint using an acrylic resin having a hydrolyzable silyl group is known, and a coating film is formed by condensation of a silyl group, which is excellent in weather resistance, heat resistance, water resistance, hardness and the like. Have been served. This type of resin does not always have sufficient pigment dispersibility when it is made into a coating material, and therefore a vinyl monomer containing a silyl group is copolymerized with acrylic acid or methacrylic acid, or a polyester resin having a polymerizable unsaturated group. The polymer is polymerized with a hydrolyzable silyl group-containing vinyl monomer to improve the pigment dispersibility. (JP-A-61
-123656)

[0003]

However, these methods still have a problem that the storage stability after preparation of the paint is not sufficient.

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors, a curable resin composition comprising a hydrolyzable silyl group-containing resin which gives a coating having good pigment dispersibility and storage stability was obtained. The present invention has been reached. That is, the present invention provides (A) a hydrolyzable silyl group-containing vinyl monomer (B) a polymerizable carboxylic acid type caprolactone derivative represented by the following formula:

[0005]

Embedded image (However, in the formula, R1 is H or CH3, R2 is COO, CH2
O or CONH, n represents an integer of 1 to 5. ) And (C) other polymerizable monomers, a curable resin composition containing a vinyl-based resin as an essential component.

In the present invention, the (A) hydrolyzable silyl group-containing vinyl monomer is specifically a vinyl silane having a hydrolyzable group, such as vinylmethyldimethoxysilane, vinyltrimethoxysilane, or vinyltriethoxysilane. , Vinyltris (β-methoxyethoxy) silane; and (meth) acryloxyalkylsilanes having hydrolyzable groups, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltri Examples thereof include methoxysilane, γ-methacryloxypropylmethyldiethoxysilane, and γ-acryloxypropyltriethoxysilane. Of these, preferred are (meth) acryloxyalkylsilanes having a hydrolyzable group.

As the polymerizable terminal carboxylic acid type caprolactone derivative (B), those represented by the following formula can be used.

[0008]

Embedded image (However, in the formula, R1 is H or CH3, R2 is COO, CH2
O or CONH, n represents an integer of 1 to 5. )

Specifically, (meth) acryloyloxycaproic acid (R2 = COO, n = 1), dicaprolactone (meth) acrylate (R2 = COO, n = 2), tricaprolactone (meth) Acrylate (R2
= COO, n = 3), tetrakiscaprolactone (meth) acrylate (R2 = COO, n = 4),
Pentacaprolactone (meth) acrylate (R2 = C
OO, n = 5), (meth) acryloylaminocaproic acid (R2 = CONH, n = 1), dicaprolactone (meth) acrylamide (R2 = CONH, n =)
2), tricaprolactone (meth) acrylamide (R2 = CONH, n = 3), tetrakiscaprolactone (meth) acrylamide (R2 = CONH, n =)
4), pentacaprolactone (meth) acrylamide (R2 = CONH, n = 5), (meth) allyloxycaproic acid (R2 = CH2O, n = 1),
Dicaprolactone (meth) allyl ether (R2 = CH2
O, n = 2), tricaprolactone (meth) allyl ether (R2 = CH2 O, n = 3), tetrakiscaprolactone (meth) allyl ether (R2 = CH2)
O, n = 4) and pentacaprolactone (meth) allyl ether (R2 = CH2 O, n = 5). Preferably n = 1-5 caprolactone (meth)
Acrylates, more preferably (meth) acryloyloxycaproic acid, dicaprolactone (meth) acrylate and tricaprolactone (meth) acrylate.

The other polymerizable monomer (C) is not particularly limited, but examples thereof include the polymerizable monomers or oligomers exemplified in (a) to (e) below. (A) (meth) acrylic acid ester having an alkyl group having 1 to 30 carbon atoms, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2
-Ethylhexyl, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate and the like. (B) Hydroxyl group-containing monomer (meth) -2-hydroxyethyl acrylate, (meth)
Acrylic acid-2-hydroxypropyl, (meth) acrylic acid monoester of diethylene glycol, etc. (C) Aromatic vinyl monomers Styrene, etc. (D) Alkyl or cycloalkyl vinyl ether Methyl vinyl ether and the like. (E) Vinyl ester Vinyl acetate, etc. (F) Nitrile group-containing monomer Acrylonitrile, etc. (To) Amide group-containing monomer (meth) acrylamide, etc. (H) Epoxy group-containing vinyl monomer Glycidyl (meth) acrylate, etc. (I) Vinyl monomer having siloxane group CH2 = C (CH3) COO (CH2) 3 [Si (CH3) 2
O] nSi (CH3) 3 and the like (where n = 1 to 130) and the like. (Nu) Vinyl monomer having a perfluoroalkyl group having 3 to 30 carbon atoms (meth) acrylic acid ester having a perfluoroalkyl group CF3 (CF2) 9 (CH2) 2OCOCH = CH2 and the like. Maleic acid mono- or diester with perfluoroalkyl group C8F17 (CH2) 11OCOCH = CHCOOCH3 etc. Olefin having a perfluoroalkyl group C7F15CH2CH = CH2 and the like. Vinyl ether or allyl ether having a perfluoroalkyl group such as C7F15CH2OCH = CH2. Vinylsulfonic acid ester having a perfluoroalkyl group C8F17SO2NHCH2SO2CH = CH2 and the like. (L) Polyvinyl monomer Divinyl monomer (divinylbenzene, diallyl phthalate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, etc.), trivinyl monomer (trimethylolpropane tri ( (Meth) acrylate, etc.), tetravinyl monomers (pentaethriate tetra (meth) acrylate, etc.), etc. (E) Polymerizable oligomer having vinyl group This is an ester of polycaprolactone diol and (meth) acrylic acid in which one or more polymerizable double bonds have been introduced into oligomers such as polyurethane, polyamide, epoxy resin, and polyester. Compounds [eg Praxel F
M-1 (manufactured by NOF CORPORATION)], a reaction product of a prepolymer of polytetramethylene glycol and isophorone diisocyanate (terminal OH) (1 mol) and ethyl isocyanate acrylate (1 mol), a polyamide and (meta). ) A reaction product of an acrylic ester, a reaction product of an epoxy resin and acrylic acid, and the like. As (C), one kind or a mixture of two or more kinds thereof is used. Among these, preferable are (a), (b) and (c), and particularly preferable are methyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( (Meth) acrylic acid and styrene.

In the present invention, the content of each constituent component in the vinyl resin is usually 0.5 to 60%, preferably 3 to 40%, and particularly preferably 5 to 60% by weight of the vinyl resin (A). 20%, (B) is usually 0.01 to 15%, preferably 0.1 to 10%, particularly preferably 0.3 to 5%. (C) is 99.49 to 25%, preferably 96.
It is 9 to 55%, particularly preferably 94.7 to 75%.
It is. If (A) is less than 0.5%, the cross-linking density of the coating film is small and the physical properties of the coating film such as weather resistance and water resistance are poor. 60
If it exceeds%, the storage stability becomes poor. (B) is 0.0
If it is less than 1%, the dispersibility of the pigment becomes insufficient, and if it exceeds 15%, the water-resistant physical properties of the coating film deteriorate.

The vinyl resin in the present invention is (A),
It can be produced by subjecting the monomers (B) and (C) to bulk or solution polymerization according to radical polymerization such as thermal polymerization, photopolymerization or radiation polymerization. The preferred polymerization method is radical polymerization performed using a radical initiator in an organic solvent. Organic solvents used include aromatic hydrocarbons (toluene, xylene, ethylbenzene, etc.), aliphatic hydrocarbons (hexane, heptane, cyclohexane, etc.), aliphatic esters (ethyl acetate, n-butyl acetate, etc.), aliphatic ketones. (Acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.), aliphatic ether (dioxane, tetrahydrofuran, etc.), alcohol (isopropanol, n-)
Butanol, isobutanol, ethyl cellosolve, n-
Butyl cellosolve, cellosolve acetate, etc.), halogenated hydrocarbons (carbon tetrachloride, ethylene dichloride, etc.) and the like, and mixtures of two or more thereof. Preferred are toluene, xylene, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, acetic acid n-.
Butyl, cellosolve acetate and ethylene dichloride, either alone or as a mixture of two or more thereof.

When radical polymerization reaction is carried out, the radical polymerization initiators used are azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), peroxides (benzoyl peroxide, di-t-). Butyl peroxide, cumene hydroperoxide, etc.), redox compounds (benzoyl peroxide /
N, N-dimethylaniline, etc.) and the like. Preferred are azo compounds. The amount of the polymerization initiator used is usually 0.0 with respect to the total weight of the monomers (A) to (C).
It is 01 to 20%, preferably 0.1 to 10%.

If necessary, a chain transfer agent (n-lauryl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.) is added, and the molecular weight of the vinyl resin is added. Can be adjusted.

The reaction temperature of the radical polymerization reaction is usually 50 to
The temperature is 160 ° C, preferably 70 to 130 ° C. The reaction time is generally 1 to 10 hours, preferably 2 to 7 hours. The end point of the polymerization can be confirmed by the disappearance of the double bond absorption (1648 / cm) in the infrared absorption spectrum or by the reduction of the unreacted monomer using gas chromatography.

The molecular weight of the vinyl resin is not particularly limited, but it is usually 1,000 to 100,000, preferably 3,
It is 000 to 50,000.

The curable resin composition of the present invention may contain various known coating resins, additives and solvents. Examples of paint resins include acrylic, urethane, melamine, silicone, ester, and epoxy paint resins. Examples of the additive include a diluent solvent, a pigment, a stabilizer of a hydrolyzable silyl group, a curing catalyst, a surfactant, an ultraviolet absorber and an antioxidant. The solvent may be the same as the solvent used when producing the vinyl resin in the present invention, but it may be diluted with another solvent. The amount of the diluent solvent is usually 0 to 600% by weight based on the vinyl resin.

As the pigment, an extender pigment (calcium carbonate,
Kaolin, talc, aluminum silicate, aerosil, etc.),
Inorganic pigments (such as titanium oxide, iron oxide, graphite, cadmium oxide, carbon black, and aluminum flakes) and organic pigments (such as azo, azo lake, phthalocyanine, quinacridone, and isoindolinone organic pigments). Can be

Specific examples of the hydrolyzable silyl group stabilizer include aliphatic alcohols having 1 to 4 carbon atoms (methanol, ethanol, isopropanol, n-butanol, etc.), trialkyl orthoformates (trimethyl orthoformate, etc.). , Trialkyl orthoacetate (trimethyl orthoacetate etc.), silanes (methyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, ethyl silicate, methyl silicate, etc.). Of these, aliphatic alcohols having 1 to 4 carbon atoms are preferable. The blending amount is 100 by weight of vinyl resin.
The amount is usually 0.5 to 60 parts, preferably 3 to 60 parts.
30 parts.

As the curing catalyst, a silyl group curing catalyst which has been conventionally used as a silanol condensation catalyst can be used. For example, an organic titanate compound (such as isopropyltriisostearoyl titanate) or an organic aluminum compound (acetoalkoxyaluminum diisopropionate) can be used. ), Carboxylic acid type tin compounds (dibutyltin dilaurate, monobutyltin triacetate, monobutyltin trilaurate, monooctyltin trilaurate, monobutyltin trichloride, etc.), sulfide type, mercaptide type sulfur-containing organic tin compounds (dibutyltin) Sulfides), other carboxylic acid metal salts (such as lead octylate), acidic phosphoric acid esters (such as monomethyl acidic phosphoric acid esters), carboxylic acids and their acid anhydrides (such as maleic acid) Amine (γ-aminopropyltriethoxysilane, etc.), amine and its salts (triethylamine, dibutylamine-2-hexoate, cyclic amidine and its salts, etc.), quaternary ammonium salts (tetrabutylammonium hydroxide, etc.), etc. A curing catalyst may be used.

The surfactant may be any of the commonly used anionic, cationic and nonionic surfactants.
Further, a UV absorber, a heat resistance improver, a leveling agent, an anti-sagging agent, a matting agent and the like which are usually used may be contained.

A coating material using the curable resin composition of the present invention can be obtained by appropriately selecting and mixing a vinyl resin and the above-mentioned known coating resin, additives or solvents according to the purpose. As a mixing apparatus for such mixing, a ball mill, a kneader, a sand grinder, a roll mill, a flat stone mill and the like can be mentioned.

The curable resin composition of the present invention or a coating material using the same can be applied to various substrates for use. For example, it can be applied by brush coating, spray coating, dip coating, coating method (for example, blade coater, air knife coater, roll coater, curtain coater, bar coater, gravure coater, etc.). After being applied to the substrate, it may be dried and cured at room temperature, or it may be heated to be cured. Examples of the base material include inorganic building materials such as glass and slate, processed products of metals such as aluminum and tin, woodwork, paper, fibers and plastic films and sheets.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

【Example】

Example 1 100 g of isopropanol was charged into a 300 ml four-necked Kolben and heated to 82 ° C. with stirring. γ-methacryloxypropyltrimethoxysilane (hereinafter referred to as MPS) 15 g, Aronix M-5300 (dicaprolactone acrylate, manufactured by Toagosei Kagaku Kogyo, CC below)
A) 2 g, methyl methacrylate (hereinafter MMA) 43 g, n-butyl acrylate (hereinafter BA)
10 g, n-butyl methacrylate (hereinafter referred to as BMA)
30 g, n-lauryl mercaptan (hereinafter referred to as LM)
A mixed solution of 1 g and 2 g of azobisisovaleronitrile (referred to as AIVN) was added dropwise over 3 hours. After reacting for 2 hours at the same temperature, 0.2 g of AIVN was added and further reacted for 2 hours. After cooling, 10 g of methanol was added. Thus, a resin composition A of the present invention having an isopropanol solution having a solid content of 46.0% was obtained.

Examples 2 to 4 and Comparative Examples 1 to 3 Resin compositions B, C and D and comparative resin compositions were prepared by reacting in the same manner as in Example 1 with the compounding ratios shown in Table 1. E, F and G were obtained.

[0027]

[Table 1]

CCMA: tricaprolactone methacrylate MAA: methacrylic acid AA: acrylic acid

Next, the resin compositions A to G were evaluated for pigment dispersibility and storage stability by the following methods. The results are shown in Table 2. First, 100 g of each resin composition 200 g, titanium oxide (CR-97) 60 g and glass beads 400 g
It was placed in a 0 ml sample can and shake-mixed for 30 minutes with a paint conditioner to prepare a paint having a weight pigment concentration of 40. Pigment dispersibility: Solid content of 2% with isopropanol
After diluting to 0%, add 25 to 300 ml mayonnaise bottle.
0 g was added. After standing at 40 ° C. for 30 days, the thickness (distance cm unit from the bottom of the mayonnaise bottle) of the pigment layer separated and settled was measured. This thickness was expressed as a ratio when the distance (cm) from the bottom to the liquid surface of the coating was 100. The smaller the value, the better the pigment dispersibility. Storage stability: The viscosity of the coating composition after hermetically storing at 40 ° C. for 30 days was expressed as a ratio to the initial viscosity.

[0030]

[Table 2]

When the curable resin composition of the present invention is used,
It can be seen that there is a good balance between pigment dispersibility and storage stability.

[0032]

The curable resin composition of the present invention has the following effects. (1) The pigment dispersibility and the storage stability are well balanced. (1) Moisture curable. By exhibiting the above effects, the curable composition of the present invention is useful for various applications such as a coating agent at room temperature to under heating, such as a coating material, a coating agent in a narrow sense, an adhesive, a primer and a binder. Specifically, for example, waterproof or weather-resistant paints for building materials (eg, inorganic materials such as glass, slate, ceramics, metals such as aluminum, woodworking, plastics, etc.), autoclave curing paints, paints for acid rain resistance, antifouling properties. Paints, anticorrosion paints, water repellents for inorganic building materials (water absorption inhibitors), inorganic building material primers or sealers, glass adhesives, electrodeposition paints, vehicle paints (excluding top coats), vehicle repair paints, vehicles Paints for parts, hard coat agents, coating agents for cans (for example, aluminum), anticorrosive paints, release agents, coating agents for plastics (for example, coating agents for PVC sheets such as PVC desk mats and wallpaper coatings for PVC), Moisture-proof coating agent for electric and electronic parts, insulation coating agent, back coating agent for ink ribbon and magnetic tape,
It is suitable as a binder for inks, a release agent for information paper (for example, sublimation type thermal transfer image receiving paper), a binder for glass fibers, an adhesive for non-woven fabrics, a coating agent for papers and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C09D 201/10 C09D 201/10

Claims (2)

(57) [Claims] 1. (A) Hydrolyzable silyl group-containing vinyl monomer (B) Polymerizable terminal carboxylic acid type caprolactone derivative represented by the following formula: (However, in the formula, R1 is H or CH3, R2 is COO, CH2
O or CONH, n represents an integer of 1 to 5. ) And (C) other polymerizable monomer, and a vinyl resin obtained by copolymerization as an essential component. 2. The curable resin composition according to claim 1, further containing an aliphatic alcohol having 1 to 4 carbon atoms.